聚氯乙烯/醋酸纤维素合金纳滤膜材料的研制及其界面性能表征

以聚氯乙烯(PVC)、醋酸纤维素(CA)为膜基材,四氢呋喃为溶剂,蒸馏水为沉淀剂,采用溶液共混法制备出PVC／CA合金纳滤膜材料作为高效液相色谱(HPLC)柱填料。由HPLC实验给出的参考溶质的保留时间计算膜-液界面的溶质平衡分配系数K和界面水层体积Ks,探讨合金化前后聚氯乙烯膜材料界面性能及亲水性的变化,并测定了PVC／CA合金的极性(av)和非极性(am)参数。     

PA-130/CA合金膜材料的研制及其性能

采用溶液共混和液-固相转变法(L-S)制备了用于高效液相色谱(HPLC)柱填料的共聚尼龙/醋酸纤维素共混物(PA-130/CA)。以小分子量化合物为探针分子,用HPLC数据表征了PA-130/CA合金膜材料的界面性能,并研究了其合金膜材料的相容性和热稳定性。结果表明:PA-130与CA有很好的相容性;该合金膜的热稳定性比纯CA膜的有所提高;质量比为30/70的PA-130/CA合金膜对不离解极性有机物的分离效率更高。     

电性拓扑态、分子形状属性研究苯砜基环烷酸酯类化合物液相色谱容量因子

1引言定量结构保留关系(QSRR)是指分子结构描述符与其色谱保留值(如气相色谱保留指数、液相色谱容量因子等,以“Se”表示)之间的数量关系。影响溶质的色谱保留值的因素主要有溶质与溶质之间、溶质与固定相之间、溶质与流动相之间的相互作用力以及测定时的外部条件(如柱温、流速     

反相高效液相色谱中溶质保留过程的热力学研究Ⅰ: 柱相比, 吉氏自由能变及其分量, 吸附和解吸附自由能变

从热力学观点给反相高效液相色谱(RP-HPLC)中的相比以新的定义,提出了测定该相比的方法并准确测定了RP—HPLC中溶质计量置换过程中的吉氏自由能变△G_(P_a).发现在RP-HPLC中相比对保留过程中溶质总自由能变的贡献值几乎可与溶质本身的保留值相当.依据液相色谱中溶质计量置换保留模型,将溶质的△G_(P_a)分成与溶质吸附及解吸有关的两项独立的自由能变分量,△G_(I_a)和△G_(Z,D).对不同流动相组成条件下的△G_(P_a)和△G_(Z,D)进行了估算,并与实验结果进行了比较,偏差一般小于±2%.     

担载材料对TiO2薄膜光催化活性的影响

ＴＩＯ２薄膜催化剂光催化治理大气和水污染，具有实际应用的前景，受到科学界的高度重视“－‘’．实验结果发现，担载材料对膜的催化活性有很大影响”’，如采用玻璃、不锈钢。石英作为ＴＩＯ。膜的载体时，由于界面离子扩散作用的不同，使得膜的光催化活性有很大的差异...     

带电溶质在电色谱中柱内富集方法的研究————-基本理论 模型和实验验证

在电色谱(CEC)中引入场增强进样技术,并与HPLC柱内富集技术结合以使带电溶质得到更好的富集效果。理论研究表明,采用较高电阻率的样品溶剂,及匹配适当的有机调节剂强度有利于带电溶质在CEC中的柱内富集,以碱性药物普罗帕酮为实验样品,采用水(φ＝40%)-乙腈(φ=60%)为样品溶剂,水(φ=15%)-乙腈(φ=85%)-Tris(2mmol/L)-TEA(0.6mmol/L,pH7.60)为运行缓冲溶液时,达到了17,000倍以上的富集效果,从理论和实验研究的角度说明了CZE与HPLC机制结合的CEC进样方法用于样品柱内富集的可行性,进一步讨论了各种操作条件对富集结果的影响规律。     

带电溶质在电色谱中柱内富集方法的研究————-基本理论 模型和实验验证

在电色谱(CEC)中引入场增强进样技术,并与HPLC柱内富集技术结合以使带电溶质得到更好的富集效果。理论研究表明,采用较高电阻率的样品溶剂,及匹配适当的有机调节剂强度有利于带电溶质在CEC中的柱内富集,以碱性药物普罗帕酮为实验样品,采用水(φ＝40%)-乙腈(φ=60%)为样品溶剂,水(φ=15%)-乙腈(φ=85%)-Tris(2mmol/L)-TEA(0.6mmol/L,pH7.60)为运行缓冲溶液时,达到了17,000倍以上的富集效果,从理论和实验研究的角度说明了CZE与HPLC机制结合的CEC进样方法用于样品柱内富集的可行性,进一步讨论了各种操作条件对富集结果的影响规律。     

利用层层自组装技术制备聚电解质多层膜高效液相色谱固定相

以聚(乙烯-alt-马来酸)的苯乙胺衍生物与聚烯丙基胺盐酸盐为原料,通过层层自组装技术(LBL)在色谱硅胶表面交替沉积得到聚电解质多层膜高效液相色谱(HPLC)固定相;利用紫外光谱、红外光谱和元素分析研究了HPLC固定相的结构和组成.结果表明,聚电解质多层膜HPLC固定相被成功构筑在硅胶颗粒表面;制备的多层膜固定相可方便地用于6种芳香烃类及4种烷基苯类物质的分离分析.本文的研究结果说明LBL技术在制备HPLC固定相方面具有一定的应用价值.     

新型亲水性高聚物色谱填料NDPM

水溶性物质的分离对生物化合物的研究具有重要意义。70年代以来各种亲水性色谱填料的发展,促使高压液相色谱(HPLC)分离技术在生命科学领域中得到广泛的应用。亲水性高聚物类型的 HPLC 填料与相应的硅类型填料比较,虽然柱效率较低,但有较好的选择性,宽的 pH 值使用范围和大的柱容量。同时填料与溶质之     

核电站结构材料的锌离子注入电化学研究

应用电化学方法研究了锌离子注入(zinc injection)技术对核电站结构材料,如304L不锈钢、316L不锈钢和600合金在高温水中形成的氧化膜的电化学性能的影响. 锌离子注入压水堆(PWR)一回路技术可有效减少材料应力腐蚀破裂(stress corrosion cracking)和职业辐照. 用动电位扫描法检测材料氧化膜的自腐蚀电位与腐蚀电流,根据Mott-Schottky曲线分析Zn离子注入对材料氧化膜半导体性质的改变. SEM和XPS观察与检测试样表面形貌及其组分. 在Zn离子参与的金属氧化膜生成过程中,可生成Zn-Ni-Cr-Fe 氧化物,从而提高了材料的抗腐蚀能力及改变氧化膜的半导体性质.     

Capillary electrochromatography with monolithic silica columns. V. Study of the electrochromatographic behaviors of polar compounds on monolithic silica having surface bound cyano functionalities

In this report, a novel polar monolithic capillary column is described for normal phase CEC (NP-CEC) of representative polar compounds including mono- and oligosaccharides, peptides, and basic drugs. The polar monolithic column, which was described in detail in the preceding paper, consisted of silica-based monolith bonded with 1H-imidazole-4,5-dicarbonitrile (IDCN) and is denoted as 2CN-OH-Monolith. Various retention parameters for neutral polar solutes (e.g., mono- and oligosaccharides) and charged polar solutes (e.g., peptides and basic drugs) were evaluated over a wide-range of elution conditions. These retention parameters yielded quantitative assessment for the polar interactions between the model solutes and the stationary phase under investigation as well as the effect of electromigration of charged solutes on their overall migration in NP-CEC. Furthermore, this investigation demonstrated that despite the possibility of achieving isocratic separation in NP-CEC for widely differing polar species, multistep-gradient elution in NP-CEC is preferred to bring about the rapid separation of a large number of polar species in a single run.     

On-column trace enrichment by sequential frontal and elution electrochromatography II. Enhancement of sensitivity by segmented capillaries with z-cell configuration--application to the detection of dilute samples of moderately polar and nonpolar pesticides

An on-column trace enrichment method for capillary electrochromatography of dilute samples is described. It involves the sequential use of frontal and elution electrochromatography on a segmented capillary column comprising of two contiguous segments each packed with a different sorbent. While the entering segment is for preconcentration by frontal electrochromatography the second segment is much longer and is meant for separation of the enriched analytes in the subsequent elution electrochromatography step. The preconcentration segment is usually packed with a sorbent that affords the highest affinity towards the solutes of interest while the separation segment is packed with a stationary phase that exhibits the highest selectivity and separation efficiency for the analytes. The detection is performed in the UV using a z-cell configuration for achieving an increased path length for detection. The effectiveness of this on-column trace enrichment is demonstrated on dilute samples of moderately polar solutes (e.g., carbamate insecticides) and nonpolar solutes (e.g., pyrethroid insecticides). Under optimal frontal and elution electrochromatography conditions. 817- and 1100-fold sensitivity increase are achieved for permethrin (a pyrethroid insecticide) and methiocarb (a carbamate insecticide), respectively, with a UV detector. The method is demonstrated with real water samples (e.g., tap and lake water samples) spiked with carbamate and pyrethroid insecticides. The limits of detection for the pesticides achieved in tap and lake waters reached 10(-8) to 10(-9) M.     

Additive action of two or more solutes on lipid membranes

A wide variety of biological processes, pharmaceutical applications, and technical procedures is based on the combined action of two or more soluble compounds to perturb, permeabilize, or lyse biological membranes. Here we present a general model describing the additive action of solutes on the properties of membranes or micelles. The onset and completion of membrane solubilization induced by two surfactants (lauryl maltoside, with nonyl maltoside, octyl glucoside, or CHAPS, respectively) are very well described by our model on the basis of their individual partition coefficients, cmc's, and critical mole ratios R e sat and R e sol as detected by isothermal titration calorimetry. This suggests that the thermodynamic phase transition is governed by a single parameter (e.g., spontaneous curvature) in spite of the complexity of structural changes. Such surfactant mixtures show unique features such as nonlinear solubilization boundaries and concentration-dependent effective partition coefficients. Other phenomena such as membrane leakage are predicted to obey additive action if the solutes act via the same mechanism (e.g., toroidal pore formation) but deviate from the model in the case of independent, synergistic, or antagonistic action.     

Chiral separations and quantitative analysis of optical isomers on cellulose tribenzoate plates

In this paper new cellulose tribenzoate/gypsum layers in the ratio up to 8/1 (w/w) were investigated for the chiral resolution of closely related aromatic ketones (e.g. tetralones and indanones), alcohols (e.g. benzhydrols) and racemates or enantiomers of other compound classes (e.g. dinitrophenyl amino acids). Among 22 investigated compounds, 16 racemates were baseline or partially resolved by eluting with methanol or 2-propanol/water mixtures on 4/1 (w/w) layers. The best results were compared with those achieved on microcrystalline cellulose triacetate plates and on cellulose tribenzoate columns. The study of structurally related solutes allowed us to increase the knowledge of the retention and resolution mechanisms on this chiral stationary phase and to highlight the role of π-π interactions between cellulose tribenzoate and solutes with different substituents on the aromatic ring. However, some results were unexpected and confirmed the complexity of enantioseparation mechanisms, thus evidencing the importance of experimental tests. Densitometric scan in the visible region of cellulose tribenzoate/gypsum plates after their exposure to iodine vapours allowed us to successfully perform the quantitative analysis of the investigated compounds, thus overcoming the detection problems normally encountered with this stationary phase.     

Separation of acidic and neutral compounds by strong anion-exchange capillary electrochromatography dynamically modified with sodium dodecylsulfate

Summary Acidic and neutral compounds have been separated by strong anion-exchange capillary electrochromatography (SAXCEC) dynamically modified by addition of sodium dodecylsulfate (SDS). It was found that separation of neutral solutes by SAXCEC without addition of SDS is difficult because of the weak interaction of the solutes with the hydrophilic packing surface. The hydrophobicity of the packing surface increases on addition of SDS to the mobile phase, however, and the capacity of separating neutral solutes increases. Acidic solutes are retained, mainly because of the ion-exchange properties of this system. The influence of mobile phase composition, e.g. SDS concentration, ionic strength, and organic modifier fraction, on the retention of acidic and neutral solutes was investigated. Three acids and five neutral solutes were separated in only 5 min under optimized conditions, because the direction of the strong electroosmotic flow (EOF) was the same as that of electrophoretic migration of the acids under the conditions used. The repeatability of this system in terms of migration time relative standard deviation (RSD) is good—less than 0.48% for 10 consecutive runs of all the solutes tested. Column efficiencies for acids were > 125000 plates m⁻¹; those for neutral solutes varied from 25000 to 100000 plates m⁻¹.     

Capillary electrochromatography with monolithic-silica columns. II. Preparation of amphiphilic silica monoliths having surface-bound cationic octadecyl moieties and their chromatographic characterization and application to the separation of proteins and other neutral and charged species

Three different synthetic routes have been introduced and evaluated for the preparation of amphiphilic silica-based monoliths possessing surface-bound octadecyl ligands and positively charged groups. The amphiphilic silica monoliths (designated as cationic C18-monoliths) have been designed for use in reversed-phase capillary electrochromatography (RP-CEC) with hydro-organic mobile phases. These amphiphilic stationary phases yielded anodic electroosmotic flow (EOF) over a wide range of mobile phase pH. The magnitude of EOF remained constant up to pH 4.0 and then decreased at pH > 4.0 due to the ionization of silanol groups and the subsequent decrease in the net positive surface charge density of the amphiphilic monoliths. The cationic C18-monoliths exhibited reversed-phase chromatography (RPC) behavior toward non-polar solutes (e.g., alkyl benzenes), which parallels that observed with octadecyl-silica (ODS) monoliths. On the other hand, the amphiphilic stationary phases exhibited both non-polar and polar interactions toward slightly polar solutes such as anilines and PTH-amino acids. CEC retention factor k* and velocity factor k*e, which reflects the contribution of the electrophoretic mobility, were evaluated for charged solutes such as anilines and proteins.     

Adsorptive micro-extraction techniques--novel analytical tools for trace levels of polar solutes in aqueous media

A novel enrichment technique, adsorptive μ-extraction (AμE), is proposed for trace analysis of polar solutes in aqueous media. The preparation, stability tests and development of the analytical devices using two geometrical configurations, i.e. bar adsorptive μ-extraction (BAμE) and multi-spheres adsorptive μ-extraction (MSAμE) is fully discussed. From the several sorbent materials tested, activated carbons and polystyrene divinylbenzene phases demonstrated the best stability, robustness and to be the most suitable for analytical purposes. The application of both BAμE and MSAμE devices proved remarkable performance for the determination of trace levels of polar solutes and metabolites (e.g. pesticides, disinfection by-products, drugs of abuse and pharmaceuticals) in water matrices and biological fluids. By comparing AμE techniques with stir bar sorptive extraction based on polydimethylsiloxane phase, great effectiveness is attained overcoming the limitations of the latter enrichment approach regarding the more polar solutes. Furthermore, convenient sensitivity and selectivity is reached through AμE techniques, since the great advantage of this new analytical technology is the possibility to choose the most suitable sorbent to each particular type of application. The enrichment techniques proposed are cost-effective, easy to prepare and work-up, demonstrating robustness and to be a remarkable analytical tool for trace analysis of priority solutes in areas of recognized importance such as environment, forensic and other related life sciences.     

混合固定相电中溶质的输运特征

 以离子交换和反相固定相构成的混合固定相电中 ,溶质迁移在受到疏水、离子交换作用的同时 ,对于带电溶质而言 ,还受到电泳迁移的影响。根据离子独立迁移原理 ,结合过程中的多种相互作用 ,得到了描述溶质表观迁移速率与其各形态迁移速率、各种相互作用之间相互关系的理论表达式 ;讨论了混合模式电中流动相的 pH及其中的有机调节剂浓度、混合固定相配比等对电渗流的影响及不同形态溶质在柱内的输运特征。结果表明 ,在电中采用混合固定相可以在较大的 pH和有机调节剂浓度范围内得到较强且稳定的电渗流。     

Transport of organic solutes through amorphous teflon AF films

Fluorous media have great potential for selective extraction (e.g., as applied to organic synthesis). Fluorous polymer films would have significant advantages in fluorous separations. Stable films of Teflon AF 2400 were cast from solution. Films appear defect-free (SEM; AFM). Rigid aromatic solutes are transported (from chloroform solution to chloroform receiving phase) in a size-dependent manner (log permeability is proportional to -0.0067 times critical volume). Benzene's permeability is about 2 orders of magnitude higher than in comparable gas-phase experiments. The films show selectivity for fluorinated solutes in comparison to the hydrogen-containing control. Transport rates are dependent on the solvent making up the source and receiving phases. The effect of solvent is, interestingly, not due to changes in partition ratio, but rather it is due to changes in the solute diffusion coefficient in the film. Solvents plasticize the films. A less volatile compound, -COOH-terminated poly(hexafluoropropylene oxide) (4), plasticizes the films (T(g) = -40 degrees C). Permeabilities are decreased in comparison to 4-free films apparently because of decreased diffusivity of solutes. The slope of dependence of log permeability on critical volume is not changed, however.     

Glass-state amorphous salt solids formed by freeze-drying of amines and hydroxy carboxylic acids: effect of hydrogen-bonding and electrostatic interactions

We studied effect of molecular interactions on the physical properties of binary freeze-dried solids and frozen aqueous solutions using model chemicals containing various functional groups (amino, carboxyl, hydroxyl). Thermal analysis of frozen solutions containing alkyl diamines and hydroxy di- or tricarboxylic acids showed thermal transitions (T(g)': glass transition of maximally freeze-concentrated phase) at temperatures higher than those of the individual solutes. A binary frozen solution containing 80 mM 1,3-diamino-2-hydroxypropane (single-solute T(g)'<-60 degrees C) and 120 mM citric acid (single-solute T(g)': -55.0 degrees C) made the transition at -30.8 degrees C. The molecular weight of the solutes had smaller effects on the transition temperatures of the frozen mixture component solutions. Lyophilization of some high T(g)' mixture frozen solutions (e.g., 1,3-diamino-2-hydroxypropane and citric acid) resulted in cake-structure amorphous solids with glass transition temperatures (T(g)) higher than those of the individual components. Networking of intense hydrogen-bondings and electrostatic interactions between the heterogeneous molecules through the multiple functional groups was suggested to reduce the component mobility in the amorphous freeze-concentrated phase and the freeze-dried solids. Controlling the interactions should be a key to optimizing the physical properties of multi-component amorphous freeze-dried pharmaceutical formulations.