金纳米粒子与蛋白质的相互作用及其应用

金纳米粒子与蛋白质间存在多种作用方式,包括物理吸附、化学共价结合以及非共价特异性吸附等.金纳米粒子表面等离子体共振效应引起可见光区的特征吸收及表面增强拉曼散射,常用来研究金纳米粒子与蛋白质间的相互作用.金纳米粒子与蛋白质间的作用与纳米粒子的尺寸、表面化学及蛋白质的大小、电荷、氨基酸残基有关.利用金纳米粒子与蛋白质的相互作用及纳米金的谱学性质,可以对疾病或环境污染进行简单、高效、低成本检测,也可用于疾病治疗.     

CdS纳米粒子与半胱氨酸相互作用的研究

合成了粒径均匀和分散性好的CdS纳米粒子.通过改变CdS纳米粒子及半胱氨酸的浓度、体系的pH值及CdCl2和CH3CSNH2摩尔比等实验条件跟踪监测了CdS纳米粒子光谱性质的变化,探讨了CdS纳米粒子与半胱氨酸之间的相互作用及化学反应机理.     

纳米颗粒与蛋白质分子的相互作用

纳米技术的快速发展和广泛应用前景,引起了人们对纳米生物效应和安全性问题的普遍关注。为保证纳米技术的健康持续发展,纳米颗粒与生物体的相互作用以及产生的生物学效应不容忽视。为充分了解纳米颗粒物产生的生物学效应,阐明纳米颗粒如何进入生物体以及与生物体相互作用的分子过程至关重要。在总结国内外相关研究的基础上,本文介绍了纳米颗粒进入机体的主要途径,并系统综述了纳米颗粒与蛋白质分子的相互作用及其表征方法,以及纳米颗粒与蛋白质相互作用对蛋白质结构功能和纳米颗粒生物效应的影响。     

粒子-聚合物相互作用与粒子-粒子相互作用对聚合物基纳米复合物力学性能的影响

聚合物基纳米复合物(PNCs)具有比传统高分子材料更加优异的光学、力学、热力学等性能,广泛应用于各个工程领域.而纳米粒子(NPs)对材料性能提高的机理则是当前聚合物纳米复合物领域研究的重要问题,聚合物纳米复合体系相互作用的影响因素众多,至今尚未明确并完整建立复合体系相互作用与性能增强之间的关系.本文总结了近年来关于纳米粒子填充聚合物基体力学性能的研究,从粒子-聚合物相互作用和粒子-粒子相互作用角度阐述了聚合物纳米复合体系力学性能的增强机理,并根据体系中不同的结构关系分别总结了聚合物/未改性纳米粒子复合体系和聚合物/聚合物接枝纳米粒子复合体系中影响力学性能的因素.该部分内容具有重要的理论和实践意义,有助于构建复合体系微观结构与宏观性能之间的关系,进而对微观层面调控PNCs的力学性能提供指导.     

荧光光谱法研究金纳米粒子和槲皮素及牛血红蛋白的相互作用

本文采用荧光光谱法研究了磷酸缓冲溶液(PBS,pH 7.2)中有无金纳米粒子(AuNP)共存时槲皮素(Qct)与牛血红蛋白(BHb)的相互作用,评估了共存AuNP对Qct和BHb的荧光猝灭效应及对Qct-BHb作用的影响。测得了不同温度下Qct-BHb结合反应的平衡常数K和结合摩尔比n,并由所得热力学常数确定了结合的作用力类型。根据F rster偶极-偶极无辐射能量转移理论,求得了Qct-BHb作用的分子间距离r=2.68 nm和能量转移效率E=0.232。     

金纳米粒子与单链DNA的相互作用

研究了金纳米粒子与单链DNA在不同pH值时的相互作用以及金纳米粒子与不同碱基序列单链DNA的相互作用. 结果表明, 在pH为12.6的强碱性条件下, 单链DNA能使金纳米粒子稳定分散在溶液中; 在pH为1.4的强酸性条件下, 单链DNA能保护金纳米粒子不发生融合, 而只发生团聚, 且团聚现象具有可逆性. 不同寡核苷酸对金纳米粒子的亲和力按poly dA>poly dC>poly dT的顺序依次减弱. 单链DNA对纳米金的保护作用强度与单链DNA的长度成正比.     

贵金属纳米粒子修饰碳纳米管的研究

碳纳米管具有独特的一维管状结构和优异的电、光、热和力学性能,是药物和纳米催化剂的理想载体。将具有独特光、电、磁和催化性能的贵金属纳米粒子负载在碳纳米管的表面,形成的碳纳米管/贵金属纳米粒子复合物不仅兼有两种纳米材料的优异性能,还可能产生新的特性,在催化、储能、燃料电池、电子器件和传感器等领域均有广阔的应用前景。本文主要从共价修饰和非共价修饰两种策略出发,综述了贵金属纳米粒子修饰碳纳米管的制备方法和研究进展。其中用天然高分子包覆的碳纳米管表面具有很好的贵金属配位结合能力,得到的纳米复合物具有良好的水分散性和生物相容性,在载药、生物传感器和肿瘤诊断治疗等生物领域具有明显的优势。     

荧光碳纳米粒子与纸张的相互作用及分析特性研究

在研究荧光碳纳米粒子与纸质材料相互作用的基础上,考察了荧光碳纳米粒子从纸质材料表面的洗脱去除方法以及残留荧光碳纳米粒子对纸质材料的性能如抗老化能力、机械强度等的影响,提出了一种可基于荧光碳纳米粒子原位、无损传感纸张表面pH的新方法,并测定了纸质文物表面的pH。     

纳米金粒子与R-藻红蛋白的相互作用

以NaBH4为还原剂, 采用化学还原法制备了纳米金溶胶, 发现以pH=7的金前驱液还原得到的纳米金粒子具有最强的紫外吸收(525 nm), 当以聚乙烯吡咯烷酮(PVP)为稳定剂时, 此吸收紫移到510 nm. TEM观察金粒子大小为5~8 nm. PVP、聚乙烯醇(PVA)和吐温-80等能较好地稳定纳米金粒子, 而十二烷基苯磺酸钠、PEG-1000和OP乳化剂等则没有稳定作用. 以紫外-可见光谱(UV-Vis)、X光荧光光谱(XRF)、透射电子显微镜(TEM)等研究了纳米金粒子与R-藻红蛋白的相互作用, 发现R-藻红蛋白本身对纳米金粒子具有良好的稳定作用. 当R-藻红蛋白与纳米金粒子共存时, R-藻红蛋白所具有的538 nm吸收带强度有所增强, 并发生紫移, 同时578 nm的荧光强度也明显减弱, 这表明R-藻红蛋白与纳米金粒子的相互作用对R-藻红蛋白的空间结构产生了影响, 导致位于R-藻红蛋白外缘藻红素发色团(PEB)的微环境发生了改变. 凝胶柱层析及分光光度分析结果进一步证实了金纳米粒子与藻红蛋白存在明显的相互作用, 这种相互作用可能与藻红蛋白分子中所包含的氨基基团有关.     

金纳米粒子的微波法合成及在蛋白质检测中的应用

通过对微波反应器中氯金酸和柠檬酸钠混合物进行直接加热,快速、一步合成了金纳米粒子.通过调节反应初始混合物中氯金酸与柠檬酸钠的比例,可获得不同粒径窄分散的金纳米粒子.进一步将所合成的金纳米粒子功能化,考察了其在蛋白质检测中的应用.     

利用泰勒分析和动态涂层毛细管电泳系统快速测定蛋白质的扩散系数

以泰勒分散理论为基础, 首次采用动态涂层毛细管来准确和快速测定蛋白质分子的扩散系数.     

Diffusion Coefficients for Binary, Ternary, and Polydisperse Solutions from Peak-Width Analysis of Taylor Dispersion Profiles

Binary mutual diffusion coefficients D can be estimated from the width at half height W _1/2 of Taylor dispersion profiles using D=(ln 2)r ² t _R/(3W ² h) and values of the retention time t _R and dispersion tube radius r. The generalized expression D _h=−(ln h)r ² t _R/(3W ² _h ) is derived to evaluate diffusion coefficients from peak widths W _h measured at other fractional heights (e.g., (h = 0.1, 0.2,…,0.9). Tests show that averaging the D _h values from binary profiles gives mutual diffusion coefficients that are as accurate and precise as those obtained by more elaborate nonlinear least-squares analysis. Dispersion profiles for ternary solutions usually consist of two superimposed pseudo-binary profiles. Consequently, D _h values for ternary profiles generally vary with the fractional peak height h. Ternary profiles with constant D _h values can however be constructed by taking appropriate linear combinations of profiles generated using different initial concentration differences. The invariant D _h values and corresponding initial concentration differences give the eigenvalues and eigenvectors for the evaluation of the ternary diffusion coefficient matrix. Dispersion profiles for polymer samples of N i-mers consist of N superimposed pseudo-binary profiles. The edges of these profiles are enriched in the heavier polymers owing to the decrease in polymer diffusion coefficients with increasing polymer molecular weight. The resulting drop in D _h with decreasing fractional peak height provides a signature of the polymer molecular weight distribution. These features are illustrated by measuring the dispersion of mixed polyethylene glycols.     

Measurements of binary diffusion coefficients for metal complexes in organic solvents by the Taylor dispersion method

Infinite dilution binary diffusion coefficients, D₁₂, of ferrocene, 1,1′-dimethylferrocene and ethylferrocene in hexane, cyclohexane and ethanol at 313.2 K and pressures from 0.2 to 19 MPa, in acetonitrile at 298.2–333.2 K and 0.2 MPa, and various metallic acetylacetonate, acac, complexes such as Co(acac)₃, Ru(acac)₃, Rh(acac)₃, Pd(acac)₂ and Pt(acac)₂ mainly in ethanol at 313.2 K and 0.2 MPa were measured by the Taylor dispersion method. The D₁₂ values in m² s⁻¹ for the three ferrocenes in the present study and those of ferrocene and 1,1′-dimethylferrocene in supercritical carbon dioxide in our previous studies were represented by the modified hydrodynamic equation over a wide range of viscosity: M^0.5D₁₂/T = 1.435 × 10⁻¹³η^−0.8446 with average absolute relative deviation of 2.40% for 316 data points, where M is the solute molecular weight, T is the temperature in K, η is the solvent viscosity in Pa s. Although the D₁₂ values for the acac complexes were roughly represented by the above hydrodynamic equation, the accuracies were lower because they were dependent on not solute molecular weight but the number of acac ligand in the complex molecules.     

Quantification of Structural Integrity and Stability Using Nanograms of Protein by Flow-Induced Dispersion Analysis

In the development of therapeutic proteins, analytical assessment of structural stability and integrity constitutes an important activity, as protein stability and integrity influence drug efficacy, and ultimately patient safety. Existing analytical methodologies solely rely on relative changes in optical properties such as fluorescence or scattering upon thermal or chemical perturbation. Here, we present an absolute analytical method for assessing protein stability, structure, and unfolding utilizing Taylor dispersion analysis (TDA) and LED-UV fluorescence detection. The developed TDA method measures the change in size (hydrodynamic radius) and intrinsic fluorescence of a protein during in-line denaturation with guanidinium hydrochloride (GuHCl). The conformational stability of the therapeutic antibody adalimumab and human serum albumin were characterized as a function of pH. The simple workflow and low sample consumption (40 ng protein per data point) of the methodology make it ideal for assessing protein characteristics related to stability in early drug development or when having a scarce amount of sample available.     

Evaluation of transversal and longitudinal dispersion in a flow injection system by exploiting laser induced fluorescence: influence of flow-cell positioning

A fully mechanized set-up was built for the experimental determination of bi-dimensional dispersion with high spatial resolution (2400 μm²). Gravitational and wall effects in a single stream were evaluated by using time-based sampling and a micro-flow cell. Vertical upward and downward flows as well as horizontal flows were investigated. Ethylene glycol (MEG) and Rhodamine B in MEG were used as carrier and sample solutions, respectively. Longitudinal profiles were obtained by laser induced total fluorescence (LIF) at up to 19 transversal sites and combined to generate high-resolution bi-dimensional profiles. A two frontal maxima pattern was observed for all flows. The volumetric fraction of RB shape was highly stretched for downward flow and there was high asymmetry for horizontal flow. The sensitivity of three dispersion parameters was evaluated: maximum peak value, peak half-width at half-height, and peak area.Data modeling showed that the tanks-in-series was more sensitive to wall effects, had good adjustment with only one tank for upward and horizontal flow and needed two tanks for downward flow which was attributed to the latter having higher dispersion. A black box empirical modeling described better the gravitational effect and allowed to identify a parameter sensitive to upward and downward flow as well as hinting to two inner streams within the horizontal flow. It also pointed to a wall dispersion contribution of twice that of the liquid-liquid dispersion.     

流动注射分析法响应曲线的方差和样品分散

根据串联釜模型，考察了响应曲线的方差与各变量（反应管长，载流流速和进样体积）间的关系以及方差与相应分散系数的关系。只有在载流流速和进样体积一定时，才能以方差表征分散系数。     

利用Schliteren效应考察流动注射分析系统中扩散作用对溶液分散的影响

本文利用FIA系统中四氯化碳、葡萄糖、氯化钠和盐酸溶液的Schlieren效应响应曲线，考察了扩散作用对溶液分散行为即对响应曲线形状、样品运行时间、保留时间及基线-基线峰宽的影响。通过分析表明，实验结果与理论是一致的     

有机物在超临界二氧化碳中的无限稀释扩散系数的测定

利用经改造的超临界流体色谱仪测定不同温度和压力下苯、丙酮在超临界二氧化碳中的无限稀释扩散系数,开发出一个针对本科高年级学生的开放性实验,旨在加深学生对超临界流体及其性质的理解。在熟悉超临界流体色谱仪的工作原理、结构及其应用并掌握其操作方法的基础上,拓展学生视野和思维的深度及广度,提升学生的实验操作技能,培养高素质化学人才。     

Complications in the Use of the Taylor Dispersion Method for Ternary Diffusion Measurements: Methanol + Acetone + Water Mixtures

The Taylor dispersion technique is used to measure the ternary mutual diffusion coefficients of aqueous nonelectrolyte solutions at 25°C. The dispersion of the injected solutes is recorded by a differential refractometer and an ultraviolet-visible detector. The diffusion coefficients are calculated directly by fitting the theoretical dispersion equations to about six experimental curves simultaneously. If the ternary diffusion effects in the measured dispersion profiles are not confused by the inaccuracy of the experimental method or an unfavorable relative detector sensitivity, the diffusion coefficients are precise. For the system methanol + acetone + water, it is shown that the Taylor dispersion method is unsuitable for the determination of all the diffusion coefficients if the methanol mole fraction is less than 0.45 or the acetone mole fraction if more than 0.001.