功能银纳米团簇的合成及其性质与应用的研究

发布时间：2018-01-10 02:22

本文关键词：功能银纳米团簇的合成及其性质与应用的研究　出处：《中国科学技术大学》2015年博士论文　论文类型：学位论文

【摘要】：银纳米团簇具有优良的光学性能以及特殊的重金属敏感性,在生物标记,生物医药,重金属识别方面有着很大的应用潜质。然而银纳米团簇的研究中仍面临着很多问题和挑战：如何快速,高产率的合成原子精确的单层保护-银纳米团簇,银纳米团簇有效的表征手段,在生物应用中是否存在生物毒性以及毒性机理的研究等等。本文主要研究了银纳米团簇的合成,以及它在生物标记和毒性方面的系统研究,基于重金属检测方面的应用,并探索了利用电化学DPV方法预测银纳米粒子在细胞中的毒性大小,研究了银纳米粒子的生物毒性机理。在本文分为五章,做了以下的几个工作：第一章：单层保护贵金属纳米团簇研究进展主要介绍了贵金属纳米团簇的合成方法,以及表征手段,综述了近些年在贵金属纳米团簇合成方法方面的进展；针对贵金属纳米团簇的荧光性质以及其应用做了综述介绍,并列举了它们在生物领域的应用。第二章：一锅一团簇法合成新的银纳米团簇-Ag14(SG)11,研究了它在生物图像方面的应用以及它的生物毒性。我们通过调整反应动力学和热力学,最终通过一锅法合成了一种新的Ag14(SG)11银纳米团簇,本实验可以达到超高的产率(96%),这是目前报道的贵金属纳米团簇合成中最高产率之一。我们通过使用ESI-MS高分辨质谱,确定了银纳米团簇的分子式为Ag14(SG)11。利用核磁共振NMR测试,通过分析1D NMR和2D COSY以及HSQC,推测了Ag14(SG)11团簇可能的表面结构。Ag14(SG)11团簇具有很好的荧光性质,本文成功的利用Ag14(SG)11团簇标记了肺癌细胞A549,这是第一次报道小分子保护的银纳米团簇在生物标记中的应用。在本文中,我们系统的探索了Ag14(SG)11团簇的生物毒性,发现其毒性很小,这使得它在生物应用方面有较大的潜力。第三章：利用电化学DPV方法预测银纳米粒子的生物毒性本文中第一次提出了利用电化学DPV的方法来预测纳米粒子的毒性,根据银在DPV测试中所产生的氧化还原峰的强弱与毒性大小的关系,快速的探测到银纳米粒子对生物的毒性。尽管这种电化学的方法不能完全取代现有的传统的生物测量方法,这种DPV检测法有一些特有的优势,例如所消耗的测试时间短,操作简易,也相对廉价,这都使得它可以在实际应用中作为一个初步预测纳米粒子毒性的方法。另外,银纳米粒子所呈现的毒性具有尺寸效应,在我们的研究范围内,尺寸越小毒性越小。这也说明了银纳米团簇比银纳米粒子更具有某些生物应用的潜力。第四章：快速高产的合成新的银纳米团簇Ag30(Capt)18,并探索了它对环境中汞离子的探测。我们通过尝试改变反应方法,最终达到了快速(30分钟)和高产率(74%)的合成Ag30(Capt)18纳米团簇的方法。通过利用高分辨ESI-MS,产物的分子式被确定为Ag3o(Capt)18,通过核磁共振测试分析,对Ag3o(Capt)18团簇的表面结构进行了初步推测。Ag30(Capt)18团簇具有优异的溶解性能,可以溶于很多种类的溶剂,在被质子化后不仅仅可以溶于水,还可以溶于许多极性有机溶剂中,如乙醇,丙酮,乙腈,二氯甲烷和乙酸乙酯中。本文第一次报道通过该变测试温度排除其他离子的干扰的方法(LTM),成功用Ag30(Capt)18团簇检测环境样本中汞离子。第五章：总结与展望对我们所做的工作作出了总结,对未来工作进行展望。
[Abstract]:Silver nanoclusters has excellent optical properties and special metal sensitivity in biological markers, biological medicine, has a great potential application of heavy metal identification. However the study of silver nanoclusters still faces many problems and challenges: how fast, high yield synthesis atomic monolayer protected silver nano - precision group clusters of silver nanoclusters effectively characterized in biological applications of the existence of biological toxicity and toxicity mechanism and so on. This paper mainly studies the synthesis of silver nanoclusters, and its biological markers and the systemic toxicity study, based on the application of heavy metal detection, and to explore the toxicity by electrochemical DPV prediction method of silver nanoparticles in the cells, the biological toxicity mechanism of silver nanoparticles. In this paper is divided into five chapters, do some work as the following: Chapter One: single Research progress of protective layer of noble metal nanoclusters mainly introduces the synthesis method of noble metal nanoclusters, and characterization methods, reviews recent progress in the synthesis of noble metal nano cluster method; according to the fluorescence properties of noble metal nanoclusters and their applications were also summarized in the introduction, and illustrates their application in biological field. The second chapter: a cluster method for the synthesis of new nano silver clusters -Ag14 (SG) 11, studied its application in biological image and the biological toxicity of it. We adjust the reaction kinetics and thermodynamics, finally through one pot method and a new synthesis of Ag14 (SG) 11 silver nanoclusters, this experiment can achieve high yield (96%), which is one of the highest yield of noble metal nanoclusters synthesized reported. Our high resolution mass spectrometry by using ESI-MS, determine the sub sub silver nanoclusters for Ag14 (SG) 11. NMR NMR testing, through the analysis of 1D NMR and 2D COSY and HSQC Ag14 (SG), speculated that the surface structure of.Ag14 11 cluster possible (SG) 11 clusters have good fluorescence property, this paper successfully using Ag14 (SG) 11 cluster labeled A549 lung cancer cells. This is the first report of the application of nano silver cluster protection in biological systems. In this paper, we explore the system of Ag14 (SG) biological toxicity of 11 clusters, found its toxicity is very small, which makes it have great potential for biological applications. The third chapter: the biological toxicity prediction of silver nanoparticles using electro chemical DPV method first proposed by electrochemical method to predict the toxicity of DPV nanoparticles, according to the relationship between strength and toxicity produced by oxidation of silver in the DPV test the reduction peak, the toxicity of silver nanoparticles to rapid detection of biological. Although completely replace the traditional method of measuring the existing biological methods cannot the electrochemical detection of DPV, this method has some unique advantages, such as short test time consumption, simple operation, relatively cheap, which makes it possible in practice as a first step prediction method of nanoparticle toxicity. In addition, silver the toxicity of nanoparticles with size effect, in our studies, the smaller the toxicity is small. It also shows that the silver nanoclusters have certain biological applications than silver nanoparticles potential. The fourth chapter: the rapid synthesis of new high yield of silver nanoclusters (Capt Ag30 18), and to explore the the detection of mercury ions in the environment. We try to change the reaction method, finally achieved the rapid (30 minutes) and high yield (74%) of the synthesis of Ag30 (Capt) 18 clusters by using high resolution ESI-MS, The molecular formula of the product was identified as Ag3o (Capt) 18, by NMR test and analysis of Ag3o (Capt) surface structure of 18 clusters were inferred.Ag30 (Capt) 18 clusters have excellent solubility and can dissolve in a variety of solvents, being protonated not only can dissolve in water can dissolve in many polar organic solvents, such as ethanol, acetone, acetonitrile, dichloromethane and ethyl acetate. The method is reported for the first time through the variable temperature test to exclude other ions (LTM), with the success of Ag30 (Capt) 18 cluster detection of mercury ions in environmental samples. The fifth chapter summary and Prospect of the work that we have done a summary, for future work.

【学位授予单位】：中国科学技术大学
【学位级别】：博士
【学位授予年份】：2015
【分类号】：O614.122;TB383.1

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