拉曼光谱技术在高分子表征研究中的应用

拉曼光谱作为一种强大的工具,被广泛应用于聚合物结构的表征.随着共振拉曼光谱、扫描角度拉曼光谱、高分辨率拉曼成像、极化拉曼光谱、表面增强拉曼散射等拉曼技术的迅速发展,拉曼光谱的应用范围不断扩大.本文首先介绍了拉曼光谱设备的基本原理和组成,总结了拉曼技术的实验技巧和数据处理中需要注意的问题,讨论了红外光谱和拉曼光谱的区别,在此基础上,综述了近十年来拉曼技术在聚合物结构表征领域的最新应用和研究进展.其应用包括以下六个方面:高分子链的构象、聚合物的聚集状态、聚合物结晶度的计算、高分子链的取向、外场作用下的结构转化、高分子共混物化学或物理成分的识别.最后,对拉曼光谱在聚合物研究中的发展进行了展望.希望本文能够对试图从拉曼光谱中获取聚合物结构信息的学者有所帮助.     

同步辐射红外显微光谱学和成像技术在分析化学中的应用

同步辐射红外显微光谱作为一种新兴的分析技术,一方面利用了红外光谱可以同时表征有机和/或无机、结晶和/或无定形样品的特点,另一方面充分发挥了同步辐射高亮度和高空间分辨率的特性,因此在对小样品或小样品区域的表征上具有传统红外光谱无法比拟的优势。经过20多年的发展,同步辐射红外显微光谱技术已被广泛地应用于多种分析化学领域并取得了丰硕的研究成果。本文总结了最近几年同步辐射红外显微光谱学和成像技术在文化遗产和考古学、地球和空间科学以及化学和高分子科学中的研究和应用进展。     

机器学习方法在高分子玻璃化研究中的应用

高分子玻璃的物理性质与其结构和动力学密切相关.揭示高分子玻璃化的微观物理图像对高分子玻璃材料的结构调控和分子设计至关重要.然而,高分子的长链结构和复杂单体结构特征致使目前仍然缺乏普适的理论或者模型来定量解释高分子玻璃化的物理机制.因此,亟需发展更为先进的研究方法从而更深入地理解高分子玻璃化.近年来,国内外学者利用基于数据驱动的信息学方法(例如机器学习)对高分子玻璃化开展了研究,并取得了丰富成果.本综述首先介绍了常用的高分子信息学数据库和机器学习算法.之后,从高分子玻璃化转变温度的预测、新型高分子玻璃材料的研发、过冷液体的结构-动力学关系和玻璃体系相变的确定四个方面总结和评述了机器学习应用在玻璃化研究中的代表性进展.最后,探讨了机器学习方法在高分子玻璃化研究中面临的主要挑战,并对玻璃信息学这一领域的发展进行了展望.     

中子散射技术在化学研究中的应用

中子散射在化学、软物质、基础物理、地球科学、工程等领域应用广泛,在不同领域的科学探索过程中发挥了关键作用.中子具有不带电荷、穿透能力强、对轻元素敏感、能够进行无损检测等特点.一方面,弹性中子散射在氢元素富集的化学材料体系、高分子体系、生物大分子等体系的结构研究中独具优势;另一方面,非弹性中子散射测量的能量、散射矢量范围与这类材料体系的时间、空间尺度吻合,非常适合化学过程的动力学研究.本文将通过结合中国绵阳研究堆(CMRR)中子散射平台上的应用实例,重点介绍国内外利用小角中子散射、中子反射、中子衍射、非弹/准弹性中子散射等代表性技术在化学反应机理研究、溶液中的化学过程、高分子化学、生物化学、材料化学、核化学和放射化学等领域的典型应用及前景.     

核酸/高分子复合体系的制备与性能

综述了近年来核酸/高分子复合体系在设计、合成、性能研究以及应用等方面的最新研究进展,主要阐述了不同种类以及不同结构核酸/高分子体系的制备方法以及其在核酸检测、生物医药以及纳米等领域的应用,并对其未来的研究方向作了展望.     

立体定向的聚合作用和催化作用

化学的二个重要分支,动力学和催化作用,在应用到高分子领域时取得了特殊的含义。 当化学家初次接触有机高分子领域的工作时(自然界在这领域中作出了很多范例),获得的意外结果是所用催化方法与合成低分子量物质中经常所用的方法截然不同。对于后者,异相催化作用代表着催化作用中最重要和最丰富的一个分支,这种催化在合成低分子量产物方面已有卓越的结果,过去在合成高分子方面,则数均相催化历程发展较高(至少在它的起始     

高分子/单链高分子纳米粒子复合体系中的界面性质

高分子与纳米粒子复合是改善高分子材料性能的有效途径.近20年来关于高分子/纳米粒子复合物的研究引起了学术界广泛的兴趣.然而由于此类体系中的影响因素复杂,虽然学者们在相关材料性能的研究方面取得了重要进展,但是相关理论的发展却相对滞后,其中一个重要原因是实验上表征手段的缺失,导致对体系中纳米粒子与本体高分子链相互作用规律的认识(尤其是两者界面性质的认识)不够.本文总结和阐述了我们近几年利用分子动力学模拟技术研究高分子/单链高分子纳米粒子复合体系的主要结果,并围绕此类复合体系中的界面结构及动力学性质,讨论并总结了纳米粒子对本体高分子链的作用范围及影响规律,指出单链纳米粒子对熔体链的作用范围与纳米粒子的自身尺寸相当,而与熔体高分子链的分子量没有直接的关系.该结论将为纳米复合体系高分子理论的发展提供重要参考.     

二维相关红外光谱分析技术在高分子表征中的应用

二维相关红外光谱作为一种先进的光谱分析方法,具有提高谱图分辨率、解析动态过程等优势,近来在高分子表征中引起了越来越多的关注.高分子体系涉及了丰富的相互作用和复杂的结构,分子光谱是常用的表征手段,而借助二维相关光谱分析技术,能够有效识别精细结构、判别动态变化机制,从而显著丰富和完善分析结果 .本文重点围绕二维相关红外光谱,简述了发展历史和基本原理,随后结合实际过程,介绍了相关实验和分析技巧,最后列举了其在高分子表征中的典型应用,展示了二维相关红外光谱分析的特点,具体涉及温度响应高分子的响应机制、可拉伸离子导体中复杂相互作用、小分子在聚合物基质中的扩散、天然高分子的结构表征等研究.希望通过本文的介绍,能够帮助读者更好地理解二维相关光谱,进一步拓展其在高分子领域中的应用.     

新型双螺噁嗪分子的合成及性能

设计合成了3个双螺噁嗪化合物, 采用核磁共振谱、红外光谱和高分辨质谱对这些化合物进行了表征. 测试了光照前后化合物在不同溶剂中的紫外吸收光谱、荧光光谱以及在高分子薄膜中的消色动力学曲线. 结果表明, 目标化合物均具有良好的光致变色性能和耐疲劳度, 在材料、分子开光及生物探针领域有潜在的应用前景.     

高分子薄膜去润湿孔增长动力学

高分子薄膜去润湿是近年国内外表界面研究领域的热点.孔增长动力学作为高分子薄膜去润湿动力学的重要组成部分,对其进行深入研究,不仅可以促进人们对高分子薄膜去润湿过程的理解,而且可为高分子表界面图案化设计提供理论依据.近年来,有关去润湿孔增长动力学的理论、实验和计算机模拟工作很多,并且取得了较大的进展.本文综述了这一领域最为重要的研究工作,分析了理论预言与现有实验结果偏离的原因以及由此而呈现的重要问题,并对这一领域的研究方向进行了展望.     

Fluorescence correlation spectroscopy studies of diffusion of a weak polyelectrolyte in aqueous solutions

We apply fluorescent correlation spectroscopy (FCS) to investigate solution dynamics of a synthetic polyelectrolyte, i.e., a weak polycarboxylic acid in aqueous solutions. The technique brings single molecule sensitivity and molecular specificity to dynamic measurements of polyelectrolyte solutions. Translational diffusion of Alexa-labeled poly(methacrylic acid), PMAA*, chains was studied in very dilute, 10(-4) mg/ml, solutions as a function of solution pH and ionic strength. The observed changes in diffusion coefficients were consistent with about twofold expansion of PMAA* coils when pH was changed from 5 to 8, and with chain contraction for alkaline metal ion concentrations from 0.01 to 0.1 M. The dependence of the hydrodynamic size of PMAA* chains on the counterion type followed the sequence: Li(+)>Na(+) approximately equal to Cs(+)>K(+). The dependence of translational diffusion on polyacid concentration was weak at the low concentration limit, but chain motions were significantly slower at higher polymer concentrations when PMAA chains overlapped. Finally, measurements of dynamics of PMAA* chains in "salt-free" solutions showed that self-diffusion of PMAA* chains significantly slowed down when PMAA concentration was increased, probably reflecting the sensitivity of PMAA* translational motions to the onset of interchain domain formation. These results illustrate the utility of the FCS technique for studying hydrodynamic sizes of polyelectrolyte coils in response to variation in solution pH or concentration of salt and polyelectrolytes. They also suggest that FCS will be a promising technique for selective observation of the dynamics of polyelectrolyte components in complex polymer mixtures.     

Fluorescence correlation spectroscopy in colloid and interface science

In the last two decades fluorescence correlation spectroscopy (FCS) has been increasingly applied to analyze systems and processes relevant to colloid and interface science. The method has become a routine tool to measure the hydrodynamic radii of small fluorescent molecules, macromolecules and nanoparticles, characterize their interactions and follow a possible aggregation. It was also used to study the diffusion of such species in inhomogeneous media like polymer melts, solutions, gels or porous structures. The formation kinetics and size of micelles of surfactants or block copolymers has been quantified. FCS has also been applied to characterize diffusion of tracers at fluid–liquid and solid–liquid interfaces and study the hydrodynamic boundary condition. The review is intended to summarize these applications and highlight perspectives but also limits of FCS in colloid and interface science.     

Translational diffusion of intermediate species in solutions

In this article, applications of the TG method to measurements of the translational diffusion of photochemically created intermediate species are reviewed. The intermediate species include unstable isomers, photochromic charged molecules, transient radicals created by photochemical reactions, and the electronically photoexcited species. Diffusional behaviors of these intermediates are different from those of stable molecules, which have been investigated extensively so far. The investigations of the diffusion of these species will provide opportunity to reveal the unique intermolecular interaction between the intermediates and matrix. Furthermore, by using products of photochemical reactions as probe molecules, the molecular dynamics of the system can be studied. This information will be valuable for understanding photochemistry in solution.     

Dynamics of trehalose molecules in confined solutions

The dynamics of trehalose molecules in aqueous solutions confined in silica gel have been studied by quasielastic neutron scattering (QENS). Small-angle neutron scattering measurements confirmed the absence of both sugar clustering and matrix deformation of the gels, indicating that the results obtained are representative of homogeneous trehalose solutions confined in a uniform matrix. The pore size in the gel is estimated to be 18 nm, comparable to the distances in cell membranes. For the QENS measurements, the gel was prepared from D2O in order to accentuate the scattering from the trehalose. Values for the translational diffusion constant and effective jump distance were derived from model fits to the scattering function. Comparison with QENS and NMR results in the literature for bulk trehalose shows that confinement on a length scale of 18 nm has no significant effect on the translational diffusion of trehalose molecules.     

Fluorescence correlation spectroscopic studies of diffusion within the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate

Fluorescence correlation spectroscopy (FCS) measurements have been performed in order to determine the translational diffusion coefficients of three differently charged fluorescent probes (cationic: rhodamine 6G, neutral: 4-dicyanomethylene-2-methyl-6-p-dimethylaminostyryl-4-H-pyran, DCM, and anionic: fluorescein) dissolved within the common room temperature ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate, [bmim][PF6]. These experiments demonstrate that FCS is a rapid, sensitive, precise (typical RSD from 4-8%), and low-consumption screening tool for the determination of analyte mobility within microliter ionic liquid samples.     

Fluorescence Correlation Spectroscopy Study of Probe Diffusion in Poly(vinyl alcohol) Solutions and Gels

In this study, we demonstrate how the diffusion of probe particles in aqueous poly(vinyl alcohol) (PVA) solutions and gels is affected by: (i) the presence of cross-links, (ii) the cross-link density, (iii) the polymer concentration. We apply fluorescence correlation spectroscopy (FCS) to measure the diffusion time of a rhodamine-based fluorescent particle (TAMRA) and TAMRA-labeled dextran in PVA solutions and gels prepared at various polymer concentrations (1% to 8.6% w/v) and cross-link densities (1/400 to 1/50 cross-link monomers per PVA monomers). The measurements indicate that the probe particles are slowed down with increasing polymer concentration and with increasing cross-link density. Also, FCS can detect differences in the diffusion times measured in “fresh” and “aged” PVA solutions. We find that FCS provides a quantitative measure of network inhomogeneities.     

Combining electrochemistry and direct force measurements: from the control of surface properties towards applications

Direct force measurements contributed in the last years much to our understanding of the diffuse double layer of charged interfaces in electrolyte solutions. Such measurements have been performed with the atomic force microscope or the surface force apparatus. This review gives an overview over the recent studies based on force measurements with electrode surfaces. Not only bare metal electrodes but also electrodes modified by different organic layers, including electroactive films, have been studied by these techniques. Direct force measurements indicate that further effects besides classical Gouy–Chapman–Stern theory have to be taken into consideration in order to describe the force profiles. In addition to the long-range forces also the adhesion between surfaces can be tuned by potentiostatic control. New single-molecule techniques based on the atomic force microscope allow to probe the extension of polymer strands or their desorption from solid interfaces. In combination with electrochemistry, it became now possible to tune the desorption behavior of polymer strands or to measure the electromechanical coupling of motors from single strands of electroactive polymers.     

Self-diffusion of rodlike and spherical particles in a matrix of charged colloidal spheres: a comparison between fluorescence recovery after photobleaching and fluorescence correlation spectroscopy

The fluorescence recovery after photobleaching (FRAP) method and the fluorescence correlation spectroscopy (FCS) have been applied on suspensions of highly charged colloidal spheres with a small content of rod-shaped tobacco mosaic virus (TMV) particles. Since these methods only determine the self-diffusion coefficient of the fluorescently labeled species, D(S) of the rods and the spheres could independently be measured. The ionic strength of the dispersion medium has been varied to measure self-diffusion of rods and spheres in dependence on the degree of order of the matrix spheres. In contrast to FRAP, which allows the determination of the long-time self-diffusion coefficient D(S) (L), FCS measures self-diffusion on a shorter time scale. Thus a comparison of the results that were obtained by FCS and FRAP, in combination with Brownian Dynamics simulations, gives insight into the time dependence of the self-diffusion coefficient of an interacting colloidal system. As the mean interparticle distance of the matrix is of the same order of magnitude as the length of a TMV rod, the rotational motion is influenced by the assembly of spheres around a TMV particle. Since FCS is sensitive both to translational and rotational motion, whereas FRAP, which probes the diffusion at much larger length scales, is only sensitive to the translational motion of TMV, the comparison of diffusion coefficients measured employing FRAP and FCS can give some insights in the rotational diffusion: the experimental data indicate a slowing down of the rotational motion of a TMV rod with increasing structural order of the matrix spheres.     

The dynamics of polymer melts as seen by neutron spin echo spectroscopy

Using the neutron spin echo spectroscopy, the internal segmental diffusion of chain molecules in polymer melts and concentrated solutions was studied. These investigations show that beyond a characteristic length d_t and after a cross over time τ_e(d_t) the segmental diffusion of the single chains is strongly impeded and deviates from the Rouse dynamics. d_t is polymer specific and depends on the temperature as well as on the polymer concentration. Within the framework of the reptation concept, where d_t is identified with the mean distance between intermolecular entanglements or with the tube diameter, the microscopically determined d_t-values agree quite well with those derived from related macroscopic measurements of the plateau modulus. A similar good agreement is also found with respect to the segmental friction coefficients obtained either from the Rouse regime of the NSE spectra or from Theological data of corresponding short chain systems, where entanglements are not yet effective.     

Molecule motion at polymer brush interfaces from single‐molecule experimental perspectives

Polymer brushes have been widely used as functional surface coatings for broad applications including antifouling, energy storage, and lubrications. Understanding the molecule dynamics at polymer brush interfaces is important in unraveling the structure–property relationships in these materials and establishing a new materials design paradigm of novel functional polymer thin films with efficient interfacial transport. By applying modern fluorescence‐based single‐molecule spectroscopic and microscopic techniques, molecule dynamics at varied polymer brush interfaces have been experimentally investigated in recent years. New insights are given to the understandings of some unique and unusual materials properties of polymer brush thin films. This review summarizes some recent studies of molecular diffusion at polymer brush interfaces, highlights some new understandings of the interfacial properties of polymer brushes, and discusses future research opportunities in this field. © 2013 Wiley Periodicals, Inc. J. Polym. Sci. Part B: Polym. Phys. 2014 , 52, 85–103