Abstract
When gelification is performed by freezing–thawing repeated cycles, the resultant gel-like polymer systems are called cryogels. This work aims to assess the effect of the addition of glutaraldehyde and 18 Crown Ether-6 on surface properties and protein loading of dried chitosan cryogel films. Residual water content of treated chitosan membranes ranged between 11.93 and 13.86%, while their water activities vary from 0.5 to 0.7 (measured from 4 to 60 °C). Based on thermal data, water evaporation peak and degradation temperatures of chitosan membranes shifted to a higher temperature for crosslinked samples. X-ray diffractograms provide high values of crystallinity for all the samples (70.67–92.86%), the highest value being for the glutaraldehyde-treated membrane. Candida rugosa lipase can be immobilized successfully on chitosan membranes. Lipase immobilized on glutaraldehyde-crosslinked chitosan yielded the highest efficiency in terms of total coupled protein and protein loading efficiency.
Similar content being viewed by others
References
Chiou SH, Wu WT (2004) Immobilization of Candida rugosa lipase on chitosan with activation of the hydroxyl groups. Biomaterials 25:197–204
Hirano S, Kondo S, Ohe Y (1975) Chitosan gel: a novel polysaccharide gel. Polymer 16:622
Bernkop-Schnurch A, Hopf TE (2001) Synthesis and in-vitro evaluation of chitosan–thioglycolic acid conjugates. Sci Pharm 69:109–118
Montembault A, Viton C, Domard A (2005) Physico-chemical studies of the gelation of chitosan in a hydroalcoholic medium, 2004. Biomaterials 26:933–943
Nakatsuka S, Andrady AL (1992) Permeability of vitamin B12 in chitosan membranes—effect of cross-linking and blending with poly(vinyl alcohol) on permeability. J Appl Polym Sci 44:17–28
Hung TC, Giridhar R, Chiou SH, Wu WT (2003) Binary immobilization of Candida rugosa lipase on chitosan. J Mol Catal B Enzym 26:69–78
Yi Y, Wang Y, Liu H (2003) Preparation of new crosslinked chitosan with crown ether and their adsorption for silver ion for antibacterial activities. Carbohydr Polym 53:425–430
Bodnar M, Hartmann JF, Borbely J (2005) Preparation and characterization of chitosan-based nanoparticles. Biomacromolecules 6:2521–2527
Dal Pozzo A, Vanini L, Fagnoni M, Guerrini M, A DB, Muzzarelli RAA (2000) Preparation and characterization of poly(ethylene glycol)-crosslinked reacetylated chitosans. Carbohydr Polym 42:201–206
Yang Q, Dou F, Liang B, Shen Q (2005) Investigations of the effects of glyoxal cross-linking on the structure and properties of chitosan fiber. Carbohydr Polym 61:393–398
Chen JP, Chiu SH (1999) Preparation and characterization of urease immobilized onto porous chitosan beads for urea hydrolysis. Bioprocess Eng 21:323–330
Lin J, Yan F, Hu X, Ju H (2004) Chemiluminescent immunosensor for CA19-9 based on antigen immobilization on a cross-linked chitosan membrane. J Immunol Methods 291:165–174
Peng X, Zhang L (2005) Surface fabrication of hollow microspheres from N-methylated chitosan cross-linked with glutaraldehyde. Langmuir 21:1091–1095
Guibal E (2005) Heterogeneous catalysis on chitosan-based materials: a review. Prog Polym Sci 30:71–109
Arroyo M (1998) Inmovilización de enzimas. Fundamentos, métodos y aplicaciones. Ars Pharmaceut 39(2):23–29
Lozinsky VI, Plieva FM (1998) Poly(vinyl alcohol) cryogels employed as matrices for cell immobilization. 3. Overview of recent research and developments. Enzyme Microb Technol 23:227–242
Mine Y, Fukunaga K, Itoh K, Yoshimoto M, Nakao K, Sugimura Y (2003) Enhanced enzyme activity and enantioselectivity of lipases in organic solvents by crown ethers and cyclodextrins. J Biosci Bioeng 95(5):441–447
Kokufuta E, Jinbo E (1992) A hydrogel capable of facilitating polymer diffusion through the gel porosity and its application in enzyme immobilization. Macromolecules 25:3549–3552
Bacheva AV, Plieva FN, Lysogorskaya EN, Filippova IY, Lozinsky V (2001) Peptide synthesis in organic media with subtilisin 72 immobilized on poly(vinyl alcohol)–cryogel carrier. Bioorg Med Chem Lett 11:1005
Plieva FM, Kotchetkov KA, Singh I, Parmar VS, Belokon YN, Lozinsky VI (2000) Immobilization of hog pancreas lipase in macroporous poly(vinyl alcohol)–cryogel carrier for the biocatalysis in water-poor media. Biotechnol Lett 22:551–554
Szczesna-Antczak M, Antczak T, Rzyska M, Bielecki S (2002) Catalytic properties of membrane-bound Mucor lipase immobilized in a hydrophilic carrier. J Mol Catal B Enzym 19–20:261
Giannouli P, Morris ER (2003) Cryogelation of xanthan. Food Hydrocolloids 17:495–501
Lazaridou A, Biliaderis CG (2004) Cryogelation of cereal β-glucans: structure and molecular size effects. Food Hydrocolloids 18:933–947
Xue W, Champ S, Huglin MB, Jones TGJ (2004) Rapid swelling and deswelling in cryogels of crosslinked poly(N-isopropylacrylamide-co-acrylic). European Polymer Journal 40:467–476
Hagiwara T, Wang H, Suzuki T, Takai R (2002) Fractal analysis of ice crystals in frozen food. J Agric Food Chem 50:3085–3089
O’Brien FJ, Harley BA, Yannas IV, Gibson L (2004) Influence of freezing rate on pore structure in freeze-dried collagen-GAG scaffolds. Biomaterials 25:1077–1086
Suh J-KF, Matthew HWT (2000) Application of chitosan-based polysaccharide biomaterials in cartilage tissue engineering: a review. Biomaterials 21:2589–2598
Lai HL, Abu’Khalil A, Craig DQM (2003) The preparation and characterisation of drug-loaded alginate and chitosan sponges. Int J Pharmaceut 251:175–/181
Kasumi T, Tsuji M, Hayashi K, Tsumura N (1977) Amino group in chitosan are useful for the immobilization of enzyme. Agric Biol Chem Tokyo 41:1865
Betigeri SS, Neau SH (2002) Immobilization of lipase using hydrophilic polymers in the form hydrogel beads. Biomaterials 23:3627–3636
Alsarra IA, Betigeri SS, Zhang H, Erans BA, Neau SH (2002) Molecular weight and degree of deacetylation effects on lipase-loaded chitosan beadcharacteristics. Biomaterials 23:3637–3644
Krajewska B (2004) Application of chitin- and chitosan-based materials for enzyme immobilizations: a review. Enzyme Microb Technol 35:126–139
Ho MH, Kuo PY, Hsieh HJ, Hsien TY, Hou LT, Lai JY, Wang DM (2004) Preparation of porous scaffolds by using freeze-extraction and freeze-gelation methods. Biomaterials 25:129–138
Helrich K (ed) (1990) Official methods of analysis of the Association of Official Analytical Chemists. AOAC International, Arlington, 1010 p
Rockland LB (1960) Saturated salt solutions for static control of relative humidity between 5 and 40°C. Anal Chem 32(9):1375–1377
Rahman S (1995) Food properties handbook. CRC Press, Boca Ratón 500 pp
Focher B, Beltrame PL, Naggi A, Torri G (1990) Alkaline Ndeacetylation of chitin enhanced by flash treatments. Reaction kinetics and structural modifications. Carbohydr Polym 12:405–408
Robson RM, Goll DE, Temple MJ (1968) Determination of proteins in “Tris” buffer by the biuret reaction. Anal Biochem 24:339–341
Rueda DR, Secall T, Bayer RK (1999) Differences in the interaction of water with starch and chitosan films as revealed by infrared spectroscopy and differential scanning calorimetry. Carbohydr Polym 40:49–56
Kang HM, Cai YL, Liu PS (2006) Synthesis, characterization and thermal sensitivity of chitosan-based graft copolymers. Carbohydr Res 341:2851–2857
Kittur FS, Prashanth KVH, Sankar KU, Tharanathan RN (2002) Characterization of chitin, chitosan and their carboxymethyl derivatives by differential sacanning calorimetry. Carbohydr Polym 49:185–193
Sakurai K, Maegawa T, Takahashi T (2000) Glass transition temperature of chitosan and miscibility of chitosan/poly(N-vinyl pyrrolidone) blends. Polymer 41:7051–7056
Fernández Cervera M, Heinämäki J, Räsänen M, Maunu SL, Karjalainen M, Nieto Acosta OM, Iraizoz Colarte A, Yliruusi J (2004) Solid-state characterization of chitosans derived from lobster chitin. Carbohydr Polym 58:401–408
Qu X, Wirsén A, Albertsson AC (2000) Novel pH-sensitive chitosan hydrogels: swelling behavior and states of water. Polymer 41:4589–4598
Khalid MN, Agnely F, Yagoubi N, Grossiord JL, Couarraze G (2002) Water state characterization, swelling behavior, thermal and mechanical properties of chitosan based networks. Eur J Pharm Sci 15:425–432
Mukoma P, Jooste BR, Vosloo HCM (2004) Synthesis and characterization of cross-linked chitosan membranes for application as alternative proton exchange membrane materials in fuel cells. J Power Sources 136:16–23
Guibal E (2004) Interactions of metal ions with chitosan-based sorbents: a review. Sep Purif Technol 38:43–74
Trung TS, Thein-Han WW, Qui NT, Ng CH, Stevens WF (2006) Functional characteristics of shrimp chitosan and its membranes as affected by the degree of deacetylation. Bioresour Technol 97:659–663
Zhang Y, Xue C, Xue Y, Gao R, Zhang X (2006) Determination of the degree of deacetylation of chitin and chitosan by X-ray powder diffraction. Carbohydr Res 340:1914–1917
Piron E, Domard A (1997) Interaction between chitosanand uranyl ions part 1. Role of physicochemical parameters. Int J Biol Macromol 21:327–335
Jaworska M, Sakurai K, Gaudon P, Guibal E (2003) Influence of chitosan characteristics on polymer properties. I: Crystallographic properties. Polym Int 52:198–205
Ogawa K (2006) Three dimensional assembly of chitin and chitosan. In: Uragami T, Tokura S (eds) Material science of chitin and chitosan. Kodansha Ltd, Tokyo
Fritzsche AK, Arevalo AR, Connolly AF, Moore MD, Elings V, Wu CM (1992) The estructure and morphology of the skin layer of polyethersulfone ultrafiltration membranes: a comparative atomic force microscope and scanning electron microscope study. J Appl Polym Sci 45:1945
Hilal N, Al-ZoubP H, Darwish NA, Mohammad AW, Abu Arabi M (2004) A comprehensive review of nanofiltration membranes: treatment, pretreatment, modelling, and atomic force microscopy. Desalination 170:281–308
Bowen W, Hilal N, Lovitt R, Williams P (1996) Atomic force microscope studies of membranes: Surface pore structures of Cyelopore and Anopore membranes. J Membr Sci 110:233–238
Calvo JI, Pradanos P, Hermindez A, Bowen R, Hilal N, Lovitt RW, Williams PM (1997) Bulk and surface characterization of composite UF membranes atomic force microscopy, gas adsorption desorption and liquid displacement techniques. J Membr Sci 128:7–21
Hung TC, Giridhar R, Chiou SH, Wu WT (2003) Binary immobilization of Candida rugosa lipase on chitosan. J Mol Catal B Enzym 26:69–78
Pereira EB, Zanin JM, Castro HF (2003) Immobilization and catalytic properties of lipase on chitosan for hydrolysis and esterification reactions. Braz J Chem Eng 20:343–355
Bezbradica D, Mijin D, Siler-Marinkovic S, Zorica Knezevic (2006) The Candida rugosa lipase catalyzed synthesis of amyl isobutyrate in organic solvent and solvent-free system: A kinetic study. J Mol Catal B Enzym 38:11–16
Acknowledgments
The authors are grateful to Dr. Alfonso Devia C. (Laboratorio de Física del Plasma, Universidad Nacional-Manizales) for the AFM and XRD data and to Dr. Andres Rosales R. (Laboratorio de Magnetismo, Universidad Nacional-Manizales) for performing DSC and TGA analysis.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Orrego, C.E., Valencia, J.S. Preparation and characterization of chitosan membranes by using a combined freeze gelation and mild crosslinking method. Bioprocess Biosyst Eng 32, 197–206 (2009). https://doi.org/10.1007/s00449-008-0237-1
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00449-008-0237-1