分子模拟技术在壳聚糖功能材料开发和应用中的研究进展

doi:10.16085/j.issn.1000-6613.2021-2176

摘要/Abstract

摘要：

壳聚糖因其优良的生物相容性、可再生性、生物降解性以及絮凝、吸附性而被广泛应用于医药、能源、环保等领域。随着统计力学和计算机科学的快速发展，应用分子模拟研究壳聚糖材料的开发和应用已成为热点。本文综述了近年来分子模拟技术在该领域的研究进展，归纳了分子模拟的基本方法及特点，详述了以量子化学为基础的分子模拟软件Materials Studio在壳聚糖研究中的常用模块以及应用。在此基础上，介绍了利用分子模拟对壳聚糖分子结构、微观反应机理、相容性的分析与预测，以及壳聚糖在生物医用材料、燃料电池、缓蚀剂、水处理应用领域的分子模拟研究进展，总结分析了分子模拟方法在壳聚糖功能材料开发和应用中的优势以及在微观机理探索方面的不足，提出了采用多尺度模拟、与机器学习相结合等提高模拟结果准确性和计算速度的研究方法，为未来设计开发新型壳聚糖材料提供新的思路。

关键词: 壳聚糖, 分子模拟, Materials Studio, 微观机理, 材料开发, 预测

Abstract:

Chitosan is widely used in medicine, energy, environmental protection and other fields because of its excellent biocompatibility, renewability, biodegradability, flocculation and adsorption. With the rapid development of computer science and quantum chemistry, the application of molecular simulation to the development and application of chitosan materials has become a hot spot. In this paper, the research progress of molecular simulation technology in this field in recent years was reviewed, the basic methods and characteristics of molecular simulation were summarized, and the common modules and applications of quantum chemistry based molecular simulation software Materials Studio in chitosan research were described in detail. On this basis, the analysis and prediction of molecular structure, micro reaction mechanism and compatibility of chitosan by molecular simulation, as well as the research progress of molecular simulation of chitosan in the fields of biomedical materials, fuel cell, corrosion inhibitor and water treatment were introduced. The advantages of molecular simulation method in the development and application of chitosan functional materials and the shortcomings in the exploration of micro mechanism were summarized and analyzed. The research methods of using multi-scale simulation and combining with machine learning to improve the accuracy and calculation speed of simulation results were proposed, which provided a new idea for the design and development of new chitosan materials in the future.

Key words: chitosan, molecular simulation, Materials Studio, micro mechanism, material development, prediction

中图分类号:

TQ015.9

冯颖, 赵孟杰, 崔倩, 解玉鞠, 张建伟, 董鑫. 分子模拟技术在壳聚糖功能材料开发和应用中的研究进展[J]. 化工进展, 2022, 41(8): 4241-4253.

FENG Ying, ZHAO Mengjie, CUI Qian, XIE Yuju, ZHANG Jianwei, DONG Xin. Research progress of molecular simulation technology in the development and application of chitosan functional materials[J]. Chemical Industry and Engineering Progress, 2022, 41(8): 4241-4253.

图/表 12

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方法	应用	优缺点
蒙特卡洛法	应用于薄膜的生长、相变、缺陷行为、材料共混等过程的研究	计算量相对较小，误差范围易确认，但其计算结果比较粗糙，难以在原子水平上解释问题的相关过程
分子动力学	广泛用于生物大分子、纳米材料和有机高分子物质等方面的研究	计算时可以对温度、压力等外部因素进行模拟，更加逼近实际状态，且程序计算量小，计算简单
分子力学	计算众多类化合物的热力学性质、谱学参数、分子构象、确定有机物的稳定性等	计算过程借助大量经验参数，使计算过程得到简化，从而节省时间，但无法获取电子分布等微观性质
量子力学	通常用于处理较小的体系，得到分子的热力学函数及电荷密度等性质	计算精度高，但计算量大，对计算设备要求高，计算的原子通常不超过几百个，应用于大分子体系的极少

方法	应用	优缺点
蒙特卡洛法	应用于薄膜的生长、相变、缺陷行为、材料共混等过程的研究	计算量相对较小，误差范围易确认，但其计算结果比较粗糙，难以在原子水平上解释问题的相关过程
分子动力学	广泛用于生物大分子、纳米材料和有机高分子物质等方面的研究	计算时可以对温度、压力等外部因素进行模拟，更加逼近实际状态，且程序计算量小，计算简单
分子力学	计算众多类化合物的热力学性质、谱学参数、分子构象、确定有机物的稳定性等	计算过程借助大量经验参数，使计算过程得到简化，从而节省时间，但无法获取电子分布等微观性质
量子力学	通常用于处理较小的体系，得到分子的热力学函数及电荷密度等性质	计算精度高，但计算量大，对计算设备要求高，计算的原子通常不超过几百个，应用于大分子体系的极少

软件名	用途介绍	适用范围	软件特色
Hyperchem	支持半经验算法、从头算法和密度泛函理论，预测可见-紫外光谱，进行分子轨道分析、几何优化等	应用于蛋白质、酶、核酸等生物大分子，分析材料的分子构造、电子结构、轨道等	灵活性高、易操作、图形美观、初学者易操作
Gaussian	基于半经验、从头算法和密度泛函理论预测光谱特性、晶体结构、周期性体系的结构和性质	研究各种有机物、金属等体系的化学反应机理、取代效应、势能面和激发能等	集成过渡态能量和结构、分子结构和能量、原子电荷和电势、化学键和反应能量、红外和拉曼光谱模拟等多种重要功能
Materials Studio	有Universial、Compass、Forcite、Castep、Dmol3等多种力场和模块可模拟聚合、催化、结晶与衍射等多种化学过程	应用于半导体、金属及陶瓷等多种材料，分析晶体的结构及性质，能开展X射线衍射模拟	唯一可以模拟溶液、气相、固体及表面的过程及性质，同时还可以考虑溶剂化效应
LAMMPS	利用不同边界条件和势函数来模拟全原子、金属、聚合物体系，实现分子动力学计算	应用于分子动力学所涉及的领域，如金属、聚合物、全原子、生物、粗粒化体系的模拟	提供支持多种势函数、应用范围广且具有良好的并行扩展性

软件名	用途介绍	适用范围	软件特色
Hyperchem	支持半经验算法、从头算法和密度泛函理论，预测可见-紫外光谱，进行分子轨道分析、几何优化等	应用于蛋白质、酶、核酸等生物大分子，分析材料的分子构造、电子结构、轨道等	灵活性高、易操作、图形美观、初学者易操作
Gaussian	基于半经验、从头算法和密度泛函理论预测光谱特性、晶体结构、周期性体系的结构和性质	研究各种有机物、金属等体系的化学反应机理、取代效应、势能面和激发能等	集成过渡态能量和结构、分子结构和能量、原子电荷和电势、化学键和反应能量、红外和拉曼光谱模拟等多种重要功能
Materials Studio	有Universial、Compass、Forcite、Castep、Dmol3等多种力场和模块可模拟聚合、催化、结晶与衍射等多种化学过程	应用于半导体、金属及陶瓷等多种材料，分析晶体的结构及性质，能开展X射线衍射模拟	唯一可以模拟溶液、气相、固体及表面的过程及性质，同时还可以考虑溶剂化效应
LAMMPS	利用不同边界条件和势函数来模拟全原子、金属、聚合物体系，实现分子动力学计算	应用于分子动力学所涉及的领域，如金属、聚合物、全原子、生物、粗粒化体系的模拟	提供支持多种势函数、应用范围广且具有良好的并行扩展性

研究者	共混物	模拟结果	实验结果
Rakkapao等^［47］	壳聚糖、聚环氧乙烷	当聚环氧乙烷质量分数小于0.58时，二者可混溶，且相容性最大值在质量分数为0.2时模拟结果与实验结果吻合较好	最大混溶性出现在质量分数为0.2时，且聚环氧乙烷质量分数小于0.6时可得到共混物
Jawalkar等^［50］	壳聚糖、聚乙烯醇	聚乙烯醇质量分数0.5~0.9时共混物不混溶，在0.1~0.4时混溶性较好	聚乙烯醇质量分数为0.2~0.4时与壳聚糖的共混物是可混溶的
Zhang等^［37］	壳聚糖、聚己内酯	共混物的性能可通过改变聚己内酯与壳聚糖的比例来调节，比例为9∶1时，共混物会出现完全无序和均匀的相	共混物的热稳定性和机械性能随着壳聚糖含量的增加而降低，比例为9∶1时，共混物具有均匀的形态和优异的延展性