advances in chitin science -...
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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
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
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
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
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
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
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
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
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
425
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),
426
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.
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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.
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