原子力显微镜在纳米生物材料研究中的应用

在过去的20年里,原子力显微镜(AFM)在纳米生物材料领域有着广泛的应用。AFM可有力地揭示纳米生物材料的表面结构与力学性质,并且可作为纳米加工工具对其进行操作与处理。本文综述了AFM在纳米生物材料中的最新应用进展,包括纳米生物材料的成像与表征,力学性能测量和纳米加工。AFM可用来观察纳米生物材料的表面形貌并对其特征高度和表面粗糙度进行分析,还可对其动态过程进行原位观察。通过AFM相图还可得到有时候高度图无法获取的一些表面特征。AFM力曲线可用于测量针尖与纳米生物材料之间的黏附力及分子内外的相互作用力。AFM纳米压痕技术可用来测量材料的相关力学性质(弹力,杨氏模量,硬度,纳米断裂行为等)。此外,AFM也已经被探索用于精准、可控、可重复地加工纳米生物材料。总之,作为一个强大的纳米技术工具,AFM已成为纳米生物材料相关研究领域的一个理想的表面分析和表面加工工具。     

无机纳米晶-生物界面作用的分子机制

无机纳米晶材料以其独特的光、电、磁、力学性质,成为疾病诊断与治疗功能的关键材料.本文总结了无机纳米晶的表面化学活性、离子释放性、晶相结构、晶格缺陷、表面吸附和表面修饰等与尺寸相关的理化性质与生物效应之间的关系.综述了无机纳米晶与蛋白质、磷脂生物膜间的界面相互作用,探讨了纳米晶-生物界面作用的分子机理.这有助于理解无机纳米晶的生物行为和毒理性质,指导设计安全、高效的纳米晶生物医学材料.     

金属配合物分子纳米结构构筑与调控的STM研究进展

金属配合物分子具有结构多样且可控以及功能丰富等特点,在催化、传感、分子识别、纳米器件等领域得到广泛应用, 对金属配合物分子的研究已是分子科学研究中的热点之一.同时, 利用配合物分子构筑表面分子纳米结构以及对配合物单分子性质的研究也日趋活跃. 近年来, 本研究组发展了配合物分子在固体表面的自组装技术, 并结合扫描隧道显微技术(STM)开展了一系列有关金属配合物分子表面纳米结构的研究工作, 在固体表面成功实现了对配体、配合物分子的高分辨STM成像、原位配合以及分子识别, 设计和构筑了多种功能配合物分子纳米结构,并系统研究了结构形成规律. 本文以本研究组近年来有关金属配合物分子组装的研究结果为主, 结合国内外相关研究小组的研究结果,综述有关金属配合物分子纳米结构的构筑与调控的STM研究进展, 介绍该类分子在固体表面的组装和分散规律, 为表面分子纳米结构的构筑和调控提供理论和实验基础.     

金属表面分子纳米结构的构筑及性质研究

结合近期研究工作, 简要介绍了在溶液环境下, 利用有机分子在金属表面构筑纳米结构, 利用光化学反应方法调控所得的纳米结构, 利用电化学扫描隧道显微镜对这些结构进行观察, 及利用毛细管隧道结方法测量纳米结构电学性质的相关结果. 并展望了表面纳米结构的构筑、控制和性质研究领域的发展趋势.     

金核银壳纳米粒子薄膜的制备及SERS活性研究

采用柠檬酸化学还原法制备金溶胶, 通过自组装技术在石英片表面制备金纳米粒子薄膜, 在银增强剂混合溶液中反应获得金核银壳纳米粒子薄膜. 用紫外-可见吸收光谱仪和原子力显微镜(AFM)研究了不同条件下制备的金核银壳纳米粒子薄膜的光谱特性和表面形貌, 并以结晶紫为探针分子测量了金核银壳纳米粒子薄膜的表面增强拉曼光谱(SERS). 结果表明, 金纳米粒子薄膜的分布、银增强剂反应时间的长短对金核银壳纳米粒子薄膜的形成均有重要影响. 制备过程中, 可以通过控制反应条件获得一定粒径的、具有良好表面增强拉曼散射活性的金核银壳纳米粒子薄膜.     

金纳米晶制备和表面修饰中的分子配体

配体在纳米晶的制备和表面功能化过程中起着至关重要的作用。本文对金纳米晶制备和表面修饰中常见的分子配体,如柠檬酸根、巯基化合物、表面活性剂、树枝状分子、生物分子等的研究进展进行了概述。重点介绍了不同分子配体在金纳米晶尺寸形貌控制及表面功能化等方面的特点和作用,并对相关研究领域未来的发展趋势进行了展望。     

碳纳米纤维与环氧树脂单体相互作用的分子动力学模拟

利用分子动力学模拟方法,以双酚A型环氧树脂(DGEBA)和异佛尔酮二胺(IPD)分子为研究对象,对环氧树脂单体体系与碳纳米纤维表面之间的相互作用进行了分析.研究结果表明,环氧树脂单体分子受到碳纳米纤维的吸引作用,能够在碳纳米纤维表面形成了浓度较高的界面相,且在界面相内IPD分子浓度高于其体相浓度,而DGEBA分子浓度低于其体相浓度;界面相内,DGEBA的分子结构更加伸展,而IPD分子结构未发生明显变化;碳纳米纤维表面能够抑制界面相内单体分子的运动,其中在垂直于表面方向上的抑制作用最强.通过分析单体分子的结合能密度可知,碳纳米纤维与IPD分子的结合强度大于其与DGEBA分子的结合强度,这与前面的结果相吻合.     

水溶液中碳纳米管的表面增强拉曼光谱研究

合成了碳纳米管和金纳米颗粒的复合物, 测量了水溶液相中复合物的表面增强拉曼光谱, 结果表明, 碳纳米管的巯基化修饰可以提高碳纳米管与金纳米颗粒复合的效率, 随着金纳米颗粒负载量的增加, 碳纳米管的拉曼信号逐渐增强. 加入己二胺分子可以减小金纳米颗粒之间的距离使表面增强效应更显著, 碳纳米管的拉曼光谱得到进一步的增强. 还可进一步在复合体系中加入对巯基苯胺和罗丹明B等小分子拉曼探针, 利用金纳米颗粒的表面增强效应, 这种多元复合体系有望作为多通道拉曼成像探针材料.     

基于分子间相互作用的纳米尺度分子传递

纳米尺度下的分子传递是以纳米先进材料为导向的材料化学工程学科所面临的关键科学问题之一.借鉴分子热力学的建模研究思路研究分子传递,从分子之间相互作用出发,结合分子模拟技术,有望最终建立理论模型,实现分子传递的定量预测.本文通过几个研究实例初步探索了如何从分子间相互作用出发开展纳米尺度下分子传递的研究,利用分子模拟手段解析纳米尺度下特殊的微结构,并以此为基础进而实现对分子传递行为的调控和预测,指导具有丰富纳米结构的膜材料以及催化材料的设计和应用.     

Cu2O/Ag纳米复合物的表面增强拉曼光谱

用一种简单的化学还原方法制备了银纳米粒子包覆的氧化亚铜（Cu2O）纳米复合物。扫描电子显微镜显示Cu2O 为八面体型的纳米粒子,表面光滑,结构对称。包覆的Ag部分占据Cu2O粒子表面。通过比较Ag/Cu2O纳米复合物、Ag溶胶及Cu纳米粒子表面吸附的4-巯基吡啶（4-Mpy）分子表面增强拉曼光谱（SERS）发现,利用此方法得到了Cu2O粒子表面吸附分子的拉曼光谱。银纳米粒子所产生的电磁场增强又增强了吸附在Cu2O上的4-Mpy拉曼信号。这种方法为初步研究Cu2O表面吸附分子性质提供了依据,扩宽了SERS的使用范围,使SERS应用在纳米半导体材料上成为可能。     

A Surface Masking Technique for the Determination of Plasma Polymer Film Thickness by AFM

A method for the determination of coating film thicknesses at nanometer resolution based on surface masking and atomic force microscopy (AFM) is described. A polymeric mask is used to cover part of a substrate during the deposition of thin polymeric coatings by plasma polymerization, allowing the production of well defined polymer steps of heights of a few tens of nanometers. Tapping mode AFM has been employed to analyze the topography of these steps at high resolution. This method has also allowed accurate measurement of the kinetics of the deposition of plasma polymer films over a range of exposure times. XPS analysis of different substrate surfaces following mask removal found barely detectable residues, suggesting that the underlying surface chemistry remains unchanged, and accessible for further modification. In combination with quartz crystal microgravimetry, the method has been applied to the measurement of the density of plasma polymer coatings in the thickness range 4–50 nm.     

Activity study of self-assembled proteins on nanoscale diblock copolymer templates

Novel methods for affixing functional proteins on surfaces with high areal density have the potential to promote basic biological research as well as various bioarray applications. The use of polymeric templates under carefully balanced thermodynamic conditions enables spontaneous, self-assembled protein immobilization on surfaces with spatial control on the nanometer scale. To assess the full potential of such nanometer-scale protein platforms in biosensing applications, we report for the first time the biological activity of proteins on diblock copolymer platforms. We utilized horseradish peroxidase, mushroom tyrosinase, enhanced green fluorescent protein, bovine immunoglobulin G, fluorescein isothiocyanate conjugated anti-bovine IgG, and protein G as model systems in our protein activity studies. When specific catalytic functions of HRP and MT, immobilized on selective domains of microphase-separated PS-b-PMMA, are evaluated over a long period of time, these enzymes retain their catalytic activity and stability for well over 3 months. By performing confocal fluorescence measurements of self-fluorescing proteins and interacting protein/protein systems, we have also demonstrated that the binding behavior of these proteins is unaffected by surface immobilization onto PS-b-PMMA diblock copolymer microdomains. Our polymer platforms provide highly periodic, high-density, functional, stable surface-bound proteins with spatial control on the nanometer scale. Therefore, our diblock copolymer-guided protein assembly method can be extremely beneficial for high-throughput proteomic applications.     

表面自由基链转移反应制备超萍聚合物膜

研究了通过自由基链转移反应原位接枝聚合物膜。所得聚合物膜经红外（FT- IR）、X射线光电子能谱（XPS）、原子力显微镜（AFM）、接触角及椭圆偏光测量 进行了表征。两种单体如苯乙烯/甲基丙烯酸甲酯共聚合时,改变单体对的组成, 可以得到不同亲水亲油性质的表面。     

Polymer scrambling: macromolecular radical crossover reaction between the main chains of alkoxyamine-based dynamic covalent polymers

A novel polymer hybridization method, "polymer scrambling", was developed on the basis of the macromolecular radical crossover reaction between the main chains of dynamic covalent polymers. The macromolecular crossover reaction was successfully monitored by GPC and NMR measurements. The present methodology is innovative for the preparation of novel polymer hybrid materials at the nanometer scale.     

Extruder processing for nanoblends and nanocomposites

Structuring multiphase polymer materials to a micrometer scale (micro-structuration) is a facile engineering practice. However, structuring them to a nanometer scale (nano-structuration) is a formidable engineering challenge. In this paper, it is shown first why traditional extruder compounding processes only lead to micro-structuration and then how one may use the extruder type of mixer to structure multiphase polymer materials at a nano-meter scale to obtain nanostructured polymer blends (nanoblends) and nanostructured polymer composites (nanocomposites).     

Single‐molecule imaging of photodegradation reaction in a chiral helical π‐conjugated polymer chain

How does the chemical reaction of a single polymer chain progress? This question is not proven, as long as it is studied the data of the ensemble average from the large number of molecules. In this study, we succeeded for the first time in the direct measurement of when, where, and how the chemical reaction of a polymer chain proceeds on a nanometer scale. That is, single‐molecule imaging of the photodegradation reaction of a chiral helical π‐conjugated polymer following laser irradiation of 405 nm was conducted. Analysis of the chemical kinetics showed that the photodegradation of the single polymer chain proceeded stepwise as a quantum phenomenon. When the motility of the chain‐end increased, reactivity of the photodegradation increased. It was also discovered that the photodegradation of the polymer chain proceeded continuously in one direction, like the “domino effect.” Our method allowed dynamic imaging of single polymer chains at a solid/liquid interface, and hence can be applied to the study of many types of polymers. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 4103–4107, 2010     

纳米级功能聚苯乙烯粒子组成研究

以聚过氧化物 (PPX)为引发剂和乳化剂制备纳米级聚苯乙烯粒子 .采用溶解溶胀法、红外光谱 (IR)、差示扫描量热分析 (DSC)、薄层色谱分离 (TLC)等测试手段对所制备聚苯乙烯 (PS)粒子的化学组成及其结构进行了研究 .结果发现PS纳米粒子主要由含有一定量未分解过氧化基团的PS PPX交联大分子组成 ,为进一步制备具有特殊性能的核 /壳结构高聚物奠定了基础 .     

Facile measurement of polymer film thickness ranging from nanometer to micrometer scale using atomic force microscopy

As many properties of polymer thin films critically depend on their thickness, a convenient and cost‐effective method for precise measurement of film thickness in a wide range is highly desirable. Here, we present a method which enables polymer film thickness, ranging from nanometer to micrometer scale, to be facilely determined by measuring the height of an artificially created film step on smooth substrates with atomic force microscopy (AFM). Three polymeric films (polystyrene, poly(methyl methacrylate) and poly(styrene–ethylene/butylene–styrene) films), spin‐coated on either mica or quartz substrate with thickness ranging from 5.7 nm to 4.4 µm, were employed to demonstrate the procedure and feasibility of our method. The proposed method is particularly suitable for thicker polymer films, thus complementing the traditional AFM ‘tip‐scratch’ method which is generally limited to polymer films of no more than 100 nm thickness. Copyright © 2010 John Wiley & Sons, Ltd.     

Fibronectin adsorption on tantalum: the influence of nanoroughness

The complex mechanisms of protein adsorption at the solid-liquid interface is of great importance in many research areas, including protein purification, biocompatibility of medical implants, biosensing, and biofouling. The protein adsorption process depends crucially on both the nanoscale chemistry and topography of the interface. Here, we investigate the adsorption of the cell-binding protein fibronectin on flat and nanometer scale rough tantalum oxide surfaces using ellipsometry and quartz crystal microbalance with dissipation (QCM-D). On the flat tantalum oxide surfaces, the interfacial protein spreading causes an increase in the rigidity and a decrease in the thickness of the adsorbed fibronectin layer with decreasing bulk protein concentration. For the tantalum oxide surfaces with well-controlled, stochastic nanometer scale roughness, similar concentration effects are observed for the rigidity of the fibronectin layer and saturated fibronectin uptake. However, we find that the nanorough tantalum oxide surfaces promote additional protein conformational changes, an effect especially apparent from the QCM-D signals, interpreted as an additional stiffening of the formed fibronectin layers.     

表面富集季胺盐的交联聚苯乙烯微球合成与表征及其溶胀行为研究

在聚合物微球表面引入不同的基团 (如亲水性的羟基或羧基 ) ,可以改善聚合物微球的稳定性甚至生物相容性[1～ 4] ;利用表面基团可以把无机半导体微粒和功能有机分子以及生物分子引入聚合物微球[5～ 8] ,赋予聚合物微球特殊的性能 ,使其广泛应用于涂料、光电功能材料和生物医用材料等领域[9～ 15] .其中 ,表面带有阳离子的聚合物微球在絮凝剂、胶粘剂、水性涂料等方面已经得到广泛研究[16～ 2 0 ] .通常阳离子聚合物微球可以根据不同的需要利用常规乳液聚合、核壳乳液聚合等方法来合成 .亲水性和疏水性单体进行的无皂乳液聚合[2 1] ,因其能在…