石英晶体微天平在高分子研究中的应用

石英晶体微天平(QCM)作为一种强有力的表征工具已被广泛应用于高分子研究之中.本文中,作者介绍了QCM的发展简史、基本原理以及实验样品制备方法 .在此基础上,介绍了如何基于带有耗散测量功能的石英晶体微天平(QCM-D)及相关联用技术研究界面接枝高分子构象行为、高分子的离子效应以及高分子海洋防污材料,展示了QCM-D技术在高分子研究中的广阔应用前景. QCM-D可同时检测界面高分子薄膜的质量变化和刚性变化,从而反映其结构变化.与光谱型椭偏仪联用后,还可同步获取界面高分子薄膜的厚度变化等信息,可以有效解决相关高分子研究中的问题.希望本文能够对如何利用QCM-D技术开展高分子研究起到一定的启示作用,使这一表征技术能够为高分子研究解决更多问题.     

耗散型石英晶体微天平在生物医用高分子材料中的应用

石英晶体微天平(QCM)是一种基于石英晶体压电效应的分析检测技术,可实时在线提供石英晶体表面吸附层质量、厚度、粘弹性等信息,由此获得表面分子相互作用关系。 耗散型石英晶体微天平(QCM-D)因其独特的对粘弹性的解析,使其在高分子材料中的应用迅速发展,尤其是生物医用高分子材料领域,已用来评价生物医用高分子材料的表界面相互作用,力学和生物相容性等。 本文简单介绍了耗散型石英晶体微天平的基本原理及理论模型,重点综述了近几年QCM-D在高分子链构象、蛋白质吸附、生物大分子相互作用、药物释放以及水凝胶中的应用,并且展望了QCM-D的未来发展趋势。     

表面引发的DNA杂交链式反应的石英晶体微天平研究

通过石英晶体振荡技术研究了杂交链式反应这种核酸扩增的方法. 石英晶体微天平可以表征在晶体和溶液的界面上的DNA层, 并获得粘性穿透深度这一重要参数. 根据石英晶体表面吸附质量和振荡频率之间的关系, 我们测量了表面引发的杂交链式反应的动力学过程, 并获得界面上的粘度、剪切模量等参数. 这一工作为研究固液界面上核酸反应过程, 特别是杂交链式反应的机制提供了新的途径.     

石英晶体微天平传感器的膜厚敏感性

近几年,石英晶体微天平(QCM)作为一种简易、灵敏的实时监测手段,广泛地应用于研究生物活性分子之间的相互作用,其中包括蛋白质吸附动力学、抗原/抗体相互作用、DNA杂交、适配体-蛋白相互作用等领域.但是QCM作为商业化的生物传感器一直发展不顺利.主要因为QCM在液态环境中的非理想行为导致了对QCM数据分析困难.我们利用阻抗分析法对QCM的数据进行分析,分离出质量和粘弹性两种因素引起的频率改变,解决粘弹性的困扰问题.同时,我们提出了"固化水层"模型,合理地处理了溶剂的影响.在该模型的基础上发展了一种基于QCM的分子尺技术,该技术能够简便、有效地测量出固定在固-液界面的生物大分子的纳米尺寸.我们的主要工作是将"固化水层"模型拓展到三维结构的高分子基质中.我们联合QCM和表面等离子共振(SPR)技术研究基于高分子基质的蛋白质的固定,抗原/抗体识别的过程,进一步采用"固化水层"模型解释高分子的溶胀行为、羧基活化、抗体固定、抗原、抗体识别等过程.理论分析表明,结合生物分子势必排出相同体积的溶剂,由于溶剂的密度接近于蛋白质溶液的密度.从而导致"固化水层"质量增加不明显.实验上也证实了石英晶体微天平的响应主要取决于"固化水层"的厚度变化(T2-T1),而并非固定的生物分子的质量.我们利用QCM实时监测在高分子基质中IgG的固定以及IgG与anti-IgG识别的过程,并将石英晶体微天平监测的频率变化与相应的厚度变化直接关联.这一方法的建立在一定的应用范围内简化了QCM的定量分析模型,有望实现QCM作为传感器在界面物理与化学等相关领域研究中的应用.     

电化学石英晶体微天平的应用

电化学石英晶体微天平（EQCM）即石英晶体微天平（QCM）与电化学检测相结合的测试技术。电化学石英晶体微天平以其简单、快速,可以在纳克级水平上对活性物质在石英晶振片上发生的沉积、吸附或溶解等过程进行动态检测等优势而成为表界面反应研究的有效手段之一。由于EQCM测试技术为原位测试方法,可以实现在线实时监测,利用其高精度和高灵敏度可以进一步对表界面上发生反应的过程及深层次的机理进行分析。本文就EQCM在电化学、生物医学及油田化学等领域以及研究机理及动力学等方面的应用进行了总结阐述,提出了EQCM的研究新方向以及发展中面临的问题。     

电化学石英晶体微天平研究普鲁士蓝修饰电极

石英晶体徽天平(Quartz Crystal Microbalance,简称QCM)是一种非常灵敏的质量传感器,其检测能力可达ng级。QCM在化学中的早期应用是检测大气中的徽量成分,目前仍较活跃。由于石英压电晶体浸入溶液后在晶体/溶液界面存在较大的能量损失而不能够稳定振荡,致使QCM的应用较长时间局限于气相。八十年代初石英压电晶体在液相中的振荡终获成功,开辟了QCM应用的一个全新领域。液相中振荡成功后,QCM很快应用于电化学研究。目前已发展成为一种全新的电化学传感器——电化学石英晶体微天平(EQCM),并已用于金属电沉积、电化学腐蚀、电分析等方面的研究。     

石英晶体微天平的纳米微球质量放大技术及短序列DNA测定

提出了一种新型质量放大系统用于提高石英晶体微天平检测的灵敏度.将DNA嵌入剂放线菌素D作为导向分子修饰在磁性微球上,通过石英晶体微天平技术识别测定短序列DNA,使最低检测限从6.2×10^-8mol/L下降到2.0×10^-12mol/L.     

QCM-D研究蛋白质与多糖的相互作用

应用具有耗散因子功能的石英晶体微天平（QCM-D）检测了多糖多层膜的构筑过程以及蛋白质在多层膜上的吸附行为。 研究结果表明,通过层层组装的方法,可以实现多糖卡拉胶多层膜的构筑,并且随着卡拉胶电荷密度的增加,其组装量减少。 研究了牛体血清蛋白(BSA)在卡拉胶上的吸附行为。 结果发现,BSA的吸附行为强烈地依赖于卡拉胶的电荷密度和基体的粗糙度。 通过QCM-D实时监测了BSA在卡拉胶上的动力学吸附曲线,同时根据ΔD值推测了BSA在不同的基底表面上所形成的结构及吸附行为。     

乙酰化处理对碱木质素在四氢呋喃中微结构的影响

通过对比碱木质素(AL)和乙酰化碱木质素(ACAL)在四氢呋喃(THF)中溶液行为和物理化学性质的差异, 揭示了乙酰化处理对碱木质素在THF中微结构的影响. 分别采用动态光散射、凝胶渗透色谱(GPC)、透射电子显微镜(TEM)、特性粘度、荧光光谱仪、耗散型石英晶体微天平(QCM-D)和自组装技术等研究了AL和ACAL在聚集形态、聚集机理以及吸附特性等方面的特征. 研究发现, 乙酰化处理会降低碱木质素在THF中的分子间和分子内聚集程度. AL在THF中以单分子和聚集体的形式共同存在, 分子较为蜷曲; ACAL在THF中则更多地是以单分子形式存在而几乎不存在大聚集体, 分子较为伸展, 其流体力学半径要比相同绝对分子量的AL更大.THF中的AL聚集体会在液固界面上发生强烈的吸附, 但ACAL由于与溶剂间的相互作用较强而几乎不会吸附在液固界面上. 由于AL分子在THF中较为蜷曲且吸附能力较强, 因此利用以THF为流动相的GPC直接测量AL的分子量时所得结果并不准确, 为保证GPC的测量结果更加全面可靠, 需要在测量前对碱木质素进行乙酰化处理.     

石英晶体微天平传感器及其在生物检测中应用的研究进展

石英晶体微天平(Quartz crystal microbalance,QCM)是一种具有灵敏度高、免标记、可实时在线检测等优点的重要分析工具。在生物检测领域,QCM与多种信号放大方法相结合,广泛应用于对生物分子的高灵敏检测。新型耗散型QCM(QCM-D)通过对薄膜厚度、粘弹性等的研究,主要用于考察生物分子的吸附分离、构型变化等微观过程。本文主要阐述了QCM及QCM-D生物传感器的构建及其在DNA、蛋白质、细胞和微生物检测中的研究进展。     

高分子在固液界面吸附构象的研究方法及手段

高分子在固液界面的构象表征对其功能实现及实际应用具有重要意义,是高分子研究领域的热点之一.由于高分子吸附构象的复杂性及其影响因素的多样性,选择合适的方法及手段成为表征的关键.本文简单介绍了影响高分子构象的一些因素,并从仪器分析的角度出发,根据研究目的综述了高分子与固体表面的键合方式、在固液界面的吸附方式、吸附行为及吸附层微观结构的研究方法和手段.     

Effect of polymer architecture on the adsorption properties of a nonionic polymer

The adsorption of a linear- and bottle-brush poly(ethylene oxide (PEO))-based polymer, having comparable molecular weights, was studied by means of quartz crystal microbalance with dissipation monitoring ability (QCM-D) and AFM colloidal probe force measurements. The energy dissipation change monitored by QCM-D and the range of the steric forces obtained from force measurements demonstrated that linear PEO forms a more extended adsorption layer than the bottle-brush polymer, despite that the adsorbed mass is higher for the latter. Competitive adsorption studies revealed that linear PEO is readily displaced from the interface by the bottle-brush polymer. This was attributed to the higher surface affinity of the latter, which is governed by the number of contact points between the polymers and the interface, and the smaller loss of conformational entropy.     

隐藏高分子界面及生物界面分子结构的和频振动光谱研究

界面的分子结构决定界面的性质.为了以优化界面的结构来改进材料的性质,原位实时地研究界面的分子结构是很重要的.近年来和频振动光谱已发展成为一个很有效及独特的手段来研究隐藏界面的分子结构,例如液/液界面、固/液界面及固/固界面等.这篇综述讨论了和频振动光谱在研究高分子界面及生物界面等复杂界面的分子结构上的应用.具体说来,本文论述了高分子表面在水里的分子结构变化,高分子及模型粘合促进剂硅烷在界面相互作用的分子机理和隐藏的高分子/高分子及高分子/金属界面的结构.另外,此文还将介绍不同二级结构的多肽及几个有代表性的蛋白分子在界面的结构.界面在诸如化学、生物、物理、材料科学及工程和纳米技术等许多领域都很重要.发展一个独特的能原位研究隐藏界面的分子结构的技术会有力地促进这些领域的研究及跨学科研究的发展.     

Adsorption of phytosterol ethoxylates on silica in an aprotic room-temperature ionic liquid

The adsorption of a nonionic surfactant at a silica/room-temperature ionic liquid interface has been characterized on the basis of analytical data obtained through a combination of surface force measurements, in situ soft-contact atomic force microscope (AFM) images, and quartz crystal microbalance with dissipation monitoring (QCM-D) data. The surfactant employed in this study is a kind of phytosterol ethoxylate (BPS-20), and the ionic liquid selected here is aprotic 1-ethyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide (EmimTFSI). This ionic liquid spontaneously forms solvation layers on silica, being composed of an Emim(+) cation layer and EmimTFSI ion pair layers. The addition of BPS-20 disrupts these solvation layers and suggests a surfactant layer adsorbed at the interface. This is the first report demonstrating the adsorption of nonionic surfactants at the solid/aprotic ionic liquid interface.     

Reversible activation of diblock copolymer monolayers at the interface by pH modulation, 2: Membrane interactions at the solid/liquid interface

A monolayer of the pH-responsive poly[2-(dimethylamino)ethyl methacrylate-block-methyl methacrylate] diblock copolymer [PDMAEMA-PMMA] was transferred from the air/water interface to a silicon substrate for evaluation as a tunable interlayer between biological material and solid substrates. Specular neutron reflectivity experiments revealed that the weak polyelectrolyte PDMAEMA chains at the solid/liquid interface can be reversibly activated by pH modulation. The thickness, scattering length density, and surface roughness of the polymer film can be systematically controlled by pH titration. As a simple model of plasma membranes, a lipid bilayer was deposited onto the polymer film. The membrane-substrate interaction was characterized by neutron reflectivity experiments, demonstrating that the membrane-substrate distance could be reversibly regulated by pH titration. These results confirm the potential of stimuli-responsive polymers for precise control of cell-surface interactions.     

Study on luminescence characteristic of the ZnO/polymer hybrid films

The cyclohexane solution of PS (polystyrene) and the ethyl acetate solution of PMMA (polymethyl methacrylate) were used as flowing liquid; the ZnO/polymer hybrid colloids were successively produced by focused pulsed laser ablation of ZnO target in interface of solid and flowing liquid. As solvent in the hybrid colloids has volatized, the ZnO/polymer hybrid films were obtained. The hybrid colloids were characterized by high-resolution transmission electron microscopy (HRTEM) and select-area electron diffraction (SEAD). The results show a good dispersion of the ZnO nanoparticles in the polymer matrix. The hybrid films were characterized by fluorescence spectrum, Fourier transform infrared spectroscopy (FTIR) spectroscopy, thermogravimetry with FTIR (TG/FTIR), and X-ray photoelectron spectrum. The results show the ZnO/polymer hybrid films can radiate strong blue light under ultraviolet. Meanwhile, the ZnO/polymer hybrid films have higher chemical stability than ZnO nanoparticles because nano-ZnO nanoparticles were enwrapped by polymers. In addition, the ZnO hybrid films have higher thermal stability then the related pure polymers because of strong interaction among ZnO nanoparticles and polymers.     

Influence of aqueous electrolytes on the wetting behavior of hydrophobic solid polymers-low-rate dynamic liquid/fluid contact angle measurements using axisymmetric drop shape analysis

The interaction of inorganic ions with low-energy hydrophobic surfaces was examined using model systems of solid polymers without ionizable functional surface groups in aqueous electrolyte solutions. Low-rate dynamic contact angle measurements with captive bubbles in conjunction with axisymmetric drop shape analysis (ADSA) were performed to study the influence of electrolyte ions (in the aqueous test solutions) on the wettability of the polymers. When various types of ions were used, no significant change in advancing and receding contact angles was observed. The contact angle hysteresis was small. The zeta potential of the model polymers in aqueous electrolyte solutions was determined from streaming potential measurements. The variation of the zeta potential at different pH levels indicates preferential adsorption of hydroxyl ions at this interface. However, the presence of electrolytes at the interface between water and the different model polymers did not influence the macroscopic contact angle. The results may suggest the absence of any specific interaction between the ions and the solid polymer, as this should result in changes of hydrophobicity. Similar to the air/water interface, the composition and the potential of the polymer/water interface are obviously determined predominantly by the aqueous phase with only slight influence from the solid phase.     

Structural analysis of organic interfacial layers by ellipsometry

Ellipsometry has ‘come of age’ as a technique for the analysis of problems related to colloid and interface science. It has advanced far beyond applications of measuring film thickness or optical constants — although these remain important uses. Studies of the structure of polymers at the solid/liquid interface have been advanced significantly by the realisation of Fourier transform ellipsometry. Another important achievement has been the calibrated measurement of the dynamic surface excess at the flowing surface of a liquid jet. The uses of ellipsometry to study critical adsorption in binary liquids and to measure the width of liquid/liquid interfaces are also noteworthy. An important development is the use of infrared — rather than visible — light, which opens up numerous possibilities for the simultaneous structural and chemical interrogation of interfaces non-invasively.     

Review: Recent applications of scanning electrochemical microscopy to the study of charge transfer kinetics

Scanning electrochemical microscopy (SECM) has been proven to be a valuable technique for the quantitative investigation and surface analysis of a wide range of processes that occur at interfaces. In particular, there is a great deal of interest in studying the kinetics of charge transfer characteristics at the solid/liquid and liquid/liquid interface. This overview outlines recent advances and applications of SECM to the investigation of charge transfer reactions at the solid/liquid interface and liquid/liquid interface.     

锂/聚合物电解质电化学固/固界面的研究

综述了聚合物锂电池中锂/聚合物电解质电化学固/固界面的研究进展。通过与锂/液体电解质体系进行比较，简要介绍了在锂/聚合物电解质界面上发生的电化学反应、锂钝化层形成及其对界面反应的影响，并侧重讨论了传统电化学方法和谱学方法，特别是现场分析技术在电化学固/固界面研究中的应用。总结了锂/聚合物电解质界面的几种不同改善途径。