纳米金簇修饰的玻璃锥形纳米孔的仿生制备、表征和传感

发布时间：2017-12-28 11:02

本文关键词：纳米金簇修饰的玻璃锥形纳米孔的仿生制备、表征和传感　出处：《华东师范大学》2017年硕士论文　论文类型：学位论文

【摘要】：当今时代,纳米孔为解决化学、生物技术、材料科学等研究领域内棘手的问题提供了一个非常重要的平台。而以玻璃纳米孔为基础的纳米孔检测平台因其制备方便、价格便宜、紧实耐用以及孔径可调节等优势,越来越受到研究者们的重视。目前将官能团修饰到纳米孔内的策略各不相同,并且发展了一系列的检测平台用于分析核苷酸、蛋白质、金属离子等物质。这些方法虽各有优点,但都面临孔内表面性质不可控、TEM表征破坏性大等问题。本文采用温和、绿色、可控的仿生生物矿化方法,利用常见的蛋白质在几十纳米孔径的玻璃纳米孔内成功修饰上结构稳定的金薄膜。该纳米金膜具有独特的荧光特性,有利于直接通过荧光成像对玻璃纳米孔实现无破坏性的快速表征。同时该纳米金簇修饰的玻璃纳米孔,无需后续修饰新的分子,就可实现对精氨酸的对映选择性识别以及半胱氨酸的选择性检测,为玻璃纳米孔的制备、表征和生物传感提供了新的思路。全文分为四部分,具体内容如下:第一章绪论本章首先介绍了纳米孔的制备与功能化,其次着重讨论了纳米孔的表征方法。然后概述了基于纳米孔的两种检测方法以及在生物传感中的应用,最后阐明本论文主要意义和内容。第二章仿生制备与荧光表征纳米金簇修饰的玻璃锥形纳米孔本章通过层层吸附的原理,利用牛血清白蛋白(BSA)还原氯金酸(HAuC14)成功在玻璃纳米孔内壁修饰上稳定的纳米金簇。此纳米金簇的成功修饰可以通过透射电子显微镜(TEM),能量散射X射线光谱(EDX),元素映射,Ⅰ-Ⅴ曲线来证明。多功能的BSA保护的金簇薄膜(BSA-AuNCs)修饰的玻璃纳米孔可以很容易地通过荧光成像进行表征,而无任何破坏性。另外,BSA-Au薄膜在很高的盐浓度或者较宽pH范围的溶液中都很稳定。利用BSA-AuNCs潜在的生物传感应用,该纳米金簇修饰的玻璃纳米孔将在生物研究领域有更加广阔的发展空间。第三章基于纳米金簇修饰的玻璃锥形纳米孔对精氨酸的手性识别本章利用BSA分子的手性区分作用,报道了 BSA-Au薄膜修饰的玻璃纳米孔对精氨酸(Arg)对映异构体的识别。AuNCs表面的BSA包覆层中的羧基可以与Arg中的胍基通过相互作用形成离子配对。通过Zeta电位、AFM等表征,BSA-AuNCs与不同构型的Arg的作用力确实存在一定的差异。然后,通过检测离子电流,考察了 L-Arg和D-Arg引起BSA-AuNCs薄膜修饰的玻璃锥形纳米孔的离子电流的差异性变化。L-Arg和D-Arg的离子电流改变比率分别达到25%和6%。结果表明此纳米传感器可以实现对不同构型Arg的区分。第四章基于纳米金簇修饰的玻璃锥形纳米孔对半胱氨酸的选择性检测本文利用半胱氨酸(Cys)可以通过形成Au-S键修饰到Au NCs内核,基于空间位阻以及静电斥力等多方面原因,实现了 BSA-AuNCs修饰的玻璃纳米孔对Cys的选择性检测。通过Zeta电位、红外光谱等表征,证明巯基(-SH)极易连接到Au NCs表面,Cys可以弥补BSA包裹的Au NCs的表面缺陷。当Cys结合到玻璃管壁内的Au膜上时,管壁电荷发生变化,并且监测-1 V时对应的离子电流变化比达到65%。该纳米金簇修饰的玻璃锥形纳米孔对于具有类似结构的硫醇具有良好的抗干扰性。
[Abstract]:Nowadays, nanoscale provides a very important platform to solve the difficult problems in the field of chemistry, biotechnology, material science and so on. Nano hole detection platform based on glass nanopore is attracting more and more attention due to its advantages such as convenient preparation, low price, compact and durable, and adjustable pore size. The appropriate strategy to group modified nano hole is different, and the development of test platform for the analysis of a series of nucleotides, proteins, metal ions and other substances. Although these methods have their own advantages, they all face the problems of uncontrollable inner surface properties and great destructiveness of TEM. In this paper, a mild, green and controllable biomimetic biomineralization method is applied to successfully modify the gold film with stable structure in the glass nanopores with tens of nanoscale holes by using common proteins. The nano gold film has unique fluorescence characteristics, which is beneficial to the rapid characterization of glass nanoport without destruction through fluorescence imaging. At the same time, the gold nanoparticle modified glass nanopores can achieve enantioselective recognition of arginine and selective detection of cysteine without subsequent modification of new molecules. It provides a new idea for the preparation, characterization and biosensing of glass nanopores. The full text is divided into four parts. The details are as follows: the first chapter is introduction. In this chapter, we first introduce the preparation and functionalization of nanopores. Secondly, we mainly discuss the characterization methods of nanopores. Then two kinds of detection methods based on nanoscale and the application in biological sensing are summarized. Finally, the main meaning and content of this paper are clarified. The second chapter biomimetic glass conical nanopore, synthesis and fluorescence characterization of nano gold clusters modified by adsorption principle, using bovine serum albumin (BSA) reduction of chloroauric acid (HAuC14) nano gold modified nano glass inner cluster successfully in the hole stability. The successful modification of this nano gold cluster can be proved by transmission electron microscope (TEM), energy scattering X ray spectroscopy (EDX), element mapping, I - V curve. The versatile BSA protected gold cluster film (BSA-AuNCs) - modified glass nanoscale can be easily characterized by fluorescence imaging without any damage. In addition, BSA-Au films are stable in very high salt concentration or in a solution with a wide pH range. Using the potential biosensing applications of BSA-AuNCs, the nano gold cluster modified glass nanoholes will have a broader space for development in the field of biological research. The third chapter is the chiral recognition of arginine based on nano gold cluster modified glass tapered nanopores. In this chapter, the recognition of arginine (Arg) enantiomers based on BSA-Au nanoparticle modified glass nanoparticle is reported using the chiral discrimination effect of BSA molecules. AuNCs BSA on the surface of the cladding layer with Arg in carboxyl guanidine through interaction between ion pairing. There are certain differences between the forces of BSA-AuNCs and different configurations of Arg through the characterization of Zeta potential and AFM. Then, by detecting the ion current, the difference in the ion current of the conical glass nanoports modified by the BSA-AuNCs film was investigated by L-Arg and D-Arg. The rate of ion current change of L-Arg and D-Arg is 25% and 6%, respectively. The results show that the nanoscale sensor can distinguish the different configurations of Arg. The fourth chapter is based on the glass cone of nanometer gold clusters modified hole selective detection based on the use of cysteine cysteine (Cys) can be modified to Au NCs kernel by forming Au-S bonds, steric and electrostatic repulsion and many other reasons based on the BSA-AuNCs modified glass nanopore selectivity for the detection of Cys. By means of Zeta potential and infrared spectroscopy, it is proved that the sulfhydryl group (-SH) is easily connected to the surface of Au NCs, and Cys can make up the surface defects of Au NCs wrapped by BSA. When Cys is attached to the Au membrane in the glass tube wall, the charge of the tube wall changes, and the ratio of the corresponding ion current to the -1 V is 65%. The nano gold cluster modified glass conical nanoscale has good anti-interference to the similar structure of mercaptan.
【学位授予单位】：华东师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TB383.1;O657.3

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