Synthesis and characterization of chitosan ethers: Hydroxypropyl chitosan and Hydroxyethyl chitosan

Year 2024, , 145 - 156, 21.06.2024

Nuran Çelikçi , Cengiz Ayhan Zıba , Mustafa Dolaz , Mehmet Tumer

https://doi.org/10.51354/mjen.1477354

Cited By: 1

Abstract

The hydroxypropyl chitosan (HPCH) and hydroxyethyl chitosan (HECH) are multifunctional chitosan derivatives with biocompatible and biodegradable properties. Due to their hydroxypropyl and hydroxethyl groups, they have water solubility, moisture retention, and gelling properties. In this study, the chitosan derivatives HPCH and HECH were obtained in two steps alkalisation and etherification. For alkalisation, chitosan was kept in an alkaline medium at - hours by mixing alkaline chitosan with propylene oxide and ethylene oxide separately in a pressure reactor. The structures of the obtained HPCH and HECH were characterised by FT-IR, 1H(13C)-NMR, XRD, and TG analysis methods. Since the degree of deacetylation (DA) of chitosan is 75-85%, the chitosan units contain N-acetyl (-N-(CO)-CH3)) groups in addition to -NH2 functional groups. When the 1H(13C)-NMR spectrum of chitosan was examined, the peak value of these acetyl groups was observed at δ1.89 ppm. When the XRD spectra were examined, it was observed that the strong peak in chitosan at 2θ=20° was weakened in HPCH and HECH. In addition, the thermal stability of HPCH and HECH was found to be higher than chitosan in TG analysis.

Keywords

Etherification, Hydroxyethyl Chitosan, Hydoxypropyl Chitosan, NMR

Project Number

2021/1-23 D

References

• [1]. Antony, R., Arun, T., Manickam, S. T. D. “A review on applications of chitosan-based Schiff bases”, International Journal of Biological Macromolecules, 129, (2019), 615-633.
• [2]. Weng, J., Durand, A., Desobry, S. “Chitosan-based particulate carriers: structure, production and corresponding controlled release”, Pharmaceutics, 15, (2023), 1455.
• [3]. Celikci, N., Ziba, C. A., Dolaz, M. “Synthesis and characterization of carboxymethyl shrimp chitosan (CMSCh) from waste shrimp shell”, MANAS Journal of Engineering, 8, (2020), 77-83.
• [4]. Elhag, M., Abdelwahab, H. E., Mostafa, M. A., Yacout, G. A., Nasr, A. Z., Dambruoso, P., El Sadek, M. M. “One pot synthesis of new cross-linked chitosan-Schiff base: Characterization, and anti-proliferative activities”, International Journal of Biological Macromolecules, 184, (2021), 558-565.
• [5]. Antunes, J. C., Domingues, J. M., Miranda, C. S., Silva, A. F. G., Homem, N. C., Amorim, M. T. P., Felgueiras, H. P. “Bioactivity of chitosan-based particles loaded with plant-derived extracts for biomedical applications: Emphasis on antimicrobial fiber-based systems”, Marine Drugs, 19(2021), 359.
• [6]. Kim, I. Y., Seo, S. J., Moon, H. S., Yoo, M. K., Park, I. Y., Kim, B. C., Cho, C. S. “Chitosan and its derivatives for tissue engineering applications”, Biotechnology Advances, 26(2008), 1-21.
• [7]. Giri, T. K., Thakur, A., Alexander, A., Badwaik, H., Tripathi, D. K. “Modified chitosan hydrogels as drug delivery and tissue engineering systems: present status and applications”, Acta Pharmaceutica Sinica B, 2, (2012), 439-449.
• [8]. Hashmi, S. A., Chandra, A., Singh, R. K., Chandra, A., Chandra, S. (Eds.). (2015). Electroactive Polymers: Materials and Devices (Vol. 5). Allied Publishers.
• [9]. Bakshi, P. S., Selvakumar, D., Kadirvelu, K., Kumar, N. S. “Chitosan as an environment friendly biomaterial–a review on recent modifications and applications”, International Journal of Biological Macromolecules, 150, (2020), 1072-1083.
• [10]. Al-Azmi, A., Keshipour, S. “Cross-linked chitosan aerogel modified with Pd(II)/ phthalocyanine: synthesis, characterization, and catalytic application”, Scientific Reports, 9, (2019), 13849.
• [11]. Matica A., Gheorghiţa M., Vasile O. "Biodegradability of Chitosan Based Products", New Frontiers in Chemistry 26, (2017), 75-86.
• [12]. Hassan, M. A., Tamer, T. M., Valachová, K., Omer, A. M., El-Shafeey, M., Eldin, M. S. M., Šoltés, L. “Antioxidant and antibacterial polyelectrolyte wound dressing based on chitosan/hyaluronan/phosphatidylcholine dihydroquercetin”, International Journal of Biological Macromolecules, 166, (2021), 18-31.
• [13]. Kim, S. “Competitive biological activities of chitosan and its derivatives: antimicrobial, antioxidant, anticancer, and anti-inflammatory activities”, International Journal of Polymer Science, (2018), Article ID 1708172
• [14]. Ahmed, S., Ikram, S. “Chitosan its derivatives: a review in recent innovations”, International Journal of Pharmaceutical Sciences and Research, 6, (2015), 14.
• [15]. Aranaz, I., Acosta, N., Civera, C., Elorza, B., Mingo, J., Castro, C., Heras Caballero, A. “Cosmetics and cosmeceutical applications of chitin, chitosan and their derivatives”, Polymers, 10, (2018), 213.
• [16]. Wang, H., Qian, J., Ding, F. “Emerging chitosan-based films for food packaging applications”, Journal of Agricultural And Food Chemistry, 66, (2018), 395-413.
• [17]. Kazemi A., M., Zandi, M., Shokrollahi, P., Ehsani, M., Baharvand, H. “Chitosan surface modified hydrogel as a therapeutic contact lens”, Polymers for Advanced Technologies, 31, (2020), 741-748.
• [18]. Elkasabgy, N. A., Mahmoud, A. A., Maged, A. “3D printing: An appealing route for customized drug delivery systems”, International Journal of Pharmaceutics, 588, (2020), 119732.
• [19]. Decante, G., Costa, J. B., Silva-Correia, J., Collins, M. N., Reis, R. L., Oliveira, J. M. “Engineering bioinks for 3D bioprinting. Biofabrication”, 13, (2021), 032001.
• [20]. Fan, L., Li, M., Gong, Y., Peng, K., Xie, W. “Preparation and characterization of alginate/Hydroxypropyl chitosan blend fibers”, Journal of Applied Polymer Science, 125, (2012), 829-835. [21]. Wang, Z., Yan, Y., Jiang, Y., Li, W., Hu, X., Fu, B., Qin, C. “Effect of orally administered hydroxypropyl chitosan on the levels of iron, copper, zinc and calcium in mice”, International Journal of Biological Macromolecules, 64, (2014), 25-29.
• [22]. Zhao, T., Jiang, L. “Contact angle measurement of natural materials”, Colloids and Surfaces B: Biointerfaces, 161, (2018) 324-330.
• [23]. Queiroz, M. F., Teodosio Melo, K. R., Sabry, D. A., Sassaki, G. L., Rocha, H. A. O. “Does the use of chitosan contribute to oxalate kidney stone formation?”, Marine Drugs, 13, (2014), 141-158.
• [24]. Yue, L., Wang, M., Khan, I. M., Xu, J., Peng, C., Wang, Z. “Preparation, characterization, and antibiofilm activity of cinnamic acid conjugated hydroxypropyl chitosan derivatives”, International Journal of Biological Macromolecules, 189, (2021), 657-667.
• [25]. Cao, J., He, G., Ning, X., Wang, C., Fan, L., Yin, Y., Cai, W. “Hydroxypropyl chitosan-based dual self-healing hydrogel for adsorption of chromium ions”, International Journal of Biological Macromolecules, 174, (2021), 89-100.
• [26]. Zhu, C., Zou, S., Rao, Z., Min, L., Liu, M., Liu, L., Fan, L. “Preparation and characterization of hydroxypropyl chitosan modified with nisin”, International International Journal of Biological Macromolecules, 105, (2017) 1017-1024.
• [27]. Nie, L., Deng, Y., Li, P., Hou, R., Shavandi, A., Yang, S. “Hydroxyethyl chitosan-reinforced polyvinyl alcohol/biphasic calcium phosphate hydrogels for bone regeneration”, Acs Omega, 5, (2020), 10948-10957.
• [28]. Guo, W., Cai, Z., Xu, Q., Sun, K., Huang, X., Cao, Z. “Synthesis and properties of dehydroabietyl glycidyl ether grafted hydroxypropyl chitosan”, BioResources, 15, (2020), 4110-4123.
• [29]. Malekshah, R. E., Shakeri, F., Khaleghian, A., Salehi, M. “Developing a biopolymeric chitosan supported Schiff-base and Cu (II), Ni (II) and Zn (II) complexes and biological evaluation as pro-drug”, International Journal of Biological Macromolecules, 152, (2020), 846-861.
• [30]. Yasmeen, S., Kabiraz, M. K., Saha, B., Qadir, M. D., Gafur, M. D., Masum, S. “Chromium (VI) ions removal from tannery effluent using chitosan-microcrystalline cellulose composite as adsorbent”, Int. Res. J. Pure Appl. Chem., 10, (2016), 1-14.
• [31]. EL Knidri H., Belaabed R., El khalfaouy R., Laajeb A., Addaou A., A. Lahsini. “Physicochemical Characterization of Chitin and Chitosan Producted from Parapenaeus Longirostris Shrimp Shell Wastes”, Journal of Materials and Environmental Sciences, 8, (2017), 3648-3653.
• [32]. Ainali, N. M., Xanthopoulou, E., Michailidou, G., Zamboulis, A., Bikiaris, D. N. “Microencapsulation of fluticasone propionate and salmeterol xinafoate in modified chitosan microparticles for release optimization”, Molecules, 25, (2020), 3888.
• [33]. Vaezifar, S., Razavi, S., Golozar, M. A., Karbasi, S., Morshed, M., Kamali, M. “Effects of some parameters on particle size distribution of chitosan nanoparticles prepared by ionic gelation method”, Journal of Cluster Science, 24, (2013), 891-903.
• [34]. Pereira, A. G., Muniz, E. C., Hsieh, Y. L. “1H NMR and 1H–13C HSQC surface characterization of chitosan–chitin sheath-core nanowhiskers”, Carbohydrate Polymers, 123, 2015, 46-52.
• [35]. Liu, Q., Zhang, J., Li, D., Lang, J., Zai, S., Hao, J., Wang, X. “Inhibition of amphiphilic N-Alkyl-O-carboxymethyl chitosan derivatives on Alternaria macrospora”, BioMed Research International, (2018). Article ID 5236324.
• [36]. Triana-Guzmán, V. L., Ruiz-Cruz, Y., Romero-Peñaloza, E. L., Zuluaga-Corrales, H. F., Chaur-Valencia, M. N. “New chitosan-imine derivatives: from green chemistry to removal of heavy metals from water”, Revista Facultad de Ingeniería Universidad de Antioquia, (89), (2018), 34-43.
• [37]. Lin, Z., Cheng, X. “Synthesis and properties of pH sensitive carboxymethylated hydroxypropyl chitosan nanocarriers for delivery of doxorubicin”, Journal of Macromolecular Science, Part A, 58, (2021), 600-609.
• [38]. Wang, P., Lv, X., Zhang, B., Wang, T., Wang, C., Sun, J., Zhang, Y. “Simultaneous determination of molar degree of substitution and its distribution fraction, degree of acetylation in hydroxypropyl chitosan by 1H NMR spectroscopy”, Carbohydrate Polymers, 263, (2021), 117950.
• [39]. Abd El-Aziz, M. E., Morsi, S. M. M., Salama, D. M., Abdel-Aziz, M. S., Abd Elwahed, M. S., Shaaban, E. A., Youssef, A. M. “Preparation and characterization of chitosan/polyacrylic acid/copper nanocomposites and their impact on onion production”, International Journal of Biological Macromolecules, 123, (2019) 856-865.
• [40]. Al Fulaij O., Abdel-Zaher Abdelaziz E., Fakharia A. "Utility of newly modified chitosan in the removal of heavy metal ions from aqueous medium: ion selectivity, XPS and TGA." Bulletin of Materials Science, 42, (2019), 237.