离子淌度质谱技术及其应用研究进展

离子迁移谱是一种以气相离子在电场和气流共同作用下发生迁移时的淌度来表征化合物的技术。离子淌度质谱提供了新一维度的离子淌度分离和测量信息,除按照质荷比区分离子外,还可根据离子尺寸和形状进行分离。其与色谱技术联用,可获取包括保留时间、迁移时间、质荷比和响应强度在内的四维数据,在提高传统质谱数据准确性和特异性的同时,还可计算离子的碰撞横截面积,从而获得样品的结构信息。该文综述了近年来离子淌度质谱技术在公共安全、毒品检测、食品安全、环境监测、药物分析以及生物大分子等领域的研究进展,并对该技术的应用前景和发展趋势进行了展望,以期为相关领域的科技人员提供理论支持和技术参考。     

聚丙烯酸水溶液的粘度和构象变化

本文测定了不同中和度聚丙烯酸在不同离子强度盐溶液中的特性粘数,研究了聚丙烯酸的分子形态及构象对聚合物浓度、电荷密度及溶液离子强度的依赖性,得到聚离子的构象变化与溶液盐浓度的对数成反比,与电荷密度的平方根成正比等规律。     

基于电解质电导的电泳淌度高精确经验方程（英文）

电解质电导率的测定具有操作简单和精确度高等优点,若用于离子淌度的研究将会是准确、简便且廉价的手段。该研究基于电解质电导率提出了新理论方法。以单价离子为研究对象,在不高于0.05 mol/L离子强度下,根据19种单价电解质的电导率数据,将最大偏差接近10%的经验方程修正为最大偏差为5%的精确等式。校正公式的预测值也与移动界面法测定的盐离子淌度和露西方程得到的32种有机离子淌度有很高的一致性。研究还表明19种无机离子与32种有机离子的电解电导率与电泳淌度高度一致。本文还给出了小于0.02 mol/L离子强度下更加准确的方程(最大偏差2%),暗示改进后的经验公式具有极高的精确度。不仅如此,文献中的大量电解质电导率数据均可用于离子淌度的研究,且测定电解质电导率的简便性使得相关研究的深入更加容易。     

Li-SGO掺杂半互穿网络型多孔单离子传导聚合物复合电解质的制备

本文成功制备了磺酸锂功能化石墨烯,通过原位聚合方式成功将其添加到单离子传导聚合物电解质中制备出磺酸锂功能化石墨烯改性半互穿网络型多孔单离子传导聚合物复合电解质.与未掺杂磺酸锂功能化石墨烯半互穿网络型多孔单离子传导聚合物电解质相比,该电解质具有更高的孔隙率、吸液率、机械拉伸强度和离子电导率.电化学测试结果表明,掺杂磺酸锂...     

梳型聚醚-聚磺酸锂共混物的锂离子导电性

本工作合成了聚甲基丙烯酸齐聚氧化乙烯酯和聚甲基丙烯酸己磺酸锂两系列聚合物,研究共聚物结构对共混物的相容性和锂离子导电性的影响.结果表明,共混物的相容性是决定离子电导率的主要因素;共混物内锂离子传导发生在非晶区,聚合物的链段运动是离子传导的主要推动力.     

聚离子液体的合成及应用

聚离子液体(PILs)是在重复单元上具有阴、阳离子电解质基团的聚合物。此类聚合物结合了离子液体和聚合物的一些性质,近年来在高分子化学和材料科学等领域受到广泛关注。本文将聚离子液体划分为聚阳离子型离子液体、聚阴离子型离子液体、聚两性型离子液体和共聚型离子液体四类并介绍了聚离子液体的性质及各类聚离子液体的合成。此外,本文还对聚离子液体在有机分散剂、纳米复合材料、电化学、吸附剂和分离等方面的应用进行了综述。     

梳型聚醚-聚磺酸锂共混物的锂离子导电性

 本工作合成了聚甲基丙烯酸齐聚氧化乙烯酯和聚甲基丙烯酸己磺酸锂两系列聚合物,研究共聚物结构对共混物的相容性和锂离子导电性的影响.结果表明,共混物的相容性是决定离子电导率的主要因素;共混物内锂离子传导发生在非晶区,聚合物的链段运动是离子传导的主要推动力.     

阴离子印迹聚合物的制备及其应用研究进展

离子印迹聚合物是利用印迹技术对模板离子进行印迹、聚合进而得到能够选择性吸附该离子的一种特殊聚合物.目前的报道大多是阳离子印迹聚合物,因为阴离子模板结构更复杂多样且电荷尺寸比更小,致使阴离子印迹聚合物的发展相对滞后.为能更有效地指导阴离子印迹聚合物的制备,本文概述了阴离子印迹聚合物的发展现状,介绍了与不同阴离子有相互作用...     

《化学通报》网络版(Chemistry Online)2003年第9期论文摘要

[W 0 65 ]基于聚氧化乙烯的离子 电子混合传导聚合物PEO BasedConductingPolymerswithbothIonicandElectronicConductivity柳　娜　官建国 (武汉理工大学材料复合新技术国家重点实验室　武汉　 43 0 0 70 )将聚氧化乙烯 (PEO)与电子导电聚合物结合 ,可获得基于PEO的离子 电子混合传导聚合物 ,它们在各种微电子装置中有着重要应用。本文综述了此类聚合物的合成方法 ,并详细讨论了聚合物结构控制策略及其与导电性能的关系。Polyethyleneoxide(PEO)basedconductingpolymerswithmixed (ionic electronic)conductivitymaybeobtainedbyc…     

聚合物微观结构对聚合物电解质膜性能的影响

聚合物的微观结构是设计具有优异的电化学性能的聚合物电解质膜(PEMs)的基础.在电解质膜中,相分离结构形成的离子簇和离子通道可以影响膜在高温低湿度条件下的离子传导和水的传输,这种结构形成的形貌也可以影响膜的吸水率、溶胀度、碱稳定性等性能.近几年来,人们对于具有微观相分离形貌的PEMs的合成和形貌开展了很多研究.本文主要...     

Transport and Deposition of Alumina Nanoparticles in Water Saturated Porous Media: An Experimental Study

Transport and deposition of nanoparticles (NPs) have drawn great attention in different fields of engineering in recent years because of their potential risk to the environment. In this study, mobility of aluminum oxide NP, one of the most popular metal oxide NPs, was studied in synthetic saturated porous media. The impacts of ionic strength using monovalent (NaCl) and divalent (MgCl₂) salt solution, pH, and NPs concentrations on nano-alumina mobility were investigated. The experimental results showed that the transport of nano-alumina was influenced by ionic strength; the highest mobility was observed at the 0.01 M solution and decreased by increasing ionic strength. Moreover, the suspension containing alumina NPs presented the best mobility behavior in the acidic solution (pH = 2) in comparison with neutral and basic solutions. Consequently, transport of NPs with particle size distribution lower than 100 nm through porous media was facilitated at the acidic, low ionic strength condition. In addition, faster elution occurred when the influent concentration was increased from 0.1 wt% to 0.3 wt%. Finally, it is expected that ionic strength, pH of solution, and NPs concentration will be key parameters to control the nano-alumina mobility.     

Temperature-dependences of cationic mobility and carrier generation in solid polyether media

The temperature-dependences of cationic conductivity and mobility in a macromolecular lithium salt/copolyether blend were investigated by means of complex impedance analysis and a time-of-flight technique, respectively. The transient ionic current after reversing the d.c. bias polarity exhibits two peaks, corresponding to cationic and anionic movement respectively, and verifying a cationic transfer number of 0.99 at 50°C. The comparison between conductivity and mobility makes it possible to reveal the temperature-dependence of the cation carrier number. As a result, the population of free ions was found to decrease exponentially with increasing temperature. However, this “anomalous” behavior of salt dissociation has little effect on the temperature-dependence of conductivity, since it is cation carrier mobility rather than its number which is the main factor influencing the ion transport process.     

The synthesis of mesogenic polymers provoked by molecular mobility. polysiloxanarylenes

An approach to the synthesis of potentially thermotropic liquid crystalline polymers based on parallel investigation of their molecular mobility was realized. The initial idea was provoked by the observation that there exists some correspondence of molecular mobility data and the ability of a polymer to form a liquid crystalline phase. Previously this phenomenon was demonstrated on the example of a series of thermotropic main chain polymers with flexible dimethylsiloxane spacers of variable length. The relation between the structure of the main chain and local molecular mobility of different fragments was investigated in a series of regular polysiloxane-silarylenes containing rigid aromatic sequences. Molecular mobility was studied by dielectric spectroscopy in solution and in solid state. The structure of the main chain has been changed by variation of the repeated fragments' length, substituents and joint groups. The data of molecular mobility and their conformity with the chain structure were used for directed synthetic search of desired mesogenic polymers.     

Simulation of DNA electrophoresis through microstructures

The dependence of the mobility of DNA molecules through an hexagonal array of micropillars on their length and the applied electric field was investigated and it was found that mobility is a nonmonotonic function of their length. Results also revealed that the size dependence of the DNA mobility depends on the applied electric field and there is a crossover around E approximately 25 V/cm for the mobility of lambda-DNA and T4-DNA. These observations are explained in terms of the diffusion process inside the structure affected by the solvent and are modeled using the Langevin and its corresponding Fokker-Planck equations. The phenomenon is generalized under three regimes in a phase diagram relating the electric field and the DNA lengths. The model and the associated phase diagram described here provide an explanation for the conflicting results reported by previous authors (Han et al. on the one hand, and Duong et al. and Inatomi et al. on the other) about the dependence of mobility on the DNA size in lattices near or below the radius of gyration.     

Bilayer-Templated Two-Dimensional RAFT Polymerization for Directed Assembly of Polymer Nanostructures

Co-localization of monomers, crosslinkers, and chain-transfer agents (CTA) within self-assembled bilayers in an aqueous suspension enabled the successful directed assembly of nanocapsules using a reversible addition–fragmentation chain transfer (RAFT) process without compromising the polymerization kinetics. This study uncovered substantial influence of the organized medium on the course of the reaction, including differential reactivity based on placement and mobility of monomers, crosslinkers, and CTAs within the bilayer.     

有机介质中酶催化的基本原理

酶在有机溶剂中催化作用的研究日益受到重视,其应用范围也越来越广.本文就有机介质中酶催化的基本原理进行了讨论,包括酶的结构和催化机理,以及溶剂和水对酶的结构和催化功能的影响.同时,本文归纳出提高酶活性的一系列方法,其中不少方法简便易行,能使酶活性提高10²-10⁵倍.     

Adsorption and Mobility of Water and Benzene Molecules in Carbon and Polymer Adsorbents

The correlation between the adsorption and the mobility of adsorbed molecules was analyzed. The peculiarities of molecular mobility in microporous adsorbents with relatively rigid (active carbons) and non-rigid (polymer super-crosslinked and methacrylate sorbents) structure were studied using pulsed nuclear magnetic resonance (NMR) techniques. It was shown that the translational behavior of water and benzene in pores are connected with the specific adsorption mechanism. The NMR data allowed analyzing the changes of molecular state in the processes of adsorption. Diffusional properties of water molecules in the super-crosslinked polystyrenes and active carbons with relatively rigid framework are similar and differ from that in methacrylate polymer sorbents. Moreover, the results of NM relaxation measurements allowed analyzing the porous structure over the scale of pore sizes, while the scale of the self-diffusion measurements comprises the areas of different porosity. The NMR data agree well with the data of adsorption measurements and complement them. Dedication: This work is devoted to memory of the professor W. Schirmer.     

The Mobility of Threaded α-Cyclodextrins in PR Copolymer and Its Influences on Mechanical Properties

The methylated polyrotaxane(Me PR) copolymer was prepared via the methylation of hydroxyl of threaded α-cyclodextrin(α-CDs) in polyrotaxane(PR) copolymer by CH_3I/Na H. Its structure was characterized by GPC, IR and NMR. The WXRD and TGA measurements showed the destruction of channel-like crystalline structure in Me PR copolymer. The sliding of threaded α-CDs along PEG axis in PR and Me PR copolymers was demonstrated by their dielectric spectra that also evidenced the presence of rotating of threaded α-CDs around PEG axis in Me PR copolymer. The frequent and vigorous molecular mobility in Me PR and PR copolymers was also verified by dynamic mechanical analysis(DMA) and rheological measurement, which was possibly assigned to the sliding and rotating of threaded α-CDs. DMA and rheological results showed that the mobility of α-CDs could simultaneously strengthen and toughen PR copolymer proved by stress-stain curves. In this paper, we report the CD mobility in PR and Me PR copolymers. The macroscopic behaviors of PR copolymer, such as mechanical properties in solid state, were also found to be benefited from CD mobility.     

An ESR spin-label study on molecular mobility in the interface between microphases of a diblock copolymer: effects of admixture of homopolymers that are miscible with one of the blocks

Molecular mobility in the interfacial region of a microphase-separated structure was studied in binary mixtures of AB-type diblock copolymers and homopolymers (miscible with only A) by the spin-label technique. In this study, we prepared (a) binary blends of polystyrene-block-poly(methyl acrylate) (PS-block-PMA) and homopolymer poly(cyclohexyl acrylate)'s having the number-averaged molecular weight (Mn) of 1000 (PCHA-S) and (b) having the Mn of 17300 (PCHA-L), and (c) binary mixtures of the PS-block-PMA and homopolymer PS with the Mn of 900 (PS-1). Emphasis was placed on effects of the molecular weight and the miscibility of added homopolymers on the mobility in the interfacial region of the microphase separation. Selective incorporation of the added PCHA-S, PCHA-L, and PS-1 into the PS phase of the PS-block-PMA was confirmed by modulated-temperature differential scanning calorimetry (MDSC) measurement as a decrease in the glass transition temperature of the PS phase. Moreover, the MDSC and small-angle X-ray scattering (SAXS) measurements suggested that the spatial distributions of the PCHA-S and PS-1 in the PS phase were relatively uniform because of their small Mn. On the other hand, the distribution of the PCHA-L in the PS phase was somewhat heterogeneous because of the large Mn of the PCHA-L. The spin-label at the junction point of the PS-block-PMA allowed us to estimate the mobility in the interfacial region of the microphase separation. Influence of the PCHA-S and PCHA-L on the mobility in the interfacial region was negligible even though the relatively uniform distribution of the PCHA-S in the PS phase was suggested by the SAXS and MDSC. More uniform distribution of the PS-1 than that of the PCHA-S in the PS phase was suggested by the SAXS, and the mobility in the interfacial region was slightly enhanced by the addition of the PS-1. However, the mobility was almost constant against an increase in the PS-1. The PS-1 was considered to be penetrated into the interfacial region and activated the mobility, but the fraction of the PS-1 in the interfacial region was constant irrespective of the blended amount of the PS-1. These results suggest that effects of homopolymers on the mobility in the interface are significantly related to their spatial distribution in the host phase.