PREPARATION AND CHARACTERIZATION OF LOW MOLECULAR WEIGHT CHITOSAN WITH DIFFERENT DEGREES OF DEACETYLATION BY THE ACID HYDROLYSIS METHOD

Authors

  • NAWZAT D. AL-JBOUR Center of Excellence for Advanced Research in Fluid Flow (CARIFF), Faculty of Chemical and Natural Resources Engineering, Universiti Malaysia Pahang, Gambang 26300, Kuantan, Malaysia, Faculty of Pharmacy, Middle East University, Amman, Jordan
  • M. D. H. BEG Center of Excellence for Advanced Research in Fluid Flow (CARIFF), Faculty of Chemical and Natural Resources Engineering, Universiti Malaysia Pahang, Gambang 26300, Kuantan, Malaysia
  • JOLIUS GIMBUN Center of Excellence for Advanced Research in Fluid Flow (CARIFF), Faculty of Chemical and Natural Resources Engineering, Universiti Malaysia Pahang, Gambang 26300, Kuantan, Malaysia
  • A. K. M. MOSHIUL ALAM Institute of Radiation and Polymer Technology, Bangladesh Atomic Energy Commission, Dhaka, Bangladesh

DOI:

https://doi.org/10.22159/ijap.2021v13i2.32229

Keywords:

Acid hydrolysis, Acetylation, Chitosan Oligomers, Degree of deacetylation

Abstract

Objective: The objective of this research is to prepare Low Molecular Weight Chitosan (LMWC) by the acid hydrolysis method, using dilute hydrochloric acid (2M). LMWC has superior properties compared to the High Molecular Weight Chitosan (HMWC), especially in terms of water solubility, antibacterial and antifungal properties. These could open new potential applications for LMWC in sectors such as the cosmetics, food, and pharmaceutical industries.

Methods: In this work, the acid hydrolysis method was used to produce LMWC with different molecular weights starting from 500 kDa and 93% degree of deacetylations (DDA). The molecular weights of the produced grades were determined by applying Mark-Houwink equation while the %DDA was determined and verified by the use of the 1st derivative UV method and 1HNMR method, respectively. The depolymerization reactions were carried out with different time intervals to produce totally deacetylated LMWC of 30 kDa, 15 kDa, and 7.5 kDa. The LMWC was characterized by FTIR, XRD, and DSC to evaluate the functionality, microstructure and thermal properties.

Results: The FTIR spectra revealed that there is no significant difference in the main skeletal structure of the LMWC and HMWC. On the other hand, the XRD and DSC results showed that the LMWC of different molecular weights and degrees of deacetylation are of semi-crystalline structure, similar to the HMWC.

Conclusion: The obtained results showed that the used acid hydrolysis procedure can produce LMWC grades of desired specifications, yields, and quality which are suitable for use in different applications.

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References

Patel DP, Singh S. Chitosan: a multifacet polymer. Int J Curr Pharm Res 2015;7:21-8

Sabnis S, Block LH. Chitosan as an enabling excipient for drug delivery systems: I. Molecular modifications. Int J Biol Macromol 2000;3:181-6.

Morsi N, Ghorab D, Refai H, Teba H. Preparation and evaluation of Alginate/Chitosan nanodispersions for ocular delivery. Int J Pharm Pharm Sci 2015;7:234-40.

Berth G, Dautzenberg H. The degree of acetylation of chitosans and its effect on the chain conformation in aqueous solution. Carbohydr Polym 2002;1:39-51.

Yadav A, Bhise S. Chitosan: a potential biomaterial effective against typhoid. Curr Sci 2004;9:1176-8.

Fahrurroji A, Thendriani D, Riza H. Hesperidin hydrogel formulation using pectin-chitosan polymer combination. Int J Pharm Pharm Sci 2017;9:98-104.

John L, Kumar A. Comparison of amlodipine transdermal patches using hydroxypropylmethylcellulose and chitosan. Asian J Pharm Clin Res 2014;7:86-90.

No HK, Meyers SP, Prinyawiwatkul W, Xu Z. Applications of chitosan for improvement of quality and shelf life of foods: a review. J Food Sci 2007;72:87-100.

Zohuriaan Mehr MJ. Advances in chitin and chitosan modification through graft copolymerization: a comprehensive review. Iran Polym J 2005;3:235-65.

Kumar MNR. A review of chitin and chitosan applications. React Funct Polym 2000;1:1-27.

Shahidi F, Arachchi JKV, Jeon YJ. Food applications of chitin and chitosans. Trends Food Sci Technol 1999;2:37-51.

Jin Li, Yumin Du, Jianhong Yang, Tao Feng, Aihua Li, Ping Chen. Preparation and characterisation of low molecular weight chitosan and chito-oligomers by a commercial enzyme. Polym Degrad Stab 2005;3:441-8.

Prabaharan M, Mano J. Chitosan-based particles as controlled drug delivery systems. Drug Delivery 2004;1:41-57.

Jeon YJ, Shahidi F, Kim SK. Preparation of chitin and chitosan oligomers and their applications in physiological functional foods. Food Rev Int 2000;2:159-76.

Qandil AM, Obaidat AA, Ali MAM, Al-Taani BM, Tashtoush BM, Al-Jbour ND, et al. Investigation of the interactions in complexes of low molecular weight chitosan with ibuprofen. J Solution Chem 2009;6:695-712.

Qinna NA, Karwi QG, Al-Jbour N, Al-Remawi MA, Alhussainy TM, Al-So'ud KA, et al. Influence of molecular weight and degree of deacetylation of low molecular weight chitosan on the bioactivity of oral insulin preparations. Mar Drugs 2015;13:1710-25.

Kumar MN, Muzzarelli RA, Muzzarelli C, Sashiwa H, Domb AJ. Chitosan chemistry and pharmaceutical perspectives. Chem Rev 2004;104:6017-84.

Rinaudo M. Chitin and chitosan: properties and applications. Prog Polym Sci 2006;7:603-32.

Aam BB, Heggset EB, Norberg AL, Sørlie M, Varum KM, Eijsink VG. Production of chitooligosaccharides and their potential applications in medicine. Mar Drugs 2010;8:1482-517.

Kumar AV, Tharanathan R. A comparative study on depolymerization of chitosan by proteolytic enzymes. Carbohydr Polym 2004;3:275-83.

Giustina A, Ventura P. Weight-reducing regimens in obese subjects: effects of a new dietary fiber integrator. Acta Toxicol Ther 1995;16:199-214.

Kim SK, Rajapakse N. Enzymatic production and biological activities of chitosan oligosaccharides (COS): a review. Carbohydr Polym 2005;4:357-68.

Lee SH, Suh J, Kim HS, Lee JD, Song J, Lee SK. MR evaluation of radiation synovectomy of the knee by means of intra-articular injection of holmium-166-chitosan complex in patients with rheumatoid arthritis: results at 4-month follow-up. Korean J Radiol 2003;3:170-8.

Macchi G. A new approach to the treatment of obesity: chitosan's effects on body weight reduction and plasma cholesterol's levels. Acta Toxicol Ther 1996;17:303-22.

Nishimura K, Nishimura S, Nishi N, Saiki I, Tokura S, Azuma I. Immunological activity of chitin and its derivatives. Vaccine 1984;2:93-9.

Tokoro A, Kobayashi M, Tatewaki N, Suzuki K, Okawa Y, Mikami T, et al. Protective effect of N-acetyl chitohexaose on listeria monocytogenes infection in mice. Microbiol Immunol 1989;33:357-67.

De Britto D, Campana Filho SP. Kinetics of the thermal degradation of chitosan. Thermochim Acta 2007;1:73-82.

Kasaai MR. Calculation of mark–houwink–sakurada (MHS) equation viscometric constants for chitosan in any solvent–temperature system using experimental reported viscometric constants data. Carbohydr Polym 2007;3:477-88.

Kumar ABV, Varadaraj MC, Gowda LR, Tharanathan RN. Characterization of chito-oligosaccharides prepared by chitosanolysis with the aid of papain and pronase, and their bactericidal action against Bacillus cereus and Escherichia coli. Biochem J 2005;391 Pt 2:167–75.

Kurita K. Chitin and chitosan: functional biopolymers from marine crustaceans. Mar Biotechnol (NY) 2006;8:203-26.

Chang KLB, Tai MC, Cheng FH. Kinetics and products of the degradation of chitosan by hydrogen peroxide. J Agric Food Chem 2001;10:4845-51.

Chen RH, Chang JR, Shyur JS. Effects of ultrasonic conditions and storage in acidic solutions on changes in molecular weight and polydispersity of treated chitosan. Carbohydr Res 1997;4:287-94.

Tang E, Huang M, Lim L. Ultrasonication of chitosan and chitosan nanoparticles. Int J Pharm 2003;1:103-14.

Einbu A, Grasdalen H, Varum KM. Kinetics of hydrolysis of chitin/chitosan oligomers in concentrated hydrochloric acid. Carbohydr Res 2007;8:1055-62.

Osorio Madrazo A, David L, Trombotto S, Lucas JM, Peniche Covas C, Domard A. Highly crystalline chitosan produced by multi-steps acid hydrolysis in the solid-state. Carbohydr Polym 2011;4:1730-9.

Jeon YJ, Kim SK. Production of chitooligosaccharides using an ultrafiltration membrane reactor and their antibacterial activity. Carbohydr Polym 2000;2:133-41.

Kuroiwa T, Ichikawa S, Hiruta O, Sato S, Mukataka S. Factors affecting the composition of oligosaccharides produced in chitosan hydrolysis using immobilized chitosanases. Biotechnol Progress 2002;5:969-74.

Anderson DR, Frisque AJ. Process for rapidly dissolving water-soluble polymers: US Patent RE28,474; 1975.

Lee MY, Var F, Shin-ya Y, Kajiuchi T, Yang JW. Optimum conditions for the precipitation of chitosan oligomers with DP 5–7 in concentrated hydrochloric acid at low temperature. Process Biochem 1999;5:493-500.

Kurita K. Controlled functionalization of the polysaccharide chitin. Prog Polym Sci 2001;9:1921-71.

Roberts G. Chitin chemistry the macmillan press. Basingstoke, Great Britain; 1992.

Knill C, Kennedy J, Mistry J, Miraftab M, Smart G, Groocock M, et al. Acid hydrolysis of commercial chitosan. J Chem Technol Biotechnol 2005;80:1291.

Elsayed A, Remawi MA, Qinna N, Farouk A, Badwan A. Formulation and characterization of an oily-based system for oral delivery of insulin. Eur J Pharm Biopharm 2009;2:269-79.

Pharmacopoeia B. Specific monograph: British Pharmacopoeia Commission: London; 2015.

Cabrera JC, Van Cutsem P. Preparation of chitooligosaccharides with degree of polymerization higher than 6 by acid or enzymatic degradation of chitosan Biochem. Eng J 2005;25:165-72.

Lee MY, Var F, Shin-ya Y, Kajiuchi T, Yang JW. Optimum conditions for the precipitation of chitosan oligomers with DP 5–7 in concentrated hydrochloric acid at low temperature. Process Biochem 1999;34:493-500.

Haider S, Park SY. Preparation of the electrospun chitosan nanofibers and their applications to the adsorption of Cu(II) and Pb(II) ions from an aqueous solution. J Membrane Sci 2009;328:90-6.

Varum K, Ottøy M, Smidsrød O. Acid hydrolysis of chitosans. Carbohydr Polym 2001;46:89-98.

No H, Meyers SP, Prinyawiwatkul W, Xu Z. Applications of chitosan for improvement of quality and shelf life of foods: a review. J Food Sci 2007;72:87-100.

Kumar MNR. A review of chitin and chitosan applications. React Funct Polym 2000;46:1-27.

Sweidan K, Jaber A, Al-Jbour N, Obaidat R, Al-Remawi M, Badwan A. Further investigation on the degree of deacetylation of chitosan determined by potentiometric titration. J Excipients Food Chem 2011;2:16-25.

Athamneh N, Tashtoush B, Qandil A, Al-Tanni B, Obaidat A, Al-Jbour N, et al. A new controlled-release liquid delivery system based on diclofenac potassium and low molecular weight chitosan complex solubilized in polysorbates. Drug Dev Ind Pharm 2010;39:1217-122.

Kumirska J, Czerwicka M, Kaczynski Z, Bychowska A, Brzozowski K, Thoming J, et al. Application of spectroscopic methods for structural analysis of chitin and chitosan. Mar Drugs 2010;8:1567-636.

Zhang Y, Xue C, Xue Y, Gao R, Zhang X. Determination of the degree of deacetylation of chitin and chitosan by X-ray powder diffraction. Carbohydr Res 2005;340:1914-7.

Islam MM, Masum SM, Rahman MM, Molla MAI, Shaikh A, Roy S. Preparation of chitosan from shrimp shell and investigation of its properties. Int J Basic Appl Sci 2011;11:77-80.

Yen MT, Yang JH, Mau JL. Physicochemical characterization of chitin and chitosan from crab shells. Carbohyd Polym 2009;75:15-21.

Sakurai K, Maegawa T, Takahashi T. Glass transition temperature of chitosan and miscibility of chitosan/poly (N-vinyl pyrrolidone) blends. Polymer 2000;41:7051-6.

Published

07-03-2021

How to Cite

AL-JBOUR, N. D., BEG, M. D. H., GIMBUN, J., & ALAM, A. K. M. M. (2021). PREPARATION AND CHARACTERIZATION OF LOW MOLECULAR WEIGHT CHITOSAN WITH DIFFERENT DEGREES OF DEACETYLATION BY THE ACID HYDROLYSIS METHOD. International Journal of Applied Pharmaceutics, 13(2), 153–164. https://doi.org/10.22159/ijap.2021v13i2.32229

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