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ADVANCES IN CHITIN SCIENCE Volume XI Editors Franco Rustichelli Polytechnic University of Marche, Italy Carla Caramella University of Pavia, Italy Sevda Senel Hacettepe University, Turkey Kjell M. Vaarum Norwegian Biopolymer Lab, Norway

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Page 1: ADVANCES IN CHITIN SCIENCE - unavdadun.unav.edu/bitstream/10171/27987/1/2009-05-Chitin-Chapter.pdf · ADVANCES IN CHITIN SCIENCE Volume XI ... 9th International Conference of the

ADVANCES IN CHITIN

SCIENCE Volume XI

Editors Franco Rustichelli Polytechnic University of Marche, Italy Carla Caramella University of Pavia, Italy Sevda Senel Hacettepe University, Turkey Kjell M. Vaarum Norwegian Biopolymer Lab, Norway

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ADVANCES IN CHITIN SCIENCE

Volume XI

EDITED BY

Prof. Franco Rustichelli EUCHIS 2009 Chair

Polytechnic University of Marche Ancona, Italy

Prof. Carla Caramella EUCHIS 2009 Co-Chair

University of Pavia Pavia, Italy

Prof. Dr. Sevda Senel

Vice-President of EUCHIS Hacettepe University

Ankara, Turkey

Prof. Dr. Kjell M. Vaarum President of EUCHIS

Norwegian Biopolymer Lab National University of Science and Technology

Trondheim, Norway

Proceedings of the 9th International Conference of the European Chitin Society

23-26 May 2009 Venice, Italy

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TABLE OF CONTENT

TITLE AUTHORS PAGE CHAPTER: BIOMEDICAL APPLICATIONS CHITOSANS AS PERMEATION ENHANCERS Di Colo G. 1 SOME BIOADHESIVE AND HEMOSTATIC PROPERTIES OF CHITOSAN/POLY(ASPARTIC ACID) LAYERED FILMS SURFACE MODIFIED WITH RGD PEPTIDES

Yamazaki M., Hudson S.M. 8

CHITOSAN–BASED NANOCAPSULES: CHARACTERIZATION OF PHYSICAL PROPERTIES AND APPLICATION IN DRUG DELIVERY

Goycoolea F. M., Stefani R., Menchicchi B., Valle-Gallego A.

15

PREPARATION OF NANOPARTICLES BASED ON N-ACYLCHITOSAN DERIVATIVES IN THE PRESENCE OF TRIPOLYPHOSPHATE

Ilyina A., Levov A., Orlov V., Popenko V., Varlamov V.

22

CHITOSAN/LECITHIN AUTOASSEMBLED NANOPARTICLES: A NEW CARRIER FOR ORAL DELIVERY OF TAMOXIFEN

Barbieri S., Marcotti E., Como C., Sonvico F., Colombo P.

27

RESEARCH PROPOSAL FOR THE OCULAR APPLICATION OF CYCLOSPORINE A: CHITOSAN NANOPARTICLES VERSUS RESTASIS®

Başaran E., Yenilmez E., Yazan Y. 34

CHITOSAN/PECTIN POLYELECTROLYTE COMPLEXES FOR NASAL DELIVERY OF ANTIPSYCHOTIC DRUGS

Luppi B. 38

ADAPTOGENIC PROPERTIES OF INTERPOLYMER CHITOSAN – BEE POISON COMPLEXES ON MATRIX OF AURUM NANOPARTICLES UNDER CONDITIONS OF HYPOXIA AND γ-IRRADIATION

Mochalova A., Koryagin A., Talamanova M., Smirnova L.A., Aleksandrova E.

44

CHITOSAN-BASED HEMOSTATIC DRESSING FOR SURGICAL APPLICATIONS

Guo J.X., Lucchesi L., Dayton A., Xie H., Teach J., Wu P.C., Gregory K.

48

REDUCING POSTSURGICAL PERICARDIAL ADHESIONS WITH KERATINOCYTE GROWTH FACTOR AND CARBOXYMETHYLCHITOSAN

Brandão Lopes J., Oliveira Dallan L.A., Felipe L.

54

SYNTHESIS AND CHARACTERIZATION OF METHYLATED CHITOSANS CONTAINING AROMATIC MOIETIES AS GENE CARRIERS

Sajomsang W., Ruktanonchai U., Gonil P., Mayen V., Opanasopit P.

60

CHITOSAN IN NANOPARTICLES FOR THE INDUCTION OF REVERSIBLE HYPOMETABOLISM

Colonna C., Conti B., Dorati R., Modena T., Biggiogera M., Genta I.

67

CHITOSAN IN TISSUE ENGINEERING: DESIGN OF HYBRID POROUS SCAFFOLDS FOR BONE REGENERATION

Dorati R., Colonna C., Genta I., Modena T., Valli M., Conti B.

70

MORPHOLOGICAL AND RHEOLOGICAL STUDY OF CHITOSAN SOLUTIONS AND HYDROGELS CROSLINKED COVALENTLY WITH GENIPIN FOR SCAFFOLDS

Matos M., Santoni N., Müller-Karger C., Sabino M.A., Müller A., Chazeau L., Bogner A., David L.

73

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DEVELOPMENT OF THE CHITOSAN DERIVATIVES EXHIBITING ANTIMUTAGENIC ACTIVITY

Alexandrova V.A., Snigireva G. 79

WASTELESS, ENVIRONMENTALY FRIENDLY AND TRACEABLE CHITIN/CHITOSAN/GLUCOSAMINE PRODUCTION FOR PHARMACEUTICAL AND INDUSTRIAL APPLICATIONS

Heppe A., Wunder A. 85

INTERACTION STUDIES OF MIXED MATRICES OF CHITOSAN-POLY- ε-CAPROLACTONE AND ALENDRONATE FOR BONE TISSUE ENGINEERING

Berghoff C.F., Cortizo M.S., Cortizo A.M.

88

CHITOSAN COATED PLGA NANOPARTICLES TO PROMOTE TARGETED CELLULAR UP-TAKE

Dorati R., Colonna C., Genta I., Modena T., Pavanetto F., Perugini P., Conti B.

93

CHITOSAN/HYALURONATE POLYELECTROLYTE COMPLEXES FOR PEPTIDE AND PROTEIN NASAL DELIVERY

Luppi B., Bigucci F., Caccamo M.G., Corace G., Mercolini L.,Musenga A., Sorrenti M., Catenacci L., Raggi M.A., Bettinetti G.P., Zecchi V.

97

NOVEL CHITOSAN DERIVATIVE AS PLASMID DNA CARRIER SYSTEM FOR PULMONARY VACCINATION

Heuking S., Borchard G. 103

CHITOSAN MICROSPHERES CROSSLINKED WITH GENIPIN FOR THE CONTROLLED RELEASE OF DRUGS

Lecumberri E., Harris R., Heras A. 107

IN VIVO STUDY OF CHITOSAN SCAFFOLDS FOR OSTEOCHONDRAL TISSUE REGENERATION

Abarrategi A., Lopiz Y., Moreno-Vicente C., Civantos A., Ramos V.M., Sanz-Casado J.V., Marco F., López-Durán L., López-Lacomba J.L.

114

CHITOSAN/BaSO4 HYBRID FIBERS WITH RADIOPAQUE PROPERTIES

Chung Y.S., Park W.H., Shin Y., Yoo D.I.

120

CONTROLLED DRUG RELEASE FROM BIOPOLYMER SYSTEMS OF VARIOUS GEOMETRY BASED ON CHITOSAN

Balcerzak J., Michalak I., Tylman M., Mucha M.

126

IMPROVEMENT OF BIOADHESIVENESS OF CHITOSAN BY MEANS OF HPMC

Amasya G., Şen T., Tarımcı N. 133

FUROSEMIDE LOADED FLOATING CHITOSAN MICROSPHERES FOR HYPERTENSION

Turkmen B., Ozdemir N. 139

CHITOSAN NANOPARTICLE-BASED INHALABLE DRY-POWDERS FOR PROTEIN LUNG DELIVERY: IN VIVO EVALUATION OF MICROENCAPSULATED INSULIN-LOADED NANOPARTICLES IN RATS

Al-Qadi S., Grenha A., Seijo B., Goycoolea F.M., Alonso M.J., Remuñan-López C.

145

CHITOSAN/PECTIN POLYELECTROLYTE COMPLEXES: CHARACTERIZATION AND APPLICATION IN COLON-SPECIFIC DELIVERY SYSTEMS

Bigucci F., Luppi B., Cerchiara T., Sorrenti M., Catenacci L., Bettinetti G.P., Rodriguez L., Zecchi V.

152

SYNTHESIS OF mPEG-CHITOSAN DERIVATIVES AND THEIR APPLICATION IN FORMULATION OF DRUG CARRIERS

Casettari L., Castagnino E., Stolnik S., Howdle S., Illum L.

158

SURFACE MODIFIED CHITOSAN NERVE CONDUIT FOR REPAIRING SPINAL CORD INJURY

Huang Y.C., Huaun Y.Y., Cheng H. 165

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PREPARATION AND EVALUATION OF PLGA NANOPARTICULATE DRUG DELIVERY SYSTEM WITH DIFFERENT SURFACE PROPERTIES: INFLUENCE OF CHITOSAN CONTENT

Sengel-Turk C.T., Hascicek C., Gonul N. 171

CHITOSAN PARTICLES ENTRAPPING ZANTHOXYLUM TINGOASSUIBA ESSENTIAL OIL – ANTIMICROBIAL ACTIVITY

Espírito Santo I., São Pedro A., Vale-Silva L., Pinto E., Velozo E., Cabral-Albuquerque E., Ferreira D., Sarmento B.

178

EFFECT OF CHITOSAN COATING ON WOUND HEALING PROPERTY OF PVA NANOFIBROUS MEMBRANE

Park W.H., Kang Y.O., Kim D.D., Yoon I.S., Chung Y.S., Shin Y., Yoo D.I.

184

CELLULAR UPTAKE STUDIES OF CHITOSAN BASED DELIVERY SYSTEMS DEVELOPED FOR MUCOSAL IMMUNIZATION AGAINST BOVINE HERPESVIRUS TYPE 1 (BoHV-1)

Gunbeyaz M., Faraji Majarashin A.R., Ozkul A., Puralı N., Senel S.

189

PREPARATION OF BIOCOMPATIBLE AND STABLE CHITOSAN-CARBOXYMETHYL DEXTRAN NANOPARTICLES

Lin Y.S., Arata F., Morimoto M., Saimoto H., Tsuka T., Imagawa T., Okamoto Y., Minami S.

195

ANTIMICROBIAL ACTIVITY OF β-CHITOSAN FROM ARROW SQUID (DORYTEUTHIS BLEEKERI) PEN

Lee S.J., Kim E.K., Lee M.S., Park P.J. 200

COMPARISON OF SILENCING EFFECT OF CHITOSAN/psiRNA COMPLEXES IN DIFFERENT CELL LINES

Şalva E., Akbuğa J. 203

CHAPTER: CHITOOLIGOSACCHARIDES MASS SPECTROMETRY OF AMINOGLUCAN OLIGOSACCHARIDES USING ELECTROSPRAY IONIZATION MS/MS AND MS/MS/MS

Issaree A., Vijayakrishnan B., Abdelnur P.V., Corilo Y.E., Riccio M.F., Sanvido G.B., Eberlin M.N., Peter M.G.

209

EVALUATION OF THE CYTOTOXICITY AND GENOTOXICITY OF CHITOOLIGOSACCHARIDES UPON HUMAN LYMPHOCYTES

Fernandes J.C., Borges M., Nascimento H., Ramos Ó.S. , Bronze E., Belo L., Pintado M. E., Xavier Malcata F., Santos-Silva A.

216

OBTENTION AND CHARACTERIZATION OF CHITOOLIGOSACCHARIDES/ACRILIC ACID INTERPENETRATING POLYMERIC NETWORK HYDROGEL AS DRUG DELIVERY SYSTEM

Furgiuele A., Gómez M.G., Sabino M.A. 222

CHEMICAL PREPARATION AND STRUCTURAL CHARACTERIZATION OF A HOMOGENEOUS SERIES OF CHITIN/CHITOSAN OLIGOMERS

Trombotto S., Ladavière C., Delolme F., Domard A.

228

IMMUNE MODULATORY ACTIVITY OF THE WATER-SOLUBLE HYDROLYTIC PRODUCTS OF CHITOSAN

Tsai G.J., Wu G.J. 237

PREPARATION, FRACTIONATION AND CHARACTERIZATION OF LOW-MOLECULAR-WEIGHT CHITOSANS

Tishchenko G., Simunek J., Brus J., Netopilik M., Walterova Z., Koppova I.

242

EFFECT OF CHITOOLIGOSACCHARIDES ON ANTIOXIDATIVE ENZYME ACTIVITIES IN LIVER OF RATS FED HIGH FAT DIET

Lee S.J., Kim E.K., Sim E.J., Lim B.O., Park P.J.

249

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THE ANTIMICROBIAL ACTION OF LOW MOLECULAR WEIGHT CHITOSAN AND CHITOOLIGOSACCHARIDES ON ANAEROBIC BACTERIA ISOLATED FROM HUMAN FECES

Simunek J., Koppova I., Tishchenko G. 254

CHAPTER: ENZYMATIC

OLIGOCHITOSAN BASED MULTIPLE ANTIGENIC PEPTIDE Neugebauer W.A., Brzezinski R., Richter M.V.

259

STRUCTURE AND FUNCTION OF CHITOSANASE Ando A., Saito A. 265 MOLECULAR WEIGHT MODULATES THE ANTIMICROBIAL EFFECT OF CHITOSAN ON ESCHERICHIA COLI

Ghinet M.G., Gagnon J. , Lacombe-Harvey M.E., Brzezinski R.

272

DIVERSITY, DOMAIN-STRUCTURES AND PHYLOGENETIC RELATIONSHIPS OF FAMILY 18 GLYCOSIDE HYDROLASES

Karlsson M., Stenlid J. 278

A CLASS V CHITINASE FROM ARABIDOPSIS THALIANA: FUNCTIONAL DIVERSITY IN PLANT FAMILY GH-18 CHITNASES

Ohnuma T., Mizuhara M., Taira T., Skriver K., Fukamizo T.

283

SWAPPING OF CHITIN-BINDING DOMAIN ENHANCES THE BINDING ABILITY TO INSOLUBLE SUBSTRATES OF CHITIN BY BACILLUS CHIMERIC CHITINASES

Chilukoti N., Moerschbacher B.M., Podile A.R.

288

THE CHITINOLYTIC ENZYME MACHINERY OF THE MYCOPARASITIC FUNGUS TRICHODERMA ATROVIRIDE

Seidl V., Gruber S., López-Mondéjar R., Zach S., Kubicek C.P.

294

NOVEL THERMOACIDOPHILIC CHITINASE FROM THE CRENARCHAEON SULFOLOBUS TOKODAII

Staufenberger T., Labes A., Imhoff J.F. 301

CHITINOLYTIC ACTIVITIES OF TWO CLOSTRIDIA ISOLATED FROM HUMAN FAECES

Simunek J., Koppova I., Tishchenko G. 307

INVESTIGATION OF ENDO- AND EXO-TYPE OF CHITOSANASE BY PROTEIN STRUCTURE SIMULATION

Cheng C.Y., Li Y.K., Juei Y.S., Wu Y.J., Yao Y.Y.

313

ENZYMATIC PREPARATION OF CHITOOLIGOSACCHARIDED AND KINETIC STUDY OF CHITOSANOLYSIS

Koppova I., Tishchenko G., Simunek J. 319

ON THE DEPOLYMERIZATION OF CHITOSAN BY PAPAIN: A RE-ASSESSMENT

Menezes B.M., Grigolon L., Todorovic Z., Peter M.G., Franco T.T.

324

PURIFICATION AND CHARACTERIZATION OF A MYZUS PERSICAE CHITINASE

Jaspar-Versali M., Francis F., Saguez J., Fossouo Z., Haubruge E., De Pauw E., Dommes J.

331

ISOLATION AND CHARACTERIZATION OF THE EXTRACELLULAR COMPLEX OF CHITINOLYTIC ENZYMES OF CLOSTRIDIUM PARAPUTRIFICUM STRAIN J4 COLONIZING HUMAN COLON

Tishchenko G., Simunek J., Dohnalek J., Koppova I., Duskova J., Rozhetsky K.

337

CHAPTER: FOOD, TEXTILE AND DIVERSE APPLICATIONS CHITOSAN: A SOFT-INTERCONNECT BETWEEN BIOLOGY AND ELECTRONICS

Payne G.F., Shi X-W., Liu Y., Yang X., Kim E., Bentley W.E.

345

CHITOSAN INTELLIGENT PACKAGING: MONITORING VARIATIONS

Pedroso Yoshida C.M., Mendonça M.E., Kato Junior E.T., Teixeira Franco T.

353

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CHITOSAN FOR FLOCCULATION PROCESSES – AN ECO-FRIENDLY APPROACH

Renault F., Badot P.M., Crini G. 360

NOVEL BIOCOMPOSITE FILMS BASED ON CHITOSAN AND BACTERIAL CELLULOSE

Fernandes S.C.M., Oliveira A.L., Freire C.S.R., Silvestre A.J.D., Pascoal Neto C., Gandini A., Desbriéres J.

367

SELETIVE CONTROL OF YEAST IN A MIXED CULTURE WITH LACTIC ACID BACTERIA USING LOW-MOLECULAR- WEIGHT CHITOSAN

Park Y.H.,Yi F. Hong Y.F. 374

MULTILAYERS AND COVALENTLY GRAFTED COATINGS BASED ON CHITOSAN AND ITS DERIVATIVES FOR PREVENTION BACTERIA ADHESION

Bratskaya S.Yu., Marinin D.V., Simon F., Zschoche F., van der Mei H.C., Busscher H.J.

378

LETHAL EFFECT OF CHITOSAN-Ag (I) FILM ON FOODBORNE PATHOGENS AS EVALUATED BY ELECTRON MICROSCOPY

Díaz V.J., García A., Cardenas G. 384

REMOVAL OF CU (II) AND PB (II) BY A STAPHYLOCOCCUS STRAIN IMMOBILIZED IN CHITOSAN BEADS

Angelim A.L.,Carvalho T.V., Melo G.C., do Nascimento R.F., Craveiro A.A., Melo V.M.M.

390

ANTIMICROBIAL ACTIVITY OF CHITOSAN AS FOOD CONTROL

Stamford T.L.M., Stamford T.C.M., Stamford N.P., Alcântara S.R.C., Berger L.R.R., Takaki G.M.C.

394

EFFECTS OF MOLECULAR WEIGHTS AND CONCENTRATIONS OF CHITOSAN ON SEED GERMINATION AND ENZYME ACTIVITY IN RICE SEEDS CV. PATHUM THANEE

Suvannasara R., Leelaporn O., Boonlertnirun S.

401

USE OF CHITOSAN AS A BIOFLOCCULANT TO TREAT BIOLOGICAL WASTEWATER FROM PULP AND PAPER PLANT

Renault F., Sancey B., Badot P.M., Crini G.

407

EFFECTS OF CHITOSAN ON PHYSIOLOGICAL AND MORPHOLOGICAL RESPONSES OF FIELD CORN SEEDLINGS UNDER HYPOXIA

Boonlertnirun S., Meechoui S., Sarobol E.

413

ADSORPTION OF REACTIVE BLACK 5 ONTO CHITOSAN IN FIXED-BED SYSTEMS

Barrón-Zambrano J., Szygula Á., Ruiz M., Sastre A.M., Guibal E.

419

DISTINCT COMPLEXING TRENDS OF CHITOSAN WITH TOXIC METALS

Lasheras-Zubiate M., Fernández J.M., Navarro-Blasco Í.

425

BIOPROCESSING OF CRUSTACEAN SHELL WASTE TO RECOVERY CHITIN, PROTEINS AND PIGMENTS

Carvalho T.V., Nogueira V.L.R., Melo G.C., Pinheiro P.D., Craveiro A.A., Melo V.M.M.

431

GREEN CHEMISTRY IN NATURAL DYEING: APPLICATION OF CHITOSAN FOR DYEING SOYBEAN/COTTON BLEND FABRIC

Shin Y., Choi M., Yoo D.I., Chung Y.S., Park W.H.

435

APPLICATION OF CHITOSAN MEMBRANE IN ALKALINE FUEL CELLS

Sanches C., Ticianelli E.A., Delezuk J.A.M., Campana-Filho S.P.

440

PRODUCTION OF CHITOSAN AND ITS USED AS SORBENT Alaa Eldin M.Y., Mukatova M.D. 446

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INCORPORATION OF α-TOCOPHEROL INTO CHITOSAN MICROSPHERES FOR COSMETIC APPLICATION

Yenilmez E., Başaran E., Yazan Y. 453

CHAPTER: PHYSICO-CHEMICAL

SYNTHESIS OF NEW CHITOSAN DERIVATIVES BY A REGIOSELECTIVE MANNICH REACTION

Saimoto H., Morimoto M., Hakone Y., Tanaka Y., Irisa Y., Taruno Y., Shigemasa Y., Ifuku S.

457

BIO-ENGINEERING OF CHITOSANS WITH NON-RANDOM PATTERNS OF ACETYLATION A NOVEL SEQUENCE-SPECIFIC CHITOSAN HYDROLASE GENERATING OLIGOMERS WITH BLOCK-PA

Kohlhoff M., El Gueddari N.E., Gorzelanny C., Haebel S., Alonso M.J., Franco T.T., Moerschbacher B.M.

463

DIALDEHYDE DERIVATIVES OF NUCLEOSIDES AND NUCLEOTIDES: NOVEL EFFECTIVE CROSSLINKING REAGENTS

Zakharova A.N., Novikov V.V., Donetskaya A.I., Perminov P.A., Kildeeva N.R., Mikhailov S.N.

469

CHITOSAN HYDROGELS CROSSLINKED WITH CARBOXYLIC ACIDS

Vílchez S., Miras J., Esquena J., Erra P. 475

A GENERALIZED MODEL OF PROTOLYTIC, COMPLEXING, AND COLLOIDAL PROPERTIES OF POLYELECTROLYTES CASE STUDY: N-(2-CARBOXYETHYL)CHITOSANS

Bratskaya S.Yu., Golikov A.P., Pestov A.V., Voit A.V., Yatluk Yu.G., Avramenko V.A.

481

BIOSORPTION OF LEAD USING CHITOSAN Benavente M., Moreno L., Martinez J. 487 CHITOSANS PRODUCTION BYPRODUCTS AS VALUABLE MATERIAL

Hussain M.H.M., Abdeen Z., Hifni H. 493

CHITOSAN-ALGINATE GELS Roberts G.A.F. 499 ULTRASOUND-ASSISTED DEACETYLATION OF BETA-CHITIN AND THE EFFECTS OF PROCESS PARAMETERS ON THE CHARACTERISTICS OF THE RESULTING CHITOSAN

Campana-Filho S.P., Domard A., Delezuk J.A.M., Cardoso M.B.

505

INFLUCENCE OF SPECIES OF INDUSTRIAL CRAB AND STAGES OF ITS MOLTING CYCLE ON PHYSICOCHEMICAL PROPERTIES OF CHITIN

Uryash V.F., Nemtsev S.V., Kokurina N.Yu., Zagorski I.A., Zagorskaya D.S., Kovacheva N.P., Sorokoumov I.M., Larina V.N., Kalashnikov I.N.

511

SOLUTION PROPERTIES OF CHITOSANS WITH DIFFERENT CHEMICAL COMPOSITIONS

Christensen B.E., Vårum K.M. 517

COMPARISON BETWEEN THE CONFORMATIONAL BEHAVIOR OF CHITOSAN AND HYALURONIC ACID

Weinhold M.X., Thöming J. 523

ANTIBACTERIAL PROPERTIES AND ECOTOXICOLOGICAL EFFECTS OF DIFFERENT CHITOSAN PREPARATIONS IN AN E. COLI AND LEMNA MINOR GROWTH INHIBITION ASSAY

Keddig N. 529

CHITIN DERIVATIVES AS SYSTEMS FOR METAL NANOPARTICLES STABILIZATION

Shirokova L.N., Alexandrova V.A., Vihoreva G.A., Revina A.A.

535

SELECTIVE SORPTION OF GOLD (III), PLATINUM (IV) AND PALLADIUM (II) BY THIOCARBAMOYLCHITOSANS

Bratskaya S.Yu., Pestov A.V., Slobodyuk A.B., Avramenko V.A., Yatluk Yu.G.

539

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PHYSICO-CHEMICAL CHARACTERIZATION OF CHITOSAN FROM M. CIRCINELLOIDES

Stamford T.C.M., Fae A.E.C., Stamford T.L.M., Stamford T.M., Alcantara S.R.C., Campos-Takaki G.

545

ZOLMITRIPTAN-CHITOSAN MICROPARTICLES FOR NASAL DELIVERY PREPARED BY SPRAY DRYING

Alhalaweh A., Andersson S., Velaga S. 552

BONE SUBSTITUTE USING CEMENTS OF CHITOSANS AND ADDITIVES

Nuñez C., Gonzalez J.P., Cardenas G. 560

MAGNETIC COLLOIDS SUPPORTED ON CHITOSAN BY IMPREGNATION METHOD

Cruzat Contreras C.A., Pena O., Diaz Visurraga J., Melendrez Castro M., Cardenas G.

566

MECHANICAL PROPERTIES OF CHITOSAN FILMS WITH DIFFERENT MOLECULAR WEIGHT

Alekseeva M.F., Fedoseeva E.N., Frolov V.G., Nistratov V.P., Smirnova L.A.

572

CHITOSAN-BASED POLYELECTROLYTE COMPLEXES SOLUBLE IN A WIDE PH-RANGE

Gorshkova M.Yu., Volkova I.F., Izumrudov V.A.

578

WATER SORPTION ISOTHERMS OF CHITOSAN AND ITS BLENDS WITH NANOFILLER

Mucha M., Matusiak B. 584

N-2-(2-PYRIDYL)ETHYLCHITOSAN – NEW CHELATE POLYMER

Pestov A.V., Bratskaya S.Yu., Avramenko V.A., Yatluk Yu.G.

590

PREPARATION AND PHYSICOCHEMICAL PROPERTIES OF CHITOSAN GELS AND CRYOGELS

Kildeeva N.R., Lozinsky V.I., Ivanov R.V., Nikonorov V.V., Perminov P.A., Mikhailov S.N.

595

A COMPARISON OF ADSORPTION ABILITIES OF CHITOSAN AND ITS DERIVATIVES FOR HEAVY METALS FROM AQUEOUS SOLUTIONS

Wu F.C., Tseng R.L., Juang R.S. 601

EFFECT OF DEGREE OF DEACETYLATION OF CHITOSAN ON PHYSICOCHEMICAL PROPERTIES AND CYTOTOXICITY OF CHITOSAN/β-GLYCEROLPHOSPHATE HYDROGEL

Tsai M.L., Wang S.T., Chen R.H. 609

DISSOLUTION OF CHITIN IN IONIC LIQUIDS Steudte S., Sauvageau J., Weinhold M.X., Thöming J.

615

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ADVANCES IN CHITIN SCIENCE - Vol. XI F. Rustichelli, C. Caramella, S. Şenel. K.M. Vårum, Eds.

Venice, 2009

DISTINCT COMPLEXING TRENDS OF CHITOSAN WITH TOXIC METALS

María Lasheras-Zubiate*, José María Fernández, Íñigo Navarro-Blasco

Departamento de Química y Edafología, Universidad de Navarra, Pamplona, Spain.

*E-mail address: [email protected]

INTRODUCTION

Chitosan is a fiberlike substance derived from chitin, a natural mucopolysaccharide of β-(1-4)-linked N-acetyl-D-glucosamine units. Chitin is known as the second most abundant biopolymer in nature after cellulose and is synthesized by a great number of organisms such as crustaceans, molluscs, insects, fungi and yeast [1-2]. However, few applications have been reported due to its low solubility in general solvents.

Chitosan, although is also present in nature in small amounts, is mainly obtained from chitin by deacetylation and is made up of acetylglucosamine and glucosamine units [3]. The proportion between non-acetylated and acetylated units is called degree of deacetylation. This parameter as well as the molecular weight, are the main parameters affecting the properties and conformation of chitosan.

The different chains of chitosan conform an extended two-fold helix stabilized by hydrogen bonds and are packed in an antiparallel manner forming a sheet structure. Water molecules are present between sheets to stabilize the structure [4].

Being soluble in aqueous solutions by the protonation on the –NH2 function of the glucosamine unit, chitosan is largely used in different applications [5-6] and has been investigated as an effective removing agent for several metals [7-10]. The binding mechanism of metal ions onto chitosan is not yet fully understood and adsorption, ions exchange and ion chelation are proposed as possible mechanisms. It seems that the complexation between metal and polymer occurs primarily though the amino groups [11].

The aim of the present work is to prove that the complexation of the metals Pb, Cd, Mo, Cu, Zn and Cr with chitosan takes place. In order to show it, voltammetric measurements have proved useful [12]. Depending on the different electrochemical behaviour on mercury electrode of the studied metals and the nature of the resulting complexes, diverse approaches have been used. The effect of the molecular weight and concentration of the polymer on the binding of the metals has also been studied.

MATERIALS and METHODS

Chitosans with different molecular weights (50-190 kDa, 190-310 kDa and 310-375 kDa, respectively) used in this study are commercial products from Sigma-Aldrich. Acetic acid and sodium acetate were obtained from Merck. The Certipure standard solutions containing 1000 ppm of the heavy metals Chromium (VI), Copper (II), Zinc (II),

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Molybdenum (VI), Cadmium (II) and Lead (II) were purchased from Merck. Chitosan and metal solutions were dissolved in acetic-acetate buffer solution (pH=4).

Voltammetric measurements, both differential pulse anodic stripping voltammetry (DPASV) and differential pulse voltammetry (DPV), were performed with a Metrohm 746 VA Trace Analyzer coupled with a 747 VA Stand equipped with a static mercury drop electrode (SMDE). A conventional three-electrode arrangement consisting of a glassy carbon counter electrode, an Ag/AgCl 3M reference electrode and a mercury electrode was used. The conditions used with each metal are specified on Table 1.

Table 1: Electrochemical conditions used for the different metals.

 

RESULTS and DISCUSSION

Electrochemical study of Pb, Cd and Zn. The electrochemical approach consisted in the titration of a given amount of chitosan

(acting as complexing ligand) with increasing amounts of added standard metals. All three metals are able to amalgamate -upon reduction at suitable electrode potential- on the mercury working electrode. Subsequent scanning of the potential in the positive going sense, forces the reoxidation of the metal giving rise to a current that is monitored in the Differential Pulse mode. Depending on the previous situation of the metal in solution (either free or chitosan-bound) the amount of metal to be deposited on the mercury electrode and subsequently reoxidised, will differ. Thus, if chitosan is in excess over the stoichiometry of the possible complex with a given metal, most of the metal added onto the chitosan-containing solution, will be stabilised by the ligand (chitosan) and it will amalgamate on the mercury electrode in a much lesser extent with respect to the amount of deposit that would be achieved when free. These results in diverse patterns when current vs. metal concentration are plotted. In general, two linear portions are obtained: a first one with a lower slope, corresponding to the anodic stripping current measured for the respective metal when complexed by the chitosan in solution, and a second steeper branch indicative of free metal in solution, that is to say, when in excess of the stoichiometric ratio of the chitosan-metal complex. The break in this type of graph allows the stoichiometry to be estimated and the population of chitosan acting as ligand to be calculated. Figure 1 shows the stripping patterns obtained for Pb (a), Cd (b) and Zn (c) when accumulated on the mercury electrode at the optimal potentials as well as the corresponding current vs. added metal plots.

All the voltammograms showed a constant potential peak which height increased with increasing metal concentrations. A surprising feature observed was the fact that the

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Zn stripping peak in presence of chitosan showed a marked decrease in its intensity and a displacement towards less negative potentials, proving the high affinity of chitosan for Zn, which is much higher than the affinity for the other two metals.

 

 

Figure 1. Stripping voltammograms for increasing concentrations of Pb (a), Cd (b) and Zn (c) in 0.5 µM chitosan solutions and their respective titration curves.

The higher the molecular weight of chitosan, the larger the binding capacity observed

for Pb and Zn, due to the fact that longer chitosan chains involve a larger number of free available amino groups. Diluted chitosan solutions showed an increase of complexation capacity irrespective of the assayed molecular weight. This finding could be ascribed to the diminishing of steric hindrances as well as to the breaking of stabilizing hydrogen bonds within the structure of the chitosan molecule. As a consequence, metals readily bind to the polymer. This trend is not shown by Cd, which complexation seems to be independent of the concentration and molecular weight of the polymer.

(a)

(b)

(c)

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Electrochemical study of Cu. DPASV was also the electrochemical technique chosen to study the behaviour of

chitosan after the addition of increasing amounts of Cu. The concentration of both ligand and metal was lower than those used for the previous metals in order to avoid the saturation of the electrode. Figure 2 shows anodic stripping voltammograms for increasing Cu concentrations in the presence of a fixed 0.05 µM chitosan.

 

Figure 2. Stripping voltammograms for increasing concentrations of Cu in presence of 0.05 µM chitosan solution and the corresponding titration curve.

The experimental data prove that the complexation occurs; an interesting aspect is that

this binding was seen to be independent of the molecular weight of chitosan. Accordingly, an inter-layer binding mechanism is proposed as the main retention factor of Cu by chitosan.

Electrochemical study of Mo and Cr. In this case, as both Mo and Cr do not amalgamate on Hg electrodes, the binding

mechanism was followed-up in a more traditional way, consisting on the observance of how the presence of increasing concentrations of ligand (chitosan) affected the peak potential and peak intensity for these two metals in a DPV mode (Figure 3). A known amount of metal was placed in the electrochemical cell and increasing amounts of chitosan were added to the solution. Mo peak intensity decreased regularly as chitosan concentration in cell increased up to a point in which the peak intensity remained constant upon addition of chitosan. Mo peak potential did not suffer any displacement in the presence of chitosan. Cr reduction peak potential was seen to take place at a more negative value as chitosan was added into the cell. This displacement was more acute once the added chitosan was enough to fully bind the initial Cr in solution, as it can be seen in Figure 3 (b). These evidences come to confirm the ability of chitosan to complex both heavy and toxic metals.

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Figure 3. Stripping voltammograms of Mo 10-4 M (a) and Cr 3.4 10-4 M (b) in the presence of increasing concentrations of chitosan.

The molecular weight of the polymer influenced the degree of complexation with

both Cr and Mo. As it has been emphasized before, when the polymer chain is longer, a higher number of linking groups are available for the retention of the metals within the three-dimensional structure of the acting ligand. This fact is consistent with a predominant intra-chain linkage of both metal atoms rather than the binding between the sheets formed by the different chitosan chains [13].

As general conclusions it may be asserted that:

- Not only adsorption but also complexation of different metals (Pb, Cd, Mo, Cu, Zn and Cr) actually takes place in acetate buffer (pH=4) with chitosans of different molecular weights.

- Chitosan molecular weight and concentration have been seen to play a key role in the chitosan binding activity with Zn and Pb but not with Cd.

- Length of chitosan chains influences the degree of complexation with both Cr and Mo, while Cu binding capacity remains independent of the molecular weight of the assayed polymers.

- A predominant intra-chain linkage for Cr and Mo is proposed. On the contrary, an inter-layer binding mechanism seems to be the main retention factor in the case of Cu. ACKNOWLEDGEMENTS

This work has been fully funded by the Ministry of Education and Science of Spain (MAT2007-65478) and FUNA (Fundación Universitaria de Navarra). M. Lasheras would like to thank the Friends of the University of Navarra, Inc. for funding support.

(a)

(b)

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