The 2nd In nternationall Conference e of the Indo onesian Chem mical Society y 2013 October, 22-23th 20133  

Prreface The interrnational co onference is an annual conference of the Indonesian Chem mical Societty (Himpunnan Kimia Indonesia, I H HKI). In thhe year 2013, the manndate of thhe organizinng committeee was given n to the HK KI Yogyakarrta branch and a also supported by Department D o of Chemistrry of Univ versitas Negeri Yogyaakarta (UN NY), Departtment of Chemistry C o of Universittas Gadjah Mada (UGM M), Departm ment of Cheemistry of U Universitas Islam Negeeri Sunan Kalijaga K (UIN N Suka), Naational Nucllear Energy Agency (BA gyakarta), annd ATAN Yog Volcano Investigatiion and Teechnologicall Developm ment Centerr (BPPTK Yogyakartaa). partment off Chemistryy, Faculty of o For the year 2013, ICICS 20013 is hostted by Dep N Scieences, Islam mic Universiity of Indoonesia, Yogyyakarta from m Mathemaatics and Natural October 22 – 23, 20013. This connference waas also prepaared to celebbrate 70th anniversary a o of Universittas Islam Inddonesia.

mprises the following: f The Sicenntific Prograamme of ICIICS2013 com 1. Innvited Speakker 2. A total 256 paaper for paraallels sessionns a. Organ nic Chemistrry b. Inorgaanic Chemisstry c. Physiccal Chemistrry d. Analyytical Chemistry e. Educaation Chemisstry f. Biochhemistry

11

papers

32 43 37 68 23 43

papers papers papers papers papers papers

The breakkdown of thhe presentatio on is as folloows: Sesssion Invitted Speaker Orgaanic Chemisstry Inorrganic Chem mistry Physsical Chemisstry Anaalytical Chem mistry Education Chem mistry Biocchemistry Tota al

Oral 11 25 38 31 61 22 34 222

Poster 0 7 5 6 7 1 8 34

Total 11 32 43 37 68 23 43 256

Yogyakkarta, 25th Noovember 20113

Editorrs

ISBN: 978-979-9 9 6595-4-5  

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  The 2nd In nternationall Conference e of the Indo onesian Chem mical Society y 2013 October, 22-23th 20133  

Welccoming A Address by y The Org ganizing C  Committe ee         

Assalamu’aalaikum Wr. W Wb.    Honorable Rector of Un niversitas Islaam Indonesiaa  The distingguished inviteed speakers, and  All participants of the IC CICS 2013   

  Welcomee  you  at  the  2nd  Internattional  Conferrence  of  the  Indonesia  Chemical  C Socciety  2013  (ICICS  ( 2013)  th his  morningg  here  at  the  t Auditoriium  Kahar  Muzakkir  Universitas  U Islam  Indon nesia,  Yogyakarrta.  The  inteernational  co onference  iss  an  annual  conference  of  the  Indo onesian  Chemical  Society  (Himpunan  ( Kimia  Indon nesia,  HKI).  In  the  year  2013,  thee  mandate  of  o the  organ nizing  committeee  was  giveen  to  the  HKI  H Yogyakaarta  branch  and  also  su upported  by y  Department  of  Chemistrry of Universitas Negeri Y Yogyakarta (UNY), Deparrtment of Chemistry of U Universitas Gaadjah  Mada  (UGM),  Departtment  of  Chemistry  of  Universitas  U I Islam  Negeri  Sunan  Kaliijaga  (UIN  Suka),  S National  Nuclear Eneergy Agency  (BATAN Yoggyakarta), an nd Balai Peny yelidikan daan Pengembaangan  Kegunungapian (BPPTK Yogyakarrta).  For thee year 2013,  the honor off hosting ICIC CS 2013 has  been  given  to  the  Departm ment  of  Chem mistry,  Facullty  of  Matheematics  and  Natural  Scieences,  Univerrsitas  Islam  Ind donesia,  Yogy yakarta.  This  conferencee  was  also  prepared  to  celebrate  c 70th  anniversaary  of  Universittas Islam Indonesia.    The  confference  com mprises  both  oral  and  poster  p presentation  in  English  E and  Indonesian  with  optional  post confereence publicattion of full p papers in Engglish in the P Procedia Cheemistry (Elseevier,  ISSN:  1876‐6196)  an nd  Proceeding  Conferen nce  for  Indo onesian  langguage.  Theree  are  211  paapers  presented d  orally  and  34  papers  presented  p by y  poster  cov vering  wide‐v variety  subjeects  of  chem mistry.  We inviteed 6 Indonesian invited sspeakers, 2 Jaapan invited speakers, 1 A Australian in nvited speakers, 1  Saudi Araabia invited sspeakers, and d 1 Malaysian Invited speeakers.   We hope you will enjo oy a pleasantt and valuablle seminar att Universitass Islam Indon nesia    Wassalam mu’alaikum W Wr. Wb.        Riyanto, Ph.D.      Chairman   

ISBN: 978-979-9 9 6595-4-5    

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  The 2nd International Conference of the Indonesian Chemical Society 2013 October, 22-23th 2013  

Opening Speech from the Rector of Universitas Islam Indonesia

Assalamu’alaikum Wr. Wb  The distinguished invited speakers, and  All participants of the ICICS 2013    Firstly, I would like to express my great appreciation to the Department of  Chemistry  UII  as  one  of  the  organizers  of  the  program  The  2nd  International Conference of the  Indonesian Chemical Society 2013 (ICICS    2013)  with  the  theme  “Research  in  Chemistry  for  Better  Quality  of  Environmental”. I am proud that this interesting event is being organized  and held in Yogyakarta.  As  the  biggest  and  the  oldest  private  university  in  Yogyakarta,  University  Islam  Indonesia  is  committed to the excellence in research and teaching. Recently, we are preparing UII as one of the  world class universities.  Knowing that committee has selected outstanding speakers from various prestigious institutions. I  believe  that  all  of  the  participants  will  enjoy  the  discussion  of  issue  covered  by  the  topic  of  this  seminar. Scientist have shown that the environment’s condition is increasingly critical, and human  industrial  activities  are  largely  to  blame.  In  fact  that  environmental  damage  is  a  crisis  we  caused  together, therefore, a responsibility we all share together. We are deeply concerned with the issues  and opportunities in the internationalization of sciences for better life, sciences have to make better  quality of environmental.    Finally, I would once again like to thank the organizer for organizing this event, and to thank all the  participants attending this ICICS 2013 event as well as delivering their scientific presentations. I do  really hope that you can enjoy this seminar and have excellent stay in Yogyakarta.    Wassalamu’alaikum Wr. Wb      Prof. Dr. Edy Suandi Hamid, M.Ec.  Rector of Universitas Islam Indonesia 

ISBN: 978-979-96595-4-5    

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  The 2nd International Conference of the Indonesian Chemical Society 2013 October, 22-23th 2013  

   

Remarks by the Chairman of the Indonesian Chemical Society  (Himpunan Kimia Indonesia, HKI) 

Indonesian  Chemical  Society  (Himpunan  Kimia  Indonesia,  HKI)  is  an  independent,  nonprofit  organization  founded  in  February  1962  to  facilitate  communication  among  Indonesian  chemists  and  other  professionals  from  chemistry  related  fields,  and  to  promote  the  advancement  of  science,  education,  and  application  of  chemistry  to  support  the  better  life  of  mankind.  HKI  organize  activities  to  enhance  communication  and  collaboration  among  chemists  in  various  institutions  in  Indonesia,  to  disseminate  new  knowledge  and  research     results  in chemistry and related fields, to improve the knowledge and   skills  of  chemists  working  in  schools,  universities,  industries,  research  institutes,  and other  sectors,  to  nurture  a  scientific  temper  on  school  children  to  ensure  strong  capabilities  of  future  chemists that are needed for humankind, and other activities that support its missions. HKI holds  various academic conferences, publishes several journals, supports the development of scientific  information systems in Indonesian; organize training for chemists in various sectors, etc.  The 2013 International Conference of the Indonesian Chemical Society will be the 2nd event in the  ICICS  conference  series,  started  in  2012,  that  brings  together  individuals  involved  in  chemistry‐ related  fields  (chemistry,  pharmacy,  environmental  science,  chemical  engineering,  molecular  biology,  material  science,  education  chemistry,  etc.)  or  institution  in  chemistry‐related  sectors.  The First International Conference of the Indonesian Chemical Society 2012 is organized by East  Java  Branch  of  HKI  in  collaboration  with  chemistry  departments  at  several  universities  in  East  Java: ITS, UB, UIN Maliki, UM, UMC, Unair, Unej, and Unesa.   ICICS  2013  will  be  organized  by  the  Indonesian  Chemical  Society  Yogyakarta  branch.  The  international  conference  was  supported  by  the  Indonesian  Chemical  Society  (Himpunan  Kimia  Indonesia, HKI), Department of Chemistry of Universitas Negeri Yogyakarta (UNY), Department of  Chemistry  of Universitas  Gadjah Mada (UGM) and Department of Chemistry of Universitas Islam  Negeri  Sunan  Kalijaga  (UIN  Sunan  Kalijaga).  For  the  year  2013,  the  honor  of  hosting  ICICS‐2013  has  been  given  to  the  Department  of  Chemistry,  Faculty  of  Mathematics  and  Natural  Sciences,  Universitas Islam Indonesia (UII), Yogyakarta, Indonesia.   Congratulations to the ICICS 2013 committee for this conference.          Dr. Muhamad Abdulkadir Martoprawiro  Chairman of the Indonesian Chemical Society   

ISBN: 978-979-96595-4-5    



  The 2nd International Conference of the Indonesian Chemical Society 2013 October, 22-23th 2013  

Committees  Steering Committee  1. Head of the Indonesian Chemical Society  2. Head of the Indonesian Chemical Society Yogyakarta Branch  3. Rector of Islamic University of Indonesia  4. Rector of Gadjah Mada University  5. Rector of Yogyakarta State University  6. Rector of State Islamic University of Sunan Kalijaga  7. Head of Geological Agency of Indonesia  8. Head of National Nuclear Energy Agency of Indonesia  Reviewers:  1. Prof. Dr. Hardjono Sastrohamidjojo (UII Yogyakarta)  2. Prof. Dr. Nurfina Aznam (UNY Yogyakarta)  3. Prof. Dr. Karna Wijaya (UGM Yogyakarta)   4. Prof. Shaobin Wang (Curtin University, Australia)  5. Prof. Dr. Nunuk Hariani Soekamto (University of Makassar, Indonesia)   6. Prof. Tatsufumi Okino (Hokkaido University, Japan)   7. Dr. Leenawaty Limantara (University of Ma Chung, East Java, Malang, Indonesia)  8. Dr. Muhamad A. Martoprawiro (Indonesian Chemical Society, ITB)  9. Prof. Katsumi Kaneko (Shinshu University), Japan)  10. Prof. Dato’ Musa Ahmad (Islamic Science University of Malaysia (USIM), Malaysia)  11. Prof. Fethi Kooli (Taibah University, Saudi Arabia)  12. Dr. Bambang Priadi  (ITB, Bandung),  13. Rahmat Wibowo, Ph.D.  (University of Indonesia)  14. Prof. Harno Dwi Pranowo (UGM Yogyakarta)  15. Prof. Drs.  Sahat Simbolon, M.Sc. (BATAN Yogyakarta)  16. Dr. Muhamad A. Martoprawiro (HKI)   17. Riyanto, Ph.D. (UII Yogyakarta)  18. Dr. Is Fatimah (UII Yogyakarta)  Editors:  1. Dr. Noor Fitri (UII Yogyakarta)  2. Drs. Allwar, M.Sc., Ph.D. (UII Yogyakarta)  3. Rudy Syah Putra, Ph.D. (UII Yogyakarta)  4. Dwiarso Rubiyanto, M.Si. (UII Yogyakarta)  5. Tatang Shabur Julianto, M.Si. (UII Yogyakarta)   

ISBN: 978-979-96595-4-5    

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  The 2nd International Conference of the Indonesian Chemical Society 2013 October, 22-23th 2013   Organizing Committee   :  Chairperson       : Riyanto, Ph.D.  Secretary      : 1. Rudy Syahputra, Ph.D.            2. Cecep Sa’bana Rahmatillah, S.Si.            3. Siswanta, S. Pd.    Treasure      : 1. Dr. Noor Fitri, M.Si.            2. Masirah, A.Md            3. Yuni Ari Rahmawati, S.Ag.    Programmer & protocol  : 1. Sunaryo MD            2. Lindung Prasetya Kurniawan, A.Md.            3. Paidi            4. Asih            5. Vira Megasari Haqni, ST      Proceedings       : 1. Thorikul Huda, S.Si. M.Sc.            2. Krisna Merdekawati, S.Pd., M.Pd.            3. Puji Kurniawati, S.Pd.Si., M.Sc.            4. Bayu Wiyantoko, S.Si., M.Sc.            5. Tri Esti Purbaningtias, S.Si., M.Si.            6. Yuli Rohyami, S.Si., M.Sc.            7. Dedy Sugiarto, S.Si.    Transportations and     : 1. Jamalul Lail, S.Si.  Accommodations      2. Ponimin, SE            3. Agus Sri Untoro            4. Sukadi            5. Parwanto    Appurtenance      : 1. Drs. Sunarwi            2. M. Achnaf, A.Md.            3. Sigit Mujiarto            4. Kuntoro Haryanto, A.Md.            5. Dwi Mahmudi, BA    Logistic      : 1. Reni Banowati Istiningrum, S.Si.            2. Indriyani, A.Md.            3. Painem            4. Syaida            5. Sukirman            6. Aprilia Risky Wijaya 

ISBN: 978-979-96595-4-5    

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  The 2nd In nternationall Conference e of the Indo onesian Chem mical Society y 2013 October, 22-23th 20133     Publicatio on and       : 1. Anaang Susilo, A.M Md.  Documen ntation    2. Siho ono                     3. Umaar Hasyim                4. Chriistanto Yuwo ono              5. Suraatmin    Supportin     ng Team  : Himpu unan Mahasiswa Kimia (H HMK UII) 

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  The 2nd International Conference of the Indonesian Chemical Society 2013 October, 22-23th 2013

CONTENT  Content  Cover 



Preface 

ii 

Welcoming addres by  The Organizing Committee 

iii 

Opening Speech from the Rector of Universitas Islam Indonesia 

iv 

Remarks by the Chairman of the Indonesian Chemical Society  (Himpunan Kimia Indonesia, HKI) 



Committe 

vi 

Reviewers and Editors 

vi 

Content 

ix 

Invited Speaker 

 

Shaobin Wang, Stacey  Indrawirawan, Yunjin Yao,  Hongqi Sun 

Graphene  Supported  Oxide  Systems  for  Catalytic  Oxidation  of  Organic Compounds in Aqueous Solution for Water Treatment 

xii 

Tatsufumi Okino 

Chemistry and biology of brominated compounds from marine algae Laurencia spp. 

xv 

Heriyanto, Leenawaty Limantara  Chlorophyll and Carotenoid Prospects on Food, Health and Energy  Katsumi Kaneko 

Fethi Kooli 

Allwar, Ahmad Md. Noor, Mohd  Asri bin Mohd Nawi 

Molecular  Functions  of  1  nm‐Scale  Pore  Spaces  and  their  Application Potential to Sustainable Technologies  Al13  Intercalated   and  Pillared  Montmorillontes  from  Unusual  Antiperspirant  Aqueous  Solutions:  Precursors  for  Porous  Clay  Heterostructures    and  Heptane  Hydro‐Isomerization  Catalytic  Activities  Characterizing  Microporous  Structures  using  Nitrogen  Adsorption‐ Desorption Isotherm for Activated Carbon Prepared with Different  Zinc Chloride Concentrations 

Papers of Inorganic Chemistry 

xviii  xxviii  xxxi 

xxxv   

Ahmad Budi Junaidi, Helda  Rahmawati dan Utami irawati 

Study  of  Carboxymethyl  Chitosan  Synthesis  :  Effect  of  NaOH  Concentration  and  Rtio  Chitosan/Monochloro  Acetic  Acid  Toword  On The Substitution Degree and Solubility In Water  

1‐5 

Ahmad Suseno, Priyono, Karna  Wijaya,Wega Trisunaryanti 

Study  of  Structure  and  Morphology  of  Surfactant–Modified  Al‐ pillared Natural Bentonite 

6‐14 

Aman Sentosa Panggabean,  Subur P. Pasaribu, Dadan  Hamdani, Nadira1 

Synthesis of A Chelating Resin Chitosan‐1,5‐Diphenyl Carbazide and  Characterization of Retention toward Cr(VI) Ions 

15‐25 

Anti K. Prodjosantoso 

Preparation  and  Characterisation  of  Chloride‐Free  Palladium  Catalysts 

26‐32 

ISBN : 978-979-96595-4-5    

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  ix 

  The 2nd International Conference of the Indonesian Chemical Society 2013 October, 22-23th 2013 Dwi Rasy Mujiyanti, Totok  Wiantoi, M. Fahmi Arif 

Synthesis and Characterization of Nanosilica from Rice Husk Ash by  Sol‐Gel Process 

33‐38 

Endang Susilowati, Triyono, Sri  Juari Santosa, Indriana Kartini 

Synthesis  of  Silver‐Chitosan  Nanocomposites  by  Glucose  As  Reducing Agent and Their Antibacterial Activity 

39‐47 

Analysis  In  Silico  on  Stucture‐Odor  Relationship  (SOR)  Of  Organoleptic‐Tested Compounds  

48‐55 

Febriyana Rizky Hapsari, Ersalina  Nidianti, Warsito, Edi Priyo  Utomo  Indah Uswatun Hasanah, Ria  Armunanto, Bambang Setiadji  Jannatin ´Ardhuha  Lia Destiarti, Nelly Wahyuni,  Ahmad Yani  Maula Eka Sriyania, Aang  Hanafiah W.S.  Muhamad Basit Febrian,  Aminudin Sulaeman,  Muhayatun Santoso 

The Oretical Study Properties of Semiconductor Metalloporphyrin  Complexes Calculated Density Functional Theory Method (DFT)  Characterization  of  The  FePd/NiTi  Shape  Memory  Alloy  Film  for  Sensor Applications  Synthesis  of  Zeolite  A  from  Capkala  Kaolin  by  Varying  Mass  of  Alumunium Oxide: XRD spectrum and CEC number of products   Physicochemical  Characteristics  of  99mTc‐dtpa‐ketoconazole  as  A  Radiopharmaceutical for Deep Seated Fungal Detection  Preliminary Study of Comparison of EDXRF and ICP‐AES Techniques  for the Measurement of Elements in Fine Particulate Matter (PM2,5)  : Accuracy and Precision of XRF Technique 

67‐76  77‐82  83‐89  90‐94 

Muhdarina, Nurhayati, Flora  Sijabat 

Characterization of Phosphated Palas Clay 

95‐100 

Nugrahaning Wuri Hakiki, Maria  Christina P., Isti Daruwati 

Penandaan M41S‐NH2 dengan Radionuklida Teknesium‐99m :   Perbandingan Metode Langsung dengan Metode Tidak Langsung   dalam Aplikasi Radiosinovektomi 

101‐111 

Nurul Hidayati Fithriyah,  Erdawati  Putu Sukmabuana, Poppy Intan  Tjahaja, and Anton Winarko 

Preservation of Paper Samples Coated With Chitosan Nanoparticle 

112‐120 

A Surveilence on Tritium Radionuclide in Surface Soil of The TRIGA  2000 Reactor Site, Bandung 

121‐128 

Ria Armunanto *, Karna Wijaya,  Radite Yogaswara 

Study of CO Adsorption on Ninq(n=3‐5; q=0, 1, ‐1) Clusters  using DFT Method 

129‐139 

Restu Kartiko Widi, Arief  Budhyantoro, Emma Savitri 

Reaction  Study  of  Phenol  Hydroxylation  on  Al/Fe  Pillared  and  HDTMA Intercalated Bentonite Catalyst 

140‐146 

Singgih Hartanto,  Achmadin  Luthfi, Sri Handayani  Triastuti Sulistyaningsih, Sri Juari  Santosa, Dwi Siswanta,  Bambang Rusdiarso 

Characterization  of  Membrane  PVA/Silica  and    PVA/Zeolite  for   147‐152  Purification Bioethanol by The Vapor Permeation Process.  Hydrothermal  Efek  on  Magnetite‐Mg/Al‐NO3‐HT  Composite  Synthesis 

153‐160 

Tutik Setianingsih, Indriana  Kartini, Yateman Arryanto 

Synthesis  of Mesoporous  Carbon  from  Fructose  by  using  Activator  of Zinc Borosilicate at Low Temperature 

161‐172 

Linda Dwitasari, Tutik Dwi  Wahyuningsih, Indriana Kartini 

HOMO and LUMO Determination of Chlorophyllin and Xanthophyll  Dyes using Cyclic Voltammetry 

173‐178 

Erni Astuti, Yateman Arryanto,  Indriana Kartini 

Facile Hydrothermal Synthesis of Various Nanostructured Titania 

179‐184 

Arief Rahmatulloh, Lukman  Atmaja, Nurul Widiastuti 

Korelasi  Konsentrasi  Silane  dan  Suhu  Operasi  Terhadap  Konduktivitas Membran Komposit  Kitosan  –  Fly Ash untuk  Aplikasi  Proton Exchange Membrane Fuel Cell 

185‐195 

ISBN : 978-979-96595-4-5    

56‐66 

  x 

  The 2nd International Conference of the Indonesian Chemical Society 2013 October, 22-23th 2013 Paulina Taba, Marthinus  Pongsendana, Eldayanti Ruru 

Thiol‐Functionalized Mesoporous Silica, MCM‐48 as Adsorbent Ag(I)  and Cd(II) Ions 

196‐201 

F. Widhi Mahatmanti, Nuryono,  Narsito 

Synthesis of Chitosan‐Silica Film using Sodium Silicate Solution from  Rice Hull Ash  

202‐206 

Maria Dewi Astuti, Dwi Rasy  Mujiyanti, Dahlena Ariyani,  Mustika Rahmadini  

Perbandingan  Sifat  Karakteristik  Silika  Gel  Sintesis  dari  Abu  Sekam  Padi Daerah Gambut dan Komersial  

207‐212 

Husna Amalya Melati   Khairi1,3, Lee Yook Heng1*,  Mohammad Bin Kassim1, Musa  Ahmad2, &SitiAishah Hasbullah1 

Corrosion  Protection  Efficiency  of  Hybrid  Polymers  Coatings  based  TMSPMA  Monomers  on  Carbon  Steel  in  Saline  Environment  Evaluated by Electrochemical Measurements  Novel Mercury Ion Selective Electrode Based on Self‐Plasticizing  Poly(n‐buthylacrylate) membrane with 4‐metil‐N‐(pyrrolidine‐1‐ carbonotioyl)benzamide (MPCB) Ionophore 

213‐219 

220‐229 

 

ISBN : 978-979-96595-4-5    

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  The 2nd International Conference of the Indonesian Chemical Society 2013 October, 22-23th 2013  

Graphene Supported Oxide Systems for Catalytic Oxidation of Organic Compounds in Aqueous Solution for Water Treatment Shaobin Wang, Stacey Indrawirawan, Yunjin Yao, Hongqi Sun Department of Chemical Engineering, Curtin University, GPO Box U1987, Perth WA 6845, Australia

Introduction Organic contaminants in water have been a big group of pollutants which are toxic and persistent. Presently, a great development has been achieved in decomposing these organic pollutants in wastewaters by advanced oxidation processes (AOPs), involving various chemical, photocatalytic, electrocatalytic methods.Among various techniques of catalytic oxidation for water and wastewater treatment, Fenton reaction is one of the cost-effective technologies where hydroxyl radicals (•OH) are usually main highly reactive oxidizing species generated to degrade organic contaminants. Similar to the activity of hydrogen peroxide for the degradation of organic pollutants, alternative oxidants such as peroxymonosulphate (PMS) have been found to be highly effective in chemically mineralizing various organic contaminants. Graphene, a single layer of carbon atoms tightly packed into a two-dimensional honeycomb sp2 carbon lattice, possesses a large surface area, open porous structure, flexibility, chemical stability, and very high electrical conductivity, which warrant it as a good candidate for constructing graphene-based composite materials with metal oxides. Here, we present synthesis of metal oxides (Co3O4 and CoFe2O4) and reduced graphene oxide (rGO) via a chemical deposition of Co3O4 and CoFe2O4 NPs onto GO, followed by reduction of GO to graphene in hydrothermal solution.These composites were tested in the catalytic performance in heterogeneous activation of peroxymonosulfate (PMS) for decomposition of phenol. Experimental GO was synthesized using the Hummers method through oxidation of graphite powder. In a typical synthesis of the Co3O4-rGOand CoFe2O4–rGO hybrids, firstly, cobalt and iron precursor were dispersed in distilled water, and GO was dispersed in 250 mL water by sonication for 2 h to achieve uniform dispersion of GO. Then, precursor solution was gradually added to the GO solution. Meanwhile, ammonia (28%) or NaOH solution was added to the above solution, which will be used for precipitation and GO reduction. Finally, the mixture was transferred into an autoclave for hydrothermal treatment at 180 Ԩ under static condition for 12 h. The solid product was separated by centrifugation, washed thoroughly with water and absolute ethanol to remove any impurities. The crystallographic structure of the catalysts was investigatedon a Bruker D8-Advance Xray diffractometer with Cu Kα radiation (λ = 1.5418 Å), with accelerating voltage and current of 40 kV and 40 mA, respectively. FT-IR spectra were recorded on a Perkin-Elmer Spectrum 100 with a resolution of 4 cm-1 in transmission mode at room temperature. The morphology of the materials were characterized by FESEM (Zeiss Neon 40EsB FIBSEM) equipped with EDS and TEM (JEOL 2011 TEM). TGA was performed by heating the samples in an air flow at a rate of 100 mL/min using a Perkin-Elmer Diamond TG/DTA thermal analyzer with a heating rate of 10 Ԩ/min. The surface area, total pore volume, and pore size distribution of all samples were determined by N2 adsorption at -196 Ԩ using Autosorb (Quantachrome Corp.). All samples were degassed at 100 Ԩ for 4 h, prior to the adsorption experiments. The Brunauer-Emmett-Teller (BET) surface area and pore volume were obtained by applying the

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BET equation and p/p0=0.95 to the adsorption data, respectively. The pore size distribution was obtained by the Barrett-Joyner-Halenda (BJH) method. To study the activity of the catalytic oxidation of phenol, batch experiments were carried out in a 150 mL batch reactor. All reactions were initiated without the pH being controlled by mixing appropriate concentrations of phenol, oxone and a catalyst. Fixed amount of oxone was added to a phenol solution and allowed to dissolve before the reaction. Later, catalysts were added to start the reaction. The reaction was carried on for 1 h and stirred at different temperatures (25, 35 and 45 Ԩ). At predetermined time intervals, 0.5 mL liquid was withdrawn using a syringe filter into a HPLC vial, and 0.5 mL of methanol was added to quench the reaction. The concentrations of phenol were analyzed using a HPLC with a UV detector at the wavelength of 270 nm. The column used was C-18 and the mobile phase was solution of 30% CH3CN and 70% water. Results and discussion The phase structure of as-synthesized samples was firstly determined by XRD. The results indicate that the hybrids consist of disorderedly stacked graphene sheets and well crystallized Co3O4 or CoFe2O4. The average crystallite sizes of Co3O4 in Co3O4–rGO and CoFe2O4 NPs in CoFe2O4–rGO were estimated to be 32.7 and 23.8 nm, respectively, which were consistent with the TEM observations (Fig.1).According to the TGA analysis, mass loss in Co3O4–rGO and CoFe2O4–rGO showed about 58% and 63.6 wt% of metal oxide deposited on the surface of graphene.

Co3O4 

CoFe2O4 

Fig. 1TEM images of Co3O4–rGO and CoFe2O4–rGO. The catalytic performances of rGO, Co3O4,CoFe2O4, Co3O4–rGO and CoFe2O4–rGO hybrids in the catalytic oxidation of phenol in the presence of PMS are shown in Figure 2. Nearly 23% of phenol (20 mg/L) was removed in 60 min in the presence of rGO, suggesting minor reaction of phenol degradation could occur. For pure Co3O4 sample, 100% of phenol was removed in 60 min while for CoFe2O4 sample, 51% of phenol was removed in 60 min. meanwhile the degradation rate of phenol with CoFe2O4–rGO and Co3O4–rGO hybrids was extremely fast and took around 30 and 20 min, respectively,for complete phenol oxidation under the same conditions.

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Figure 2. Phenol degradation using different catalysts (Reaction conditions: [Phenol] = 20 mg/L, [PMS] = 0.3 g/150 mL, [Catalyst] = 10 mg/150 mL) The catalytic performance of Co3O4–rGO/PMS and CoFe2O4–rGO/PMS at different temperatures are shown in Figure 3.As can be seen the rate of disappearance of phenol increased at increasing temperature.It was found that phenol degradation in Co3O4–rGO/PMS process is well formulated by the pseudo-zero-order kineticsand that CoFe2O4–rGO/PMS process is well formulated by the pseudo-first-order kinetics.The activation energy (Ea) values for Co3O4–rGO and CoFe2O4–rGO were obtainedas 26.5 and 15.8 kJ mol-1, respectively.

Figure 3. Effect of reaction temperature on phenol degradation using Co3O4–rGO/PMS andCoFe2O4–rGO/PMS. Acknowledgement The authors are grateful to the China Scholarship Council and CRC CARE for financial supports. References 1. Sie King Ling, Shaobin Wang, Yuelian Peng, J. Hazard. Mat., 2010, 178, 385-389. 2. Yunjin Yao,Zeheng Yang, Hongqi Sun, Shaobin Wang, Ind. Eng. Chem. Res., 2012,51, 14958−14965. 3. Yunjin Yao, Zeheng Yang,Dawei Zhang, Wenchao Peng, Hongqi Sun, Shaobin Wang,Ind. Eng. Chem. Res., 2012, 51, 6044-6051.

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Chemistry and biology of brominated compounds from marine algae Laurencia spp. Tatsufumi Okino Faculty of Environmental Earth Science, Hokkaido University, Sapporo, 060-0810, Japan ([email protected])

Fouling organisms such as barnacles and mussels cause decrease of fuel efficiency of ships. Antifouling coatings are urgently needed to prevent fouling organisms, to reduce carbon dioxide emissions from ships, and to prevent invasive organisms. Especially international treaty of the International Maritime Organization (IMO) to ban the use and existence of ship’s hull of organic tin compounds as antifouling agents went into effect in 2008. A number of

antifouling marine natural products have been reported in the past decade. Previously we screened marine invertebrate for antifouling against barnacle larvae. As a result, we found several

antifouling

compound

such

as

isocyano

compounds.

For

example,

10-isocyano-4-cadinene (1) is one of potent compounds, of which total synthesis was completed recently. In addition, 3-isocyanotheonellin (2) was explored as a leading compound. Over 90 compounds were synthesized and one of them was selected for the field test. Since the result was promising, we are currently collaborating with a paint company to pursue industrial application. Also their mode of action is being studied.

Recently we screened marine algae for antifouling activity against barnacle larvae using Amphibalanus amphitrite. Especially we focused on red algae Laurencia spp., because they have precedent antifouling compounds. For example, elatol is a well-known example, but it was not pursued in industry due to its toxicity. Laurinterol is another example. We found laurinterol acetate (3) is more active (EC50 = 0.37 g/mL). A triterpenoid, thyrsiferol (4) also showed a potent antifouling activity (EC50 = 0.11 g/mL).

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A new compound, omaezallene (5) showed EC50 of 0.22 g/mL and LC50 of 3.4 g/mL against barnacle larvae. Determination of planar structure of omaezallene was straight forward by comparing spectroscopic data with literature data of a known bromoallene. Absolute configuration of bromoallene moiety was predicted by Lowe’s rule. Lowe’s rule is an empirical rule to predict absolute configuration of simple allenes, which was applied for fungal metabolite, diyneallene moiety containing compounds. If the optical rotation is positive, allene is S. If negative, allene is R.To clarify relative configurations of other parts, omaezallene was derivatized into an acetonide. NOESY experiments of the acetonide indicated relative configurations of other chiral centers except C-9. Total synthesis of proposed structure was achieved by using D-glucose as a starting material. Both epimers at C-9 were synthesized. Comparison of NMR data and optical rotation concluded all absolute configurations of omaezallene. Interestingly epimers of C-9 showed opposite sign of optical rotation. All bromoallenes which were isolated from Laurencia so far followed Lowe’s rule. 9-epi-omaezallene is only exception. In fact, Lowe mentioned that the rule could not be applied if the substituent of bromoallene contained configurational asymmetry. Br Br

O OH HO

• Br

5

The well-known acetogenin, laurencin from L. nipponica also showed potent antifouling activity against barnacle larvae (EC50 = 0.23 g/mL), but did not show any toxicity even at 100 g/mL. We tested ecotoxicities of laurencin against the copepod Tigriopus japonicus, the water flea Daphnia magna, the medaka Oryzias latipes juveniles and the clown fish Amphiprion ocellaris larvae and juveniles. These toxicities of laurencin were 10 – 100 times weaker than those of currently available antifouling agent copper pyrithione.

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Laurencia is one of the richest producers of brominated secondary metabolites. Biosynthesis of brominated compounds such as laurencin, have been studied since late 1990s. Nevertheless, it remains poorly understood. We conducted cDNA cloning and heterologous expression of vanadium dependent bromoperoxidase (VBPO) from L. nipponica. Properties of recombinant enzymes were characterized. In addition, bromination activity to a proposed natural precursor of laurencin was observed. The results suggest that VBPOs are pivotal candidates of biosynthetic enzymes that catalyze the bromination of secondary metabolites inLaurencia spp.

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Chlorophyll and Carotenoid Prospects on Food, Health and Energy Heriyanto and Leenawaty Limantara* *

Ma Chung Research center for Photosynthetic Pigments Universitas Ma Chung Villa Puncak Tidar N-1 Malang, East Java, Indonesia, *email: [email protected]

Abstract Indonesia is rich in biodiversity with the abundant natural resources. Most of Indonesia natural resources, i.e. plant, algae, microorganism, have potency as pigment sources. Chlorophyll (Chl) and carotenoid (Crt) are the main pigments in photosynthesis process and have been known to be responsible for health benefits as antioxidant, pro-vitamin A, anti-cancer, anti obesity, etc., and also natural colorants. Basic experiments of Chl and Crt, that is extraction and purification of pigment, content of pigment, composition of pigment, chemical and physical properties of pigment, have been extensively investigated to get fruitful experimental results for the prospect of these pigments. Three prospects of Chl and Crt are pigment on food, health, and energy. The prospect of pigment on food applies Chl and Crt as natural food colorants which have additional health benefits. Pigment on health utilizes Chl and Crt for better health and improved quality of life such as Vitamin A deficiency (VAD), and iron deficiency anemia (IDA). Another subject of this prospect is invention and improvement of stable Chl-based photosensitizer in photodynamic therapy for cancer and tumor. The last prospect of Chl and Crt is for energy. Optimization of design principle of natural systems in light harvesting, energy transfer and energy conversion could be used for the next generation of solar cells. Keywords: chlorophyll, carotenoid, antioxidant, pro Vitamin A, anti cancer, anti obesity, photosensitizer, solar cell

Introduction Photosynthesis is a fundamental process for living organisms. Chlorophyll (Chl) and carotenoid (Crt) are photosynthetic pigments which play important roles in this process (Telfer et. al., 2008; Berera et. al., 2009). The former pigment performs a light harvesting (LH) role and serves to funnel absorbed solar radiation to reaction center where photochemical reaction occurs. The latter is also involved in LH and plays photo-protective roles by quenching Chl triplet state and scavenging singlet oxygen. These pigments are naturally found in photosynthetic organisms, for example plant, bacteria, and algae which abundantly occur in Indonesia natural resources. In addition, Crt is present in human and animal as well (Gross, 1991). Britton et. al., (2004) listed more than 700 known naturally occurring Crts that have been isolated from natural resources. The major Crts, that is beta-carotene (β-carotene), fucoxanthin, bixin, crocin, safranal, lycopene,

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lutein, zeaxanthin and asthaxanthin, are well known as provitamin A, food colorant, antioxidant, etc. The functions and abundance of these pigments in nature attract us to perform comprehensive experiments from basic to applied fields. Experiments in the basic level have been conducted to gain fruitful information for the next steps of experiments. Limantara et. al., (1994; 1996) applied a series of isotopes-labelled bacteriochlorophyll (BChl; Chl form in photosynthetic bacteria) to determine the excited states of BChl. The invention of BChl excited states has an important contribution to the usage of BChl and its derivatives as photosensitizers in photodynamic therapy (PDT) for cancer and tumor treatments (Limantara et. al., 2006). Other basic experiments on chemical and physical properties of BChl and its derivatives, such as: photostability (Limantara et. al., 2006; Susanti et. al., 2007; Limantara and Heriyanto, 2010b), aggregation, coordination state, and pH effect (Limantara et. al., 1997; Koyama et. al., 2006; Santosa et. al., 2008; Heriyanto et. al., 2009) were carried out to determine the best photosensitizer.

Material and Method Photosynthetic organisms, i.e. indigenous plants, macroalgae, microalgae, photosynthetic bacteria, were used as samples for Chl and Crt experiments. The screening of potential Indonesian natural resources as pigment sources was conducted based on the pigment content, tha is relatively Chl content of leaves was determined by portable chlorophyll meter (Rahayu and Limantara, 2005; Heriyanto and Limantara, 2006b) and nitrogen meter (Tantono et. al., 2013), in vitro Chl and Crt contents were determined from crude pigment extracts by spectrophotometry (Madalena et. al., 2007) and high performance liquid chromatography (HPLC) (Limantara and Heriyanto, 2010a) methods; and pigment composition was determined by thin layer chromatography (TLC) (Heriyanto and Limantara, 2006a) and HPLC (Limantara and Heriyanto, 2010). Column chromatography and HPLC were applied for pigment purification (Sukoso et. al., 2010; Pringgenies et. al., 2011) then the purified pigment was identified by UV-Vis spectrophotometer, TLC, HPLC, and nuclear magnetic resonance (Limantara et. al., 1995; Sukoso et. al., 2010). Tests of pigment stabilities against thermal and irradiation treatments (Heriyanto and Limantara, 2010b; Wijaya et. al., 2010; Prihastyanti et. al., 2010) and pH values

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effect (Heriyanto et. al., 2004; Kusmita and Limantara, 2009;) were performed for the purified pigment and crude pigment extract.

Biopigment research Sources of major pigments have been well recognized, that is carrot (contain(s) βcarotene), tomato (lycopene), brown seaweed (fucoxanthin), photosynthetic bacteria (BChl a), leafy vegetable and Chlorella sp. (Chl a), saffron ‘Crocus sativus’ (crocin and safranal), Bixa orellana (Bixin), salmon fish and Haematococcus pluvalis (astaxanthin). Rahayu and Limantara (2005) revealed that katuk (Sauropus androgynus) and suji (Pleomele angustifolia N.E. Brown) leaves have relatively high Chl content from several green leafy plants. Fucoxanthin is known as the main Crt in brown seaweed and Padina australis has the highest fucoxanthin content from 5 species of brown seaweed (Limantara and Heriyanto, 2010). Optimization of fucoxanthin extraction efficiency by several organic solvents in P. australis was done by Limantara and Heriyanto (2011a) and methanol was the best solvent for fucoxanthin extraction. Indrawati et. al., (2010b) did a similar experiment for simultaneus BChl and Crts extraction in Rhodopseudomonas palustris. Some experiments on pigment composition have been conducted for brown seaweeds (Limantara and Heriyanto, 2010; Indrawati et. al., 2010a), Kappaphycus alvarezii (de Fretes et. al., 2011), leafy plant (Christanti et. al., 2011), palm oil (Syahputra et. al., 2008). Chl a is the dominant Chl in brown seaweeds, K. alvarezii, leafy plant, while fucoxanthin, zeaxanthin, lutein are their main Crts, respectively. Syahputra et. al., (2008) concluded that βcarotene is the main Crt in palm oil. Lycopene, neurosporene, γ-carotene, β-carotene and phytoene are Crts of Neurospora Intermedia which is purified from Indonesian fermented peanut cake (Priatni et. al., 2010). Chl a is unstable pigment towards acid, temperature, and light (Gross, 1991). The addition of other compounds as Chl a protector and chemical modifications of Chl a could improve its stability. Kartikaningsih et. al., (2010) used fucoxanthin as a photoprotector for Chl a against irradiation treatment. Absorption spectra of Chl a and fucoxanthin in acetone are shown in Figure 1a. Intensity of Qy band (at 662 nm) of Chl a decreased after Chl a solution was exposed to the light. Decreasing this intensity of Chl a (Figure 1b) was bigger than that of mixture of Chl a and fucoxanthin (Figure 1c). This result indicates the photoprotection function

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of Crt. Photoprotection function of β-carotene and lutein against Chl a was investigated by da Costa et. al., (2007). Chemical modifications of Chl a at its central metal and peripheral chains to be chlorophylin increased its solubility in aqueous solution and its stability (Sumpana, 2013). 1.5

(c)

(b)

430

430

Fucoxanthin Chl a

Absorbance

3

1.5

(a)

430

0 min 446

1

662

662

1

2 0 min

60 min

0.5

0

0.5

400

500

600

700

0

662

1

400

500

600

700

0 800

60 min

400

500

600

700

800

Wavelength [nm]

Figure 1. Absorption spectra of fucoxanthin and Chl a in acetone (a), photostability tests of Chl a (b), mixture of fucoxanthin and Chl a (1:1, mol/mol) (c) during irradiation treatment for 60 minutes. Application of pigment on food, health and energy Ingested Chl and Crt are directly obtained from natural food especially vegetables and fruit. In their development, these pigments are applied to food industry as natural food colorants. Chl and Crt have been proven to have health benefits as antioxidant, anti-cancer, antiinflammation, anti-obesity, pro-vitamin A, and in age-related degenerative diseases. Therefore Chl and Crt are highly potential to be used as healthy food ingredients and functional food. In Indonesian traditional snacks, pigment extracts from P. angustifolia and pandan (Pandanus amaryllifolius Roxb.) leaves are commonly used for natural green colorant. Recently, Arifin (2013) made prototype of natural green food colorant powders and investigated their stabilities and pigment composition. The addition of Chlorella pyrenoidosa and Monascus purpureus, which is rich in pigments, into the tea as functional drink increased the antioxidant activity and acceptability by the panellist (Megawati et. al., 2013). In addition, the occurrence of red colour in red palm oil, coming from Crts, is becoming the healthful choice for oil cooking. Indonesia has been known as the world’s largest exporter of crude palm oil (CPO) and also one of the most important exporters of seaweeds and some of decapods crustaceans. However, these natural resources have not been maximally exploited as the source of β-carotene,

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astaxanthin, fucoxanthin, Chl, etc., which are important for maintaining healthcare. Astaxanthin is a potential antioxidant, because of this Crt has the strongest antioxidant activity compared to other natural antioxidants, such as: vitamin E and β-carotene (Shimidzu et. al., 1996 ; Bagchi, 2001). Therefore, astaxanthin is used as cosmetic ingredient due to its antioxidant and photoprotector functions (Andyka et. al., 2013). Herbal medicine containing P. australis and Sprirulina platensis, which contain fucoxanthin, lutein, Chl a and Chl b as dominant pigments, showed anti-atherosclerotic (Indrawati et. al., 2013). The potency and efficacy of astaxanthin as anti-cholesterol was reviewed by Wijaya et. al., (2013). PDT is photo-chemotherapy combining the use of light, oxygen and photosensitizer. Recently, there are a number of efforts to invent and develop the stable Chl-based photosensitizer in PDT for cancer and tumors. Zn-pheophorbide a is a very promising low-cost, synthetically easily accessible, second generation photosensitizer against human cancer (Jakubowska et. al., 2013). There are increasing numbers of pigment application to energy utilization especially solar cells. Dye-sensitized solar cell (DSSC) is one technology of solar cells which mimics a basic principle of photosynthesis (Heriyanto and Limantara, 2010a). Synthetic dyes, i.e. ruthenium complexes, are commonly applied to this solar cell as sensitizers for gathering solar energy with the conversion efficiency of sunlight to electric power up to 11% (Gratzel, 2004). Besides the usage of synthetic dyes, photosynthetic pigments, that is Chl and its derivatives (Tributsch and Calvin, 1971; Wang et. al., 2010), Crts (Wang et. al., 2005; Yamazaki et. al., 2007), have been used as sensitizers with a low cost, although their values of the conversion efficiency are lower than the use of synthetic dyes. Currently, bio-hybrid solar cells, a novel photo-nano-device, have been constructed from LH complexes of photosynthetic bacteria on metal surface. Plasmon excitation in metallic nanoparticles provide an excellent way to control the optical properties of matter and enhance the productive photochemistry of the LH complexes (Bujak et. al., 2011 and 2012). Fiedor et. al., (2004) and Akahane et. al.,. (2004) modified native LH complexes by reconstitution approach to enhance the efficiency of singlet energy transfer from Crt to BChl.

Acknowledgement

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The financial support from the Directorate of Higher Education, Ministry of Education and Culture (National strategic grant number 182/SP2H/PL/Dit.Litabmas/V/2013) and Ministry of Research and Technology (Sinas grant number 187/M/Kp/XI/2012) are greatly appreciated.

References Akahane, J., Rondonuwu, F.S., Fiedor, L., Watanabe, Y., and Koyama, Y. (2004). Dependence of singlet-energy transfer on the conjugation length of carotenoids reconstituted into the LH1 complex from Rhodospirillum rubrum G9. Chem. Phys. Lett., 393: 184-191. Andyka, M.I.R., Brotosudarmo, T.H.P. and Limantara, L. (2013). Utilization of Aloe vera gel and astaxanthin as active ingredients in cosmetics. Proceedings of 2nd Natural Pigments Conference for South-East Asia (NP-SEA), Malang, July 12-13, 2013. Arifin, V. (2013). Studi komposisi dan stabilitas pigmen pada prototype serbuk pewarna makanan hijau alami daun pandan wangi (Pandanus amaryllifolius Roxb.) dan suji (Pleomele angustifolia N.E. Brown). Skripsi Teknik Industri, Universitas Ma Chung, Malang. Bagchi, D. (2001). “Oxygen Free Radical Scavenging Abilities of Vitamins C, E, B-Carotene, Pycnogenol, Grape Seed Proanthocyanidin Extract, Astaxanthin and BioAstin in Vitro.” On file at Cyanotech Corporation. Berera, R., van Grondelle, R., Kennis, J.T.M. (2009). Ultrafast transient absoption spectroscopy: principles and application to photosynthetic systems. Photosynth. Res., 101: 105-118. Britton, G., Liaaen-Jensen, S., and Pfander, H. (2004). Carotenoids: Handbook. Birkhauser, Boston. Bujak, L., Czechowski, N., Piatkowski, D., Litvin, R., Mackowski, S., Brotosudarmo, T.H.P., Cogdell, R.J., Pichler, S. and Heiss, W. (2011). Fluorescence enhancement of lightharvesting complex 2 from purple bacteria coupled to spherical gold nanoparticle. Appl. Phys. Lett., 99: 173701. Bujak, L., Brotosudarmo, T.H.P., Czeckowski, N., Olejnik, M., Ciszak, K., Litvin, R., Cogdell, R.J., Heiss, W. and Mackowski, S. (2012). Spektral Dependence of Fluorescence Enhancement in LH2-Au Nanoparticle Hybrid Nanostructures. Acta Physica Polonica A, 122: 252-254. Christanti, M., Fidelia, A., Heriyanto, Brotosudarmo, T.H.P., and Limantara, L. (2011). Fence Plants – A Study of Photosynthetic Pigments Compositions and Their Crude Extract Photostability. Proceeding of International Conference on Natural Sciences, ISBN 978-38440-1403-7. Malang, July 9-11. da Costa, J.F., Karwur, F.F. dan Limantara, L. (2007). Fotoproteksi beta Karoten dan Lutein terhadap Klorofil a dalam Aseton. Proceeding of National Conference on Back to Nature with Natural Pigment. ISSN: 979-978-89-2. Salatiga, 24 Agustus. de Fretes, H., Susanto, A.B., Limantara, L., Prasetyo, B., Heriyanto and Brotosudarmo, T.H.P. (2011). Pigment Composition, Photostability and Thermostability Studies of Crude Pigment Extracts from Red, Brown, and Green Varieties of Red Algae Kappaphycus alvarezii (Doty) Doty. Proceeding of International Conference on Natural Sciences, ISBN 978-3-8440-1403-7. Malang, July 9-11. Fiedor, L., Akahane, J., and Koyama, Y. (2004). Carotenoid-induced cooperative formation of bacterial photosynthetic LH1 complex. Biochemistry, 43: 16487-16496. ISBN: 978-979-96595-4-5   xxiii   

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Gratzel, M. (2004). Conversion of sunlight to electric powder by nano crystalline dye-sensitized solar cells. Journal of Photochemistry and Photobiology A: Chemistry, l64: 314. Gross, J., 1991. Pigment in Vegetables: Chlorophylls and Carotenoids. New York: Van Nostrand Reinhold. Heriyanto, Hartini, S. and Limantara, L. (2004). The Content of Chlorophylls, Pheophytins and Pheophorbides in Leaf Mustard (Brassica juncea (l.) czern. & coss.) during Processing and Pickled Storage. Proceedings of National Conference on Research, Education and Application of Science, Universitas Negeri Yogyakarta. ISSN: 979-96880-4-3.Yogyakarta, 2 Agustus. Heriyanto and Limantara, L. (2006a). Komposisi dan Kandungan Pigmen Utama Tumbuhan Taliputri Cuscuta australis R.Br. dan Cassytha filiformis L. Makara Seri Sains, 10: 69-75. Heriyanto dan Limantara, L. (2006b). Studi Lapangan Kandungan Klorofil In Vivo Daun Cincau Hitam, Cincau Perdu, Cincau Hijau and Cincau Minyak, Journal Natur Indonesia, 9: 41-47. Heriyanto, Trihandaru, S. dan Limantara, L. (2009). Keadaan Koordinasi dan Proses Agregasi Bakterioklorofil a and Turunannya: Studi pada Pelarut Aseton-Air and Metanol-Air, Indo. J. Chem. 9: 113-122. Heriyanto dan Limantara, L. (2010a). Dye-sensitized solar cell: Teknologi pembentuk sumber energi listrik alternatif. Proceeding of National conference on Technopreneur Day, “Save our earth with green technology”. Universitas Ma Chung, Malang, 15 Mei. Heriyanto and Limantara, L. (2010b). Photo-Stability And Thermo-Stability Studies Of Fucoxanthin Isomerization. Proceedings of Natural Pigments Conference For South-East Asia. ISBN: 978-602-97123-0-8. Malang, 20-21 Maret. Indrawati, R., Heriyanto, Limantara, L., and Susanto, A.B. (2010a). Study of Pigments Distribution in the Stem, Leaf and Vesicle of Sargassum filipendula, Sargassum polycystum and Sargassum sp. from Madura Waters using High Performance Liquid Chromatography. Proceedings of Natural Pigments Conference For South-East Asia, ISBN: 978-602-97123-0-8. Malang, March 20th-21st. Indrawati, R., Wijaya, W., Prihastyanti, M. N. U., Heriyanto, Prasetyo, B., and Limantara, L. (2010b). Efisiensi Ekstraksi Bakterioklorofil dan Karotenoid dari Rhodopseudomonas palustris dengan berbagai rasio pelarut Aseton dan Metanol. Prosiding Seminar Nasional Sains dan Pendidikan Sains V. ISSN: 2087-0922. Salatiga, 10 Juni. Indrawati, R., Wijaya, D.E., Indriatmoko, Sulistiawati, E., Suparto, I.H., and Limantara, L. (2013). Hypocholesterolemic effect and pigments composition of herbal medicine containing higher and lower plants. (in Press). Jakubowska, M., Szczygiel, M., Michalczyk-Wetula, D., Susz, A., Stochel, G., Elias, M., Fiedor, L., and Urbanska, K. (2013). Zinc-pheophorbide a-highly efficient low-cost photosensitizer against human adenocarcinoma in cellular and animal models. Photodiagnosis and Photodynamic Therapy. 10: 266-277. Kartikaningsih, H., Zaelaniea, K., Puspitasari, F.R., Heriyanto and Limantara, L. (2010). PhotoStability of Fucoxanthin, Chlorophyll a, Fucoxanthin-Chlorophyl a Mixtures and Crude Pigment Extracts from Brown Algae: Acetone-Water Solvents Study. Proceedings of Natural Pigments Conference For South-East Asia. ISBN: 978-602-97123-0-8. Malang, March 20th-21st. Koyama, Y., Kakitani, Y., Limantara, L., and Fujii, R. (2006). Effects of Axial Coordination, Electronic Excitation and Oxidation on Bond Orders in the Bacteriochlorin Macrocycle, and Generation of Radical Cation on Photo-Excitation of in vitro and in vivo

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Bacteriochlorophyll aAggregates: Resonance Raman Studies. In Advances in Photosynthesis and Respiration. Chlorophylls and Bacteriochlorophylls: Biochemistry, Biophysics, Functions and Applications (Eds: Grimm, B., Porra, R.J., Rüdiger, W., and Scheer, H.). Springer, The Netherlands. Kusmita, L. dan Limantara, L. (2009). Pengaruh Asam Kuat dan Asam Lemah terhadap Agregasi dan Feofitinasi Klorofil a dan b. Indo. J. Chem. 9: 70-76. Limantara, L, Koyama, Y., Katheder, I. and Scheer, H. 1994. Transient Raman spectroscopy of 15Nsubstituted bacteriochlorophyll a.an empirical assignment of T1 Raman lines. Chem. Phys. Lett., 227: 617-622. Limantara, L., Kurimoto, Y., Furukawa, K., Shimamura, T., Utsumi, H., Katheder, I., Scheer, H. and Koyama, Y. (1995). The Environment of the Four Nitrogen Atoms of Bacteriochlorophyll a in Solutions as Revealed by 15N-NMR Spectroscopy. Proceedings of the Annual Meeting of Japanese Society of Plant Physiologists. In Plant and Cells Physiol. Vol. 36 (Supplement). Shimane University, 29 March. Limantara, L., Katheder, I., Scheer, H., Schafer, W. and Koyama, Y. 1996. The T1 and S1 Raman spectra of 15N and 2H-enriched bacteriochlorophyll a : Changes in bond order upon triplet and singlet excitation. Chem Phys. Lett., 262: 656-662. Limantara, L., Sakamoto, S., Koyama, Y., and Nagae, H. (1997). Effects of Nonpolar and Polar Solvents on the Qx and QY Energies of Bacteriochlorophyll a and Bacteriopheophytin a. Photochem. Photobiol., 65: 330-337. Limantara, L., Koehler, P., Wilhelm, B., Porra, R.J., and Scheer, H. (2006). Photochem Photobiol., 82: 774-780. Limantara, L., dan Heriyanto. (2010). Komposisi Pigmen dan Kandungan Fukosantin Rumput Laut Cokelat dari Perairan Madura dengan Kromatografi Cair Kinerja Tinggi. Indonesian Journal of Marine Sciences. 15: 23-32. Limantara, L., dan Heriyanto. (2011a). Optimasi Proses Ekstraksi Fukosantin dari Rumput Laut Cokelat, Padina australis Hauck, dengan Pelarut Organik Polar, Indonesian Journal of Marine Sciences.16: 86-94. Limantara, L., dan Heriyanto. (2011b). Photostability of Bacteriochlorophyll a and Its Derivatives as Potential Sensitizers for Photodynamic Cancer Therapy: The Study on Acetone-Water and Methanol-Water Solvents. Indonesian Journal of Chemistry. 11: 154162. Madalena, Heriyanto, Hastuti, S.P. dan Limantara, L. (2007). Pengaruh Lama Pemanasan Terhadap Kandungan Pigmen Serta Vitamin A Daun Singkong (Manihot esculenta Crantz) and Daun Singkong Karet (Manihot glaziovii Muell. Arg), Indo. J. Chem. 7: 105-110. Megawati, Brotosudarmo, T.H.P. and Limantara, L. (2013) Analytical assays on product quality, organoleptic and antioxidant activity of functional drinks. Proceedings of 2nd Natural Pigments Conference for South-East Asia (NP-SEA), Malang, July 12-13, 2013. Priatni, S., Limantara, L., Heriyanto, Singgih, M., and Gusdinar, T. (2010). Identification of Carotenoids in Neurospora Intermedia N-1 Isolated from Indonesian Fermented Peanut Cake (Oncom Merah). Proceedings of Natural Pigments Conference For South-East Asia. ISBN: 978-602-97123-8. Malang, March 20th-21st. Prihastyanti, M., Heriyanto, Trihandaru, S., and Limantara, L. (2010). Photostability Of Crude Pigment Extract From Three Species Of Brown Seaweed Based On Spectrum Pattern And Identifying The Degradation Product Based On HPLC Chromatogram. Proceedings of

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Natural Pigments Conference For South-East Asia. ISBN: 978-602-97123-0-8. March 20th21st, Malang. Pringgenies, D., Ridlo, A., Indriatmoko, Heriyanto and Limantara, L. (2011). Production of Phenazine Pigments From Marine Symbiotic Bacteria in Gastropod Cerithidea sp. with Different Growth Media. Proceedings of The International Conference On Natural Sciences(ICONS). ISBN 978-3-8440-1403-7. Malang, July 9-11. Rahayu, P. and Limantara, L. (2005). Field Evaluation of In Vivo Chlorophyll Content from Several Green Leafy Plants in Around of Salatiga. Proceedings of National Conference on The Scientific Meeting, FMIPA UI, Jakarta. November 25-26. Santosa, V., Prasetyo, B., and Limantara, L. (2008). The Effect of Aggregation, Acidification and Incubation of The Spectral Pattern of Pd-Bacteriopheophorbide (Tookad). Eksplanasi, 3: 61-70. Shimidzu, N., Goto, M., and Miki, W. (1996) Carotenoids as singlet oxygen quenchers in marine organisms. Fisheries science. 62: 134-137. Sukoso, Kartini Zaelanie, Dadang A. Setiyawan, Heriyanto and Leenawaty Limantara. (2010). Antioxidant Activity Study of Fucoxanthin and Crude Pigment Extracts from Three Species of Brown Algae (Sargassum duplicatum, Sargassum filipendula, and Sargassum polycystum). Proceedings of Natural Pigments Conference For South-East Asia. ISBN: 978-602-97123-0-8. Malang, March 20th-21st. Sumpana, A.F. (2013) Stabilitas bahan baku dan prototype masker wajah dengan perpaduan Chlorella pyrenoidosa-klorofilin dan Spirulina platensis-klorofilin. Skripsi Teknik Industri, Universitas Ma Chung, Malang. Susanti, N. I., Trihandaru, S. dan Limantara, L. (2007). Fotostabilitas Bakterioklorofil a dan Bakteriofeofitin a dalam Pelarut Aseton-Air: Potensi terhadap Terapi Fotodinamika Kanker. Proceedings of National Conference on Back to Nature with Natural Pigment. Magister of Biology, Satya Wacana Christian University. ISSN: 979-978-89-2. Salatiga 24 Agustus. Syahputra, M.R., Karwur, F.F., and Limantara, L. (2008) Analisis Komposisi dan Kandungan Karotenoid Total dan Vitamin A Fraksi Cair dan Padat Minyak Sawit Kasar (CPO) menggunakan KCKT Detector PDA. Jurnal Natur Indonesia, 10: 89-97 Tantono, C., Adhiwibawa, M.A.S., Prilianti, K.R., Prihastyanti, M.N.U., Limantara, L., and Brotosudarmo, T.H.P. (2013) Mata Daun: a mobile application for measuring chlorophylls and nitrogen content of soybean leaf. Proceedings of 2nd Natural Pigments Conference for South-East Asia (NP-SEA), Malang, July 12-13, 2013. Telfer, A., Pascal, A., and Gall, A. (2008) Carotenoids in Photosynthesis. In Carotenoids Volume a: Natural Functions (eds. Britton, G., Liaaen-Jensen, S., Pfander, H.). Birkhauser Verlag Basel, p. 265-308. Tributsch, H., and Calvin, M. (1971) Electrochemistry of excited molecules: photoelectrochemical reactions of chlorophylls. Photochem. Photobiol., 14: 95-112. Wang, X.-F., Xiang, J., Wang, P., Koyama, Y., Yanagida, S., Wada, Y., Hiamada, K., Siasaki, S.-I., and Tamiaki, H. (2005). Dye-sensitized solar cells using a chlorophyll a derivative as the sensitizer and carotenoids having different conjugation lengths as redox spacers. Chemical Physics Letters, 408: 409-414. Wang, X.-F., Koyama, Y., Kitao, O., Wada,Y., Sasaki, S.-I., Tamiaki, H. and Zhou, H. (2010) Significant enhancement in the power-conversion efficiency of chlorophyll co-sensitized solar cells by mimicking the principles of natural Photosynthetic light-harvesting complexes. Biosens. Bioelectron., 25: 191l-1916.

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Wijaya, D.E., Delfiana, Y., and Limantara, L. (2013) The potency and efficacy of astaxanthin pigment as a raw material of canti-cholesterol traditional medicine. Proceedings of 2nd Natural Pigments Conference for South-East Asia (NP-SEA), Malang, July 12-13. Wijaya, W., Heriyanto, Prihastyanti, M. N. U., Indrawati, R., Prasetyo, B., and Limantara, L. (2010): Termostabilias Bakterioklorofil a pada Ekstrak Pigmen Kasar Rhodopseudomonas palustris. Prosiding Seminar Nasional Sains dan Pendidikan Sains V. ISSN: 2087-0922. Salatiga, 10 Juni. Yamazaki, E., Murayama, M., Nishikawa, N., Hashimoto, N., Shoyama, M. and Kurita, O. (2007). Utilization of natural carotenoids as photosensitizers for dye-sensitized solar cells. Solar Energy, 81: 512-516.

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The 2nd International Conference of the Indonesian Chemical Society 2013 October, 22-23th 2013

Nanoscale Pore Space Science for Sustainable Chemistry Katsumi Kaneko Research Center for Exotic Nanocarbons, Nagano, 380-8553, Japan [email protected]

Abstract The unique nanoscale pore structures of nanocarbon and high surface area carbon, which induce highly dense adsorbed state, are shown. The superhigh pressure-compression effect and stabilization effect of unstable phase of nanoscale pore spaces are given using the examples of 1D atomically 1D metallic sulfur chain crystals, KI nanocrystals and CH4, respectively. The quantum fluctuation of light molecules such as H2 and CH4 should not be neglected in the nanoscale spaces; the quantum fluctuation induces an evident quantum molecular sieving effect on adsorption in nanoscale pores for their isotopes. The intensive confinement of ions in the nanoscale pore spaces gives rise to a partial desolvation and highly packed structure. These results can contribute to sustainable chemistry. Keywords: nanoscale pore, metal sulfur, single wall carbon, interfacial solid, desolvation, adsorption, nanoconfinement.

All component carbon atoms of graphene, single wall carbon nanotube (SWCNT), single wall carbon nanohorn(SWCNH), and double wall carbon nanotube (DWCNT) are exposed to the interfaces. Figure 1 shows monolayers on the external and internal wall surfaces of SWCNT; all component carbon atoms can interact with molecules on the external and internal sides. Therefore, these systems are not ordinary solids, but interfacial solids. These carbons can easily vary the local structure depending on the stimuli through the morphological defects.1) Activated carbon fiber (ACF) or carbidederived carbon (CDC) can be also regarded as the interfacial solid, Figure 1. Monolayers on the because their surface area is close to that of graphene. These materials external and internal tube have an intensive potential for contribution to interfacial science. At wall surfaces having opposite sign of nanoscale curvature the same time, these carbons except for graphene have nanoscale pores in SWCNT. which have the deep interaction potential well for molecules, giving rise to a highly dense adsorbed state in the pore spaces and unique functions due to moleculemolecule and molecule-pore wall collective interactions. Recently we have obtained clear evidence that confinement of KI nanocrystals below 0.1 MPa induces the solid phase transition into high pressure phase, which occurs above 1.9 GPa for the bulk KI crystals; this remarkable effect is named super high pressure effect.2) Thus, phase transition can be influenced remarkably by the nanoconfiment of substances. We measured the rotational-vibration spectra of methane in single walled nanoscale pores near the boiling temperature (111.5 K). The rotational structure almost disappears around 111 K, although the vibration spectrum of methane in the bulk phase has a clear rotational structure. The rotational structure can be observed at 140 K, showing the elevation of boiling temperature of methane adsorbed in the nanoscale tube spaces by 30 K3). Very recently, we obtained intensive evidence on the in-pore superhigh pressure effect of the tubular carbon

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The 2nd International Conference of the Indonesian Chemical Society 2013 October, 22-23th 2013 spaces. It is well-known that solid sulfur consists of 8-member rings, being insulator. We introduce sulfur vapor below 0.1 MPa in the tubular spaces of SWCNT and DWCNT. High resolution transmission electron microscopic (HR-TEM) observation elucidated the presence of a complete one-dimensional sulfur chain in the tubular space. Figure 2 shows the HRTEM images of the 1D sulfur chain in the tube spaces of DWCNT whose internal tube diameters are 0.68 and 0.60 nm. The zigzag sulfur chain and complete linear chain are observed in the internal tubes of 0.68 nm and 0.60 nm, respectively. Surprisingly we observed clear X-ray diffraction peaks corresponding to the 1D chain structures of sulfur. 4) This facts indicate that the in-pore superhigh pressure corresponds to 90 GPa at least. In case of Se, a unique helix structure is formed.5) The quantum molecular sieving effect is a representative function of the nanoscale pore spaces. The quantum fluctuation difference between light molecules such as H2 and D2 is only 0.03 nm at 77 K, leading to an explicit adsorption difference of more than 5 % for H2 and D2.6) The clear adsorption difference of 2 % even between CD4 and CH4 was evidenced in the higher fractional filling for 0.7 nm slit-pores. 13CH4 and 12CH4 can be efficiently separable using the nanoscale pores of SWCNH at 112 K with the quantum molecular sieving.7) The EXAFS study of Rb+ ions in the slit pores of ACF indicated partial dehydration.8) Also organic ion “solution” confined in the slit pores of ACF and CDC was studied with synchrotron X-ray diffraction analysis, providing a highly oriented molecular packing structure.9) These carbon nanotube spaces can be electronically modified with the aid of chargetransfer interaction using adsorption of aromatic hydrocarbon molecules. The charge transfer interaction can donate charges to the nanotube walls, changing molecular adsorptivity and dispersion stability in water. Then, these electronically modified SWCNT and/or DWCNT should induce new functions for atoms, ions, and molecules.10,11)

Zigzag structure

Linear structure Walls of DWCNT

2 nm Figure 2. High resolution transmission electron microscopic images of atomically 1-dimensinal metallic sulfur chain crystals in double wall carbon nanotube.

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The 2nd International Conference of the Indonesian Chemical Society 2013 October, 22-23th 2013 Acknowledgements K.K. was supported by Exotic Nanocarbons, Japan Regional Innovation Strategy Program by the Excellent, JST. This work was supported by the Grant-in-Aid for Scientific Research (A) (No. 24241038) by JSPS. References 1) T. Fujimori, K. Urita, D. Tomanek, T. Ohba, I. Moriguchi, M. Endo, K. Kaneko, J. Chem. Phys. 136 (2012) 064505-1. 2) K. Urita, Y. Shiga, T. Fujimori, Y. Hattori, H, Kanoh, T. Ohba, H. Tanaka, M. Yudasaka, S. Iijima, I, Moriguchi, F. Okino, M. Endo, K. Kaneko, J. Amer. Chem. Soc. 133(2011) 10344. 3) S. Hashimoto, T. Fujimori, H. Tanaka, K. Urita, T. Ohba, H. Kanoh, T. Itoh, M. Asai, H. Sakamoto, S. Niimura, M. Endo, F. Rodoriguez-Reinoso, K. Kaneko, J. Amer. Chem. Soc. 133 (2011) 2022. 4) T. Fujimori, A. Morelos-Gómez, Z. Zhu, H. Muramatsu, R. Futamura, K. Urita, M. Terrones, T. Hayashi, M. Endo, S. Y. Hong, Y. C. Choi, D. Tománek , K. Kaneko,, Nature Comm. 4 (2013) 2162. 5) T. Fujimori, R. B. Santos, T. Hayashi, M. Endo, K. Kaneko, D. Tománek, ACS Nano, 7 (2013) 5607. 6) H. Tanaka, D. Noguchi, A. Yuzawa, T. Kodaira, K. Kaneko, J. Low Temp. Phys. 157 (2009)352. D.Noguchi, H. Tanaka, T.Fujimori, T. Kagita, Y. Hattori, H. Honda, K. Urita, S. Utsumi, Z.-M. Wang, T. Ohba, H. Kanoh, K. Hata, K. Kaneko, J.Phys.:Condens.Matter. 22 (2010) 334207. 7) T. Fujimori, D. Minami,T. Tamura, S. Niimura,T. Ohba, T. Itoh, H. Kanoh, K. Kaneko, in preparation. 8) T. Ohkubo, T. Konishi, Y. Hattori, H. Kanoh, T. Fujikawa, K. Kaneko, J. Am. Chem. Soc. 124 (2002) 11860 9) A. Tanaka, T. Iiyama, T. Ohba, S. Ozeki, K. Urita, T. Fujimori, H. Kanoh, K. Kaneko, J. Amer. Chem. Soc. 132 (2010) 2112. M. Fukano, T. Fujimori, J. Ségalini, E. Iwama, P.L. Taberna, T. Iiyama, T. Ohba, H. Kanoh, Y. Gogotsi, P. Simon, K. Kaneko , J. Phys. Chem. C, 117 (2013)5752. 10) F. Khoerunnisa, T. Fujimori, T. Itoh, K. Urita, T. Hayashi, H. Kanoh, T. Ohba, S. Y. Hong, Y. C. Choi, S. J. Santosa, M. Endo, K. Kaneko, dx.doi.org/10.1021/jp303630m | J. Phys. Chem. C 116(2012)11216. 11) F. Khoerunnisa, D. Minami, T. Fujimori, S.Y. Hong, Y.C. Choi, H. Sakamoto, M. Endo, K. Kaneko, Adsorption, in press.

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  The 2nd International Conference of the Indonesian Chemical Society 2013 October, 22-23th 2013  

Al13 Intercalated and Pillared Montmorillontes from Unusual Antiperspirant Aqueous Solutions: Precursors for Porous Clay Heterostructures and Heptane Hydro-Isomerization Catalytic Activities Fethi Kooli Taibah University, Department of Chemistry, POBOX 30002, Al-Madinah Al-Munawwarah, Saudi Arabia. E-mail: [email protected]

We propose to use antiperspirant solution as pillaring agent, containing ACH and other organic modifiers. Montmorillonite clay (Mt) was directly added to an aqueous solution of the antiperspirant dissolved in a certain volume of water at 80 oC, and at different Al/clay ratios (in weight, R), resulting to Al intercalated Mt precursors (Al-MtR). The amount of Al species incorporated in Al-MtR precursors, depended on the R values, it varied between 8.70 to 19.75 % with a maximum at R value of 12. The pure pillared clays were obtained after calcinations at 500 o C for R values above 4. For further studies we have selected R value of 6 (Al-Mt6sample). The thermal stability of Al-Mt6 precursor depended on calcination temperatures. The PXRD patterns indicated that the layered structure was stable up to 800 oC with a decrease of the 001 intensity's reflection and shrinkage of the basal spacing from 1.94 to 1.72 nm. A complete collapse of the layered structure was achieved at 900 oC., with an amorphous phase being formed (Figure 1).

Figure 1. PXRD patterns of Al-Mt6 precursor Figure 2. PXRD patterns of PAl-MtCH prepared from Al-Mt6 precursor calcined at calcined at different temperatures different temperatures 27

Al-NMR spectral analysis confirmed the presence of Al species in Al-Mt6, with an additional band between 60 and 70 ppm, mostly assigned to the tetrahedral Al from the pillaring species. The position of the Al octahedral peak at 3 ppm shifted to 2.3 ppm. The calcination at 500 oC resulted to the increase of the tetrahedral peak intensity, with a shift of the octahedral peak at 1.4

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ppm, due to the reaction of aluminum species with the Mt sheets. This conclusion was proved by the reaction of the pillared clays with docylamine (C10 amine) solution. After reaction, no expansion of the interlayer spacing was achieved, and it remained constant close to 1.76 nm. Meanwhile, further expansion of the basal spacing was achieved from 1.90 nm to 3.58 nm when the Al-Mt6precursor (no calcined) reacted with C10 amine, and indicated that the intercalated Al species in Mt-Al-6 precursor were easily exchanged with C10 amine molecules. This finding opened new horizons and the preparation of porous clay heterostructures (PCH) materials was investigated. This method allowed us to minimize the consume of surfactants, by using one directing template (dodecylamine, C12 amine), in order to reduce the organic chemical waste, and to introduce the aluminium species in the mesostructured silica, instead of post grafting in one step reaction, during the preparation of PCH materials. The synthesis of the PCH samples was achieved by mixing Al-Mt6 precursor or its pillared derivatives with dodecylamine, (C12 amine) and TEOS at molar ratios of clay/C12H25NH2/TEOS about 1/20/150. The mixture was stirred for 4 h at room temperature. The organic molecules were removed by calcinations at 550 oC in air. The sample is identified as PAl-MtCH. When pillared clays were used, the calcination temperature was added in the sample identification as PAl-MtXCH, Figure 2 presents the PXRD of the calcined PCHs, the interlayer spacing of Al-Mt6 increased dramatically from 2.00 nm to 3.80 nm with no multiple reflections. However, only slight variation of the interlayer spacing was observed for P-Al-MtXCHs, and it varied from 1.81 to 1.60 nm. We have noticed that the interlayer spacing of the PAl-MtCH precursor depended on the length of the used amine, it shifted to higher values as the length of the aliphatic chains increased. The presence of silica was confirmed by XRF data with an increase of its content from 56% to 79%. A significant decrease in Al2O3 content was detected from 22 % to 5% for PAl-MtCH. In case of PAl-MtXCH materials, we noticed slight variations in SiO2 and Al2O3 contents. These data confirmed that the alumina species were difficult to be exchanged with C12 amine when pillared clays were used. 27

Al MAS NMR spectrum of PAl-MtCH material exhibited different feature than Al-Mt6, with a significant increase of resonance at 52 ppm ( AlIV), and two resonance peaks related for AlVI at 1.5 and 0 ppm. The last two peaks could be attributed to the AlVI in the clay sheets and to an extra AlIV existing in different environments, for example, within the intercalated silica species. Meanwhile, P-Al-Mt500CH material exhibited a similar spectrum to that reported for the starting pillared clay (described above), indicating that the stability of the alumina species between the clay sheets.

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Table 2 summarizes the textural properties of the starting pillared clays and their PCH derivatives. The PAl-MtCH material exhibited a specific surface area (SSA) of 880 m2/g, with a total pore volume of 0.851 mL/g. This data indicated that our PAl-MtCH was mainly a mesoporous material with an average pore diameter of 3.82 nm (Table 2). The P-Al-MXCH samples exhibited SSA values lower than that of PAl-MtCH, however, higher than those of the starting pillared clays. The total acidity of the PAl-Mt6CH (using the temperature desorption of cyclohexylamine) reached a value of 0.61 mmol/g, and higher to that of Al-Mt6 precursor and the pillared clays. Using pyridine as probe molecule, The PAl-MtXCH exhibited strong Lewis (1452 and 1617 cm1 ) and strong Bronsted (1540 cm-1 and 1640 cm-1) acid sites, even at desorption temperature of 300 oC . While pillared clays exhibited mainly Lewis acid sites at 300 oC. The hydro-isomerization reaction of heptane requires bifunctional catalysts, based on the cooperation between noble metal particles and the Bronsted acid sites. The conversion of Pt impregnated Al-Mt6 pillared clays was affected by the temperature of the catalytic reaction, and of the calcination of Al-Mt6 precursor itself. Low conversions of 2% at catalytic temperature of 250 oC was obtained and reached a maximum of 30 % at 350 oC. the calcinations of Al-Mt6 precursor at 600 oC and above resulted a loss of catalyst activities, up to 15 % at 350 oC. The selectivity to isomers and cracking products were in the range of 60% and 40 %, respectively. At catalytic temperature of 350 oC. The impregnated PAl-MtCH catalyst exhibited a maximum conversion of 50 % with selectivity and cracking yields of 63 and 33 %, respectively. The improvement of the conversion could be related to the nature and the strength of the acid sites in this catalyst. However, PAl-MtXCH catalysts exhibited similar conversion values compared to their starting pillared clays, calcined at temperatures higher than 400 oC. The ratio of isomerization to craking (I/C) yields gave an indication on the suitability of the catalysts to the hydro- isomerization reactions. In general the I/C ratios were improved for the PAl-MtCH or PAl-MtXCH products compared to their starting pillared clays, However, the ratios were still lower than the zeolites related catalysts ( in the range of 5 to 6). The stability of the catalyst was carried out at 300 oC, and by expanding the time on stream. The conversion and selectivity values were unchanged for a period of 12h, then a significant decrease was observed, due to the coke formation which blocked the acid sites. However, the PAl-MtCH catalyst showed a decay in catalytic activities for a period on stream of 18 h, with a mild decrease in conversion and selectivity. In case of PAl-Mt500CH, the conversion values decreased quickly for a period less than 8 h, with an improvement of the cracking products. In conclusion, the intercalated Al13-montmorillonite precursor was used to prepare pillared clays and porous clay heterostructures (PCHs). The resulting PCH from the intercalated precursor exhibited different physico-chemical properties than the pillared clays. Higher surface areas and

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pore volumes were obtained. The presence of aluminum in PCH material in different environments were proofed by 27Al MASNMR. Strong Lewis and Bronsted acid sites were detected at temperature of 300 oC. These sites were able to hydro-isomerize heptane molecules with a conversion of 50 % and selectivity of 63 % at 350 oC. The cracking products were about 30 %.  

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  The 2nd International Conference of the Indonesian Chemical Society 2013 October, 22-23th 2013  

Characterization of Surface Area, Pore Volume and Pore Size Distribution of Activated Carbon by Physisorption Methods Allwar1*, Ahmad Md. Noor2, Mohd Asri bin Mohd Nawi2 1

Chemistry Department, Faculty of Mathematics and Natural Sciences, Islamic University of Indonesia, Indonesia 2

School of Chemistry, University Sains Malaysia, Malaysia *[email protected]

Abstract

In this study, oil palm shell as solid waste from palm oil mills was used for the production of activated carbon by chemical activation using 50% ZnCl2 and KOH as activating agents. Determinations of pore structures were carried out by physisorption methods using nitrogen adsorption-desorption isotherm data at 77K. Pore structures of the activated carbon were investigated and tested by variety of methods to differentiate the surface area, pore volume and pore size distribution. The difference of Langmuir shapes obtained between lower relative pressure (P/Po 2 are usually for porous materials with very homogeneous micropores, while the values of n < 2 are used for heterogeneous pores with wide range micropore distributions. In this study clearly shown that the values of n are 1.9 nm which exhibit the more homogeneous pores consisting of the predominantly micropore structures. In contrast, the values of n are between 1.6 and 1.7 consisting of heterogeneous pores with wide size range of micropores. Table 4 describes the distribution of pore diameter. Table 4: The distribution of micropore diameter of the activated carbon Type of

Temperature

chemical

BJH Average Mesopore Diameter

D-A (nm)

Micropore diameter (nm)

ZnCl2

KOH

500

-

1.46 (n=1.9)

600

-

1.52 (n=1.9)

700

-

1.48 (n=1.9)

800

-

1.50 (n=1.8)

500

-

1.76 (n=1.7)

600

-

1.52 (n=1.9)

700

7.56

1.70 (n=1.7)

800

7.87

1.76 (n=1.6)

Conclusion The model nitrogen isotherm shapes lead the different methods that are used in the determination of pore structures. The Langmuir isotherm method, D-R and D-A methods were reliable to estimate Langmuir pore structures which have lower relative pressure, while The BET, t-plot and BJH methods were applied to estimate pore structures which have wider relative pressure. The highest surface areas of the activated carbon are 889 and 1295 m2g-1 and total pore volumes are 0.35 and 0.74 m3g-1 for ZnCl2 and KOH, respectively. The activated carbon prepared with ZnCl2 clearly show micropore size distribution, while the activated carbon prepared with KOH exhibit heterogeneous-pore size distribution: wider micropores and narrow mesopores

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Acknowledgment The authors acknowledge the scientific fund of University Islam Indonesia, Yogyakarta, Indonesia and Universiti Sains Malaysia, Malaysia for financial support.

References ALAM, M. Z., MUYIBI, S.A., MANSOR,M.F., WAHID, R. (2007) Activated carbon deriver from oil palm empty-fruit bunches: Application to environmental problem. Journal of Environmental Sciences,. ALLWAR (2013) Porous Structures of Activated Carbons Derived from Oil Palm Empty Fruit Bunch by Phosphoric Acid Activation under Nitrogen and Carbon Dioxide. International Journal of Research in Chemistry and Environment, 3, 62-68. ALLWAR., A., M. N., ASRI, M. (2008) Textural Characteristics of Activated Carbons Prepared from Oil Palm Shells Activated with ZnCl2 and Pyrolysis Under Nitrogen and Carbon Dioxide. Journal of Physical Science, 19, 93-104. BARRETT, E. P., JOYNER, L.G., HALENDA, P.P. (1951) The determination of pore volumes and area distributions in porous substances. J. Am. Chem. Soc, 73, 373-380. BRUNAUER, S., EMMET, P.H., TELLER, F. (1938) Surface area mesurements of activated carbons, silica gel and adsorbents. Am. Chem. Soc, 60. BUDINOVA, T., EKINCI, E., YARDIM, F., GRIMM, A., BJÖRNBOM, E., MINKOVA, V. AND GORANOVA, M., . (2006) Characterization and application of activated carbon produced by H3PO4 and water vapor activation Fuel Processing Technology, 87. GIL, A., AND GANDIA, L.M. (2003) Microstructure and quantitative estimation of the micropore-size distribution of an alumina-pillared clay from nitrogen adsorption at 77 K and carbon dioxide adsorption at 273 K. Chemical Engineering Science, 58, 3059 - 3075. GO´MEZ-SERRANO, V., GONZA´LEZ-GARC´ıA, C.M. AND GONZ´ALEZ-MART´ıN, M.L. (2001)) Nitrogen adsorption isotherms on carbonaceous materials. Comparison of BET and Langmuir surface areas. Powder Technology, 116, 103-108. GUO, J., AND LUA, A.C (2000) Preparation of activated carbons from oil palm stone char by microwave induced carbon dioxide activation. Carbon, 38, 1985-1993. GUO, Y., ROCKSTRAW, D. A. (2007) Activated carbon prepared from rice hull by one-step phosphoric acid activation. Microporous and Mesoporous Materials, 100, 12-19. HU, Z., SRINIVASAN, M.P. (2001) Mesoporous high-surface-are activated carbon. Microporous and Mesoporous Materials, 43, 267-275. HUDEC, P., SMIESKOVA, A., ZIDEK, Z., SCHNEIDER, P., SOLCOVA, O. (2002) Determination of Microporous Structure of Zeolites by t-Plot Method - State-of-the-Art. Studies in Surface Science and Catalyst, 142, 1587-1594. HUSSEIN, M. Z., ABDUL RAHMAN, M. B., YAHYA, A., TAUFIQ-YAP, Y. H., AHMAD, N. (2001) Oil palm trunk as a raw material for activated carbon production. Journal of Porous Material, 8, 327-334. JAAFAR M., S. J. (2001) The future of palm oil in the new millennium in Malaysia. Burotrop Bulletin, 16, 123-131.

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JOGTOYEN, M., DERBYSHIRE, F. (1998) Activated carbon from yellow poplar and white oak by H3PO4 activation. Carbon, 36, 1085-1097. KHALILI, N. R., CAMPBELLA, M., SANDI, G., GOLAS, J. (2000) Production of micro- and mesoporous activated carbon from paper mill sludge I. Effect of zinc chloride activation. Carbon, 38, 1905-1915. LASTOSKIE, C., GUBBINS, K.E. AND QUIRK. . J. PHYS. CHEM., 97, 4786-4796 (1993) Pore size distribution analysis of microporous carbons: a density Functional theory approach. J. Phys. Chem., 97. LOWELL, S., SHIELDS, J.E. (1984) Powder Surface Area and Porosity. second ed ed. New York., John Wiley. LUANGKIATTIKHUN, P., . TANGSATHITKULCHAI, C., TANGSATHITKULCHAI, M. (2008) Non-isothermal thermogravimetric analysis of oil-palm solid wastes. Bioresource Technology, 99, 986-998. NGUYEN, C., DO, D. D. (2001) The Dubinin–Radushkevich equation and the underlying microscopic adsorption description. Carbon, 39, 1327-1336. SING, K. (2001a) Review: The use of nitrogen adsorption for the characterisation of porous materials. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 187-188, 3-9. SING, K. (2001b) The use of nitrogen adsorption for the characterisation of porous materials. Colloids and Surfaces A: Physicochemicala nd Engineering Aspects, 187-188, 3-9. SING, K. S. W. (2001c) Review. The use of nitrogen adsorption for the characterization of porous materials. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 187-188,, 3-9. STORCK, S., BRETINGER, H. AND MAIER, W. F (1998) Characterization of micro- and mesoporous solids by physisorption methods and pore-size analysis. Applied Catalysis A: General, 174, 137-146. ZHANG, Y., ZHENG, J., QU, X., CHEN, H. (2007) Effect of granular activated carbon on degradation of methyl orange when applied in combination with high-voltage pulse discharge. Journal of Colloid and Interface Science, 316, 523-530.

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  The 2nd International Conference of the Indonesian Chemical Society 2013 October, 22-23th 2013  

Study of Carboxymethyl Chitosan Synthesis : Effect of NaOH Concentration and Ratio Chitosan/Monochloro Acetic Acid Toward On The Substitution Degree and Solubility In Water Ahmad Budi Junaidi, Helda Rahmawati dan Utami Irawati Program Studi kimia FMIPA Universitas Lambung Mangkurat Jl Jend.Ahmad Yani Km 35,8 Banjarbaru Kalimantan Selatan e-mail: a_budi_j @yahoo.co.id

Abstract This study aims to determine the effect of NaOH concentration and the ratio of chitosan /monochloro acetic acid used in the synthesis process toward on the degree of substitution (DS) and solubility carboxymethyl chitosan (CMCts) synthesized in water. The concentration of NaOH used in the alkalination process were 10, 20, 30, 40 and 50%(w/v). The ratio of chitosan/monocloro acetic used for etherification 2/1 ; 1/1 ; 2/3 and 1/2 (w/w). The results showed that the NaOH concentration of 1030% (w/v) increased the DS and solubility of produced CMCts, but at concentration above 30% (w/v) the DS and solubility were decreased. The ratio of chitosan/monochloro acetic acid also effect to DS and the solubility of synthesized CMCts. The higher amount of monochloro acetic acid added to chitosan, the higher is substitution degree and solubility of CMCts synthesized in water. The best of synthesized CMCts was resulted with a solubility of 28.05 g/L and DS of 0.72. Keywords : chitosan, monochloro acetic acid, carboxymethyl chitosan, degree of substitution and solubility in water.

Pendahuluan Dewasa ini, kitosan telah banyak menarik perhatian para peneliti baik dalam penelitian dasar maupun penelitian aplikasi. Penelitian tersebut meliputi bidang biologi, biokimia, kimia organik, polimer, farmakologi, dan obat-obatan. Di samping penelitian dasar, telah banyak dilakukan penelitian untuk menemukan aplikasi yang baru dari kitosan. Salah satu terobosan yang dapat dilakukan dalam kimia dan teknologi kitosan adalah pengembangan modifikasi kimianya. Modifikasi kimia dari kitosan perlu terus dikembangkan dengan lebih aktif untuk menjelajahi aplikasi produk yang baru (Kaban, 2009). Permasalahan utama aplikasi kitosan adalah sifat kelarutan dalam air yang rendah (Hernawan, et al., 2012). Sifat kelarutan kitosan dalam air dapat diperbaiki dengan memodifikasi kitosan menjadi derivatnya (Champagne, 2008). Penelitian mengenai modifikasi kitosan untuk meningkatkan kelarutannya salah satunya adalah karboksimetil kitosan (KMK) yang disintesis dengan eterifikasi kitosan (Mourya et al., 2010 ; Farag & Mohammed, 2013). Dalam penelitian ini dilakukan sintesis KMK dengan variasi konsentrasi NaOH dalam proses alkalinasi dan variasi kitosan/asam monokloro asetat (AMCA) dalam proses eterifikasi untuk mendapatkan KMK dengan kelarutan dalam air yang tinggi.

ISBN: 978-979-96595-4-5    



  The 2nd In nternationall Conference e of the Indo onesian Chem mical Society y 2013 October, 22-23th 20133  

Bahan dan d Metode B Bahan-bahan yang digunnakan dalam m penelitiann ini adalahh kitosan higgh moleculaar weight dengan d viskkositas 800.000 cps daan DD 80--85% (sigm ma-aldrich), NaOH pelllet (Merck), AMCA pelllet (Merck), KBr pellett (Merck), metanol m (p.a Merck), HC Cl pekat (p.a Merck) dan d CH3COO OH pekat (p..a Merck). Prosedur sintesis KMK dengan d variaasi konsentraasi NaOH dillakukan den ngan membuat k 1% (v/v) dalam m asam asettat 1%. Larrutan tersebuut kemudiann dialkalinaasi larutan kitosan menggun nakan larutaan NaOH deengan variassi konsentrassi 10, 20, 330, 40, 50% (b/v) hinggga terbentukk gel berw warna putihh. Endapann yang terrbentuk ditambah AM MCA dengaan perbandinngan 1,5 kali berat kitosan. L Larutan dinaaikkan pH--nya sampaai 5 dengaan menggun nakan larutann NaOH keemudian diprresipitasi deengan mengggunakan meetanol dengaan perbandinngan volum me 1 : 6. Prossedur untuk variasi jumllah AMCA ini sama sepperti proseduur sintesis KMK K dengaan variasi koonsentrasi NaaOH. Konseentrasi NaOH H yang diguunakan adalaah 30% (b/vv) dengan vaariasi AMCA A 0,5; 1,0; 1,,5; 2,0 (b/b). A Analisis DS KMK deengan metode titrasi. Sebanyak 100 mg serbuk s KMK ditambah hkan dengann 10 ml NaO OH 0,1 M daan ditambahkkan indikatoor metil meraah. Kelebihaan NaOH diititrasi dengaan HCl 0,1 M. M Uji kelaruutan KMK dilakukan d denngan cara 0,,5 gram KMK dilarutkaan dalam 100 ml air dallam tabung reaksi dan dipanaskan dalam watter bath padda temperatuur 60oC selaama 30 mennit. Padatan yang tidak larut dipisahhkan dengann metode daan dikeringkkan dalam ovven pada suhhu 80oC sam mpai beratnyaa konstan.   Hasil dan Pembaha asan Derajat Substitusi Karboksime K etil Kitosan          

Gambar 1. Pengaruh konsentrasi NaOH padaa proses alkaalinasi kitosaan terhadap DS KMK

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  The 2nd In nternationall Conference e of the Indo onesian Chem mical Society y 2013 October, 22-23th 20133  

G Gambar 1 meenunjukkan nilai n DS KM MK dengan variasi v konseentrasi NaOH H pada prosees alkalinasi masing-maasing perlakuuan. Derajatt substitusi KMK K mengaalami peninggkatan dengaan meningkatnya pemakkaian konseentrasi NaOH H 10-30% (b/v) pada ttahap alkalin nasi. Namunn, D mengalam mi pada perlakuan alkallinasi dengaan konsentraasi NaOH dii atas 30% ((b/v) nilai DS k n disebabkaan tingginya konsentrasii NaOH, dim mana ion Naa+ penurunaan. Hal ini kemungkinan berlebih akan bereak ksi dengan ioon Cl- dari A AMCA yang g dapat mennghasilkan garam g natrium m d natrium glikolat g sehiingga pembeentukan KM MK tidak sem mpurna dan menurun m nilai klorida dan DS (Basm mal et al., 20005).  

       

 

Gambar 2. 2 Pengaruh rasio mol kitosan k : asam m monokloroo asetat terhhadap nilai DS D KMK hassil sintesis G Gambar 2 menunjukkan m n bahwa sem makin tinggii jumlah AM MCA yang ditambahkaan selama proses p eterifiikasi, maka nilai n DS sem makin meninngkat. Penam mbahan AM MCA ke dalam m kitosan selama s eteriffikasi telah meningkatka m an jumlah gu ugus karbokksimetil (CH H2COO-) yanng bereaksi dengan kitoosan alkali pada atom C6 (Kitosann-ONa) dan atom C2 (K Kitosan–NH H 2) 05). Dapat disimpulkan d n bahwa sem makin banyak jumlah AMCA yanng (Basmal et al., 200 hkan pada prroses eterifikkasi, maka seemakin besaar pula nilai D DS yang dihhasilkan. ditambah Kelarutaan Karbokssimetil Kitossan dalam A Air        

Gambar 3. Pengaruuh konsentraasi NaOH pada proses alkalinasi a kiitosan terhaddap kelarutaan (g/L) KM MK.

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  The 2nd In nternationall Conference e of the Indo onesian Chem mical Society y 2013 October, 22-23th 20133  

G Gambar 3 menunjukkan bahwa kelaarutan KMK K pada konsentrasi NaO OH 30% (b/vv) menunjukkkan nilai kelarutan k yan ng paling tinnggi. Kelaruutan ini berhuubungan eraat dengan DS S, semakin besar nilai DS D maka sem makin besar pula nilai kelarutan k KM MK (Oktaviaa et al., 20055 ; g, et al., 2012). Tungtong            

Gambar 4. 4 Pengaruh variasi rasio o mol AMCA A : kitosan terhadap t kelaarutan KMK K G Gambar 4 menunjukkan m n tingkat keelarutan KM MK yang dihasilkan melalui m prosees eterifikassi dengan variasi v jumlaah AMCA. Kecenderunngan bahwaa semakin tinggi t jumlaah AMCA yang ditam mbahkan. Tingkat keelarutan inii berhubunngan dengaan nilai DS D B et all., 2007). Seemakin banyyak jumlah karboksimet k til (Suryaninngrum, et al., 2005 ; Basmal yang terssubstitusi paada kitosan, maka akan meningkatkkan kepolarann suatu kitoosan. Semakiin tinggi keepolaran kitoosan tersebuut maka sem makin tinggi pula kelaruttan kitosan dalam d pelaruut air. Kesimpu ulan Kesimpuulan yang daapat diambill dari peneliitian sintesiss KMK yanng telah dilaakukan antarra lain: Kon nsentrasi NaaOH pada tahhap alkalinaasi dan rasio kitosan/monnokloro asettat pada tahaap eterifikassi berpengarruh terhadapp nilai DS ddan kelarutann KMK dalaam air. Deraajat substituusi dan kelarrutan KMK dalam air semakin s bessar dengan semakin s bessarnya konseentrasi NaOH untuk konsentrasi 10 0-30%, sedanngkan pada kkonsentrasi NaOH di atas 30% DS dan kelarutaan m S Semakin m meningkat rrasio AMC CA/kitosan pada tahaap eterifikaasi KMK menurun. menyebaabkan DS daan kelarutan KMK juga meningkat. Kualitas KM MK terbaik yang berhassil disintesiss dalam peneelitian ini memiliki m DS sebesar 0,72 2 dengan keelarutan dalaam air sebesaar 28,02 g/L L.

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  The 2nd International Conference of the Indonesian Chemical Society 2013 October, 22-23th 2013  

Ucapan Terima Kasih Penulis mengucapkan terima kasih yang sebesar-besarnya kepada DIKTI yang telah memberikan hibah penelitian bersaing 2013 untuk mendanai penelitian ini dan ucapan terima kasih juga kami sampaikan kepada Panitia International Conference of The Indonesian Chemical Society 2013 Yogyakarta yang memberikan kesempatan kepada kami untuk memaparkan makalah kami ini. Daftar Pustaka Basmal, J., Prasetyo, A., & Fawzya, Y.N. 2005. Pengaruh konsentrasi asam monokloroasetat dalam proses karboksimetil kitosan terhadap karboksimetil kitosan yang dihasilkan. J. Penel. Perik, Indonesia. 11(8): 47-58. Basmal. J., Prasetyo, A., & Farida, Y. 2007. Pengaruh Suhu Eterifikasi pada Pembuatan Karboksimetil kitosan. Jurnal Pascapanen dan Bioteknologi Kelautan dan Perikanan. 2(2): 99-106. Champagne L. M. 2008. The Synthesis of Water Soluble N-Acyl Chitosan Derivatives for Characterization as Antibacterial Agents. Disertasi. Departement of Chemistry, Louisiana State University. Farag R. K. & Mohammed K. K., 2013, Synthesis and Caracterization of Carboxymethyl Chitosan Nanogels for Swelling Studies and Antimicrobial Activity, Molecules, 18, 190-203 Hernawan, Kismortono, Nisa K., Hayati S.N. & Kumalasari R., 2012, Modifikasi Sifat Fungsional Karboksimetil Kitosan dan Pemanfaatannya Sebagai Bahan pembantu Alternatif dalam Sediaan Farmasi, Laporan Intensif Peningkatan kemampuan Peneliti dan Perekayasa, LIPI, Jakarta Kaban. J. 2009. Modifikasi Kimia dari Kitosan dan Aplikasi Produk yang Dihasilkan. Pidato Pengukuhan Jabatan Guru Besar Tetap dalam Bidang Kimia Organik Sintesis. Medan. Mourya, V. K., Inamdar, N. N., & Tiwari, A. 2010. Carboxymethyl chitosan and its applications. Government College of Pharmacy, India. Adv. Mat. Lett. 2010. 1(1): 1133. Oktavia, D. O., Wibowo, S., dan Fawzya, Y.N. 2005. Pengaruh Jumlah Monokloro Asetat Terhadap Karakteristik Karboksimetil Kitosan Dari Kitosan Cangkang Dan Kaki Rajungan. Jurnal Penelitian Perikanan Indonesia. 11(4): 79-88. Suryaningrum, T. D., Basmal, J., dan Aumelia, W. 2005. Pengaruh Konsentrasi Asam Monokloro Asetat Dan Jenis Pelarut Sebagai Bahan Pengendap Terhadap Produksi Karboksimetil Kitin. Jurnal Penelitian Perikanan Indonesia. 11(4): 89-100. Tungtong S., Okonogi S., Chowwanapoonpohn S., Phutdhawong W., & Yotsawimonwat S., 2012, Solubility, Viscosity and Rheological Properties of Water-soluble Chitosan Derivatives, Maejo Int. J. Sci. Technol, 6(02), 315-322

ISBN: 978-979-96595-4-5    



  The 2nd International Conference of the Indonesian Chemical Society 2013 October, 22-23th 2013  

Study of Structure and Morphology of Surfactant–Modified Al-pillared Natural Bentonite Ahmad Suseno1*, Priyono2, Karna Wijaya3,Wega Trisunaryanti3 1

Postgraduate Student of Chemistry Department, Faculty of Mathematics and Natural Sciences, Gadjah Mada University 1 Department of Chemistry, Faculty of Sciences and Mathematics, Diponegoro University 2 Department of Physics, Faculty of Sciences and Mathematics, Diponegoro University 3 Department of Chemistry, Faculty of Mathematics and Natural Sciences, Gadjah Mada University, *) Corresponding author, E-mail : [email protected]

Abstract Bentonite is a clay mineral with expandeble layer structure. Mesoporous pillared bentonite can be prepared by intriducing gallery templates, such as simple metal cation, surfactant and hydroxyed inorganic metal ions. In this study, natural bentonite from Indonesia were used in the preparation of pillared bentonite intercalated by aluminium and surfactant. The function group, crystal surface morphology, structure and porosity were measured by FT-IR, TEM, XRD and N2 adsorption-desorption. The results indicate that intercalation of aluminum and surfactant leads to an increase in the basal spacing and surface area significantly. Keywords : natural bentonite; pillared clay; surfactant

Introduction Bentonites present a significant group of natural sorbents mostly composed from fine-grained particles of minerals from the group dioctahedral smectite [1,2].Bentonite which belong to smectite clay mineral group is the most popular type of clay applied in pillaring processes. The basic unit structure of this group of clays consists of two tetrahedral Si sheets separated by one octahedral Al or Mg sheet [3]. Pillaring is a process of bentonite modification used to obtain materials that have found a wide range of applications in catalytic, adsorption and separation processes. Common procedure for pillared clay (PILC) preparation is: swelling of bentonite in water, exchange of the interlayer cations by partially hydrated polymeric or oligomeric metal cation complexes in the interlamellar region of the starting clay, drying and calcining of wet cake formed of expanded clay in order to have the metal polyoxocations transformed into metal oxide pillars[4].Pillaring process that use polyoxcations are facilitated by a preswelling step whereby interlayer regions are exposed to quaternary ammonium[5,6]. However,preswelling procedures are problematic because they are complex,non-quantitative and require reagents[6]. Recently, we reported a method of

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  The 2nd International Conference of the Indonesian Chemical Society 2013 October, 22-23th 2013  

introducing cationic surfactant into bentonite without a preswelling step, focusing on the simultaneous intercalation of aluminates and surfactants into the natural bentonite. Here, the cationic surfactant played the role of an interlayer space expander and a liquid crystal template by forming a molecular assembly in the interlayer space in a similar manner to that observed with mesoporous molecular sieves.This aluminate pillaring process using cationic surfactants is a very promising route to mesoporous materials with large surface area.The family of new porous materials combining micro and mesoporous structures, are very attractive for potential separate and catalytic applications because of their very large surface area, porosity and high thermal stability.Integrating the synthetic methodologies of mesoporous solids into that of pillared layered structure, using the surfactants, such as cetyltrimethylammonium hydroxide (CTMAB) intercalated into the interlayer space of a mineral clay to be used as template of a aluminate array obtained by hydrolysis and condensation in the interlayer space of a aluminate source,to remove surfactant molecules by calcination and finally to obtain porous materials with textural properties similar to mesopore materials [7-10].The main objective of this work is to investigate the possibility of synthesizing a thermally stable and wide pore Al-pillared bentonite catalyst from natural clay deposit. Furthermore, it aims to characterize the structures and textural of these Al-pillared. Experimental Clay source and sampling: Sample of the natural clay was collected from the open clay deposit in Boyolali, central-java,Indonesia.The clay sample free of quartz, kaolinite, and carbonate, was obtained by sedimentation

after washing it three times with a 1 M NaCl

solution and removing the excess electrolyte (Bentonite). The cation-exchange capacity (CEC) measured by the mmonium acetate technique was 48,08 meq/100 g on an air-dried basis. Surfactant intercalated Bentonite: After the natural bentonite was allowed to be swellable in the water overnight the bentonitewater mixture was addes with 0,024 M cetyltrimethylammonium hydroxide (CTMABr) aqueous solution. The clay-surfactant mixture was vigorously stirred at room temperature for 8 h. The solution was kept at room temperature for 24 h, separated from the solution by filtration a n d

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  The 2nd International Conference of the Indonesian Chemical Society 2013 October, 22-23th 2013  

washed with distilled water till no Br- was detected and then dried in oven at 110 °C. The modified clay (signed as CTMA-Bentonite). Al-pillared synthesis: The transformation of natural bentonite into pillared clay requires the use of a pillaring solution prepared by NaOH to 0.1M AI(Cl)3.9H20

adding slowly a basic solution of 0.2 M

under constant stirring. The pillaring s o l u t i o n was left

overnight at room temperature under constant stirring. Thereafter, the pillaring solution was added drop wise to about 2.5g of the clay in 250 mL suspension with constant stirring and aged overnight at room temperature. Afterwards, the pillared clay suspension was f i l t e r e d a n d washed w i t h distilled water and neutralized until Cl-1 w a s free. The pillared clay was air-dried at ambient temperature and at 105°C for 4 h and then calcined at temperature variation 350°C,450°C,550°C, 650°C,750°C for 4 h. The resulting product is Aluminum Pillared Bentonit (Al-Bentonite). Characterization of Al-pillared sample: The elements, Na and Ca were analyzed

using

atomic absorption spectrophotometry, and then anlaysis Si, AI, Fe, and Mg using Energydispersive X-ray spectroscopy (EDS). The vibrational framework of the clay samples was studied using FTIR spectroscopy. Surface area and pore volume analyzed using Nitrogen adsorption- desorption isotherm were determined analyzer NOVA 1000 (Quantachrome Instruments version 11.0). Determination of basal spacing product were characterized by Xray diffraction (XRD) on a Shimadzu model X-RD 6000 using Cu Kα radiation. The transmision electron microscopy (TEM) micrographs were obtained on a JEOL Hitachi H-600 at 120 kV was used to observe the surface morphology of the pillared clays.

Results And Discussion Analysis of bentonite The chemical composition of natural clay is shown in Table 1. the results indicate that the natural clays contains silica and alumina as major constituents while magnesia, iron (III) oxide, potassium oxides traces of exist as impurities.The results of cation analysis contained in the bentonite was conducted by atomic absorption spectrophotometry (AAS) as shown that the analysis of bentonite is a type of Na-bentonite.

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  The 2nd International Conference of the Indonesian Chemical Society 2013 October, 22-23th 2013  

The identification results of bentonite with X-ray diffraction methods can be seen in figure 1. From the diffractogram is seen a broad reflection on the region 2θ = 6,39 ° and 19,96 ° with a value of d = 1.38 nm and 0.44 nm which is a typical reflection of montmorillonite sample. From these results it can be concluded that the bentonite contains montmorillonite minerals. In addition, bentonite is also composed of the mineral feldspar and quartz as impurities. Infrared spectra data of Na-bentonite samples provide information on the functional groups present in the sample. The results of the infrared spectra of Na-bentonite are presented in Fig. 2. can be seen the identification of bentonite which is the wave number absorption bands at 3626.17 cm-1 and 3448.72 cm-1 is identified as a -OH band stretching vibrations of octahedral and -OH band stretching vibration of water molecules. This is confirmed by the absorption band at wave number 1643.35 cm-1 is a -OH band bending vibration of water molecules. The wave number absorption band at 462.92 cm-1 indicates the bending vibration of Si-O-Si. The wave number absorption band at 794.67 cm-1 is characteristic of bending vibrations of O-Si-O, whereas the -OH bending vibrations of the Al-Al-OH appears as a weak absorption band at 918.12 cm-1 wave number region [11].

Key: M=montmorillonite, F=Feldspar, Q=Quartz Fig.1. XRD pattern of Na-bentonite Na-bentonite

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Fig. 2. Infrared spectra of



  The 2nd International Conference of the Indonesian Chemical Society 2013 October, 22-23th 2013  

While the absorption band at wave number 1033.85 cm-1 indicates the typical absorption Si-O

stretching vibrations in the tetrahedral layer. While the absorption at wave numbers around 3448.72 cm-1 is -OH band stretching vibration absorption of structural octahedral sheet (Al-OH). The natural clay characterization results with the infrared spectra indicate the presence of functional groups of the tetrahedral and octahedral sheets which constitute the mineral Bentonit. Synthesis Al-Pillared Bentonite XRD

pattern: The XRD

bentonites

are

patterns

of

the

shown in F i g . 3 . The XRD

natural, Al-Intercalated,

and A l -pillared

pattern of the n a t u r a l bentonite exhibits a

peak at 2θ = 1.38 nm commonly a s s i g n e d to the basal (001) plane. The d-spacing for the CTMA-bentonite and Al-pillared bentonites

is 2.00 nm and 1.28 nm, respectively. The

natural intercalated a n d pillared clays prepared in this present work showed expanded clay layers. Peaks corresponding to 001, 002,003 and 004 planes were detected. These results reveal that the pillared clay samples have good ordered layers with insertion of alumina pillars which caused an increase in the clay basal spacing.

Fig 3. XRD pattern of (a) Na-bentonite, (b) CTMA-bentonite and (c) Al-bentonite The phenomenon of intercalation, pilarization and exfoliation of Poycationic Aluminum particles into the silicate interlayer of bentonite was analyzed by X-ray diffraction methods were observed with a shift in the peak of the (001) planes.The basal spacing d001 has an important role in

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catalytic processes, ion exchange and intercalation [12].The Basal spacing determined need to know in order to increase the distance the silicate interlayer of bentonite during intercalated CTMA.If there has been a shift it will show the distance the silicate interlayers of bentonite was characterized by changes in basal spacing.The results of the intercalated CTMA bentonite and pillaring of Aluminum oxide particles as shown in figure 3.From the results diffractogram in Fig.3 (a) and (b) can be seen the shift of the (001) planes and an increase in the basal spacing d001 reflection peak areas at 2θ = 6.39o of Na-bentonite shifted toward 2θ = 4.39o in the bentonite intercalated CTMA with basal spacing d001=1.18 nm or ∆d001 =(1.38 – 0.96) nm = 0.42 nm to 2.00 nm or ∆d001 = (2.00 – 0.96) nm = 1.04 nm.This indicates the occurrence of intercalation of CTMA that have larger sizes in the interlayers of bentonite resulted in basal spacing d001 on bentonite increases. While the figure 3 (c) is a Al-bentonite diffractogram. From the results diffractogram seen the peak in the 2θ = 6.88° with basal spacing d001 = 1.28 nm. Changes in basal spacing showed that the interlayer of bentonite was deformed due to the calcination treatment (350oC) of shape hydroxide to form oxides or Al oxide pillars. Surface area and porosity:Table 2 shows the total BET and micropore surface areas,pore volumes and average pore diameter for both pillared and unpillared bentonites.In the case of pillared sample, the BET surface area (ca. 80.73 m2 g-1),the total pore volume(0.33 crrr3 g-l) and the average pore diameter are significantly higher than of the unpillared sample due to the presence of micropores created by aluminium pillar in the inter layer regions.The average pore diameter is within the range typical of smectite clays [ 13].From the data in table.3 it can be seen that the Al-Bentonite has a specific surface area higher than Na-bentonite. An increase in the specific surface area is due to the increased distance the silicate interlayers resulting from pillar formed SiO2-Al2O3 oxide on bentonite and formation of delamination structures. The formation of the pillar where the micropore transformed into a new micropore or because of the Al2O3 oxide pillars of mesoporous higher than Na-bentonite. in addition to the structure of the delamination structure led to the formation of mesoporous pores with sizes indicated by the decrease in micropore surface area on bentonite, thus contributing to increasing the specific surface area. However, the increase is minimal, it is caused to an accumulation of Al2O3 nanoparticles on the surface of bentonite resulted in the closing of interlayer or high density pillars lead to the closing some of the pores. The pillarization also lead to increased porosity in

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bentonite. Changes in porosity due to the pillarization of Al2O3 oxide into the silicate interlayers of bentonite indicated total pore volume data (table. 2).

From the data in the table shows that the Al-bentonite has total pore volume greater than Nabentonite. Total pore volume is a combination of micropore volume to the volume of mesoporous which shows that the pore size distribution in the form of bentonite micropore and mesopores. Morphological analysis by TEM methods TEM analysis is used to determine the morphological structure and size of the Al-bentonite and Na-bentonite were produced. TEM characterization results are presented in Fig.4. Figure 4 (a) is a TEM micrograph of the Al- bentonite and the composite interlayers are arranged in a disorganized or random which is a delamination structure. The Delamination is a structure that different from general micropore pillared clays. Delamination meso-micropore structure can be formed from intercalation and pilarization to form larger pores. Almost the same results obtained by Yuan et al., [14] in which the synthesis of structural delamination of clay pillared clays showed irregularities due to interlayer delamination meso-micropore structure of the clay. Overlapping the silicate interlayers of bentonite by a aggregate of metal cations on the outer layer of bentonite causes the delamination structures formation of mesopore characterized by widening of basal spacing d001. The Al-bentonite TEM analysis was compared with the Nabentonite to determine the occurrence of intercalation or delamination on bentonite as shown in Fig.4 (a). From these results it can be seen the composition and the distance the interlayers of the Al-bentoniteas shown in Figure 4 (b). From the results obtained by measuring the distance the interlayers of the Al-bentonite have distances 0.86 nm. The layers are dark and thick in figure 6 (b) is a silicate layer, whereas among the layers visible light which is the distance between the pores or layers of bentonite.This indicates that the distance the interlayers of Al-bentonite having micropore size and mostly mesoporous.

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Fig. 4 (a) TEM micrograph of Na-bentonite (b) Al-bentonite Conclusion I t was observed that phys ico-chemical properties of Al-pillared bentonite clay changed as a result of pillaring. The presence of aluminium

pillars

on bentonite

produced materials

enhance physico-chemical properties of bentonite such as specific surface area increased from 52.83 m2/g to 80.73 m2/g, average pore diamter increased from 5.76 nm to 8.14 nm, total pore volume increased from 0.15 mL/g to 0.33 mL/g and the surfactant intercalated and insertion of alumina pillar does not cause damage the (001) planes of bentonite. Acknowledgements This work was carried out as a program supported by Dikti Kementerian Pendidikan dan Kebudayaan Republic of Indonesia through Fundamental Grant Research 2013.

References 1. Sparks DL (2003) Environmental soil chemistry. Academic Press, London 2. Meunier A (2005) Clays. Springer, Berlin 3. Lee JO, Kang IM, Cho WJ (2010) Smectite alteration and its influence on the barrier properties of smectite clay for a repository. Appl Clay Sci 47(1–2):99–104 4. H.J. Chae, I.-S. Nam, S.W. Ham, S.B. Hong, Catal.Today 68, 31 (2001). 5. Kwon, O.Y.,Shin,H.S., Choi, S.W.,2000.Preparation of porous silica-pillared layered phase: simultaneous intercalation ofaminetetraethylorthosilicate into the H+ Magadiite and intragallery aminecatalyzed hydrolysis of tetraethylorthosilicate. Chem. Mater. 12, 1273– 1278. 1. Park, K.W., Jung, J.H., Kim, J.D., Kim, S.K., Kwon, O.Y., 2009a. Preparation of

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2. 3. 4. 5. 6. 7. 8. 9.

mesoporous silica-pillared H+-titanosilicates. Micropor. Mesopor. Mater. 118, 100–105. A. Galarneau, A. Barodawalla, T.J. Pinnavaia, Nature 374, 529 (1995) M. Polverejan, Y. Liu, T.J. Pinnavaia, Stud. Surf. Sci. Catal. 129,401 (2000) J. Pires, A.C. Arau´ jo, A.P. Carvalho et al., Microporous Meso- porous Mater. 73, 175 (2004) J.A. Martens, E. Benazzi, J.B. Rendle, Stud. Surf. Sci. Catal. 130,293 (2000) Komadel, P., 2003, Clay Mineral, 38, 127-138 Wijaya et al., 2002, Indonesian J. of Chemistry, 2 (1), 12-21 N arsito, F.I. S. and K. Wijaya, 2011. Effect of Aluminium pillared montmorillonite on its surface acidity properties. ITB J. Sci., 43: 123-138. Yuan, P., et al., 2008, Journal of Colloid and Interface Science, 324, 142-14

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Synthesis of A Chelating Resin Chitosan-1,5-Diphenyl Carbazide and Characterization of Retention Toward Cr(Vi) Ions 1

Aman Sentosa Panggabean*1, Subur P. Pasaribu1, Dadan Hamdani2, Nadira 1

Department of Chemistry-FMIPA, University of Mulawarman-Indonesia 2 Department of Physic-FMIPA, University of Mulawarman-Indonesia *[email protected]

Abstract Synthesis of the derivative chelating resin of chitosan-1,5-diphenyl carbazide (DPC), and characterization of retention for Cr(VI) ions has been carried out. Synthesis chitosan-DPC resin can be done by coupling reacts between diazonium ion from diazotation chitosan with DPC at temperature 1-3˚C during 1 hour, the product of 70% yield was obtained. The optimal conditions to modified of chitosan-1,5-diphenylcarbazide microcapsules resin were 0.1 M CaCl2 and 1% Na-alginate. Caalginate-chitosan-1,5-diphenylcarbazide microcapsule resin before and after interacted with Cr(VI) has characterization by using FT-IR spectroscopic, shows the spesific functional groups of the resin. Retention characteristic of resin was investigated for Cr(VI) ions. The optimal conditions for the analytical performance of resin with retention at pH 1, minimum contact time was 30 minutes, retention capacity was 1.7350 mg Cr(VI)/g microcapsule resin.

Keywords : Chitosan, alginate, Chelating resin, Diphenyl carbazide, Cr(VI). Introduction Chromium occurs in nature at very low concentrations predominantly in two oxidation states, which differ significantly in their toxicity. While Cr(VI) is toxic and carcinogenic upon inhalation, Cr(III) is known to be an essential nutrient for humans supplied also in pharmaceutical products as a dietary supplement. Increasing production of Cr(VI), due to oxidation of Cr(III) in industrial plants or from its spontaneous oxidation in soils, may pose pollution problems to drinking and surface waters. (Paleologos et al., 2001). In recent years, the determination of chromium especially Cr(VI) is become very important in environmental samples. One technique of determining Cr(VI) developed in recent years is preconcentration technique based chelating resin, using a spectrophotometer detector. Chelating resin basically is consisted of two components that are functional of chelating group and polymer matrix as supported. Nature of from both this components will determine usage and performance from a chelating resin. The selectivity will be determined by type chelating group, while capacities, mechanic strength and the chemistry resistance determined by supporter polymer type who applied (Saitoh, et al. 2007; Trochimczuk et al., 2004). This means that a chelating resin with certain characteristic can be synthesis by considering both the compiler components.

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The strategy determines in preconcentration to apply chelating resin is how to incorporate chelating reactant into polymer supporter material (Bilba et al., 1998). Way of simple is through impregnation technique, but chelating resin yielded generally gives unfavourable performance because chelating group which only tied in physical to earn easily escapes again at the time of its use (Amran and Heimburger, 1996; Alexandratos and Smith, 2004). To solving problems explained above, hence chelating group shall tie chemically through covalent bond at polymer applied as supporter material (Prasada et al., 2004). The existing finite, chelating resin this type has not many checked more than anything else is commercial and still be classified as fine-chemicals. Chitosan can be synthesized with deacetylation reaction by removal acetyl group (COCH3) from chitin using alkali solution (Dutta et al, 2004). Pure chitosan is generally used as an absorbent for heavy metals in flakes and powder form. Adsorption ability of chitosan against heavy metals is strongly influenced by physical-chemical properties of chitosan. Chitosan which not cross-linked have an adsorption capacity is greater than the cross-linked chitosan, but the cross-linked chitosan have the physical endurance to acid better than not cross-linked chitosan (Wan Ngah, 2002). In recent years, the synthesis of chitosan have been carried out and modification of chitosan with the addition of side groups with the aim to analytical using such chelating resin against heavy metals contained in natural samples in trace concentrations (Katarina et al., 2005). Based on above description this research

has been synthesized chelating resin

chitosan modified with the addition of 1,5-diphenyl carbazide (DPC) compound and modified

into form of microcapsules in alginate salt which expected to be used as a

microcapsule resin for retention of

Cr(VI) ion. Chitosan obtained from chitin by

deacetylation reaction from windu shrimp’s (Penaeus monodon) shells with 60 % sodium hydroxide, and then DPC group is added as a chelating group to increase the retention capacity of the Cr(VI) ions. Experimental Instrumentation. A set of reflux system, three-neck flask, blender, sieve size of 100 mesh, filter paper, analytical balance, porcelain bowls, glass funnel, the volume pipettes, stopwatch, oven, hot plate with stirer, Spectronic 20 D+, Spectrophotometer FT-IR (Fourier Transform Infra Red) Prestige 21-D., was used for all measurements.

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Reagents. All reagents were of analytical-reagent grade; sodium hydroxide, hydrochloric acid, sulfuric acid, nitrate acid, calcium chloride, acetic acid, ethanol, acetone, sodium nitrite, sodium alginate, 1,5-diphenyl carbazide, potassium bichromate, glacial acetic acid and aquabidest. Synthesis of Chitosan -1,5-diphenylcarbazide Resin 2 g of chitosan added to 100 mL 1M HCl alternating with addition of 75 mL 1 M NaNO2 until resin was azotated in the presence of iodine paper color change, by keeping the temperature between 1-3 oC. Then add dropwise 100 mL of 10% 1,5-diphenylcarbazide and stirred for 1 h with temperature between 1-3 oC and left for 24 h in the refrigerator. The mixture was then filtered and rinsed with destillated water until neutral pH and dried in oven at 60 oC (Panggabean et al., 2009) Production of Ca-Alginate-Chitosan-1,5- diphenylcarbazide Microcapsules Resin 25 mL CaCl2 solution prepared with various concentration of 0.1 - 1 M into each 100 mL glass beaker, then added 0.025 g Chitosan -1,5-diphenylcarbazide resin synthesis and stir until homogeneous with magnetic stirrer. 1% Na-alginate was added dropwise with a burette while stirring with a magnetic stirrer on to form of Ca-alginate-chitosan-1,5diphenylcarbazide microcapsules, adjust the flow rate in the buret and the rotational speed of the magnetic stirrer and Ca-alginate-chitosan-1,5-diphenylcarbazide

microencapsulated

granules dried at room temperature for ± 24 hours. For the same steps, varied concentrations of Na-alginate 0.5 and 0.75% at the optimum concentration of CaCl2 solution. Subsequently the dried resin microcapsules can be determined retention of the ion Cr(VI) (Panggabean et al., 2012). Characterization of Ca-Alginate-Chitosan-1,5- diphenylcarbazide Microcapsules Resin Microcapsule of resin before and after interacted with Cr(VI) has characterization by using FT-IR spectroscopic. The retention capabilities of chelating resin synthesis will be evaluated through a batch method are determining the optimum pH, minimum contact time, and retention of capacity. 0.05 g of Ca-alginate-chitosan-1,5-diphenylcarbazide microcapsule resin

added

10 mL

of standard metal ion Cr(VI)

1

mg/L,

stirred and allowed

30 minutes, filtered. The amount of metal ions retented will be calculated by measuring the amount of residual determined by visible spectrophotometry at λ = 540 nm. The data obtained can describe the character retention of the chelating resin synthesized.

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Results and Discussion Synthesis of Chitosan-1,5-diphenylcarbazide Resin Synthesis of chitosan-1,5-diphenylcarbazide resin is done through the diazotation reaction. Diazotation is a way to change the amine group into a diazo group using concentrated acid solution (Panggabean, et al, 2009). In this process chitosan reacted with HCl 1 M and NaNO2 1 M alternately at 1-3 ˚ C until the resin azotated. Reaction temperature is maintained at below 3 oC because the reaction is highly exothermic. Hydrochloric acid is a strong acid which serves as a catalyst and forming chitosan chloride salt. NaNO2 serves as forming nitrosonium ion together with HCl (Sykes, 1989) to produce diazonium salt. The mixture then reacted with 1,5- diphenyl carbazide 5 % dropwise and stirred for ± 1 hours at 1-3 oC. Diazonium salt is stable at low temperature (0-4 oC) and sensitive to light and can easily be damaged at ultraviolet wavelength and visible light (Panggabean, et al, 2009). Diazonium salt has coupling reaction with 1,5- diphenylcarbazide to produce chitosan- 1,5diphenyl carbazide compound (Figure 1). The obtained Chitosan-1,5- diphenylcarbazide resin after diazotation is reddish brown with a yield of 39.43%. O H

H H O H O

H

O

H

NH

H

O H

H

2O

H

O H O

H

H

N

H

O H

H

O

O H

O H O

O

H

H

H N

H

N

O H

N

HN HN

N H

NH

O

HN N H

O

NH

NH

H N

O NH

HN H N N N H O

H H O

H

O H O H

O H

N H O

H

2

H HO

H

N O H O H

O H

H

N O

H

H

H O

O H O H H

Figure 1. Structure of Chitosan-1,5-Diphenylcarbazide Production of Ca-Alginate-Chitosan-1,5- Diphenylcarbazide Microcapsule Resin The production of Ca-alginate-chitosan-1,5- diphenylcarbazide microcapsules conducted by reacting the Na-alginate solution with chitosan resin-1,5-DPC in CaCl2

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solution. The formation of the microcapsules characterized by changes in the morphology of the

original

microcapsule

Na-alginate shaped

gel

solution

into

Ca-Alginate-Chitosan-1,5-Diphenylcarbazide

sphere

then

Ca-Alginate-Chitosan-1,5-Diphenylcarbazide

microcapsule dried at room temperature. The concentration of CaCl2 and Na-alginate solution be varied to obtain the microcapsules resin able to maximum retention of Cr(VI) ion. On the variation of the concentration of CaCl2 solution with a solution of 1% Naalginate, the % retention of ions Cr(VI) are the most significant at concentrations of 0.1 M CaCl2 solution is 84.60%, whereas the concentration of CaCl2 solution 0.5 M and 1 M,% retention of the metal ions Cr(VI) is very small at just under 20% (Figure 2). This is because the form of the microcapsules at a concentration of 0.5 and 1 M CaCl2 solution denser and less porous which in this case acts as a matrix Ca metal in metal uptake.

% Retention of  Cr(VI)

100 80 60 40 20 0 0

0,2

0,4

0,6

0,8

1

1,2

CaCl2 (M)

Figure 2. Effect of CaCl2 concentration on making Ca-alginate-chitosan-1,5diphenylcarbazide microcapsules From the optimum concentration of CaCl2, subsequently varied Na-alginate concentration of 0.5 and 0.75% respectively at remains 0.1 M CaCl2, and measured the retention of the ions Cr(VI). Variations in the concentration of Na-alginate obtained results are best retention occurred in 0.75% Na-alginate with retention of 96.90% (Figure 3). However, because of the texture of the mixture is less well rounded in form microcapsules so feared ineffective in its application for preconcentration stage in minicolumn, then

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subsequently used for the manufacture of microcapsules composition of 1% Na-alginate which also has a high retention% was 90.20%.

% Retention

100 95 90 85 80 0,25

0,5

0,75

1

1,25

Na‐Alginate (%) 

Figure 3. Effect of Na-Alginate Concentration on the Preparation of Ca-alginate-chitosan1,5-diphenylcarbazide

Analysis of Ca-Alginate-Chitosan-1,5-Diphenylcarbazide microcapsule Ca-Alginate-Chitosan-1,5-Diphenylcarbazide microcapsule were analyzed by FTIR spectroscopy.

Spectrum

analysis

of

Ca-Alginate-Chitosan-1,5-Diphenylcarbazide

microcapsule before interacted with Cr(VI) compared to the spectrum of Ca-AlginateChitosan-1,5-Diphenylcarbazide microcapsule that after interacted with Cr(VI) can be seen in Figure 4 and 5. 100

87.5

499.56

688.59

619.15 588.29

860.25 750.31

945.12

1309.67

1122.57 1080.14 1028.06

1490.97

90

1431.18 1382.96

1708.93

92.5

2366.66

2924.09

95

1234.44

%T 97.5

1602.85

85 82.5

3446.79 3427.51 3414.00

80 77.5

75 4500 Re

4000

3500

3000

2500

2000

1750

1500

1250

1000

750

500 1/cm

Figure 4. FTIR spectrum of Ca-Alginate-Chitosan-1,5-Diphenylcarbazide microcapsule

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FTIR spectrum in Figure 4 shows a broad absorption peaks at wave number 3446.79; 3427.51 and 3414.00 cm-1 indicate typical absorption peak of O-H stretching vibration. Absorption peaks at wave number 2924.09 cm-1 is the CH stretching vibration of alkanes. Absorption peaks at wave number 1708.93 cm-1 indicate typical absorption of stretching vibrations of carbonyl group (C=O) where is possibility of amide groups at 1.5 DPC and carboxylic acid salt of alginic. Absorption peaks at 1062.85 and 1490.97 cm-1 is typical of the stretching vibration peak symmetry and asymmetry -N=N- groups that is likely to come from diazo bond between chitosan and 1.5-diphenylcarbazide or 1.5-difenilkarbazone. Absorption peaks at wave number 1028.06; 1080.14 and 1122.57 cm-1 showed C-O stretching vibration from the compound chitosan and alginate. Absorption peaks at wave number 750.31 cm-1, is typical absorption of stretching vibration of N-O (Silverstein, et al, 1986). 100

85

547.78

727.16

601.79

871.82

945.12

1313.52

1091.71

1031.92

2382.09

87.5

1608.63

2926.01

90

1409.96

2856.58

92.5

1741.72 1716.65

95

810.10

%T 97.5

82.5

3448.72 3427.51 3412.08

80 77.5

75 4500 Recr

4000

3500

3000

2500

2000

1750

1500

1250

1000

750

500 1/cm

Figure 5. FTIR spectrum of Ca-Alginate-Chitosan-1,5-Diphenylcarbazide microcapsule + Cr(VI)

FTIR spectrum Ca-Alginate-Chitosan-1,5-Diphenylcarbazide microcapsule has interacted with Cr(VI) (Figure 5), shows that most of the wave number has changed absorption intensity. It can be seen at 1741.72 and 1716.65 cm-1 absorption peaks showed reduced uptake in group C=O and C-O followed by increased uptake in the wave number 1031.92 cm-1. This is expected because there has been a change in the structure of 1.5diphenylcarbazide to 1.5-diphenylcarbazone binds to Cr(VI). Intensity decrease also occurred in the -N=N- stretching vibration in wave numbers 1608.63 cm-1 and also the NH- bending

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vibration at wavenumber 727.16 cm-1, this may occur due to the interaction between the 1.5diphenylcarbazone complexing with Cr(VI). Determination of Characteristic Retention of Microcapsules Resin In the process of Cr(VI) ion retention by Ca-Alginate-Chitosan-1,5-Diphenylcarbazide microcapsule resin was carried out by batch method. That is by soaking the resin into Cr(VI) standard solution. The ability of Ca-Alginate-Chitosan-1,5-Diphenylcarbazide microcapsule resin in the retention of the metals Cr(VI) is obtained as a characteristic of the resin, which includes: optimum pH, minimum contact time, and retention capacity. Determination of optimum pH Determination of optimum pH microcapsules resin using a batch method or immersion is done by measurements the concentration of Cr(VI) with varying pH standard solution. 0.05 g microcapsules resin soaked for 30 min in 10 ml of 1 mg/L Cr(VI) standard solution so that can be determined the optimum pH Cr(VI) retented well.

% Retention  

100 80 60 40 20 0 0

1

2

3

4

5

6

7

8

pH

Figure 6. Determination of pH optimum Figure 6. shows the microcapsule resin at pH 1, absorption has most favorable to the Cr(VI) ion is more than 80%. This is due to the pH stability of the complex formation occurs between DPC ligand with Cr(VI) ions which causes the metal ions can be maximum retented. Determination of the minimum contact time Determination of minimum contact time aims to find out how long it will need microcapsules resin in the retention of Cr(VI) ions well. At this stage of the research was done by 0.05 g of microcapsules resin into 10 ml of 1 mg/L Cr(VI) standard solution at the optimum pH 1 by varying the contact time from 1 - 120 min.

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% Retention 

120 100 80 60 40 20 0 0

20

40

60

80

100

120

140

Time (minute)

Figure 7. Determination of optimum contact time on the retention Cr(VI) Figure 7. known that level of absorption of Cr(VI) is very fast at the beginning of the absorption process. This is caused by rapid diffusion and molecules absorption into contact to the external surface of resin. After the retention process is very fast. Cr(VI) retention rate gradually declined during the interval of time and reached equilibrium values. Where is this process due to the diffusion speed of Cr(VI) in the matrix of resin particles (Gong, 2010). From the calculation results showed minimum contact time required microcapsules resin to retent metal ions Cr(VI) is 30 minutes, where more than 80% of Cr(VI) ions has retented by resin and in the next minutes, the retention of Cr(VI) ions obtained is not much different. Determination of the retention capacity Retention capacity is a parameter that indicates the ability of Ca-Alginate-Chitosan1,5-Diphenylcarbazide microcapsule resin to retent Cr(VI) ions. Determination of retention capacity is done by batch method, which is made of resin soaking 0.05 g of Ca-AlginateChitosan-1,5-Diphenylcarbazide microcapsule resin into 10 ml of Cr(VI) standard solution with pH 1 with various concentrations of Cr(VI) ions 1-15 mg/L, so it can be determined the ability of Ca-Alginate-Chitosan-1,5-Diphenylcarbazide microcapsule resin to retent Cr(VI)

Retention Capacity  (mg/g)

ions. 2,5 2 1,5 1 0,5 0 0

5

10

15

20

25

Cr(VI)  (ppm)

Figure 8. Determination Retention Capacity of microcapsule resin

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Figure 8, relationships equation between Cr(VI) concentrations with many Cr(VI) ions retented by resin. By extrapolation method obtained two curves crossover point represents the value of the capacity retention of microcapsule resin. Where the two lines of equation y = 0.117 x + 0.113 and y = -0.110 x + 3.260 and the intersection between the two lines is the optimum retention capacity of Ca-Alginate-Chitosan-1,5-Diphenylcarbazide microcapsule resin was 1.7350 mg Cr(VI)/g resin. Where the results indicated that for every 1 g of resin microcapsule may retain 1.7350 mg Cr(VI). Conclusion Chitosan-1,5- Diphenylcarbazide resin compound can be synthesized and modified to became Ca-alginate-chitosan-1,5- Diphenylcarbazide microcapsule resin by reaction between Naalginate solution with chitosan-1,5- Diphenylcarbazide resin in CaCl2 solution. The optimal conditions were obtained by 0,1 M CaCl2 and 1% Na-alginate. Characterization of Caalginate-chitosan-1,5-diphenylcarbazide microcapsule resin for Cr(VI) ion was indicated that optimal Cr(VI) ion retention at pH 1, minimum contact time 30 and retention capacity was 1.7350 mg Cr(VI)/gr microcapsule resin. Acknowledgement We thank to SIM-LITABMAS-DIKTI Jakarta for the Penelitian Hibah Fundamental 2013 project for the financial support.

References Alexandratos, S.D., and Smith, S.D. 2004. High Stability Solvent Impregnated Resins: Metal Ion Complexation as a Function of Time. Solvent extraction and ion exchange. 22(4), pp. 713–720. Amran, M.B. and Heimburger, R. 1996. Arsenic speciation in marine organisms: from the analytical methodology to the constitution of reference materials. Fresenius’ J. Anal. Chem. 354, pp. 550-556. Bilba, D., Bejan, D. and Tofan, L. 1998. Chelating sorbents in Inorganic Chemical Analysis. Croatica Chemica Acta. 71(1), pp. 155-178. Dutta, P.K., Dutta, J. and Tripathi, V.P. 2004. Chitin and Chitosan: Chemistry, properties and applications. Jounal of Scientific & Industrial Research. Vol. 63. pp 20-31. Gong, R., Li, N., Cai, W., Lui, Y., and Jiang, J. 2010. α-ketoglutaric Acid-Modified Chitosan Resin as Sorbent for Enhancing Methylene Blue Remove from Aqueous Solutions. Int. J. Environ. Res., 4(1): pp. 27-32. Katarina, R.S., Takayanagi, T., Oshima, M., and Motomizu, S. 2006. Synthesis of chitosanbased chelating resin and its application to the selective concentration and ultratrace determination of silver in enviromental water samples. Anal. Chim. Acta. 558. pp. 246-253.

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  The 2nd International Conference of the Indonesian Chemical Society 2013 October, 22-23th 2013

Panggabean, A.S., Amran, M.B. dan Pasaribu, S.P. 2009. Sintesis dan karakterisasi Resin Pengkhelat Polystyrene Divinylbenzene -1-(2-Pyridilazo) 2-napthol Serta Penggunaannya Dalam Modul Prakonsentrasi Ion Logam berat. Laporan Penelitian Hibah Bersaing XV, Lembaga Penelitian UNMUL. Samarinda. Panggabean, A.S., Subur P. Pasaribu, dan Sari, I.Y.L. 2012. Prakonsentrasi ion Cu(II) Berbasis Mikrokapsul Ca-Alginat Secara off-Line Dengan Metode kolom. Chemistry Progress. 5(2). Hal. 70-76 Paleologos, E.K., Stalikas, C.D., Tzouwara-Karayanni, S.M., and Karayannis, M.I. 2001. Selective speciation of trace chromium through micelle-mediated preconcentration, coupled with micellar flow injection analysis–spectrofluorimetry. Anal. Chim. Acta. 436. pp. 49–57. Prasada, T.R., Praveen, R.S. and Daniel, S. 2004. Styrene-divinyl benzene copolymer: synthesis, caracterization, and their role in inorganic trace analysis. Critical Reviews in Anal. Chem. 34, pp. 177-193. Saitoh, T., Nakane, F., and Hiraide, M. 2007. Preparation of trioctylamine-impregnated polystyrene-divinylbenzene porous resins for the collection of precious metals from water. Reactive & Functional Polymers. 67, pp. 247–252. Silverstein, R.M., Bassler, G.C. dan Morril, T.C. 1986. Penyidikan Spektrometrik Senyawa Organik. Erlangga Jakarta. Sykes, P. 1989. Penuntun Mekanisme Reaksi Kimia Organik. Gramedia. Jakarta. Trochimczuk, A.W., Kabay, N., Arda, M. and Streat, M. 2004. Stabilization of solvent impregnated resins (SIRs) by coating with water soluble polymers and chemical crosslinking. Reactive & Functional Polymers. 59, pp. 1–7. Wan Ngah, W.S. 2002, Removal Copper (II) Ions from Aqueous Solution onto Chitosan and Cross-linked Chitosan Beads, Reactive and Functional Polymers, 50. pp 181-190.

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Preparation and Characterisation of Chloride-Free Palladium Catalysts Anti K. Prodjosantoso Jurusan Pendidikan Kimia, FMIPA, UNY Yogyakarta, Yogyakarta DIY 55281 [email protected]

Abstract This research aims to prepare and characterize chloride-free palladium catalysts. An organometallic compound of ammonium bisoxalatopalladium(II) hydrate was used to prepare unsupported and aluminium supported Pd/PdO catalysts. A series method including XRD, IR, SEM, TEM, EDA, and XPS was used to characterize samples. The studies showed that (NH4)2Pd(ox)2.2H2O was synthesized and used to prepare unsupported and alumina supported Pd/PdO free of chloride impurities. Keywords: organometal, catalysts, palladium, XRD.

Introduction Organometallic compounds are widely used as catalyst precursor [1, 2].

By

impregnating the support with a solution containing the appropriate organometallic species heat treatment can yield metal and/or metal oxide particles uniformly distributed over the surface of the support. Unfortunately since multi-step reaction pathways are frequently involved, the preparation of particular organometallic precursor is often time consuming. A second problem is that chloride containing species are typically the most easy-prepared organometallics [3].

Thus its possible that chloride will be present in of the resulting

catalysts [4]. Chloride ions have been reported to be absorbed at [5, 6], and hence block, the active site of metal catalysts [7]. As such chloride ions can inhibit a number of metal catalysed reactions [8]. Removing such chlorides can be both difficult and time consuming since requires additional processing. Potassium bisoxalatometallate complexes are simple chloride-free compounds. Potassium bisoxalatopalladium(II) [9] is well known and easy prepared. This complex can be thermally decomposed at relatively low temperatures to the metal and/or metal oxide [1] and such to be ideal precursors for the formation of chloride-free catalysts. The high solubility in aqueous solutions suggests it may be straight forward to deposit this compound onto high surface area supports. When heat treated it can be proposed that the metal and/or metal oxide crystallites dispersed over the surface of the support will be obtained. Thermal

decomposition

of

supported

and

unsupported

potassium

bisoxalatopalladium(II) produces PdO, Pd and unidentified amorphous potassium species [10]. It appears that while some the more volatile K is lost during heating, the majority,

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forms amorphous species. The presence of K as a product of heat treatment of potassium bisoxalatopalladium(II) was confirmed. In general potassium is not believed enhance the catalityc activity of Pd, and there is some evidences that potassium acts as inhibitor. Fortunately the K species could be removed by washing the heat reated samples with water. However, washing heat treated K2Pd(ox)2.2H2O with water failed to removed all the potassium since in this case the insoluble oxide was formed [10]. The structural studies of K2Pd(ox)2.2H2O demonstrate the presence of discrete Pd(ox)22- [11] and therefore it should be possible to replace potassium with ammonium cation [12]. The advantages should be realized by avoiding the use of K. Since the ammonium cation will be oxidized during heat treatment, subsequent washing of the Pd product should be unnecessary. This paper was to establish if chloride-free Pd catalysts could be prepared using complex of the type (NH4)2Pd(ox)2.2H2O. Experimental procedure and data analysis Ammonium bisoxalatopalladium(II) [(NH4)2Pd(ox)2.2H2O] was prepared by dissolving (NH4)2PdCl6 in a hot 2 M (NH4)2(ox) solution. The solution was then evaporated until about 10 mL remained. The resulting fine yellow needles were then collected by filtration and wash successively with cold water, alcohol and acetone. The crystals were air dried. Alumina supported (NH4)2Pd(ox)2.2H2O was prepared by dissolving (NH4)2Pd(ox)2.2H2O in 25 mL of hot water containing a suspension of Al2o3. evaporated to about 10 ml.

The mixture was stirred and

After cooling, the yellow solid was collected and washed

successively with cold water, alcohol and acetone. Samples were heat treated in a muffle furnace for four hours at 950 oC and 1100 oC for unsupported and supported samples, respectively. Infrared (IR) spectra were recorded on a Biorad FTS-40 spectrophotometer between 400 to 4000 cm-1. Powder X-ray diffraction (XRD) patterns were recorded on a Siemens D5000 diffractometer operating the DIFFRAC 500 software. Scanning electron micrographs (SEM) were collected using a JEOL JSM6000F microscope.

Transmission electron

microscopy (TEM) studies were performed on a Phillips CM12 microscope.

Energy

dispersive analysis (EDA) were performed with an EDAX PV9900 system on a Phillips 505 scanning electron microscope. X-ray photoelectron spectra (XPS) were recorded on a Kratos XSAM 800 spectrometer.

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Result and Discussion Untreated unsupported and alumina supported (NH4)2Pd(ox)2.2H2O are characterized using some methods. The broad and strong bands at the region 2800-3700 cm-1 of infrared spectra of the (NH4)2Pd(ox)2.2H2O sample feature the characteristic of NH4+ group and water. Electron micrographs of (NH4)2Pd(ox)2.2H2O is shown in Figure 1.a. The complex forms needles having a wide range of size; 10-250 µm long. In this case there is no evidence for any minority phases. Electron micrograph of alumina supported (NH4)2Pd(ox)2.2H2O is given in Figure 1.b. The particle size of supported material is considerable smaller than the unsupported material. In this case well dispersed crystallites of oxalate complex is present on the surface the alumina particles. Chloride was not observed in the EDA of the sample studied (Figure 2).

(a)

(b)

Relative Intensity

Figure 1. Electron micrographs of unsupported (a) and alumina supported (NH4)2Pd(ox)2.2H2O (b).

1

2

3

Energy (keV)

4

5

Figure 2. EDA spectra of alumina supported (NH4)2Pd(ox)2.2H2O. The XRD measurement confirms that the structure of the NH4+ salts of Pd(ox)22- is retained when it is deposited into alumina (Figure 3). There is noticeable changes in the relative intensities of the Bragg reflections in the pattern of (NH4)2Pd(ox)2.2H2O, however this is believed to be a result preferential growth of the complex on the support.

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Relative Intensity

The 2nd International Conference of the Indonesian Chemical Society 2013 October, 22-23th 2013

2θ (Degrees)

Figure 3. XRD patterns of (a) alumina supported and (b) unsupported (NH4)2Pd(ox)2.2H2O. Lines marked (∗) are due to alumina. The XRD patterns of the decomposition products of unsupported (NH4)2Pd(ox)2.2H2O formed at different temperatures are given in Figure 4. Heat treatment at 400 oC produces a mixture of poorly cryistalline PdO and Pd. Heating the sample at temperatures between 550 o

C to 750 oC results in both the oxidation of Pd and crystallization of PdO. At 850 oC, PdO

decomposes to Pd metal. As for the unsupported materials at intermediate temperatures the only crystalline species present is PdO. However, as is evident from Figure 5, some PdO persists in the supported material even after heating to 1100 oC. This is presumably a consequence of Pd-O-

Relative

Al interactions.



Figure 4. XRD patterns of heat treatment products of (NH4)2Pd(ox)2.2H2O at a range of temperature. Lines marked (∗) are due to Pd.

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2θ (Degrees)

Figure 5. XRD patterns of heat treatment products of alumina supported (NH4)2Pd(ox)2.2H2O. Lines marked (∗) are due to alumina and (+) due to Pd. SEM and EDA were also employed to characterized heat treated unsupported and supported (NH4)2Pd(ox)2.2H2O. The electron micrographs of (NH4)2Pd(ox)2.2H2O heated at 550 oC show the sample lack any obvious dominant particle morphology and consists of irregular shaped particles, ~100 nm in size. The size of the particles become larger, up to ~10 µm, and these appear to sinter yielding a net-like structure, when the samples were heated at higher temperature, up to 850 oC. EDA on various heat treated samples shows that the only element present was Pd. Comparing these results with the powder XRD patterns of the samples, it is seen that the PdO→Pd transformation is accompanied with this dramatic change in morphology. TEM was used in order to characterize any small particles that may form on the surface of heat treated alumina supported materials. For the Pd containing complexes a range of particle sizes were observed, and the precise size of the cryatallites depended on the heating conditions.

For example, the heat treating the alumina supported palladium

o

complexes at 950 C produces particles with size ranging from 36 to 200 nm distributed over the alumina support (Figure 6.). It is proposed that the smaller particles are result from a strong Pd-O-Al interaction which reduces the crystallite mobility and hence the ultimate particle size. Conversely, the larger particles are believed to form palladium crystallites which only interact weakly with the support and hence are more mobile at higher temperatures.

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Figure 6. TEM of heat treated alumina supported (NH4)2Pd(ox)2.2H2O at 950 oC. The surface composition on the heat treated alumina supported samples was studied by XPS. The survey spectra on the alumina supported sample after heating at 400 oC for 4 hours was collected. The spectra are dominated by strong Al and O signals from alumina support, all other lines observed are as expected. No lines due to Cl were observed. The Pd 3d spectra of alumina supported (NH4)2Pd(ox)2.2H2O after heating at 950 oC is a single broad line (Figure 7). Using well established procedures [12] and a series of peak constrains [13] it is possible to identify two doublets. The stronger of these has a Pd 3d5/2 BE of 334,5 eV and is typical of Pd(O) while the weaker doublet has a higher BE 3d5/2 = 339,6 eV typical of PdO. This is in agreement with the XRD studies where the two species Pd and

Relative

PdO were observed.

Energy (keV)

Figure 7. Pd 3d spectra of alumina supported (NH4)2Pd(ox)2.2H2O after heated at 850 oC. Conclusion IR, XRD, SEM, TEM, EDA and XPS studies showed that (NH4)2Pd(ox)2.2H2O can be synthesized and can be used to prepare unsupported and alumina supported Pd/PdO free of chloride impurities. References Blokhin, A.I., Solo’ev, L.A., Blokhina, M.L., Yakimov, I.S. & Kirik, S.D., Russ. J. Inorg. Chem., 1995, 40, 1241.

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Ivanov-Emin, B.N., Borzova, L.D., Sudzhben, D., Ivanova, N.N. & Ezhov, A.L., Russ. J. Inorg. Chem., 1974, 19, 1026. Kukushkin, Y.N., Antonov, P.G. & Dubonos, K.I., Russ. J. Inorg. Chem., 1976, 21, 1348. Cao, X. & Cao, L.L., XPS Australia-Asia Symposium, Abstract, Sydney, 1995. Lane, R.F & Hubbard, A.T., J. Phys. Chem., 1975, 79, 808. Burch, R. & Garla, L.C., J. Catal., 1981, 71, 360. Snell, K.D. & Keenan, A.G., Electrochim. Acta, 1981, 26, 1339. Snell, K.D. & Keenan, A.G., Electrochim. Acta, 1981, 27, 1683. Krogmann, K., Z. anorg. Allg. Chem., 1966, 346, 188. Prodjosantoso, A.K., The Structure and Properties of Oxalate Materials: Precursor for Catalysts, Thesis, 1996. Kobayashi, A., Sasaki, Y., Shirotani, I. & Kobayashi, H., Solid State Commun., 1977, 26, 653. Hausmann, S. & Löwenthal, J., Liebigs Ann., 1854, 89, 104.

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Synthesis and Characterization of Nanosilica from Rice Husk Ash by Sol-Gel Process Dwi Rasy Mujiyanti *1, Totok Wianto2, M. Fahmi Arif1 1

Chemistry Department, Faculty of Science and Mathematics Universitas Lambung Mangkurat 2 Physic Department, Faculty of Science and Mathematics Universitas Lambung Mangkurat Jl. Jend. A. Yani Km 35,8 Banjarbaru 70714 Kalimantan Selatan, Indonesia * email: [email protected]

Absract It has been synthesized and characterization nanosilica from rice husk ash of Gambut by sol-gel process. Synthesis of nanosilica were calculated using three different concentration of sodium hydroxide solution (2.0; 2.5 and 3.0 N), respectively with methods of destruction, while for phase condensation polymerization using concentrated sulfuric acid. Nanosilica characterized by XRD and SEM analysis. The results of the analysis of X-ray diffraction patterns have the same broad pattern of peaks and amorphous structure. For the analysis of morphology and particle size using SEM, where the increases concentration of sodium hydroxide showed a decrease of particle size, for an average particle size of 2.0 N NaOH for 74 nm, 2.5 N NaOH for 40 nm and 3.0 N NaOH for 29 nm. From the asect of uniformity of particles, 2.0 N NaOH (less uniform), 2.5 N NaOH (rather uniform) and 3.0 N NaOH (uniform), judging from the size distribution and number. From the aspect of the acquisition of mass produced nanosilica obtained 7.96 grams (2.0 N NaOH); 6.35 grams (2.5 N NaOH) and 5.54 grams (3.0 N NaOH). Associated with the concentration of sodium hydroxide solution, it can be concluded that increasing the concentration of sodium hydroxide solution as phase destruction resulted in decrease of particle size, uniformity of shape and mass gains. Observations of morphology and particle size of powder nanosilica who successfully made measuring between 130 to less than 24,09 nm. Keywords : nanosilica, sodium hydroxide solution, morphology and particle size

Pendahuluan Kalimantan Selatan memiliki lahan gambut yang luasnya sekitar 171.970 hektar. Sebagian besar dari lahan tersebut dimanfaatkan untuk pertanian khususnya tanaman padi pasang surut. Budidaya tanaman pangan khususnya padi di lahan gambut harus menerapkan teknologi pengelolaan air, yang disesuaikan dengan karakteristik gambut dan jenis tanaman (Fahmuddin dan Subiksa, 2008). Abu sekam padi yang berasal dari pembakaran sekam padi menggandung silika kadar tinggi yaitu 87-97% serta sedikit alkali dan alkali tanah sebagai unsur minor. Berdasarkan penelitian yang telah dilakukan oleh Mujiyanti dkk (2010) yang melaporkan bahwa kandungan silika dalam abu sekam padi daerah Gambut Kabupaten Banjar Kalimantan Selatan mencapai 95,6%. Tingginya ketersediaan bahan baku sekam padi ini yang kemudian dapat dimanfaatkan untuk mengekstrak material berbasis silika dari abu sekam.

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The 2nd International Conference of the Indonesian Chemical Society 2013 October, 22-23th 2013 Seiring perkembangan dengan kebutuhan partikel nano, teknik yang dipakai adalah penggilingan mekanik dengan menggunakan ball mill. Akan tetapi produk akhir yang dihasilkan tidak homogen, perlu teknik kombinasi agar bisa membuat partikel lebih homogen dan juga teknik ini dilakukan dalam skala besar dan memakai suhu tinggi dalam prosesnya. Pembuatan nanomaterial dalam skala laboratorium yang baru-baru ini dikenal adalah proses sol-gel (reaksi pengendapan larutan kimia). Sol-gel merupakan pendekatan yang menarik untuk produksi di saat ini dan produk sol-gel dapat diperoleh sebagai bulks, film tipis dan serbuk (ukuran nano). Proses sol-gel merupakan teknik yang sederhana, murah, memakai suhu rendah dan memungkinkan untuk mengontrol hasil partikel yang lebih halus dan homogen (Maruszewski et al, 2002). Ketersediaan sumber silika pada limbah sekam padi di Gambut, Kalimantan Selatan, dapat dijadikan sebagai bahan dasar pembuatan material berbasis silika, dan diolah lebih lanjut sebagai nanomaterial dengan karakteristik ukuran yang sangat halus berukuran sekitar nanometer (10-9 meter). Penggunaan peralatan X-ray diffractometer (XRD) dan scanning electron microscope (SEM) akan memberikan gambaran yang lengkap menyangkut struktur, bentuk, ukuran partikel, dan morfologi bahan. Dalam penelitian ini, dilakukan kajian sintesis nanosilika dari abu sekam padi Gambut dengan proses sol-gel dengan bahan baku prekursor larutan natrium silikat dengan mengkaji pengaruh konsentrasi natrium hidroksida terhadap karakterisasi ukuran dan bentuk partikel yang dihasilkan. Bahan Dan Metode Penelitian dilakukan di Laboratorium Dasar Fakultas Matematika dan Ilmu Pengetahuan Alam (FMIPA) Universitas Lambung Mangkurat Banjarbaru. Analisis sampel untuk XRD dilakukan di

Laboratorium Difraksi Sinar-X LPPM-ITS dan Pusat Penelitian Pengembangan Geologi dan Kelautan Bandung (Analisis SEM). Sintesis nanosilika gel Serbuk silika yang terbentuk direfluks dengan 80 mL HCl 6 N selama 4 jam pada suhu 950C. Sampel kemudian dicuci dengan akuades hangat sampai filtrat terbebas dari asam dan dikeringkan kembali dalam oven. Silika hasil refluks dilarutkan kembali dengan 80 mL NaOH (2,0, 2,5 dan 3,0 N) lalu diaduk terus menerus selama 10 jam menggunakan pengaduk magnetik, kemudian ditambahkan H2SO4 pekat secara perlahan ke larutan sampai endapan putih terbentuk dan diteruskan sampai

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The 2nd International Conference of the Indonesian Chemical Society 2013 October, 22-23th 2013 pH 7. Nanosilika gel dicuci berulang kali dengan akuades hangat sampai filtrat sepenuhnya bebas dari garam. Nanosilika gel dikeringkan pada suhu 50 0C selama 48 jam di oven. Karakterisasi Pengukuran difraksi sinar X (XRD) menggunakan difraktometer sinar-X Philips Analytical Xpert MPD yang memiliki sumber sinar-X λ Cu Kα = 1,54 Å, dioperasikan pada 40 kV dengan slit divergensi dan pantulan 10. Karakterisasi SEM dilakukan menggunakan SEM JEOL JSM-6360. Sampel membran dipotong kemudian direkatkan pada kepingan spesimen holder dan disputtering menggunakan mesion ion sputter JFC-1100. Hasil dan Pembahasan Abu sekam padi yang diperoleh dari pembakaran sekam padi di daerah Gambut dimasukkan ke cawan porselen lalu diabukan dalam furnace pada temperatur 650 oC selama 1 jam. Pengabuan bertujuan untuk mengubah sisa karbon dalam abu menjadi CO2, hidrogen menjadi H2O dan silikon menjadi SiO2. Karena CO2 dan air menguap pada temperatur tinggi maka diharapkan abu terdapat SiO2. Hasil dari furnace digerus untuk memperoleh ukuran yang kecil dan homogen dan kemudian digunakan sebagai bahan dasar pembuatan prekursor berbasis silika. Produk silika gel yang ditambahkan H2SO4 5 M pada pH 7 menghasilkan produk berupa gelatin besar (agrerat) sedangkan untuk pH 2 didapatkan produk larutan dengan gel kecil-kecil yang terdispersi di seluruh larutan. Larutan H2SO4 pekat yang ditambahkan sudah jenuh direntang pH 10 dengan produk gelatin kasar (agrerat besar). Agregat tadi, dengan pengolahan yang baik, dapat dipecahkan menjadi beberapa nm di tahap akhir (Julbe el al, 1993) yaitu diteruskan sampai pH 7. Karakterisasi dengan difraksi sinar-X (XRD) Metode XRD (X-Ray Diffraction) merupakan suatu metode analisis kualitatif yang memberikan informasi mengenai kekristalan suatu mineral tertentu. Pola difraktogram pada sampel (a), (b), (c), dan (d) ditunjukkan pada Gambar 1.

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Gambar 1. Pola XRD (a) Abu sekam padi Gambut (Mujiyanti dkk, 2010), (b) nanosilika NaOH 2,0 N, (c) nanosilika NaOH 2,5 N dan (d) nanosilika NaOH 3,0 N. Berdasarkan Gambar 1, terlihat nanosilika (b) dan (c) tidak terdapat intensitas maksimum yang terbaca ( No peak in the peak list ) sedangkan nanosilika (d) terdapat satu peak list. Kesamaan pola difraksi bisa diartikan material tersebut amorf atau bentukan struktur semikristal dari amorf. Karakterisasi menggunakan SEM SEM dapat memberikan informasi tentang struktur mikro permukaan sampel dan melihat morfologi serbuk n-SiO2.

A

B

C Gambar 2. Hasil SEM masing-masing sampel nanosilika (A) NaOH 2,0 N; (B) NaOH 2,5 N dan (C) NaOH 3,0 N perbesaran 40.000x) Tabel 1. Pengaruh konsentrasi NaOH terhadap ukuran partikel nanosilika. Sampel A B C

Konsentrasi NaOH 2,0 N 2,5 N 3,0 N

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Rentang ukuran Partikel (nm) 41,6-130 30,12-48,19 24,09-30,12

Ukuran partikel rata-rata (nm) 74 nm 40 nm 29 nm

keseragaman partikel Tidak seragam Agak seragam Seragam

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The 2nd International Conference of the Indonesian Chemical Society 2013 October, 22-23th 2013 Karakterisasi SEM dapat melihat ukuran partikel rata-rata yang dihasilkan mengalami penurunan ukuran dan keseragaman bentuk seiring dengan kenaikan konsentrasi NaOH. Pengaruh konsentrasi NaOH Proses sol-gel melibatkan pembentukan sol, dimana larutan sol disini merupakan natrium silikat yang diperoleh dari reaksi silika dengan larutan NaOH Tabel 2. Pengaruh NaOH terhadap volume H2SO4 untuk kondensasi (pengendapan) larutan Na2SiO3. Sampel A B C

Konsentrasi NaOH 2,0 N 2,5 N 3,0 N

Konsentrasi H2SO4 pekat (97%) pekat (97%) Pekat (97%)

Volume H2SO4 Total (mL) 3,9 4,9 5,6

Spesi anion silikat (Na2SiO3) sedikit sedang meningkat

Volume dari H2SO4 pekat yang ditambahkan, semakin tinggi konsentrasi NaOH untuk memperoleh natrium silikat maka semakin banyak pula volume yang dibutuhkan untuk tahap kondensasi (pengendapan) dan pemecahan gel (agrerat), bisa dilihat di Tabel 3. Volume tersebut memberikan asumsi bahwa adanya peningkatan spesi-spesi anion silikat dalam larutan. Faktorfaktor seperti konsentrasi prekursor, suhu dan capping agent sebagai waktu reaksi adalah parameter penting yang mempengaruhi ukuran dan morfologi nanopartikel (Moloto et al (2006) dan salah satu pengaruh yang sangat sensitif pada pembentukan nanopartikel adalah konsentrasi ion-ion dalam larutan prekursor (Masuda, 2010), jadi larutan natrium silikat yang dibuat mempunyai pengaruh yang besar dalam terbentuknya morfologi dan ukuran partikel. Secara kseluruhan dapat dilihat, nanosilika yang dihasilkan mengalami penurunan berat massa (gram) seiring dengan peningkatan konsentrasi prekursor, hal ini kemungkinan diakibatkan penurunan ukuran partikel yang semakin mengecil . Kesimpulan Karakteristik XRD nanosilika dari abu sekam padi Gambut menunjukkan puncak yang melebar dan berstruktur amorf. Peningkatan konsentrasi NaOH berpengaruh tehadap karakteristik morfologi dan penurunan ukuran partikel dengan ukuran rata-rata nanosilika NaOH 2,0 sebesar 74 nm (kurang seragam), nanosilika 2,5 N sebesar 40 nm (agak seragam) dan nanosilika 3,0 N sebesar 29 nm (seragam). Daftar Pustaka Amutha, A, Ravibaskar, R and G. Si vakumar. 2010. Extraction, Synthesis and Characterization of Nanosilica from Rice Husk Ash. International Jurnal of Nanotechnology and Applications. 4 : 1. .

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The 2nd International Conference of the Indonesian Chemical Society 2013 October, 22-23th 2013 Edelstein, A.S. 1996. Nanomaterials: Syntesis, Properties and Aplication, Institute of Physics Publishing Bristol and Philadelpia, USA Fahmuddin, A dan G. Subiksa, I. 2008. Lahan Gambut: Potensi untuk Pertanian dan Aspek Lingkungan. Balai Penelitian Tanah dan World Agroforestry Centre (ICRAF). Bogor.. Kalapathy, U., A. Proctor, & J. Shultz. 2002. An Improved Method for Production of Silica from Rice Hull Ash. Bioresource Technology. 85: 285-289. Kalyana, C., Pingali, D. Shuguang and D.A Rockstraw. 2007. Direct Synthesis of Ru-Ni Nanoparticles with Core and Shell Structure. Journal of Chem. Eng. Comm. 194:780–786. Moloto, N., N. Revaprasadu., P.L. Musetha & M.J. Moloto. 2006. The Effect of Temperatu, Precursor Concentration and Capping Group on the Shape of CdS nanoparticles. Nanostructured Materials, Council for Scientific and Industrial Research. 3:1. Mujiyanti, D.R, M.D. Astuti & D. Umaningrum. 2010. Pembuatan Silika Amorf dari Limbah Sekam Padi Gambut Kabupaten Banjar Kalimantan Selatan. FMIPA Unlam, Banjarbaru. Serio, M.D., Cozzolino, M., Giordano, M., Tesser, R., Patrono, P.,and Santacesaria, E., 2007. From Homogeneous to Heterogeneous Catalysts in Biodiesel Production. Ind. Eng. Chem. Res. 46: 6379–6384

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The 2nd International Conference of the Indonesian Chemical Society 2013 October, 22-23th 2013

Synthesis Of Silver-Chitosan Nano composites By Glucose As Reducing Agent and Their Antibacterial Activity Endang Susilowati1,2, Triyono3, Sri Juari Santosa3, Indriana Kartini3* 1

Chemistry Postgraduate Program, Department of Chemistry, FMIPA Universitas Gadjah Mada Sekip Utara PO BOX BLS 21 Yogyakarta 2 Chemistry Education Department FKIP Universitas Sebelas Maret Jl. Ir Sutami 36 A Surakarta Indonesia 53126 3 Department of Chemistry FMIPA Universitas Gadjah Mada Sekip Utara PO BOX BLS 21 Yogyakarta *Corresponding authors:[email protected], [email protected]

Abstract Silver-chitosan nano composites were successfully synthesized by chemical reduction method at room temperature using glucoseas reducing agent, sodium hydroxide (NaOH)as accelerator reagent, silver nitrate (AgNO3) as metal precursor and chitosan as stabilizing agent. The effect of molar ratio of AgNO3/Glucose and AgNO3 concentration toward surface plasmon resonance (SPR) of Ag nano particle wasi nvestigated. It is also reported the antibacterial activity of silver-chitosan nano composites against Escherichia coli. The formation of silver nanoparticles was monitored using UV-Vis absorption spectroscopy. Size and shape of silver nanoparticles were determined by Transmission Electron Microscopy (TEM). The antibacterial activity of silver-chitosan nanocomposites was measured by difusion method. The formation of silver nanoparticles was shown by the appearance of surface plasmon resonance at 405.5 nm – 414.0 nm. The resonance was influenced by concentration of AgNO3 and glucose. According to SPR phenomenon, the higher concentration of glucose the smaller the size, while the higher concentration of precursor the bigger the size of silver nanoparticles. Silver nano particles was spherical in shape as identified by TEM images. The silver-chitosan nanocomposites have also showed high antibacterial activity against Escherichia coli. Keywords: nanocomposite, silver nanoparticles, chitosan, reduction method, glucose, antibacterial activity

Introduction In recent years, studies on the synthesis of nanocomposite materials for medical applications has been a lot of attention. A nanocomposite is a multiphase material derived from the combination of two or more components, including a matrix (continuous phase) and a discontinuous nanodimensional phase [1]. For example incorporation of silver nanoparticles into biopolymer chitosan to produce colloidal silver-chitosan nanocomposites that is interesting to study due to their high antibacterial activity [2,3]. In this case, chitosan can act as stabilizing agent for silver nanoparticles synthesis and dispersing material in nanocomposite. Chitosan, a polysaccharide biopolymer derived from naturally occurring chitin, displays unique polycationic and chelating agent due to the presence of active amino and hydroxyl functional

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groups. Chitosan also has good biocompatibility, biodegradability and antimicrobial activity [4].Meanwhile silver nanoparticles are of particular interest for applications in medical devices and healthcare products because of their antibacterial activity and low toxicity to humans cells [5,6]. Incorporation of silver nanoparticles in chitosan is expected to have a great antibacterial activity. The synthesis of silver nanoparticles via chemical reduction with chitosan as stabilizing agent requires the use of the components of metal precursor and reducing agent. The mechanism of formation of silver nanoparticles in colloidal solutions from the reduction of silver ions consists of two stages: nucleation and crystal growth. Recently, the use of weak reducing agent who environmentally friendly has been widely investigated, such as glucose[7,8,9]. The use of glucose as a reducing agent requires accelerator agent NaOH [9]. Because chitosan solution turned into a gelunder alkaline conditions, the formation of silver nanoparticles can be made through the gel phase. The focus of this study was to investigated the effect of molar ratio of AgNO3/Glucose and AgNO3 concentration toward surface plasmon resonance (SPR) of Ag nanoparticle. It is also reported the antibacterial activity of silver-chitosan nanocomposites against Escherichia coli. The formation of silver nanoparticles was monitored using UV-Vis absorption spectroscopy. Meanwhile, the size and shape of silver nanoparticles were determined by Transmission Electron Microscopy (TEM). Experimental section Materials Chitosan with molecular weight (MW) of 1,233,623.96 Da and degree of deacetylation (DD) of 75.16 % was purchased from Biotech Surindo Cirebon Indonesia. Silver nitrate (AgNO3), acetic acid (CH3COOH), glucose (C6H12O6) and sodium hydroxide (NaOH) were purchased from Merck. Procedure Preparation of silver nanoparticles A solution of chitosan (1 % w/v) in acetic acid solution (1 % v/v) was firstly prepared. Due to the poor solubility of chitosan, the mixture was stirred to achieve complete dissolution, and then kept overnight at room temperature. The solution was filtered to remove any impurity before use. 0.5

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mLof aqueous solution of AgNO3 (0.024 g/mL) was added to 25 mL of Chitosan (1 % w/v) in a flask.These solution was stirred at room temperature for 10 min and then various of glucose aqueous solutionwere added, so that the molar ratio of AgNO3/glucose are1:1 (A1), 1:2 (A2), 1:4 (A3), 1:6 (A4), 1:8 (A5), 1:10 (A6), 1;12 (A7) The solution was stirred for 10 min. After that2.5 mLaqueous solution of NaOH (2M) were added and the gel was immediately formed in the solution and then the color was turned brown. The reaction was continued for 25 min under stirring. Then, the resulted gel was dissolved in 35 mL chitosan (1 % v/v) and stirred to achieve complete dissolution to formsilver nanoparticles colloidal. The similar procedure was carried out, but use various volume of AgNO3 (0.024 g/mL) so that the concentration of AgNO3 (% w/w (AgNO3/Kit)) in solution are 0.2 % (B1), 0.4 % (B2), 0.6 % (B3), 0.8 % (B4), 1.0 % (B5), 1.2 % (B6), 1.4 % (B7), 1.6 % (B8), 1.8 % (B9), 2.0 % (B10)), with molar ratio of AgNO3/glucose is 1:4. Characterization of nanoparticles UV–vis spectra were performed with a Shimadzu UV3150 UV–Vis spectrophotometer operating in the absorbance mode. UV-Vis absorption spectra of the samples were recorded in the wavelength range of 300 to 600 nm and all sampleswerediluted10 timesbeforeanalysis.while size and distribution of particles were characterized by Transmission electron microscopy JEM2000EX at an accelerating voltage of 120kV. Particle size analyses were performed using Image J 1.43u software. Antibacterial test The antibacterial activity of the nanoparticles was evaluated against E. coli and S. aureus (clinical isolate) by the agar diffusion method with MHA (Muller Hilton Agar) as the medium. An aliquot of silver-nanoparticle dispersion (20 µl) was added into well in a plate, and then incubated for 24 h at 37 °C. Antibacterial activity was measured as the diameter of the inhibitory zones in the plates. Chloramphenicol solution (1 mg/mL) was used as positive control.

Result and Discussion Colloidal silver-chitosan nanocomposites was synthesized by wet chemistry method. Green synthesis approach was employed by using glucose as reducing agent in the reduction reaction of silver ions with chitosan as stabilizer agent and NaOH as an accelerator agent. The UV–Vis absorption spectra of the resulting colloidals of silver chitosan nanocomposites with various of

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molar ratio of AgNO3/glucose are shown in Figure 1. The value of λmax (nm) and absorbance are shown in Table 1. It is clear that all spectra display the characteristic of surface plasmon resonance (SPR) band of silver nanoparticles at about 405.5 – 407 nm, indicating the formation of silver nanoparticles [2,10].The observed single SPR band (Figure 2) indicates that the silver nanoparticles are spherical in shape [11]. The color of the colloid resulted from different molar ratio of AgNO3/glucose are brown and dark brown, as shown in Figure 2.The intense colors due to the plasmon resonance absorption of silver nanoparticles. Since electrons on surface metal are limited to specific vibrations modes by the particle’s size and shape metallic nanoparticles have characteristic of optical absorption spectrums in the UV-Vis region [12]. It is evident that, with an initial increase in glucose concentration (A1 to A2), the SPR band intensity also significantly increase. Greater glucose concentration (S3 to S7) are not significantly increase the absorbance.A blue-shifting SPR absorption bands at higher glucose concentration (A1 – A5) has also been observed. This phenomenon could be related to a decrease in the particle size of Ag nanoparticles Silver nitrate was successfully reduced by glucosein the presence of chitosan as stabilizing agent. Formation of silver nanoparticles follows the following equation: Ag+ (aq) + chit (aq)

[Ag(chit)]+ (aq)

2[Ag(chit)]+ (aq) +2OH- + C5H11O5-CHO

2Ag + 2chit + H2O + C5H11O5-COOH

BASED ON THE REACTION, IT CAN BE SEEN THAT THE COEFFICIENT RATIO OF AG+ AND GLUCOSE IS 2:1. HOWEVER IN THIS EXPERIMENT, optimal molar ratio is 1:4 based on concentration of silver nanoparticles and amount of glucose.

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Figure F 2.Phottograph of prepared n nanocompos itessilver-chhitosan w various molar ratio of AgNO3/gglucose with

Figure 1.U UV-Vis abso orption speectra of sillverchitosan nannocompositees prepared at a various molar m ratio of AgN NO3/glucosee Table 1. The vallue of SPR band and absorbbance of o silveer-chitosan nanoccomposites prepared at a various molarr ratio of AgN NO3/glucosee

Table 2. 2 The valuue of SPR band and absorbaance of silveer-chitosan nanocom mposites prepared p att various concenttration of AggNO3

Sample

λ max (nm))

Absorbancee

Sample

λ max (nm)

Absorbance

A1

407.00

0.874

B1

414.00

0.097

A2

406.50

1.507

B2

407.00

0.576

A3

406.00

1.588

B3

406.50

0.920

A4

405.50

1.490

B4

406.50

1.201

A5

405.00

1.476

B5

406.50

1.480

A6

405.50

1.715

B6

406.50

1.771

A7

405.50

1.473

B7

407.50

1.947

B8

407.00

2.091

B9

407.50

2.177

B10

409.00

2.280

The UV V–Vis absorrption specttra of silver-chitosan nanocompoosites produuced in vaarious concentraations of silv ver nitrate arre shown in Figure 3 annd the value of λmax (nm m) and absorbbance are show wn in Table 2.The graddual increasee in the AgN NO3 concenntration from m B1 to B88 also increasedd absorbancce indicatingg increase ofsilver nannoparticlesconcentrationn.The absorrption peak duee to SPR of silver nanopparticles waas blue-shifteed (B1 – B66), indicatingg the decreaase of the size of o the silver nanoparticlees [12].

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Figure 3.UV-Vis 3 ab bsorption speectra of silveerchitosann nanocompo osites preparred at variouus concentrration of Ag gNO3

Figuree 4.Photoggraph of colloidal nanocoomposites silverr-chitosan preparred with various AgNO3 concenntration Figure 5 shows the representativ r ve of TEM micrographs m s of the collooidal nanocoomposites siilverchitosan corresponding to the sample preppared at conncentration of AgNO3 of 1.0 % (w/w, ( AgNO3/C Chit). The TEM T image shows that silver nanopparticles are spherical. Based B on Im mageJ analysis from 362 particles, p thee size of silvver nanoparrticles are inn the range (3 - 30)nm with average 9.362 nm, as showed at Figure 6. Some of the largerr particle siize may bee due EM tooverlappping particlles were observed by TE

Frequency (%)

20 15 10 5 -

Figure 5. TEM im mage of sillver nanopaarticles (Sam mple B5)

Figure F 2 4 6 6.Pa 8 articles 10 12 14 size 16 188 distribituti 20 22 24 26ion 28 30of silver n nanoparticle s (Sample B5) B Particle size (nm)

Antibacteerial activity y of colloidaal silver-chitosan nanocoomposites aggainst E. colliare indicateed by the inhibition zone (m mm), presennted in Table 3.

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Table 3. Antibacterial activity of colloidal silver-chitosan nanocomposites prepared at various AgNO3 concentration Sample Zone of inhibition (mm) B0

12.25 (not clear)

B1

14.77

B3

14.33

B5

15.31

B7

15.89

B9

15.94

Chloramfenicol1 16.80 Figure 6.Inhibition zone of silverchitosannanocomposites

mg/mL

Table 3 shows that increasing concentration of the metal precursor (AgNO3) tends to increase antibacterial activity of the resulted silver-chitosan nanocomposites for E.coli. The colloidal nanocomposites silver-chitosan showed high antibacterial activity against gram negative of Escherichia coli. The performance is comparable to the chloramphenicol as the positive control. The Inhibitory zone chitosan solution is not obvious and less prevalent. Mean while inhibitory zone silver-chitosan nanocomposite clearly visible and evenly. This means that the diffusion process of silver nanoparticles have better range than the chitosan solution. Although the exact mechanism for the growth inhibition by silver nanoparticles has not yet been elucidated, many possible

mechanisms

have

been

proposed.

The

possible

mechanism,

silverionsfromnanoparticlesarebelievedtobecomeattachedtothenegativelychargedbacterialcellwall andruptureit,which leadsto denaturation of protein and finally cell death [13]. Another proposed mechanism involves the association of silver with oxygen and its reaction with sulfhydryl (–S– H) groups on the cell wall to form R–S–S–Rbonds, there by blocking respiration and causing cell death [14]. Conclusion Colloidal silver-chitosan nanocomposites were successfully prepared from AgNO3/chitosan solution by using glucose as a chemical reduction agent at room temperature. The result of the

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research shows the formation of silver nanoparticles by exhibiting the typical single surface plasmon resonance band of silver nanoparticles at 405.5 – 414.0 nm. The SPR bands were influenced by molar ratio of AgNO3/glucose and concentration of AgNO3. Based on the TEM image, the silver nanoparticles are spherical in shape and the size were in the range of3-30nm. In addition, the colloidal silver-chitosan nanocomposites has showed high antibacterial activity against gram negative bacteria of Escherichia coli References [1] Jean-Marie , 1998, Composite Materials: mechanical behaviour and Structural Analysis, Mechanical engineering series, 2, 15 [2] Shameli, K., Ahmad, M.B., Zargar, M., Yunus, W.M.Z.W., Ibrahim, N.A., Shabanzadeh, P., Ghaffari, M., Moghaddam,2011, Synthesis and characterization of silver/montmorillonite/chitosan bionanocomposites by chemical reduction method and their antibacterial activity, Int. J. Nanomed.,6, 271–284 [3] Honary, S.,Ghajar,K.,Khazaeli,P. and Shalchian, P., 2011, Preparation, Characterization and Antibacterial Properties of Silver-Chitosan Nanocomposites Using Different Molecular Weight Grades of Chitosan, Trop. J. Pharm. Res., 10, 1,69-74 [4] PranotoY, Rakshit S.K., Salokhe V.M., 2005, Enhancing antimicrobial activity of chitosan films by incorporating garlic oil, potassium sorbate and nisin. LWT-Food Sci Technol., 38 :859– 65. [5] Slawson, R.M.; Van Dyke, M.I.; Lee, H.; Trevors, J.T. Germanium and silver resistance, accumulation, and toxicity in microorganisms. Plasmid. 1992, 27, 72–79. [6] Zhao, G.J.; Stevens, S.E., 1998, Multiple parameters for the comprehensive evaluation of the susceptibility of Escherichia coli to the silver ion, Biometals,11, 27–32. [7]Raveendran, P.; Fu, J.; Wallen, S.L., 2003, Completely "green" synthesis and stabilization of metal nanoparticles. J. Am. Chem. Soc., 125, 13940–13941 [8]Sharma, V.K., Yngard, R.A., and Lin, Y., 2008, Silver nanoparticles: Green synthesis and their antimicrobialactivities, Adv. Colloid Interface Sci., 145, 83–96 [9] Darroudi, M., Ahmad, M.B., Abdullah, A.H., Ibrahim N.A., and Shameli, K., 2010, Effect of Accelerator in Green Synthesis of Silver Nanoparticles, Int. J. Mol. Sci. 11, 3898-3905 [10] Wei, D., Sun, W.,Qian, W., Ye, Y. and Ma, X., 2009, The synthesis of chitosan-based silver nanoparticles and their antibacterial activity, Carbohydr. Res., 344, 2375–2382 [11]Guzmán, M.G, Dille, J., and Godet, S., 2009, Synthesis of silver nanoparticles by chemical reduction method and their antibacterial activity, International Journal of Chemical and Biological Engineering, 2, 3, 104-111. [12] Šileikaitė, A., Puišo, J., Prosyčevas, I. and Tamulevičius, S., 2009, Investigation Of Silver Nanoparticles Formation Kinetic During Reduction Of Silver Nitrate With Sodium Citrate, Mater. Sci.,(Medžiagotyra), 15, 1, 21-27 [13] Lin,Y.E.,Vidic,R.D.,Stout,J.E.,McCartney,C.A.,Yu,V.L.,1998.InactivationofMycobacteriumaviu mbycopperandsilverions.Water Res.32,1997–2000. [14] Kumar,V.S.,Nagaraja,B.M.,Shashikala,V.,Padmasri,A.H.,Madhavendra,S.S.,Raju,B.D., 2004, HighlyefficientAg/Ccatalystpreparedby

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electrochemicaldepositionmethodincontrollingmicroorganismsinwater.J. Mol. Catal.A, 223,313– 319.

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Analysis In Silico on Stucture-Odor Relationship (SOR) of OrganolepticTested Compounds Febriyana Rizky Hapsari1, Ersalina Nidianti1, Warsito2, Edi Priyo Utomo2 1

Graduate Student of Chemistry Departement, Faculty of Mathematic and Natural Sciences, University of Brawijaya 2 Senior Lecturer of of Chemistry Departement, Faculty of Mathematic and Natural Sciences, University of Brawijaya Correspondence : [email protected].

Abstract Olfactory receptors, involved in first step of the physiological processes that leads to olfaction of many odorants. Elucidating amino acid residues of olfactory receptor can be aided by a computation on the molecular structure of odorant and also an understanding of its interactions with amino acid residue of receptor. By using porcine olfactory receptor downloaded from Protein Data Bank with code of E100, an interaction between odorant and porcine receptor has been established where Autodock Tools was used for docking analysis. The molecules of three odorant type consist of fruity, woody and balsamic based on Sigma-Aldrich Organoleptic Test has been geometrically optimazied by using Hyperchem prior to docking. Interaction between odorant and amino acids residue in the site active of the receptor was explored by Discovery Studio Visualizer. The analysis of SOR showed that each type molecule of the odorant interact to the residue of amino acid at least at Ile21, Phe35, Val37, Met114, Thr115, Gly116. These residue is an odorant pocket in the reseptor, however, a specific interaction occurred at several amino acids of the residue according to molecular type of odorant both in van der waals and or hydrogen bonding interaction. Keywords : Odorant, SOR, In silico

Introduction Various procedures and theories have been proposed for describing odor character. Researchers have taken a multidisciplinary approach in order to understand the comprehensive picture of how and why humans detect aromas as being pleasant or unpleasant. The methods consist of recording the words or descriptions that come to mind when one smells a substance. Such words or descriptions are called odor character descriptors or odor aspect attributes, and usually several are necessary for describing how a scent resembles other common odors A

method to recognize an odor is consists of using a numeric scale to determine

similarity between a test odor and a series of reference odorants chosen as standards for different descriptors (Zarzo, and Stanton2009). By using this procedure, many perfumerist conduct a panel of several individuals to smell pure odorant chemicals and score each odorant according to smell descriptors. Because odor descriptions can be influenced by personal experience and

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subjectivity (Richardson & Zucco, 1989), the use of a panel is recommended in order to avoid bias in the assignment of odor profiles. Unfortunatele, there is no general agreement about which materials should be chosen as references for the odor descriptors used in perfumery. Smell is a sensation that is difficult to describe, measure, and predict, and hence, perfume research is still rather empirical and unclear yet. However, impression of smell has been mapped and revised several times according to the invention of a new description of smell (Table 1). Not all of the terms commonly used to describe a given odor are independent. For example, if a certain substance smells fruity, it is expected that different descriptors, such as apricot, cherry, peach, pineapple, banana, or apple, may be applied to describe the odor character. The four standard families declared in 1983 are Floral, Oriental, Woody and Fresh, although the chart was modified in 2008 and 2010. Table 1. Description of smell Smell perception Floral

Oriental Fougere Woody

Fresh

Version 1983 Floral Soft Floral Floral Oriental Soft Oriental Oriental Woody oriental Mossy Dry Dry woods Citrus Green Water

Version 2008 Floral Soft Floral Floral Oriental Soft Oriental Oriental Woody oriental Wood Mossy Dry Dry woods Citrus Fruity Green Water

Version 2010 Floral Soft Floral Floral Oriental Soft Oriental Oriental Woody oriental Wood Mossy Dry Dry woods Aromatic Citrus Fruity Green Water

How to detect an odorant as being pleasant and unpleasant? One group of chemical compounds that have typically been associated with pleasant smells is esters. Many esters have distinctive odors and as a result have been used in artificial flavorings and fragrances. Recognizable smells may include citrus odors such as pineapple, cherry, and raspberry. Other pleasant smells, such as lavender, cinnamon and peppermint are also examples of esters. There are also some esters that could be classified as unpleasant, such as airplane glue, nail polish remover and model paint. Carboxylic acids are very polar compounds that contain the carboxyl group, COOH due to the presence of hydrogen bonding sites. Carboxylic acids are organic compounds that contain

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the carboxyl group, COOH. They are weak acids. Straight chain carboxylic acids of up to 9 carbons long are liquids at room temperature and have strong odors such as pungent, rancid, cheese, oily and waxy. Larger carboxylic acids are odorless, water insoluble solids. Esters are organic compounds with the polar functional group R-C-O-R’. Esters are made by reacting a carboxylic acid with and alcohol in the presence of an acid catalyst. Esters are known for their pleasant odors. Most ester have fruity smell while carboxylic acids often have sharp, unpleasant odors. There are several factors that may influence molecular codes and odor perception. The first is that a small change in the structure of a molecule may result in a dramatic change in the way mammals perceive the odor. The change of a functional group may result in the perception of two very different odors. For example, the carboxylic acids listed above were described as unpleasant using terms such as rancid or repulsive while alcohols with the same chain length were described as pleasant using terms such as herbal or flower-like. Malnic et al. (1999) compared the odorant receptors that recognized acids and alcohols with the same carbon chain and found that while some of the odorant receptors recognized both, they were recognized by different combinations of odorant receptors. This research suggests that changes in the perceived quality of the odorant where the structure has been altered may be a direct result of changes in the receptor codes (Malnic et al., 1999). Many efforts in obtaining structure–odor relationships (SORs) that may guide a rational approach for odorant discovery, this goal is still mainly achieved by trial and error. Several theories of SOR have been stated by researchers to improve and develop previous theory. The use of molecular descriptors as an alternative approach in the prediction of SOR by the mean of statistically regression techniques (Rossiter, 1996). Principal Component Analysis (PCA) and PLS techniques are used to reduce the dimensionality of data. Molecular descriptors accounts for a specific aspect of the molecule structure. As examples, simply count of atoms, functional groups and characteristic fragments are some of the constitutional descriptors family of the studied structure. Topological descriptors are related to the two-dimensional representation of the molecular structure. Korichi et al. (2006) determined SOR of anise, balsam, honey, vanilla and sweet. The results are only valid for balsamic flavor. It means that SOR is still mystery.

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To elucidate the detailed mechanism of olfaction, one must investigate the interaction between odor molecules and the olfactory receptors at the molecular level. In this paper, study on SOR was carried out in silico by using Autodock program for reviewing on interaction between odor which act as ligand and odor receptor downloaded from www.pdb.org. Metodology Receptor of odorant was downloaded from www.pdb.org. with 1E00 code which is receptor composed of 157 amino acid residues were taken from the nasal mucosa of pigs and has been crystallized in the form of the receptor-ligand complex at a molarity ratio of 1:1 (Vincent et al ., 2000). The receptor then was visualized by Discovery Studio Visualizer software to view the amino acid sequence and its active sites which directly faced to odorant as the fit ligand. Prior to conducting the statistical analysis of this database, we checked the odor descriptions of the materials in source Sigma–Aldrich (2003). This catalog presents 29 main odor categories under the ‘organoleptic properties’’ section. Seven of them are subdivided into a different number of subcategories: fruity, citrus, floral, herbaceous, nutty, balsamic, and fatty. Then the carboxylic acids and its ester derivatives were tabulated from C2 to C12 included their description of smell. Prior to docking analysis, both acids and esters were drawn in 3 dimesion performance and optimized of their molecular structures by using Hyperchem software. The algorithm of Conjugate-Directions algorithm was used as optimizer at convergence limit = 0.01, iteration limit = 50, criterion of RMS gradient = 0.1000 kcal/(A mol) and maximum cycles = 165 for each molecule. Optimized molecular structures were then saved as file.mol or file.pdb in the same folder of receptor 1E00. Each molecules, both acids and esters were docked at odorant receptor (OR) using Autodock Tools software, further followed by analyzing of the complex OR-Ligand to obtain parameter value of binding energy and its inbibition constant (Ki). For this purpose, Ki is defined as dissociation constant, and its values was related with a number of carbon atom of the ligand, that means a larger of Ki will be more odorant attacked to receptor and unpleasant.

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Result and Discussion Each helix of odorant receptor is represented by an idealized helical wheel, where amino acids occupy every 20° on the wheel. The effective hydrophobicity, Θθ at each 20° interval on this wheel is calculated using the following expression (Crasto, 2009) :

Θθ is computed by summing the arc contributions to the hydrophobicity moment on that residue from all other points along the helical, while µθ is the hydrophobicity for a residue. Equation (1) allows the hydrophobicity to be defined along a cumulative hydrophobic effect at a specific angle contributed from hydrophobicities at all other angles as opposed to the hydrophobicity at a specific residue. By using Discovery Studio Visualizer, this hydrophobicity can be obtained after the script menu was run to determine a ligand interaction with amino acid residue.

The

relationship between the amount of carbon of the ligand with hydrophobicity of the receptor showed lineary increase until it reaches a maximum at acid and esters with 7 carbon atoms (Figure 1, left). It is known heptanoic acid has cheese and sour smell, whiles its ester derivatives smell fruity such as berry,

melon, peach, pineapple and plum. Indiviually, one can feel

unpleasant for heptanoic acid. In increasing number of carbon atoms of the acid and ester, thus Ki value decreases (figure 1, right). In average, most of Ki of acid show more larger than those of ester, while ester has smell pleasant that one can smell more longer in very small concentration. Both ligand, acid and ester show a decline Ki when the number of carbon atom increase. It means that lower atomic carbon of ester and acid, usually more volatile due to the smell more harder or pungent. But for higher atomic carbon in the ligand, the vapor pressure more lower and its smell not so hard.

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200

hydrophobicity

Ki (mM) Acid

Ki (mM)

20

Ki (mM) Ester

150

15

100

10 Ester

5

Acid 0 2

3

4

5

6

7

8

9 10 11 12

50 0 2 3 4 5 6 7 8 9 10 11 12

No of Carbon

no of carbons

Figure 1. An effect of number of carbon atom on its hydrophobicity (left) and Ki for both odorant, acid and ester Table 2. Relationship of odor description based on organoleptic test (Flavors and Fragrances, Sigma-Aldrich, 2003) with hydrophobicity (Log P) of odorant (esters and acids) as ligand and inhibition constant Log P

Odor Description

2 3

Ki (mM) Ester 7.8 5.52

0.71 1.24

4

1.28

1.77

6

1.71 1.09

2.314 2.83

7

0.605

3.37

8

0.384

3.9

9 10 11 12

0.254 0.147 0.09 0.025

4.43 4.96 5.49 6.02

pineapple; ethereal fruity; sweet; ethereal; wine-like banana; pineapple; sweet; ethereal fruity, apple apple; banana; wine-like berry; melon; peach; pineapple; plum banana; floral; pear; pineapple; wine-like oily; fruity; nutty grape; oily; wine-like coconut green; fruity; floral

No of C

Ki (mM) Acid 190.36 91.32

Log P

Odor Description

-0.28 0.25

pungent, Spicy pungent, rancid

44.19

0.78

cheese

25.36 16

1.31 1.84

animal; earthy cheese; fatty; sour

8.87

2.37

cheese, sour

5.7

2.9

cheese, oily

4.41 2.26 1.27 0.797

3.43 3.96 4.5 5.03

cheesy, waxy citrus; fatty oily fatty

Residue of amino acid of receptor had been explored by using Discovery Studio Visualizer 2.5 that show a conserved region for both ligands, e.g. ILE21, PHE35, ILE100, MET114, THR115, GLY116. Based on the type of acid and ester, more longer carbon chain (C8 - C12) will be more amino acid residue involved in the conformation of the receptor. The smell character of acid tend to be oily and waxy, whiles ester smell more pleasant than C2-C5.

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Figure 2. Amino sequence of receptor 1E00 show a conserved region (red cap) for each ligand (acid and ester). Hydrofobic region is shown as blue arrow below the residue.

Figure 3. Model of receptor-odorant interaction between 1E00 with decanoic acid (blue ball stick) and Ethyl decanoate (brown). Both odorant occupy at almost the same active site of amino acid residue. Conclusion Based on docking analysis, both acid (unpleasant) and ester (pleasant) have Ki increased when the number of carbon atom decrease. Ester derivatives have Ki more lower than the acid, that show most of the acid smell have unpleasant for each panel test. There should be an obyective organoleptic scoring to void bias panel. References Crasto, C.J., 2009, Computational Biology of Olfactory Receptors, Current Bioinformatics, 4, pp. 8-15. Korichi, M., Gerbaud, V., Pascal, F., Meniai, A. H., Nacef, S., and Joulia, X., 2006, Quantitative Structure – Odor Relationship: Using of Multidimensional Data Analysis and Neural Network Approaches, 16th European Symposium on Computer Aided Process Engineering, and 9th International Symposium on Process Systems Engineering, Published by Elsevier B.V. Malnic, B., Hirono, J., Sato, T. & Buck, L. B., 1999, Combinatorial receptor codes for odors. Cell 96, 713–723

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Richardson, J. T., & Zucco, G. M. (1989). Cognition and olfaction: A review. Psychological Bulletin, 105, 352-360. doi:10.1037/0033 -2909.105.3.352 Rossiter KJ. 1996. Structure–odor relationships. Chem Rev 96:3201–40 Vincent F, Spinelli S, Ramoni R, Grolli S, Pelosi P, Cambillau C, Tegoni M. Complexes of porcine odorant binding protein with odorant molecules belonging to different chemical classes. J Mol Biol. 2000 Jun 30;300(1):127-39. Zarzo, M., and Stanton, D,T, 2009, Understanding the underlying dimensions in perfumers’ odor perception space as a basis for developing meaningful odor maps, Attention, Perception, & Psychophysics, 71 (2), 225-247

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The Oretical Study Properties of Semiconductor Metalloporphyrin Complexes Calculated Density Functional Theory Method (DFT) Indah Uswatun Hasanah*, Ria Armunanto, Bambang Setiadji Department of Chemistry, Universitas Gadjah Mada, Sekip Utara P.O. Box Bls. 21, Yogyakarta 55281, Indonesia *Corresponding author. Tel.: +628111203432 E-mail address: [email protected]

Abstract A theoretical study of metalloporphyrin complexes has been performed based on electronic transition and values of band gap. Porphyrin doped with Cu, Ag, and Au with two conformation models; conformation of the metalloporphyrin complex with opposite posisition and conformation of the metalloporphyrin complex with parallel posisition. Each model has six conformations of the metalloporphyrin complexes structures, which are Cu-Porfirin, Ag-Porfirin, Au-Porfirin, Cu+-Porfirin, Ag+-Porfirin, Au+-Porfirin. Transition electronic spectra and band gap values of the complexes were calculated by Density Functional Theory using LanL2DZ basis set. The result showed that the most stable metalloporphyrin complexes are Cu+-porphyrin’s opposite and parallel conformations and the values are -163,28; -164,58 Kcal/mol. Metal doping in porphyrin will decrease value of bandgap metalloporphyrin complexes, thus the value of the bandgap energy will also be influential. The result also showed that Cu-porphyrin, Ag-porphyrin, Au-porphyrin, on opposite and paralel conformation have smaller band gaps and respectively coresponding semiconductor properties. In contrast Cu+-porphyrin, Ag+-porphyrin, Au+-porphyrin on opposite and paralel conformation have higher band gaps and respectively coresponding semiconductor for photocatalyst application. Based on electronic transition spectra, the twelve complexes showed sensitivity to visible wavelengths. There are changes in absorption wave numbers due to the addition of atoms at the porphyrin. Keywords: Porphyrin, bandgap, electronic transition

Introduction Solar cells are storage technology as well as converter of solar energy into electrical energy. Solar cells are made of semiconductor material that can change the light of the sun as particles (photons) directly into electricity using photovoltaic principle. Solar cells contain semiconductor as a major factor in the manufacture of solar cell. Semiconductors are used in solar cell technology as essential factor.

Furthermore semiconductors are the suitable

material because of the band gap value. Thus more easily excited electron orbitals of the low level to a higher orbital level [9]. Porphyrin is macromolecul that has potential as a organic semiconductors because of the electroluminescence effect. Porphyrin structure is a part of chlorophyll structure that has double bond causing towards Uv-vis absorption [1]. Wavelength absorbed by porphyrin is related to bandgap, Highest Occupied Molecular Orbital (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO) [12]. The difference between these two orbital levels will affect

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The 2nd International Conference of the Indonesian Chemical Society 2013 October, 22-23th 2013 the energy needed for electron excitation from HOMO to LUMO. The energy bandgap shows wether it is easy to excitation and therefore, it affect the photosensitivity of a material. One of the parts that has an important role in semiconductor properties is an atom type conjugated to porphyrin, which is substantial to decrease the bandgap value. The previous research about semiconductor has been done using phthalocyanine with ab initio method HF level with STO 3G basis set [2].

The research also discussed molecular vibration in

phthalocyanine doped by Cu. A theoretic research also has been done on photesensitivity of antibacteria fluorokuinolon based on the caracteristic of electronic spectrum and the difference HOMO-LUMO [3]. A theoretic research on electronic structure in transition state showed that polivinil sinamat has a photosensitivity [4]. The research with computational chemistry approach is importante to determine the connection between porphyrin conjugated structure with the activity. Porphyrin has been researched with DFT computational chemistry method, such as conjugated porphyrin with metal using Fe [5]. Fe-porphyrin can aborb UV wavelength, so the energy needed is very high to do electron excitation. The next researched has been done showing a few metals conjugated with porphyrin such as Zn, Mg, and Ni [6]. These three metals were conjugated in central position using ab initio method.

Zn-porphyrin and Ni-porphyrin have a the

oportunity as an organic infrared detector because they have small bandgap, 0.63 eV. Metallo porphyrin complexes researched needs a long time for the geometrical optimitation because the basis set used is ab initio. Based on studies that have been conducted, this research examines the conjugated porphyrin with metal so the wavelength absortion will occure in visible area and therefore, energy excitation is small. In addition, this research uses faster computational chemistry DFT method and the results is close to value calculation from ab initio method that uses electron correlation [11].

Experimental Section Hardware and Software This study used a PC with Intel® Core™ Processor Core i5 3.2 GHz, Hardisk 1 TB, Display Card (VGA) 64 MB. The programs were used are Gaussian® 09 [10], Chemcraft, Gabedit 2.2.0.

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H C

N H C

H C

N C H

H

H C

H

H C

The 2nd International Conference of the Indonesian Chemical Society 2013 October, 22-23th 2013 Research Object Porphyrin doped with Cu, Au, and Ag with two conformation models; conformation of the metalloporphyrin complexes with opposite posisition and conformation of the metalloporphyrin complexes with parallel posisition. Each model has six conformations of the metalloporphyrin complex structures, which are Cu-Porfirin, Ag-Porfirin, Au-Porfirin, Cu+-Porfirin, Ag+-Porfirin, Au+-Porfirin.

M M

(a)

(b)

Fig 1. Chemical Structure (a) Opposite conformation (b) Parallel Conformation Result and Discussion Metode Validation

Fig 2. Structure Optimized Porphyrin

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The 2nd International Conference of the Indonesian Chemical Society 2013 October, 22-23th 2013 Table 1. Comparition Bond Between Length Crystalography and Bond Length Optimization R N4-C9 C5-C13 N3-C6 C4-C5 C9-C4 C9-C19 C20-C19 C14-C13 N4-N2 N1-N3 N4-H13 H14-H13

Bond Length Crystalography (Å) 1.38000 1.45200 1.37700 1.37600 1.38700 1.43100 1.36500 1.34500 4.11200 4.05600 1.01340 2.20020

Bond Length Optimization (Å) 1.36689 1.46825 1.38636 1.43909 1.35337 1.46518 1.33744 1.34025 4.20114 4.08748 0.99548 2.21110

From the results calculated by Density Functional Theory using LanL2DZ basis set, value of bond length has a small difference from the experimental results. A is a bond length crystallographic results [7]. The optimization structure produces a stable one, leading the value of the bond length optimization results close to the value of the bond length experimental results. Therefore the method and basis set used are suitable for the research role in the structure metalloporphyrin complexes. Structure Analyze Structure transformation of metaloporphyrin complexes is occured after optimation, which is caused by the interaction among porphyrin compositional atom. This interaction causes the atoms angles in porphyrin are transforming resultant to a smaller condition. The angle built is the smallest electron interaction to reach stable condition. One of the atomic interactions of the porphyrin is the interaction between lone pair electron of N atom with electron cloud built from C-C single bond and conjugated C=C double bond. These bonds have a properti dominated by electron π system that creates electron cloud in the chain. If analyzed from metal properties as central atom, the structure changing of optimation result will be affected by metal charge. It is because the higher positif charge on metal will bring the effect for easier polarisation of electron to ligan, so structure will be more stable Empty orbital on metal will cause ligan attractive force as lone pair electron stronger. N atom on porphyrin has high electronegativity that can neutralize positive charge. So, a few structures of metalloporphyrin complexes rough which is cause by strong electrostatic

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The 2nd International Conference of the Indonesian Chemical Society 2013 October, 22-23th 2013 attractiv force. Table 2. Bond Length Metal-Nitrogen Atom Metalloporphyrin Complexes Opposite Conformation Compound Metal N1 (Å) N2 (Å) N3 (Å) N4 (Å) Cu-porfirin Cu 1.96 2.37 1.96 2.35 Cu+-porfirin Cu+ 1.95 2.37 1.95 2.35 Ag-porfirin Ag 2.07 2.49 2.07 2.49 Ag+-porfirin Ag+ 2.07 2.44 2.07 2.44 Au-porfirin Au 2.01 2.62 2.01 2.62 Au+-porfirin Au+ 2.01 2.57 2.01 2.57 Table 3. Bond Length Metal-Nitrogen Atom Metalloporphyrin Complexes Parallel Conformation Compound

Metal

N1 (Å)

N2 (Å)

N3 (Å)

N4 (Å)

Cu Cu+ Ag Ag+ Au Au+

2.00 1.99 2.37 2.42 2.06 2.06

2.45 2.44 2.66 2.72 2.68 2.65

2.00 1.99 2.37 2.42 2.06 2.06

2.41 2.44 2.65 2.71 2.68 2.66

Cu-porfirin Cu+-porfirin Ag –porfirin Ag+-porfirin Au-porfirin Au+-porfirin

Table 2 and 3 show the bond length and Nitrogen around 2-3 Å. It causes metal and Nitogen atom on porphyrin will bond weakly, so the interaction will also be weak. The bond length between metal and Nitrogen atom in N1 and N3 position tends to be smaller than N2 and N4 position both happening in opposite conformation and parallel conformation metalloporphyrin complexes. It is because in N2 and N4 position there is hydogen bonding. Hydrogen bonding will interupt the interaction between metal and nitrogen atom that causes higher bond length. The smaller the bond length between metal and nitogen atom means the easier the interaction of metal toward porphyrin. Table 2 and 3 show that Cu-porfirin complex on opposite and parallel conformations have smaller bond length compared to the other metalloporphyrin complexes. It is because Cu has the smallest atomic radii compared to Ag an Au, causing bond length between nitrogen atom and Cu smaller and the stronger interaction. This also happens to Cu+-porfirin complex on opposite and parallel conformation.

Interaction Energy On geometrical optimation, energy minimization will occur, which causes the stability

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The 2nd International Conference of the Indonesian Chemical Society 2013 October, 22-23th 2013 of conformation structre, so the energy will be much smaller.

During the energy

minimization the structure with less energy changing and the energy gradient approaches zero is seeked.

The gradient shows that molecular system has reached lowest energy

conformation. Therefore it needs much iteration for that. The stability of metalloporphyrin complexes are seen based on the interaction energy. A stable structure is the one with attractive force and repulsive force on balance, so interaction energy becomes minimum and the potensial energy became smaller. The lower the energy potential means the bigger disociation energy needed to break the bond in stable condition. Table 4. Interaction Energy Metalloporphyrin Complexes Opposite Conformation Compound Interaction Energy (Kcal/mol) Cu-Porfirin -96.49 Cu+-Porfirin -163.28 Ag-Porfirin -51.52 + Ag -Porfirin -114.96 Au-Porfirin -56.38 -156.77 Au+-Porfirin Table 5. Interaction wenergy Metalloporphyrin Complexes Parallel Conformation Compound Interaction Energy (Kcal/mol) Cu-porfirin -98.95 Cu+-porfirin -164.58 Ag-porfirin -67.41 + Ag -porfirin -133.96 Au-porfirin -58.09 -158.20 Au+-porfirin Table 4 and 5 show the interaction energy from metalloporphyrin complexes on opposite and parallel conformation. If compared to all of the complexes with cation metal, Cu-porphyrin has the lowest value, so this complex has the strongest and the most stable. It is related to Cu atom’s first ionitation energy. Ionitation energy is energy needed to released the outermost electron. Cu atom has higher ionitation energy than Ag and Au ayoms because the atomic radii is smallest thant the others. Therefore central atom acctractive force towards electron becomes stronger, so the outermost is more difficult to disengange and the energy needed to release the outermost electron is bigger thanAg, and Au atoms. Cu+-porphyrin on opposite and parallel conformation have smaller interaction energy

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The 2nd International Conference of the Indonesian Chemical Society 2013 October, 22-23th 2013 than the others so it is the most stable. It is because positive charge on metal will bring easier polarisation, so the stability is higher. Electron density from metalloporphyrin complexes with positive charge will be bigger that metalloporphyrin complexes with netral charge so the stability of metalloporphyrin complexes with positive atom is higher than metalloporphyrin complexes with netral atom. Bandgap Energy HOMO (Highest Occupied Molecular Orbital) is higher orbital in valensi band placed by electron. LUMO (Lowest Unnoccupied Molecular Orbitals) is lower orbital in conduction band not filled by electron [8]. Bandgap describes the easier molecular system for excitation. Bandgap is physical properties of molecul, where on that energy level it is very potential for electron to interact. A smaller bandgap value reflect an easier electron excitation, so photosentivity will be higher. Table 6. Bandgap Energy Metalloporphyrin Complexes Opposite Conformation Compound

Bandgap (e.V)

Cu-porfirin Cu+-porfirin Ag-porfirin Ag+-porfirin Au-porfirin Au+-porfirin

1.23 2.80 1.35 2.88 1.41 2.93

Table 7. Bandgap Energy Metalloporphyrin Complexes Parallel Conformation Compound Cu-porfirin Cu+-porfirin Ag-porfirin Ag+-porfirin Au-porfirin Au+-porfirin

Bandgap (e.V) 1.23 2.74 1.18 2.91 1.31 2.76

Table 6 and 7 show that mettalloporphyrin complexes with cation metal in opposite and paraller conformation have a smaller bandgap compared to metalloporphyrin complexes with cation metal. It show that metalloporphyrin complexes with cation metal is easier to excitation from groundstate to eksitation state and has higher photosensitivity. On electronic component, semiconductor is needed with a smaller bandgap in order to

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The 2nd International Conference of the Indonesian Chemical Society 2013 October, 22-23th 2013 make the excitation easier from HOMO to LUMO orbital. Complexes with higher bandgap are more suitable as semiconductor for photocatalyst application.

On photocatalyst

application the semiconductor needed is the one with bigger bandgap. The purpose is to minimalize recombination process, which is condition where the excitation electron to higher level comes back to the starting lecel, because of the small bandgap. Electronic Transition Table 8. Wavelength and Intensity Metalloporphyrin Complexes Opposite Conformation Wavelength Intensity Compound (nm) (%) Porfirin 353.34 100 Cu-porfirin 763.53 4.17 Ag-porfirin 683.45 8.47 Au-porfirin 663.02 7.94 Cu+-porfirin 539.65 0.05 Ag+-porfirin 550.87 0.09 + Au -porfirin 535.25 0.08 Table 9. Wavelength and Intensity Metalloporphyrin Complexes Parallel Conformation Compound

Wavelength (nm)

Intensity (%)

Cu-porfirin Ag-porfirin Au-porfirin Cu+-porfirin Ag+-porfrin Au+-porfirin

812.95 796.40 691.95 608.27 409.45 495.72

2.29 3.56 3.69 0.60 1.29 0.23

Table 8 and 9 show higher shift in wavelength of metalloporphyrin complexes (red shift). It’s caused by delocalization effect on π electron bonding in conjugated metalloporphyrin complexes so it will reduce the anti-bonding character. Therefore molecules that have conjugated double bonds will shift to higher wavelengths. Moreover, it will produce energy difference between the ground state and the excitation state which causes energy transitions π Æ π * getting smaller. Because of energy required for the transition π Æ π * getting smaller, the absorption peak will occur at higher wavelengths.

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The 2nd Internation I nal Conferen nce of the Indonesian Chemical Society 20133 October, 22-23th 20 013 Moleculaar Vibration n c

b

a Porfirin

F Fig 3. Inrareed Spectra Combination M Metalloporpphyrin Compplexes Oppossite C Conformatioon

Cu‐ Porfirin Ag‐ Porfirin Au‐ Porfirin

c Cu+1‐ Porfirin m 1500 1300 1 1100 90 00 700 500 300‐ c

b

1

a

Combination n Fig 4. Inrareed Spectra C Metalloporpphyrin Compplexes Parrallel Confoormation

P or C f… u‐

c P… 1700150 0013001100 900 0 700 500 300 0 100m ‐

1

A arreas shows a spectrum m with atomss that have bending C--H twisting out of planne (OOP), b area showss a spectrum with atoms that have beending C-H wagging w OO OP, and c areea w shows thhat spectra with w atoms that t have beending C-H scissoring O OOP. The red r line show porphyrinn spectrum that t will be refrence r for the metallop porphyrin coomplexes in this researchh. There aree three peakks to observeed because oof the high intensity of the porphyrrin, located in i area 7899 that is ben nding C-H twisting t OO OP, 923 ben nding C-H w wagging OO OP, and 10997 bending C-H C scissoriing.

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The 2nd International Conference of the Indonesian Chemical Society 2013 October, 22-23th 2013 Table 10. Wavenumber Shifting Metalloporphyrin Complexes Opposite Conformation Senyawa Porfirin Cu-porfirin Ag-porfirin Au-porfirin Cu+-porfirin Ag+-porfirin Au+-porfirin

Bending C-H Twisting OOP (cm-1) 789 785 829 712 657 695 637

Bending C-H Wagging OOP (cm-1) 923 896 863 864 919 907 906

Bending C-H Scissoring OOP (cm-1) 1097 1095 1073 1037 1017 1029 1050

Table 11. Wavenumber Shifting Metalloporphyrin Complexes Parallel Conformation Senyawa Bending C-H Twisting Bending C-H Wagging Bending C-H -1 -1 OOP (cm ) OOP (cm ) Scissoring OOP (cm-1) Porfirin 789 923 1097 Cu-porfirin 789 892 1091 Ag-porfirin 790 893 1084 Au-porfirin 786 877 1095 Cu+1-porfirin 820 925 1097 825 930 1098 Ag+1-porfirin Au+1-porfirin 817 915 1100 The change of wavenumber infrared absortion is caused by the induction effect from dopped metal located in the center of porphyrin.

Metal will cause N atom more

electronegative that leads to higher electronic density, resulting in the bond length. The change of bond length will cause bigger steric effect repulsive force among group metalloporphyrin complexes.

in

To reduce repulsive force the bond length will increase

automatically to reach more stable structure in optimitation. The changed bond length will affect the absortion of wavenumber.

Conclusion DFT methods can be used as a method for the calculation of metalloporphyrin complexes. Optimization shows that porphyrin’s bond length has a small difference from the experimental results. The result shows that the most stable metalloporphyrin complexes are Cu+-porphyrin’s opposite and parallel conformations and the values are -163,28; -164,58 Kcal/mol.

Metal doping in porphyrin will decrease value of bandgap metalloporphyrin

complexes, thus the value of the bandgap energy will also be influential. Electronic transition study explains that all metalloporphyrin complexes are sensitive to visible wavelengths. There are changes in absorption wave numbers due to the addition of

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Reference 1.

Hanse, E. P., Nguyen, Tuyet, P., Krake, J., Spanget-Larsen, J., Lund, T., 2012, Spectrochemistry Acta Part A: Molecular and Biomolecular Spectroscopy, vol 98: 247251. 2. Bintarti, A., 2008, Skripsi FMIPA UGM, Yogyakarta. 3. Tahir, I. dkk., 2005, Makalah Regional Conference on Pharmaceutical and Biomedical Analysis School of Pharmacy Institut Teknologi Bandung, 15-16 September 2005. 4. Tsuda, M. dan Oikawa, S., 1976, J. Am. Chem. Soc., 29, 446-475. 5. Rovira, C., Kunc, K., Hutter, J., Ballone, P., and Parrienello, M., 1997, J. Phys.chem, A, 1001, 8914-8925. 6. Pedersen, T.G., 2004, Phys.Rev., B 69075207. 7. Verdal, N., 2005, J.Phys. Chem. A, 109, 5724-5733. 8. Hill, L. G., Milliron, D., Schwartz, J., and Kahn, A., 2000, Organic Semiconductor Interfaces: electronic structure and transport properties, Applied Surface Sciense, 166, 354-362. 9. Brutting, W., 2005, Physics of Organic Semiconductors, WILLEY-VC Verlag Gmbh and Co. KgaA, Weinheim. 10. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, Jr., J. A.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, Ö.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J., 2009, Gaussian 09, Revision A.02, Gaussian, Inc., Wallingford CT. 11. Ramachandran, K. I., Deepa, G., and Namboori, K., 2008, Computational Chemistry and Molecular Modellin: Principles and application ©Springer-Verlag, Berlin. 12. Pavia, L., Donald, Lampman, M., Garry, Kriz, S., George, Vyvyan, R., James, 2009, Introduction To Spectroscopy, Brooks/Cole, CENGAGE Learning, Belmont, USA.

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Characterization of the FePd/NiTi Shape Memory Alloy Film for Sensor Applications Jannatin ´Ardhuha FKIP Universitas Mataram Jl. Majapahit No. 62 Mataram, NTB 83125 Phone +62 (0370) 623873 Fax +62 (0370) 634918 [email protected]

Abstract Shape memory alloy composites (FePd/NiTi) thin films have been fabricated by magnetron sputtering and subsequent heat treatment (annealing and aging). The FePd/NiTi thin film can be employed as a thin film sensor for mechanical properties (such as strain in%-range) when the change in magnetization of FePd layer is detected, while the superelastic NiTi is used to recover to the initial strain. Annealing of FePd/NiTi thin film at 650°C for 10 minutes and 450°C for 10 minutes has a strong influence on the microstructure of the film. A highly crystalline NiTi austenite (NiTi-A) or trigonal (NiTi-R) structure was obtained. During annealing process, both of materials (FePd and NiTi) underwent decompositon and the diffusion process accured at interface between the FePd and NiTi layer. The phase transition temperatures of the thin film are Ms of -23.1°C, Mf of -34°C, As of 12.7°C and Af of 23.6°C. Hence, combination of the superelastic properties of NiTi film and martensitic detwinning of the Fe70Pd30 in the annealed FePd/NiTi thin film was not observed. The specific heat treatment and suitable fabrication process of the FePd and NiTi thin film, therefore, needs to be optimized in order to obtain functional of FePd/NiTi thin film for sensor. Keywords : FePd/NiTi, sensor

Introduction Smart materials are exciting topic and they have attracted huge attention from the material science and engineering community due to the inherent intelligent capability to convert one type of energy into another.1 Their response to external stimuli makes them suitable for being use in different applications such as sensors and actuators. Among these materials are pyroelectric, piezoelectric, electrostrictive, magnetostrictive, shape memory alloys (SMAs), ionic polymer metal composites (IPMCs), electroluminescent (EL) materials, etc.2 Shape memory alloys (SMAs) are smart materials and they belong to a unique class of metallic compounds that have the ability to change shape with temperature.3,4 By cooling an SMA below a certain transition temperature, the alloy undergoes a change in crystal structure and can be deformed into any new shape with an applied the external stress. However, heating the alloy above its transition temperature causes the alloy to transform into original crystal structure and recovers its original shape. Therefore, they are said to have the so-called shape memory effect (SME) and superelasticity or pseudoelasticity, respectively.3,4

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The most popular material among many SMAs used in a variety of application is an alloy of nickel and titanium. This alloy exhibits a good mechanical, electrical and fatigue properties, corrosion and abrasion resistances, as well as biocompatibility.5 In particular, NiTi shows up to 8% strain recovery or large stress recovery (up to 700 MPa). It also shows a superelastic behavior in a temperature range close above martensite-austenite transition temperature. Superelastic NiTi has several advantages i.e. high mechanical performances and large transformation strain and stress capabilities. A new class of SMA called magnetic shape memory alloys (MSMAs) was introduced in 1996.6 In these materials, the arrangement of variants in the martensitic phase that lead to very high strains can be induced by the application of a magnetic fields. Hence, faster response times compared to conventional shape memory alloys can be obtained. Fe70Pd30 has been identified as a promising MSMA,7,8 because it has a high magnetocrystalline anisotropy, a high saturation magnetization, a relatively high blocking stress and a high ductility. These properties collectively make it suitable for many applications9,10-12. Application of MSM materials is not only limited to actuator applications, but the inverse MSM effect (a change in strain leads to a change in the magnetic properties) also offers the possibility to use this material for sensor applications. A shape memory alloy (SMA) composites may be constructed by combining the FePd and the NiTi thin films. Combining SMA and MSMA is an approach to develop composites that inherit beneficial properties from both classes of material, for instance, thin film structures can be fabricated that the resulted comosites preserve the functionality of FePd and NiTi in terms of their MSM and superelastic behavior, respectively. Hence, a thin film sensor for mechanical properties (such as strain in the %-range) can be realized where the change in magnetization of the FePd layer is detected while the superelastic NiTi is used to recover to the initial strain. The fabrication process to obtain these composites is however difficult because both materials require a specific heat treatment and a suitable fabrication process for both film layers needs to be identified. The purpose of the present study is to characterize the annealed FePd/NiTi thin film for possible application in sensors. This present study focuses on investigating properties of the FePd/NiTi thin film after annealing at 650°C for 10 minutes and 450°C for 10 minutes that allows us to maintain the functionality properties of each layer.    

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Experimental procedures FePd/NiTi thin films were fabricated using magnetron sputter deposition onto Sisubstrates. Ni46.8Ti53.2 and Fe70Pd30 are used as target materials. Prior to the sputtering of FePd/NiTi, 10nm of Cr are deposited on the Si-substrate as sacrificial layer. The Cr layer is etched away at a later stage of the fabrication process to obtain freestanding films. To determine the influence of the combination of FePd and NiTi, single layer thin films of each material were fabricated as references. Figure 1 shows the schematic of the samples structure.

Figure 1. Schematic structure of FePd/NiTi, NiTi and FePd thin films.

The resulteed thin films were subjected to heat treatment by annealing at 650°C for 10 minutes and 450°C for 10 minutes. Heat treatment was performed by rapid thermal annealing (RTA). The phase of the thin films were determined by using a Seifert PTS four-circle x-ray diffraction system. The phase transformation temperatures of samples in this study were determined by a Perkin Elmer Pyris 1 DSC system. Dual beam Helios Nanolab (FIB/SEM) that additionally equipped with an EDX system from Oxford was used to fabricate lamella of FePd/NiTi thin films.

Measurements of the mechanical properties of the sample were

performed by using a Zwick/Roell tensile testing machine.

Result and discussion Phase of FePd/NiTi thin film Figure 2 shows the XRD pattern for films after annealing at 650°C for 10 minutes and 450°C for 10 minutes. The red line corresponds to XRD pattern of FePd, the light green and the black line correspond to FePd/NiTi and NiTi thin films, respectively. In the FePd thin film, the phase transformation from bcc to fcc/fct takes place so that the desired MSM active phase is achieved. Additional peak appears at 2θ equal 44.7° which corresponds to the (110) reflection of Fe bcc phase. A highly crystalline structure of NiTi-A (austenite) or NiTi-R (trigonal) phase and also Ni4Ti3 precipitates appear in the NiTi thin film.

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In the FePd/NiTi thin film, the crystalline structure of austenite NiTi or trigonal NiTi structure, fcc Pd or TiPd and Fe bcc are obtained. The Fe70Pd30 fcc/fct is not observed in this film. Decomposition of Fe70Pd30 into Fe50Pd50 and fcc Pd or TiPd are however undesired, because Fe70Pd30 is the only compositional range that is MSM active and even a partial decomposition of Fe70Pd30 would lead to precipitates that it hinder twin boundary movement and therefore influences the MSME. 1400

Fe70Pd30 fcc/fct (111)

41.7

1200

42.4 NiTi-A (100) / NiTi-R (112) 42.5 NiTi-A (100) / NiTi-R (112)

Intensity [cps]

1000 800 600

Fe50Pd50 (111) 41.20

Fe50Pd50 (111)

40.3

400

44.6 Fe bcc(110)

44.7 Fe bcc(110)

41.04

48.5 Fe70Pd30 fcc (200)

Pd fcc (111)/

Ti0.1Pd0.9(111)

FePd

43.4 Ni4Ti3 (122)

200

FePd/NiTi

43.4 Ni4Ti3 (122)

NiTi

0 30

40

50

60

70

2 θ [°]

Figure 2. XRD patterns of annealed NiTi, FePd/NiTi and FePd thin films. Phase transition temperature The phase transition temperatures of NiTi, FePd and FePd/NiTi thin films determined by DSC, are shown in figure 3. The black line corresponds to NiTi, the light green and red lines correspond to FePd/NiTi and FePd film, respectively. In this DSC curves, it is shown that the phase transition temperatures of FePd/NiTi film are relatively close to that of the NiTi thin film. The NiTi thin film exhibits the martensite start (Ms), the martensite finish (Mf), the austenite start (As) and the austenite finish (Af) temperatures of -27.4°C, -42.7°C, 14.9°C and 23.5°C, respectively. The phase transition temperatures of the FePd/NiTi thin film are Ms = -23.1°C, Mf = -34°C, As = 12.7°C and Af = 23.6°C. Hence, the FePd/NiTi and the NiTi thin film have a high crystalline NiTi-A or NiTi-R phase and the phase transition is strongly dependent on the Ni-content. In the case of the FePd thin film, the phase transition temperatures are not observed, due to a weak first order fcc-fct transformation of FePd film.

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Heat flow endo up [mW]

5

Cooling

Mf = -42.7 Ms = -27.4

4 3

Ms = -23.1 Mf = -34

1

Af = 23.6

As= 12.7

0

-1

As= 14.9

-40

-20

0

Heating

Af = 23.5

20

40

60

80

100

Temperature[°C]

Figure 3. DSC curves of annealed NiTi (black line), FePd/NiTi (light green line) and FePd (red line) thin films. Microstructure A STEM image of the entire cross section of the annealed FePd/NiTi thin film is presented in Fig. 4(a). The NiTi and FePd layers are marked as L1 and L1, respectively. The protective layer (PL) consists of Pt. The different grains are observed in L1 and L2 as shown in STEM image. The interface between L1 and L2 is clearly distinguished. Spot-EDX measurement indicates that L2 consists of pure Fe, pure Pd and TiPd grains. It suggestes that the FePd layer underwent decomposition during the annealing process. EDX mapping shows a strong correlation between Fe and Pd in L2. Areas with high concentration of Fe correspond to low Pd concentration, and vice versa, as shown in Fig. 4b and c. At the interface between L1 and L2, diffusion of Fe and Pd into NiTi is found. Fe and Pd are well soluble in the NiTi phase where Fe and Pd are likely to occupy the places of Ni. A high and relatively homogeneous concentration of Ni and Ti over the entire layer is found in L1 (Fig. 4d and e). A significant concentration of Ti is also observed in L2.

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Pd Lα1

PL L2 L1 (b)

(a)

Ni Kα1

Pt Lα1

Ti Kα1

(d)

(c)

(e)

(f)

Figure 4. STEM image (a) and EDX maps for Fe, Pd, Ni, Ti and Pt (b-f) of the annealed FePd/NiTi thin film, magnification of PL, L1 and L2. Mechanical properties Tensile tests were carried out at selected temperatures for the martensite and austenite state of annealed Fe70Pd30 thin film, i.e. at temperature of -20°C and at room temperature (RT). The Young’s modulus of the FePd can be calculated to 35.3GPa at -20°C, which is lower than its Young’s modulus at RT (42.4GPa). A large strain due to the reorientation the martensite variants in applied stress at martensite state of this material is not observed. Due to temperature range restrictions of the tensile testing device, the FePd/NiTi thin film was tested at a lowest temperature of -20°C. The measurement at this temperature shows the elastic behavior of the material. At 32°C, the material reveals a similar behavior with a slightly higher Young’s modulus of 26GPa (as shown in Fig. 5). The superelastic property of the annealed NiTi thin film is observed when the material was tested at 35°C. This property is a desired functionality for the FePd/NiTi film.

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-20°C

800

600

Stress [MPa]

Stress [MPa]

600

32°C

400

E = 21.8 GPa

400

E = 26.0 GPa

200

200

0

0 0.0

0.5

1.0

1.5

Strain [%]

2.0

2.5

3.0

0.0

0.5

1.0

1.5

2.0

2.5

3.0

Strain [%]

(a) (b) Figure 5. Stress-strain curves at two different temperatures for the annealed FePd/NiTi thin film. Material was tested at -20°C(a) and 32°C(b).

Discussion A highly crystalline NiTi austenite (NiTi-A) or trigonal (NiTi-R) structure is obtained in the annealed FePd/NiTi thin film. During the isothermal annealing at 650°C for 10 minutes, the NiTi is completely soluble and the austenite phase of NiTi is stable. Followed by aging at 450°C for 10 minutes, the Ni-rich (NiTi) alloy is decomposed into NiTi and Ni4Ti3 precipitates. Ni4Ti3 precipitates are desired because they facilitate the martensitic transformation. During this annealing process, the FePd layer however undergoes decomposition. Due to the lower annealing temperature compared to the normal FePd annealing temperature, the FePd decomposes into Fe-rich bcc (α-Fe), Fe50Pd50 and a Pd fcc phase. At the interface between the FePd and the NiTi layer, diffusion of Fe and Pd into NiTi layer is observed. The diffusion of Pd is, however, much faster than that of Fe. On the other hand, a significant concentration of Ti is observed in the FePd layer. Spot-EDX measurement indicates that FePd layer consists of pure Fe, pure Pd and TiPd grains. The TiPd phase is also observed in XRD analysis. The phase transition temperatures of the annealed FePd/NiTi thin film are relatively close to that of the annealed NiTi thin film. The transition temperatures of these films are strongly dependent on the Ni content, where an increase in the Ni-content causes a decrease of Ms.13 Fig. 6a shows the Ms as a function of the Ni content for Ni-Ti alloys.

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Ni4Ti3

Figure 6a. Ms as a function of Ni content for binary Ni-Ti alloys. Different data symbols represent data from different authors. The solid line is given by thermodynamic calculations.13

Figure 6b. STEM image shows the Ni4Ti3 precipitates on the bottom area of NiTi layer in the annealed FePd/NiTi thin film.

The difference in the Ni content in these films is due a compositional gradient during the sputtering process and also due to the foramtion of precipitates such as Ni4Ti3 precipitates which present in these films. However, an increase of the Ni4Ti3 causes a decrease in Ni content in the NiTi matrix. As the result, Ms will increase.13 The microstructure of the Ni4Ti3 precipitates is shown in Fig. 6b. The XRD patterns of these films shows that the amount of Ni4Ti3 precipitates in the FePd/NiTi film is lower than that in the NiTi film. This is an indication that the Ni content in the FePd/NiTi film is lower than that in the NiTi film. As the result, the Ms of the FePd/NiTi film is lower than the Ms of the NiTi film. This interpretation need further analysis because the distribution of Ni4iTi3 precipitates in the FePd/NiTi film is not homogenous and the second phase such as Ni-Ti-Pd and Ni-Ti-Fe phases present in FePd/NiTi film also gives contribution to the value of the Ms. A prerequisite for SME i.e the martensitic detwinning in the FePd/NiTi thin film is not observed. Decomposition Fe70Pd30 into a Fe50Pd50 is undesired because Fe70Pd30 is the only compositional range that is MSM active. Furthermore a partial decomposition would lead to precipitates (such as Pd fcc or Ti0.1Pd0.9) that hinders twin boundary movement and therefore affecting the magnetic shape memory effect (MSME). The superelastic property of the single layer NiTi thin film subjected to heat treatment is observed. The yield stress to induce austenite-martensite phase transformation is ~ 470MPa. This high yield stress is due to the presence of Ni4Ti3 precipitates in this film that improves the superelastic property and strength of the film. The superlastic property is a desired functionality for the FePd/NiTi film.

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In the annealed FePd/NiTi thin fim, the combination of the shape memory properties of FePd and the superelastic of NiTi is not fully observed. Due to the diffusion during annealing and the absence of the Fe70Pd30 fct phase in this film. One approach to reduce diffusion is the use of an appropriate diffusion barrier layer such as molybdenum (Mo) or tantalum (Ta), so that intermixing of the two layers during annealing process does not occurr. A second approch would be used annealing at high temperature, such as 850°C. Annealing at 850°C is required for FePd to obtain the stable austenite phase (MSM active phase). And the last approach would be the independent fabrication of functional NiTi and FePd films, followed by a mechanical bonding of the two films.

Conclusion Annealing of FePd/NiTi thin film at 650°C for 10 minutes and 450°C for 10 minutes has a strong influence on the microstructure of the film. A highly crystalline NiTi austenite (NiTi-A) or trigonal (NiTi-R) structure is obtained. During annealing process, FePd and NiTi layers undergoes decompositon and the diffusion process accour at interface between the FePd and NiTi layer. Due to a compositional gradient during the sputtering process and Ni4Ti3 precipitates formatio, phase transition temperatures of the annealed FePd/NiTi thin film are relatively close to that of the annealed NiTi thin film. Hence, combination of the shape memory properties of FePd and the superelastic properties of NiTi film is not observed in the annealed FePd/NiTi thin film. In the future study, the specific heat treatment and suitable fabrication process of the FePd and NiTi thin film needs to be optimized in order to obtain functional FePd/NiTi thin film for sensor.

Acknowledgements Author thanks to Prof. Dr.-Ing Eckhard Quandt, Faculty of Engineering, University of Kiel, Germany for allowing the author to conduct this reseach. Also, thank goes to Dr. -Ing Christoph Bechtold and Dr.-Ing. Rodrigo Lima de Miranda for their technical assistance and guidance during this research, as well as to Dr.rer.nat. Christiane Zamponi for TEM lamella preparation. References 1.

Neelakanta. R. S, Handbook of electromagnetic material: monoclinic and composites version and their application, CRC Press.

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2. 3. 4.

5. 6. 7. 8. 9. 10. 11. 12. 13.

Lane. R and Craig. B, An introduction to smart materials, The AMPTIAC Quarterly, Vol. 7, No. 2. Otsuka. K, et al., Science and technology of shape memory alloys: new developments, MRS Bulletin 27, 2002. Ray. D. K, et al., Structural and Mössbauer spectroscopic investigation of Fe substituted Ti–Ni shape memory alloys, Journal of Alloys and Compounds, Volume 482. Issues 1-2, p. 28-32, 12 August 2009. Otsuka. K and Wayman. C. M, Shape memory materials, Cambridge University Press, UK, 1998. Ullakko. K, et. al, Magnetically controled shape memory effect in NI2MnGa intermetallics, Scripta ;aterialia, Vo. 36, No. 10, 1997. Schwartz. V. M, Smart materials, CRC Press, USA, 2005. Suorsa. I, et al., Magnetic shape memory actuator performance, J. Magn. Magn. Mat. 272-276, (2029-2030), 2004. James. R. D and Wuttig. M, Magnetostriction of martensite, Phil. Mag. Vol. 77, No. 5, (1273-1299), 1998. Cui. J, Shield. T. W and James. R. D, Phase transformation and magnetic anisotropy of an iron-palladium ferromagnetic shape memory alloy, Acta materialia 52 (35-47), 2004. Opahle. I, et al., Jahn-Teller-like origin of the tetragonal distortion in disordered Fe-Pd magnetic shape memory alloys, Appl. Phys. Lett. 94, 072508, 2009. Buschow. K. H. J, Handbook of magnetic materials, Vol. 16, Elsevier B. J, Amsterdam, 2006. Otsuka. K and Ren. X, Physical metallurgy of Ti-Ni based shape memory alloys, Progress in Materials Science 50 p. 511–678, 2005.

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Physicochemical Characteristic of 99mTc-DTPA-ketoconazole as a Radiopharmaceutical for Deep Seated Fungal Detection Maula Eka Sriyani1*, Aang Hanafiah Ws2 1 Center of Nuclear Technology for Materials and Radiometry - BATAN Jl. Tamansari No. 71 Bandung, *email: [email protected]; [email protected] 2 STFI- Bandung

Abstract According to WHO, infectious diseases caused 27% of the total deaths in 2008. A common cause of infection is bacteria, but the infections caused by fungal pathogens such as Candida albicans is also very harmful because it can invade the lungs, blood, brain, kidneys, digestive tract, etc. One of the solutions for early diagnosis for deep seated infection is the application of nuclear technology, such as imaging techniques. 99mTc-ciprofloxacin and 99mTc-ethambutol as radiopharmaceutical agents for detection of deep seated infection has been observed by previous researchers and has satisfactory results, but only limited to infections caused by bacteria. One of the antifungal drugs used in the treatment of systemic fungal infections is ketoconazole that can be formulated as a radiopharmaceutical labeled with technetium-99m (99mTc). Some physicochemical parameters have been characterized by using paper chromatography and paper electrophoresis methods; lipophilicity (log P) was determined by the partition coefficient of the organic-water solvent, and plasma protein binding was determined by in vitro deposition method of human serum albumin using trichloro acetic acid (TCA) 5%. The radiochemical purity of 99mTc-DTPA-Ketoconazole obtained from the results was 97.02 ± 0.64%, electrically neutral; lipophilicity (log P) -1.34 and plasma protein binding of 37.10 ± 3.10%. 99mTc-DTPA-ketoconazole complex was stable up to 5 hours after labeling, whereas in the plasma was only stable up to 4 hours, then desreased below 90% Keywords: radiopharmaceuticals, physicochemical characteristics, ketoconazole, fungal infections

Introduction Infectious diseases is one of the health problems leading causes of death in the world [1]. There are several techniques for diagnosis infections including clinical history, physical examination, laboratory tests, identification of pathogens in the body, biopsy, and imaging [2]; however, deep seated infection or infection of the internal organs such as lung, blood, brain tissue, kidney and gastrointestinal tract are still difficult to be diagnosed, and one of the worrying infectious diseases are caused by fungi. About 50-70% of cases of the most pathogenic fungi infections were caused by Candida albicans [3, 4, 5]. Infectious disease that is caused by the fungi known as candidiasis. The treatment of candidiasis commonly used to provide certain antifungal agents such as ketoconazole. Ketoconazole is an antifungal azole class that works specifically against fungal cells by inhibiting the cytochrome P450 14-alphademethylase (P45014DM) enzyme involved in sterol biosynthesis pathway. The inhibition will cause disruption of the synthesis of fungal cell membrane and decrease the amount of ergosterol, thus resulting in increased levels of methylated sterol precursors that are toxic [6].

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Ergosterol will increasing the membrane permeability, resulting in the contents of the cell essential to get out and cause permanent damage and cell death [7]. Current diagnostics test that performed now is the culture techniques that have lower sensitivity and takes time, furthermore, the histopathology techniques have limitations because it is invasive and cause bleeding and other complications. Radiological examinations, such as computed tomography scans (CT scans) and conventional radiography, gave the less specific result and can not clearly distinguish between infection caused by bacteria, fungi, or sterile inflammation [8,9]. Nuclear medicine techniques using radiopharmaceutical is one of the options that can be implemented quickly and accurately to determine the infection at an early stage. In the previous study, which used others radiopharmaceutical for the detection of deep seated infection by 99m

Tc-Ciprofloxacin and

99m

Tc labeled Leucocytes,

99m

Tc-Ethambutol can not distinguish between infections caused by

bacteria, fungi or sterile inflammation, although it sensitive, but can not detect specific infections caused by fungi [2]. A radiopharmaceutical used for diagnostic purposes should be accumulated at the target 99m

organ and the labeling process with radionuclides

Tc does not affect its properties.

Radiochemical purity analysis of the radiopharmaceutical is necessary to ensure that it has a high purity. Therefore, it will be accumulated mainly in the target organs and less in other organs. Ketoconazole can lead to the infection area, and radionuclide of technetium-99m can be captured by a gamma camera outside the body so that the presence of infection can be easily known. This paper described the labeling technique of

99m

Tc-DTPA-Ketoconazole, followed by

physicochemical evaluation, including radiochemical purity, electrical charge, lipophilicity and plasma protein binding, and the stability of stability of

99m

Tc-DTPA-Ketoconazole as well as the

99m

Tc-DTPA-ketoconazole in vitro.

Material and Method Equipments and Materials The test tubes, laminar air flow cabinet, analytical balances, vortex mixer, micropipette 0-200 mL, syringe 1 mL, 3 mL, 5 mL and 10 mL; centrifugation with small size tubes of 5 mL, glass vial, oven, needle loop (ose), petri dishes, glass column, dose calibrator (RI Deluxe Isotope calib II, Victoreen, models 139000N), single channel analyzer (ORTEC, model of 4890), and the paper electrophoresis equipment were used in this research. ketoconazole,

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Na99mTcO4 (made by PT. Batan Technology), SnCl2.2H2O (Sigma Aldrich), DTPA (Fluka), aquabidestilata sterile (IKA Pharma), physiological saline sterile solution (IKA Pharma), HCl, NaOH , Na2HPO4, NaH2PO4, acetonitrile (E. Merck), human blood plasma (PMI), noctanol (Merck), Whatman 3 MM, Whatman 31 ET and Whatman 1 for paper chromatography were used for the materials in this research. Labeling of 99mTc-DTPA-Ketoconazole About 100 µL solution of ketoconazole (20 mg / mL 0.1 N HCl) in a vial was added 150 µL solution of Sn-DTPA (containing 75 µg SnCl2·2H2O and 2.25 mg DTPA), pH was adjusted to 3.5 with addition of HCl 0,1N or NaOH 0,1N and Na99mTcO4 solution (±2 mCi) were added to the solution. The final volume was 2 mL with the addition of physiological saline solution (NaCl 0,9%). Determination of Radiochemical Purity Radiochemical purity of

99m

Tc-DTPA-ketoconazole was determined by ascending paper

chromatography. The first system was acetonitrile as a mobile phase and Whatman 3 MM as a stationary phase to determine the impurities of Na99mTcO4 at Rf 0.9-1, while 99mTc-DTPA, 99m

Tc-DTPA-ketoconazole and

99m

TcO2 at Rf 0 (10). The second system was acetonitrile

50% as a mobile phase and Whatman 31 ET as a stationary phase to determine the impurities of 99mTcO2 at Rf 0, whereas 99mTc-DTPA, 99mTc-DTPA-ketoconazole and Na99mTcO4 at Rf 10.9 (10). 99mTc-DTPA-ketoconazole spotted at the zero point of the stationary phase, and then eluted with a mobile phase. The chromatogram was dried and cut into pieces with a distance of 1 cm, then each piece was counted using Single Channel Analyzer with NaI (Tl) detector. Determination of Electric Charge Paper electrophoresis method performed by using Whatman 1 as a stationary phase (1 x 39 cm) and an electrolyte solution of 0.02 N phosphate buffer, pH 7.5.

99m

Tc-DTPA-

ketoconazole spotted at the zero point of the stationary phase. The electrophoresis process was performed for 1 h at a voltage of 350 volts. The electrophoregram was dried and cut into pieces with a distance of 1 cm and counted using Single Channel Analyzer with NaI (Tl) detector. Determination of Lipophilicity (log P) An amount of 100 µL of

99m

Tc-DTPA-Ketoconazole was added into the centrifuges tube

containing 1 mL of NaCl and 1 mL of octanol, then it was shaken using a vortex mixer for 3 minutes, and centrifuged for 5 minutes to separate water and octanol phases. Each phase of 5

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µL were taken, and then counted with SCA. The partition coefficient can be calculated by the equation [a] count of octanol phase count of NaCl 0,9% phase log P = log of Lipophilicity Lipophilicity (P) =

[a]

Plasma protein binding About 500 µL of human blood plasma in the centrifuges tubes was added with 50 µL of 99m

Tc-DTPA-Ketoconazole, then shaken with a vortex mixer for 1 minute. The mixture was

incubated at 37 ° C for 10 minutes, then added with 1 mL of physiological saline solution (0.9%) and 1 mL of trichloro acetic (TCA) 5%, and shaken with a vortex mixer. The mixture was centrifuged for 15 min, the supernatant and the precipitate was then separated. One mL of 5% TCA was added into the supernatant phase, and the process was repeated for 2-3 times. Precipitate was washed with 1 mL of physiological saline solution (0.9%), centrifuged and the precipitate was separated. Each fraction counted with a single channel counter. The amount of binding fraction with plasma proteins can be calculated using the equation [b] plasma protein binding (%) =

count of precipitat e count of supernatan t

[b]

The stability Testing of 99mTc-DTPA-Ketoconazole The radiochemical purity of

99m

Tc-DTPA-Ketoconazole was determined at certain times (15

min, 30 min, 1, 2, 3, 4 and 5 hours) using the previous procedure, the testing was also performed in the blood plasma with a temperature of 37 °C. Result and Discussion Radiochemical purity test is done to ensure that the preparations are made in compliance with the requirements of the preparation of radiopharmaceuticals. Radiochemical purity of

99m

Tc-DTPA-ketoconazole was determined by ascending paper chromatography

method. The result showed that the radiochemical purity of

99m

Tc-DTPA-ketoconazole was

about 97.02 ± 0.64% with low radiochemical impurities of TcO4- and TcO2 of 1.19 ± 0.75% and 1.79 ± 0.45% respectively. The test results shown in Figure 1.

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2

3

TcO2

4 TcO4‐

5 Tc‐keto o

6

F Figure 1. Raadiochemicaal purity of 999mTc-DTPA--ketoconazole and impurrities ween radiophharmaceuticcal with the body's b surfacce cell mem mbrane depennd The interractions betw on the naature of the electrical e chharge of the m molecule annd membranee permeabiliity. The resuult of electriical charge testing t of

99m

Tc-DTPA--ketoconazolle using elecctrophoresis methods caan 99m

be seen in i Figure 2. The electroophoregram shows that spotted point, p whereeas the impu urities of

Tc-DTPA A-ketoconazzole remain in i

99m m

Tc-DTPA and a

(negativeely charged)). It can bee proved thhat the

99m

TcO4- move towaard the anodde

99m

Tc-DTPA-ke T etoconazole is a neutral

900 800 700 600 500 400 300 200 100 0

99mTc c‐DTPA‐ketokonazzol

(99mTcO4)‐

99mTc‐DTPA

‐14 ‐12 ‐10 ‐8 ‐6 ‐4 2 ‐2 0 2 4 6 8 10 12 14 16 18 20 22 24

counts per second (cps)

compoun nd.

migration(cm)

Figurre 2. Electropphoregram of o 99mTc-DT TPA-Ketoconnazole, 99mTcc-DTPA andd 99mTcO4bes the abilitty of a comppound to pennetrate the lippid membraanes. It can be b Lipophiliicity describ determin ned by measuuring the paartition coeff fficient of th he compoundd in a mixtuure of organic solvent - water (O/A) in vitro. Th he higher paartition coeffficient of thee compound,, means that it was lipophilic, or viice versa when w the com mpounds aree readily sooluble in thee water phasse c in thhe (hydrophhilic). Lipopphilicity wass calculatedd by comparring the raddioactivity counts octanol phase p with thhose in the water w phase. Lipophilicitty expressed by log P. Frrom the resuult log P waas obtained of o -1.34 ± 0.0 09. This indiicates that th he compoundd was highlyy hydrophilic, it means 99mTc-DTPA A-ketokonazzole was nott easily pass the lipid meembrane andd the excretioon mainly th hrough the kidneys k (11) .

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Labeled compounds used for diagnosis are generally intravenous administered, therefore it will occur an interaction between

99m

Tc-DTPA-ketoconazole with blood components,

including plasma proteins and blood cell surface . Plasma protein binding indicates the number of compounds bind to the protein in the blood that would cause effects on the tissue distribution and uptake by organs or tissues target and plasma clearance. Determination of 99m

Tc-DTPA-ketoconazole plasma protein binding acquired value of 37.10 ± 3.21 %.

Figure 3 shows the decreasing radiochemical purity of 99mTc-DTPA-ketoconazole occurred at 4 hours (91.34 ± 0.09 %) and 88.64 ± 0.70 % at 5 hours at temperature of 37 °C in plasma; whereas the radiochemical purity of 99mTc-DTPA-ketoconazole remains high (> 95 %) up to 5 hours at room temperature. 100% 95% 90% 85% 80% 75% 0

2 plasma

4 keto

6

Figure 3. Stability profile and plasmatic stability of 99mTc-DTPA-Ketoconazole Conclusion Ketoconazole can be labeled with 99mTc through the indirect method by adding DTPA as coligand. Optimum labeling conditions of

99m

Tc-DTPA-ketoconazole was obtained using 2 mg

of ketoconazole by adding 150 µL solution of Sn-DTPA (containing 75 µg SnCl2·2H2O and 2.25 mg DTPA). The reaction takes place at pH 3.5. The reaction conditions produce 99mTcDTPA-ketoconazole with radiochemical purity of 97.02 ± 0.64%, and remain stable up to 5 hours at room temperature, electrically charged with a log P value of -1.34 ± 0:09, and plasma binding of 37.10 ± 3.21%. The radiochemical purity decreased up to 88.64 ± 0.70% after 5 hours stored in plasma. As a new drug, in addition to the physico-chemical characteristics that have been carried out in this study, at the next stage, it is necessary to study preclinical experiments and clinical trials to ascertain whether the

99m

Tc-labeled DTPA-ketoconazole worthy to serve as a

diagnostic kit fungal infection.

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Acknowledgement The author would like to thank Mr. Epy Isabela who has helped during this research. References Signore. A; C.D. Alessandria. E. Lazzeri. R. Dierekx (2008). Can we produce an image of bacteria with radiopharmaceuticals. Eur. J. Nucl.Med. Imaging, 2008, 35: 10511055. DOI. 10.1007/s00259-008-0762-9 Das, Satya S., Hall, Anne V., Wareham, David W., Britton, Keith E (2002). Infection Imaging With Radiopharmaceuticals in The 21st Century. Brazilian Archives of Biology and Technology, An International Journal Vol. 45, Special n. :pp 25-37 september 2002. Arendrup MC (2010) Epidemiology of invasive candidiasis. Curr Opin Crit Care 16(5):445–452. doi:10.1097/MCC.0b013e32833e84d2 Grossi PA (2009) Clinical aspects of invasive candidiasis in solid organ transplant recipients. Drugs 69(Suppl 1):15–20. doi:10.2165/11315510-000000000-00000 Leleu G, Aegerter P, Guidet B (2002) Systemic candidiasis in intensive care units: a multicenter, matched-cohort study. J Crit Care 17(3):168–175 Hall, Gerri S. (2011). Interactions of Yeasts, Moulds, and Antifungal Agents: How to Detect Resistance. Springer, Humana press. Ghannoum, M.A dan Rice L.B (1999) Antifungal Agents : Mode of Action, Mechanisms of Resistance adn Correlation of These Mechanisms with Bacterial Resistance. Clinical Microbiology Reviews, 12(4):501. [Online] http://cmr.asm.org/ march, 11; 2012 Gompelmann D, Heussel CP, Schuhmann M, Herth FJ (2011) The role of diagnostic imaging in the management of invasive fungal diseases—report from an interactive workshop. Mycoses 54 (Suppl 1):27–31. doi:10.1111/j.1439-0507.2010.01983.x Groll AH, McNeil Grist L (2009) Current challenges in the diagnosis and management of invasive fungal infections: report from the 15th International Symposium on Infections in the Immunocompromised Host: Thessaloniki, Greece, 22– 25 June 2008. Int J Antimicrob Agents 33(2):101–104. doi:10. 1016/j.ijantimicag. 2008.08.014 IAEA. Technetium-99m radiopharmaceuticals: manufacture of kits. Technical reports series no.466. Vienna: International Atomic Energy Agency; 2008. Saha GB. Fundamentals of nuclear pharmacy. 5th ed. Springer. p. 98-102, 2004.

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Preliminary Study of Comparison of EDXRF and GFAAS techniques for the Measurement of Elements in Fine Particulate Matter (PM2,5) : Accuracy and Precision of XRF technique Muhamad Basit Febrian1,2*, Aminudin Sulaeman1, Muhayatun Santoso2 1

Departement of Chemistry, Bandung Institute of Technology Jalan Ganesha Bandung 40135, email : [email protected] 2 Centre of Nuclear Material Technology and Radiometry, National Nuclear Energy Agency

Abstract This study was integrated part of main study to compare Energy Dispersive X-Ray Flourescence (EDXRF) and Graphite Furnace Atomic Absorbance Spectrometry (GFAAS) technique for the measurement of elements in fine particulate matter (PM2,5). The purpose of this study was to evaluate accuracy and precision the measurements of elements (Al, As, Ca, Cu, Cr, Fe, K, Mg, Mn, Ni, Pb, S, Si, Ti and Zn) in PM2,5 collected on nucleopore filters at Serpong site using XRF technique. The SRM 2738 measurement has shown that XRF accuracy was good enough with 90%-110% recovery value. Repeatability was conducted to evaluate precision of XRF technique for elemental analysis of PM. Ten real samples from Serpong area were collected in nucleopore filters and measured in four times to determine Relative Standard Deviation (RSD) for each elements in each samples . RSD are vary from 1,76% to 8,93% except for Mg having RSD value above 10% in one of ten samples. Horrat value lies between 0,3 – 1,3. Homogeinity of samples was good enough marked by comparison between the measurements results at the two different measurements points were in the range of 0.9 to 1.1 This study shows that XRF technique is suitable for analysis of elements in particulate matter in the context of accuracy and precision. Keywords : PM2,5, XRF, Accuracy, Precision

Introduction Determination of air quality has now become a necessity that could not be left out in the effort to control the quality environment. Efforts to reduce the negative impact of the decline in air quality due to increasing urbanization and economic activities such as transportation and industry continues to be prepared and planned based on air pollution characterization results . One of the main parameters that has a significant impact on health is air particulate (particulate matter / PM). Particulates in the atmosphere generally had sized from 0.1 to 50 µm or more, which varies depending on the time of existence of the small size. Airborne particulate matter having aerodynamic diameter less than 2.5 µm (or PM2, 5) is called fine particulate. The particulates are usually sampled using an air filter with a certain size. Fine particulate matter contributes substantially to mortality caused by air pollution-related health problems as estimated by some researcher (Katouyanni K, et al, 2005). Particulate air itself is majority composed of organic and

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inorganic components in minor. The chemical inorganic contents of particulate matter (PM) have been determined since many years because of their toxicity (Schlesinger et al., 2006; Kampa and Castanas, 2008; Zhang et al., 2011) and for source apportionment purposes (Hopke et al., 2003). During this time, the chemical constituents, especially metals in airborne particulate, are spectrometry determined using wet chemical methods in terms of sample preparation for use in the measurement using analytical methods such as GFAAS and ICP-MS (Zhang, W. et al 2011). These methods have been known to have a high precision and low detection limit compared to other spectrometric methods. However, these analysis methods have drawbacks in terms of sample preparation and qualifications of personnel who should really qualified. These methods require expensive sample pre-conditions, qualified operators and labor instensive. In addition, the treatment of the sample can lead to contamination of the sample or the reduced number of samples (Yatkin, et al, 2012). These shortcomings led many researchers looking for alternative methods. One alternative method that has been widely used for the determination of metals in airborne particulate is X-ray flourescence method (XRF). In Indonesia, there was only National Nuclear Energy Agency whose working with XRF to determinate the elements on PM2,5 sample. For validation purposes, accuracy, precision and homogeneity should be carried out. Material and Method PM2.5 and PM10 sampling performed for 24 hours using the Gent Stacked Filter Unit sampler which is a dichotomous sampler with two Nuclepore polycarbonate filters smooth and rough porous respectively 0.4 and 8 µm (Hopke, 1997). Sampling was conducted in the Environmental Management Center, MoE Pusarpedal Serpong, South Tangerang City. Sampling locations were selected based on the fact of excess Pb concentration in Serpong area (Santoso et al, 2011). All filters were analyzed using the PANalytical Epsilon 5 (PANalyatical) EDXRF spectrometer. (Gd/W anode, 100 W maximum power, 100 kV maximum voltage, 0.02-1.98 mA currentThe instrument was calibrated using pure thin film standards (Micromatter® XRF Calibration standards, 50 mg cm2, Nuclepore® polycarbonate aerosol membranes, USA). and NIST SRM 2783 (see Table 2). Before analysis, the filter holders and chamber of the EDXRF spectrometer were cleaned using dry filtered air. To evaluate the precision, samples were measured repeatedly five times, while for purposes of determining the accuracy of measurements of the NIST SRM

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2738 using the same parameters as the sample. SRM measurements performed after each measurement of five samples, in addition to determine accuracy, as well as control of the measurement conditions. Homogeneity test of airborne particulate samples were done by taking measurements at two different points, the middle point of the filter and the point at the edge of the filter, at approximately the midpoint of the half-diameter of the filter. Homogeneity testing was performed on five different filters. So that the filter can be placed in the filter holder to be measured using XRF, then the filter needs to be cut into two parts. Result and Discussion Accuracy of the EDXRF method in the determination of elements in airborne particulate was performed by determining the percent recovery of SRM NIST 2738 measurements. With calibration curve and linear regression equations that have been made, it can be seen the value of measurement of each elements in the SRM. The percent recovery is determined by dividing the

Recovery

measured value of SRM by the value listed on the certificate. 160% 110% 60% Al Ca Cu K Mn Pb Sb Ti Zn Figure 1. Recovery of SRM NIST 2738 Determination of recovery was performed simultaneously between samples after six times of measurement. This was done as a control to determine the accuracy of measurements of samples at the same time EDXRF. From six measurements of NIST SRM 2738, it was obtained most of the elements have a recovery value in the acceptance range of 90% to 110%. Some elements have recovery less than 90% or more than 110% were As, Co, Cr, Sb and V.  according to the Horwitz equation, an acceptable recovery range can be extended if the levels of elements in the SRM is too low and close to the MDL. Precision of a measurement or test method can be observed from the value of diversity and the deviation of the measured average value, also known as variance and standard deviation (SD). Comparison with a standard deviation value of the average value of the test results yield a value of the relative standard deviation (RSD) calculated in terms of percent. Some standard or

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procedure requires that % RSD of a method or measurement must below 10% so that result of measurement could be accepted. 20% 10%



RSD

15% 5% 0%

Al Ca Cu K Mn Ni S

Si V

Figure 2 . (A) Average RSD value of measurement 10 real samples and SRM 2738 (B) Horwitz Ratio (HorRat) from 10 real samples Figure 2 (A) shows that most elements have a relative standard deviation (RSD) were satisfied enough below 10%, except for Mg.  Measurement of Mg in real sample was constrained by low Mg levels approaching the limit of detection. Mg measurement uncertainty increases due to lower levels of X-ray spectral lines are much weaker and is located in the region where the Compton effect is large enough, so that RSD of XRF in low level Mg were increased. Another test that express the precision of a measurement is Horwitz Ratio. According to AOAC, it could be expressed that less weight or content of element in samples means higher range of RSD values that could be accepted in a measurement. Figure 2 (B) shows that average horwitz ratio for 10 real samples has fulfilled the requirements of acceptable range between 0,3 to 1,2, Homogeneity was evaluated by the tests performed in different position of the filter. Comparison between the measurements at the midpoint and the edge points are in the range of 0.9 to 1.1 from the ideal value of 1.0 except for the elements Co, Cr, Cu, Mn and V (see figure 3 ). The cause of the low homogeneity of these elements is the low weight of the element in the filter which results in uneven distribution when sampling and large deviations XRF measurement. But the statistic ttest between two means of same samples and t-test for paired data shown there was no significant differences between two samples means in 95% level of confidence.

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Fiigure 3. Ratio Measurem ment of EDX XRF Result from f 10 Pairred Samples,, Point A : Meaasurument at the Center of o the Filter,, Point B : Measurument M t at the Edgee of the Filterr Conclusiion The accuuracy and precision of XRF X method for the deteermination of element coontent in sam mples of airborrne particulaate Serpong area have been b determ mined. Accurracy and preecision was good enough with w recoverry between 90% - 110% % and precission markedd with RSD values