壳聚糖酰基化衍生物的合成及其两亲性研究
Fabrication and Amphiphilicity of Acylated Chitosan Derivatives
摘要: 本文从壳聚糖结构特点出发，采用氨基保护法在羟基上引入长链疏水性基团合成三种不同两亲性能的壳聚糖酰基化衍生物，红外光谱(FT-IR)和核磁共振氢谱(1H NMR)证实了两亲二硬脂酰基壳聚糖酯的化学结构。利用Langmiu-Blodgett槽制备两亲二硬脂酰壳聚糖酯单分子层，通过对二硬脂酰壳聚糖酯Langmiur膜的表面压–单分子层表观面积(π-A)等温曲线分析表明，硬酯酰基取代度4.8的二硬脂酰壳聚糖酯(DSCS-4.8)具有较强的两亲性，能形成稳定致密的Langmiur单分子膜，且Langmiur单分子膜的平均单分子极限表面积等于268.75 cm2，崩溃压等于44.35 mN/m。三种二硬酯酰壳聚糖酯对水的静态接触角随着两亲性的增加而增大。通过LB技术将单分子膜转移制备多层膜修饰的硅片。
Abstract: The acylated chitosan, distearyl chitosan, was synthesized by the selective protection of amino groups in MeSO3H, and characterized by means of Fourier translation infrared spectroscopy (FT-IR), nuclear magnetic resonance hydrogen spectrum (1H NMR) and water contact angle measurements. The preparation of the distearyl chitosan monolayer was carried out and amphiphilic behavior was investigated via Langmuir technique. By analyzing surface pressure-area (π-A) isotherm, the condensed distearyl chitosan monolayer fabricated at air-water interface had a collapse pressure of 44.35 mN/m and the average limited area (A*) of 268.75 cm2, indicating the formation of the stable Langmuir monolayer. Furthermore, the distearyl chitosan monolayer was successfully transferred onto Si electrode by Langmuir-Blodgett technique.
文章引用：关怀民, 张新丽, 阚巡, 廖梦廉, 林俊炎, 童跃进. 壳聚糖酰基化衍生物的合成及其两亲性研究[J]. 化学工程与技术, 2019, 9(2): 117-125. https://doi.org/10.12677/HJCET.2019.92017

参考文献

[1] Dash, M., Chiellini, F., Ottenbrite, R.M. and Chiellini, E. (2011) Chitosan-A Versatile Semi-Synthetic Polymer in Bi-omedical Applications. Progress in Polymer Science, 36, 981-1014. [Google Scholar] [CrossRef] 
[2] Tong, Y.J., Wang, S.F., Xu, J.W., Chua, B.S. and He, C.B. (2005) Synthesis of O, O-dipalmitoyl Chitosan and Its Amphiphilic Properties and Capability of Cholesterol Abeorption. Carbohydrate Polymers, 60, 229-233. [Google Scholar] [CrossRef] 
[3] Li, X.L., Tong, Y.J., Jia, L. and Guan, H.M. (2015) Fabrication of Molecularly Cholesterol-Imprinted Polymer Particles Based on Chitin and Their Adsorption Ability. Monatshefte für Chemie, 146, 423-430. [Google Scholar] [CrossRef] 
[4] El Knidri, H., Belaabed, R., Addaou, A., Laajeb, A. and Lahsini, A. (2018) Extraction, Chemical Modification and Characterization of Chitin and Chitosan. International Journal of Bio-logical Macromolecules, 120, 1181-1189. [Google Scholar] [CrossRef] [PubMed]
[5] Mourya, V.K. and Inamdar, N.N. (2008) Chitosan-Modifications and Applications: Opportunities Galore. Reactive and Functional Polymers, 68, 1013-1051. [Google Scholar] [CrossRef] 
[6] Dufes, C., Muller, J.M., Couet, W., et al. (2004) Anticancer Drug Delivery with Transferrin Targeted Polymeric Chitosan Vesicles. Pharmaceutical Research, 21, 101-107. [Google Scholar] [CrossRef] 
[7] 李昆, 孙婷, 孙媛, 杨伯涵, 孟新雷, 李亚鹏, 王静媛. 两亲性壳聚糖衍生物的制备及其包覆量子点[J]. 高分子学报, 2012(2): 180-186.
[8] Yuan, W.Z., Zhao, Z.D., Gu, S.Y. and Ren, J. (2010) Synthesis, Characterization, and Properties of Amphiphilic Chitosan Copolymers with Mixed Side Chains by Click Chemistry. Journal of Polymer Science Part A: Polymer Chemistry, 48, 3476-3486. [Google Scholar] [CrossRef] 
[9] 隋卫平, 杨秀利, 杨倩, 陈国华. (2-羟基-3-丁氧基)丙基-羟丙基壳聚糖的应用性质[J]. 应用化学, 2002, 19(9): 890-893.
[10] Chan, P, Kurisawa, M, Chung, J.E. and Yang, Y.Y. (2007) Syn-thesis and Characterization of Chitosan-g-Poly(ethylene glycol)-Folate as a Non-Viral Carrier for Tumor-Targeted Gene Delivery. Biomaterials, 28, 540-549. [Google Scholar] [CrossRef] [PubMed]
[11] Ke, W.Y., Xin, R.L., Zhuo, L.Y., Ping, Z.L., Wang, F. and Liu, Y. (2009) Novel Polyion Complex Micelles for Liver-Targeted Delivery of Diammonium Gly Cyrrhizinate: In Vitro and in Vivo Characterization. Journal of Biomedical Materials Research Part A, 88, 140-148.23
[12] Félix, L., Hernández, J., Argüelles, W.M. and Goycoolea, F.M. (2005) Kinetics of Gelation and Thermal Sensitivity of N-isobutyryl chitosan Hydrogels. Biomacromolecules, 6, 2408-2415. [Google Scholar] [CrossRef] [PubMed]
[13] Li, M.C. and Xin, M.H. (2007) Mixed N, N-dilauryl Chitosan/Cholesterol Monolayer and Corresponding Vesicle Property. Acta Physico-Chimica Sinica, 23, 1291-1295.
[14] Wu, Y.S, Hisada, K., Maeda, S. and Sasaki, T.K. (2007) Fabrication and Structural Characterization of the Langmuir-Blodgett Films from a New Chitosan Derivative Containing Cinnamate Chromophores. Carbohydrate, 68, 766-772. [Google Scholar] [CrossRef] 
[15] Motiei, M., Kashanian, S., Lucia, L.A. and Khazaei, M. (2017) Intrinsic Parameters for the Synthesis and Tuned Properties of Amphiphilic Chitosan Drug Delivery Nanocarriers. Journal of Controlled Release, 260, 213-225. [Google Scholar] [CrossRef] [PubMed]
[16] Zhang, A.D., Ding, D., Ren, J., Zhu, X.L. and Yao, Y.H. (2014) Synthesis, Characterization, and Drug-Release Behavior of Amphiphilic Quaternary Ammonium Chitosan Derivatives. Journal of Applied Polymer Science, 131, 39890.
[17] 马宁, 汪琴, 孙胜玲, 王爱勤. 甲壳素和壳聚糖化学改性研究进展[J]. 化学进展, 2004, 16(4): 643-653.
[18] Hirano, S. and Osaka, T. (1983) Some O-Stearoyl Derivatives of Chitosan Prepared via Its Schiff’s Base Intermediates. Agricultural and Biological Chemistry, 47, 1389-1391. [Google Scholar] [CrossRef] 
[19] Mekhail, G.M., Kamel, A.O., Awad, G.A.S. and Mortada, N.D. (2012) Anticancer Effect of Atorvastatin Nanostructured Polymeric Micelles Based on Stearyl-Grafted Chitosan. International Journal of Biological Macromolecules, 51, 351-363. [Google Scholar] [CrossRef] [PubMed]
[20] Ma, G.P., Yang, D.Z., Kennedy, J.F. and Nie, J. (2009) Synthesize and Characterization of Organic-Soluble Acylated Chitosan. Carbohydrate Polymers, 75, 390-394. [Google Scholar] [CrossRef] 
[21] Zhang, H. and Neau, S.H. (2001) In Vitro Degradation of Chitosan by a Commercialenzyme Preparation Effect of Molecular Weight and Degree of Deacetylation. Biomaterials, 22, 1653-1658. [Google Scholar] [CrossRef]