论文总字数：16483字

摘 要

本文基于层层自组装（LBL）和仿生矿化法原理，采用壳聚糖、海藻酸钠和二氧化硅为原料，通过制备设计不同尺度的具有“壳-壳”结构的杂化微胶囊，表征微胶囊的外观形态、组成成分和结构，为多酶系统的构建奠定基础。主要研究内容如下：

1. 以CaCO₃为核心模版，通过添加晶型调节剂羧甲基纤维素（CMC）和不断搅拌，使核心达到接近理想的圆球形；以壳聚糖和海藻酸钠为层层自组装的囊壁材料，交替包裹核心5/6层；以调节pH至中性的硅酸钠作为仿生硅化壳的材料进行硅化，制备出LBL杂化微胶囊。
2. 以壳聚糖、海藻酸钠和LBL杂化微胶囊为材料，采用滴定法制备得到白色球形大胶囊，进行分隔式多酶系统的尝试构建。
3. 通过扫描电镜和红外光谱法对杂化微胶囊进行表征。扫描电镜表征的结果表明，核心模版得到成功的固定化，微胶囊粒径均一，存在一定的团聚现象。红外光谱表征的结果表明，微胶囊的纯度较好，构成囊壁材料的高分子之间可能存在羟基缔合。

关键词：杂化微胶囊 层层自组装 仿生矿化

Preparation of enzyme immobilized hybrid microcapsules

Abstract

This paper is based on the principle of layer by layer self-assembly and biomimetic mineralization. Chitosan, sodium alginate and silica are adopted as raw materials. By designing hybrid microcapsules with "shell-shell" structure at different scales, characterizing appearance form，composition and structure of micro capsule, we can lay the foundation for the construction of multi enzyme system. The main research contents are as follows:

(1)With CaCO₃ as the core template, by adding crystal modulators of carboxymethyl cellulose (CMC) and constantly stirring, so that the core can be close to ideal spherical shape. With chitosan and alginate as the layer by layer self-assembly of the capsule wall material, microcapsules are alternately wrapped core 5/6 layers. With regulating pH to neutral sodium silicate as the material of bionic shellto do the siliconization. Then, I get the LBL hybrid microcapsules.

(2)With chitosan, sodium alginate and LBL hybrid microcapsules as materials, I use titration method to get big white spherical capsules, as the attempt of constructing partition type multi enzyme system.

(3) By scanning electron microscope and infrared spectrum, the hybrid microcapsules were characterized. The results of electron microscope show that the core template has been successfully immobilized with some agglomeration phenomena. The size of microcapsules was uniform. The results of infrared spectrum show that The purity of the microcapsule is good, and there may be hydroxy hssociation between the polymer and the polymer.

Keyword: Hybrid microcapsule; Layer by layer self-assembly; biomimetic mineralization

目录

摘 要 I

Abstract II

目录 III

第一章 文献综述 1

1.1固定化酶的研究进展 1

1.1.1酶的固定化的方法 1

1.1.2酶的固定化载体 2

1.2辅酶的研究进展 4

1.2.1辅酶介绍 4

1.2.2辅酶固定化存在的问题 4

1.3层层自组装法 4

1.3.1层层自组装的基本原理 4

1.3.2自组装模板 5

1.3.3囊壁材料 6

1.3.4自组装驱动力 6

1.4仿生矿化法 7

1.4.1生物矿化的概念 7

1.4.2生物矿化用于杂化酶固定化载体的制备 7

1.5本课题的研究思路图示 8

第二章 实验部分 9

2.1试剂与仪器 9

2.1.1试剂 9

2.1.2仪器 9

2.2 组装模板与囊壁材料的制备 10

2.2.1壳聚糖的醋酸溶液制备 10

2.2.2海藻酸钠溶液的制备 10

2.2.3 CaCO₃核心的制备 10

2.3层层自组装（LBL）微胶囊制备 11

2.4仿生硅化壳的合成 11

2.5分隔式多酶系统的尝试构建 11

2.6样品的性能表征 11

2.6.1微胶囊形态观察 11

2.6.2红外光谱测定 12

第三章 结果与讨论 13

3.1微胶囊形态观察 13

3.1.1光学显微镜图片 13

3.1.2扫描电镜图片 15

3.2杂化微胶囊的红外表征 16

第四章 结论和展望 18

参考文献 19

致谢 22

第一章 文献综述

1.1固定化酶的研究进展

酶是具有生物催化功能的高分子物质，它有着高效性、专一性、多样性、温和性、活性可调节性等各种优点，应用领域广泛，涉及工业生产、医药治疗和食品加工等各方面。而与自然游离的酶相比，固定化酶又具有如下优势^[1]：

一、可以做成各种形状，便于连续、反复使用

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