胶束中的磺化酞菁镓,磺化酞菁的二聚行为研究

本文研究了二磺化酞菁镓，三磺化酞菁在胶束中的二聚行为，计算了Ｓ３Ｐｃ，Ｓ２ＰＣＧａ在胶束中的二聚常数ＫＤ及分配系数Ｋ，并对磺化酞菁在胶束中的增敏，解聚机理进行了探讨。     

H_5GaMo_6W_6O_(40)·14H_2O及其钐盐的合成与表征

首次采用分步酸化、分步加料及乙醚萃取法合成了钼钨镓酸Ｈ５ＧａＭｏ６Ｗ６Ｏ４０．１４Ｈ２Ｏ，并用复分解法合成了钐的钼钨镓酸盐ＳｍＨ２ＧａＭｏ６Ｗ６Ｏ４０．１５Ｈ２Ｏ．用元素分析、电位滴定、红外光谱、紫外光谱、Ｘ射线粉末衍射和热分析等方法对合成产物进行了表征．结果表明，合成产物具有Ｋｅｇ－ｇｉｎ结构，且具有很高的热稳定性．     

四磺化酞菁钴轴向配位反应研究

采用分光光度法研究了四磺化酞菁钴（ＣｏＴＳＰｃ）与配体Ｌ（Ｌ＝ｅｎ，ＮＨ３，ＣＮ）的配位反应，研究了配位反应学，测定了配合物的稳定常数Ｋ，并讨论了配位反应机理，研究表明：ＣｏＴＳＰｃ与Ｌ形成ＣｏＴＳＰｃ（Ｌ）２的配合物，动力学方程为：－ｄＣＭ／ｄｔ＝ｋＣＭＣＬ，ＣＭ、ＣＬ分别为ＣｏＴＳＰｃ的单体和配体的浓度（ｅｎ；ｎ＝１；ＮＨ３，ＣＮ：ｎ＝２）；ＣｏＴＳＰｃ（Ｌ）２的稳定常数为：Ｌ＝ｅｎ，ｌｇＫ＝     

理化因子对嗜盐隐杆藻细胞生长及胞外多糖产量的影响

比较不同ＮａＣｌ、Ｃａ２＋、ＰＯ３－４等离子浓度对嗜盐隐杆藻（Ａｐｈａｎｏｔｈｅｃｅｈａｌｏｐｈｙｔｉｃａ）细胞生长及胞外多糖（Ｅｘｏｐｏｌｙｓａｃ－ｃｈａｒｉｄｅＥＰＳ）产量的影响。在各影响因子不同浓度的培养条件下,０．５ｍｏｌ／Ｌ的ＮａＣｌ、１．０ｇ／Ｌ的Ｃａ（ＮＯ３）２·４Ｈ２Ｏ、０．１ｇ／Ｌ的ＫＨ２ＰＯ４分别是其最佳生长浓度。ＥＰＳ的产量在０．５ｍｏｌ／ＬＮａＣｌ、,０．５ｇ／ＬＣａ（ＮＯ３）２·４Ｈ２Ｏ、０．５ｇ／Ｌ的ＫＨ２ＰＯ４培养条件下最高。在较低的Ｃａ２＋、Ｍｇ２＋、ＰＯ３－４浓度下可提高ＥＰＳ产率。     

CaO-SiO_2-P_2O_5-H_2O系统中CBC材料的溶胶凝胶过程研究 Ⅱ凝胶的烧成过程

利用ＸＲＤ，ＩＲ，ＳＥＭ及２９Ｓｉ，３１ＰＮＭＲ等测试技术研究了ＣａＯＳｉＯ２Ｐ２Ｏ５Ｈ２Ｏ系统中干凝胶在烧成过程中的物相变化及物相间发生的化学反应。认为凝胶在烧成过程的不同阶段发生的主要化学反应如下：（１）６７３～７７３Ｋ：由Ｃａ２Ｐ２Ｏ７和Ｃａ（ＮＯ３）２·４Ｈ２Ｏ反应生成了ＯＨＡｐ；（２）７７３～８７３Ｋ：由Ｃａ２Ｐ２Ｏ７和ＣａＯ反应生成了βＣ３Ｐ；（３）８７３～９７３Ｋ：由ＣａＯ和ＳｉＯ２反应生成βＣ２Ｓ。因此粉末材料的主要晶相有：ＯＨＡｐ，βＣ３Ｐ和βＣ２Ｓ，其中Ｓｉ和Ｐ之间有相互固溶现象。     

Cd~（2＋）与Cu~（2＋）、Co~（2＋）、Ni~（2＋）的非有机溶剂萃取分离研究

本文研究了ＰＥＧ－Ｚｉｎｃｏｎ－（ＮＨ＿４）＿２ＳＯ＿４体系对Ｃｕ~（２＋）、Ｃｏ~（２＋）、Ｎｉ~（２＋）、Ｃｄ~（２＋）的非有机溶剂萃取行为，结果表明：在ｐＨ５．５～８．５（Ｋ＿２ＨＰＯ＿４－ＫＨ＿２ＰＯ＿４）的水溶液中，Ｃｕ~（２＋）、Ｃｏ~（２＋）、Ｎｉ~（２＋）可被ＰＥＧ相几乎完全萃取，而Ｃｄ~（２＋）基本上不被萃取，从而获得了Ｃｄ~（２＋）与Ｃｕ~（２＋）、Ｃｏ~（２＋）、Ｎｉ~（２＋）混合离子的定量分离。     

液膜分离富集测定镓

用ＴＯＰＯ「（Ｃ８Ｈ１７）３ＰＯ」为流动载体,Ｎ２０５为表面活性剂,液体石蜡为膜增强剂,正己烷为膜溶剂,Ｈ２Ｃ２Ｏ４作内相试剂的乳状液膜体系,迁移富集Ｇａ＾３＋,研究了乳状液膜的稳定性、温度、Ｇａ＾３＋的浓度、外相ｐＨ值、乳水比（Ｒｅｗ）、油内比（Ｒｏｉ）等因素对富集Ｇａ＾３＋的影响。实验结果表明,在适宜的条件下,Ｇａ＾３＋的富集率可达９９．５％～１００．５％,在相同条件下,常见共存的Ｃｕ＾２＋、Ｃｏ＾２＋、Ｎｉ＾２＋、ＭｎＡ＾２＋、Ｆｅ＾３＋、Ａｌ＾３＋、Ｃｒ＾３＋、Ｔｉ＾４＋、Ｚｒ＾４＋、Ｐｂ＾２＋、Ｚｎ＾２＋、碱金属离子、碱土金属离子等不被迁移富集;大量Ｃｌ＾－、Ｆ＾－、、ＮＯ３＾－、ＳＯ４＾２－、ＰＯ４＾３－等都不影响Ｃａ＾３＋的富集,高式样应预先用氯化氢除硅,以防止影响迁移富集Ｇａ＾３＋,只ａ＾３＋可     

CaSO4—H3PO4—H2SO4—H2O四元系统及其应用（下）

ＣａＳＯ４－Ｈ３ＰＯ４－Ｈ２ＳＯ４－Ｈ２Ｏ四元系统及其应用（下）吴佩芝（上海天山路４６８弄９号３０４室２０００５１）中图分类号ＴＱ１２６．３５３四元系统在二水物流程中的应用〔１〕ＣａＳＯ４－Ｈ３ＰＯ４－Ｈ２Ｏ三元系统研究的结果指出：形成二水物硫酸钙的...     

CaO—SiO2—P2O5—H2O系统中CBC材料的溶胶—凝胶过程研究：II.凝胶的…

利用ＸＲＤ，ＩＲ，ＳＥＭ及＾２９Ｓｉ，＾３１Ｐ－ＮＭＲ等测试技术研究了ＣａＯ－ＳｉＯ２－Ｐ２Ｏ５－Ｈ２Ｏ系统中干凝胶在烧成过程中的物相变化及物相间发生的化学反应，认为凝胶在烧成过程的不同阶段发生的主要化学反应如下：（１）６７３～７７３Ｋ，由Ｃａ２Ｐ２Ｏ７和Ｃａ（ＮＯ３）２．４Ｈ２Ｏ反应生成了ＯＨＡｐ；（２）７３３～８７３Ｋ，由Ｃａ２Ｐ２Ｏ７和ＣａＯ反应生成了β－Ｃ３Ｐ；（３）８７３～９７３Ｋ；由Ｃ     

CaSO4—H3PO4—H2SO4—H2O四元系统及其应用（上）

ＣａＳＯ４－Ｈ３ＰＯ４－Ｈ２ＳＯ４－Ｈ２Ｏ四元系统是湿法磷酸领域中的主要相图，直到１９５８年才由日本学者池野亮当等人＊首先发表，而且只是其中关于ＣａＳＯ４·１２Ｈ２ＯＣａＳＯ４·２Ｈ２Ｏ转化过程部分的研究结果。７０年代中，笔者在研究半水—二水再结晶流程时发现：在温度恒定的条件下，四元系统中的ＣａＳＯ４·１２Ｈ２ＯＣａＳＯ４·２Ｈ２Ｏ转化过程的平衡点轨迹呈线性，可以用直线方程式计算有关参数，扩大了它的意义。随后，笔者在进行半水—二水再结晶流程的中试时，曾用上述计算参数控制ＣａＳＯ４·１２Ｈ２Ｏ—→ＣａＳＯ４·２Ｈ２Ｏ转化过程中二水物结晶的形成，取得满意结果。     

Development and characterization of homogeneous membranes prepared from sulfonated poly(phenylene oxide)

This article investigates the comprehensive properties of sulfonated poly(phenylene oxide) (SPPO) membranes with different sulfonation degrees and presents the completion of previous work necessary for the application of SPPO membranes to proton‐exchange membrane fuel cells. The sulfonation level has been accurately determined by conductometric titration and ¹H‐NMR, and the glass‐transition temperature has been obtained with both differential scanning calorimetry and dynamic mechanical thermal analysis. Sulfonic groups attached to the aromatic ring in the poly(phenylene oxide) backbone split at 220–340°C, but the main‐chain splitting temperature of SPPO is similar to that of the pure polymer. In addition, the effects of sulfonic groups and water on the tensile strength of these membranes have been studied. An increase in the sulfonate groups in the polymer results in an increase in the water uptake. Atomic force microscopy phase images of the acid‐form membranes clearly show the hydrophilic domains, and the ionic regions of the membranes with a low sulfonation degree are isolated and become connected to produce a cocontinuous morphology as the degree of sulfonation increases. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1244–1250, 2005     

离子聚合物金属复合材料的电形变性能研究

以乙烯-乙烯醇共聚物（EVOH）的主链为骨架,利用直接磺化反应制得离子聚合物膜（EVOH—g—SO3H）,然后以戊二醛为交联剂对其进行交联改性,得到EVOH—g—SO3H交联基体膜（EVOH—g—GSO3H）。最后采用化学还原工艺得到了以EVOH—g—GSO3H为基体的离子聚合物金属复合材料（IPMC）。讨论了磺化度、失水速率、负载电压等对IPMC电形变性能的影响。结果表明：磺化度dx为15．64％、33．25％、43．53％的IPMC顶点最大形变位移分别为7．53mm、17．02mm、32．11mm。涂有油脂保护层的IPMC失水速率和失水量均比未涂保护层的要小,涂有油脂保护层的IPMC顶点最大形变位移可达29．02mm,IPMC可以连续形变32次。负载电压越高形变量越大,频率越高形变量越小。     

Sulfonated multi-walled carbon nanotubes for the removal of copper (II) from aqueous solutions

Sulfonated multi-walled carbon nanotubes (s-MWCNTs) was prepared from purified multi-walled carbon nanotubes (p-MWCNTs) by concentrated H₂SO₄ at elevated temperature. The structure was characterized by SEM, FTIR, Raman, XPS, and BET. It could be dispersed steadily in water at a dosage of 1.0 mg/mL for a week. The adsorption performance of s-MWCNTs toward Cu(II) was investigated including the effects of pH and ionic strength. Results indicated the adsorption was much dependent on pH but not on ionic strength. The adsorption capacity for Cu(II) was enhanced 58.9% via the sulfonation. Moreover, the adsorption mechanisms were carefully analyzed by Freundlich and D-R models.     

Characterization of strong polyelectrolyte hydrogels based on poly(vinyl alcohol)

Maleic anhydride (MA) was grafted onto both partially and fully hydrolyzed poly(vinyl alcohol) (PVA) in the presence of an initiator. Strong polyelectrolyte polymers were prepared by sulfonation of PVA–MA grafts. The sulfonation was completed by reaction of hydroxyl groups of PVA–MA grafts with two different sulfonating reagents (chlorosulfonic acid and pyridine sulfonic acid). The sulfonation degree was evaluated by acid–base titration and ¹H NMR analysis. The solution behaviour of the prepared grafts was evaluated from viscosity measurements. Four kinds of water‐insoluble PVA–MA and PVA–MA‐SO₃H hydrogels were prepared by heat treatment, physical gelation and chemical crosslinking with different weight ratios of N,N‐methylene bisacrylamide (MBA) crosslinker. The swelling parameters were measured for all prepared gels in deionized water and aqueous solutions at different pH values from 2 to 12 having constant ionic strength (I = 0.1). All gels exhibit a different swelling behaviour upon environmental pH changes. Copyright © 2004 Society of Chemical Industry     

Physicomechanical and dielectric properties of magnesium and barium ionomers based on sulfonated maleated styrene‐ethylene/butylene‐styrene block copolymer

Ionomers, containing both carboxylate and sulfonate anions on the polymer backbone, based on metal cations like Mg⁺² and Ba⁺² were prepared by sulfonating maleated styrene‐ethylene/butylene‐styrene block copolymer, hereafter referred to as m‐SEBS, followed by its neutralization by metal acetates. Infrared spectroscopic studies reveal that sulfonation reaction takes place in the para position of the benzene rings of polystyrene blocks and metal salts are formed on neutralization of the precursor acids. Dynamic mechanical thermal analyses show that sulfonation causes increase in T_g of the rubbery phase of m‐SEBS and decrease in tan δ at T_g of the hard phase, along with formation of a rubbery plateau. The changes become more pronounced on neutralization of the sulfonated maleated SEBS, and the effect is greater in the case of Ba salt. Dielectric thermal analyses (DETA) show that incorporation of ionic groups causes profound changes in the dielectric constant (ϵ′) of m‐SEBS. In addition to the low temperature glass–rubber transition, the plot of ϵ′ vs. temperature shows occurrence of a high‐temperature transition, also known as the ionic transition. Activation energy for the dielectric relaxation could be determined on the basis of frequency dependence of the ionic transition temperature. Two values of the activation energy for the dielectric relaxation refer to the presence of two types of ionic aggregates, namely multiplets and clusters. Incorporation of the ionic groups causes enhancement in stress–strain properties as well as retention of the properties at elevated temperatures (50° and 75°C), and the effect is more pronounced in the case of Ba ionomer. Although sulfonated ionomers show greater strength than the carboxylated ionomers, the sulfonated maleated ionomers show higher stress–strain properties in comparison to both sulfonated and carboxylated ionomers. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 816–825, 2000     

Miscibility and mechanical properties of sulfonated polystyrene–polyurethane blends

A sulfonated polystyrene (SPS) and a polyurethane containing a tertiary amine group (NPU) were blended in solution. The effect of blend composition was studied in the blend of SPS with 9.83 mol % of sulfonation (SPS-9.83) and NPU with 33 mol % of MDEA (NPU-33). As the SPS concentration increases, a significant improvement of miscibility is observed. The tensile strength of the blends is greater than either pure NPU or SPS. A maximum strength and a maximum density occur at 50 wt % SPS. The stress–strain curve shows a well-defined yield when the SPS concentration in the blend is 30 or 50 wt %. The yield is more dramatic in the blend with 50 wt % SPS than that of 30 wt % SPS. At a lower SPS concentration, the blend behaves like a rubber, while a higher SPS concentration in the blend results in a brittle failure before yield. An increase in the sulfonation level of SPS in the SPS–NPU-33 (30/70) blends leads to an improved miscibility. A significant enhancement of tensile strength is observed as the sulfonation increases. A clear yield point on the stress–strain curves occurs when the sulfonation of SPS in the blend is 4.79 mol % or greater. Increasing the MDEA content of NPU up to 8.3 mol % can lead to an enhancement of tensile strength. A further increase in the MDEA content has little influence on the tensile strength, but a clear yield on the stress–strain curve occurs. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:2035–2045, 1998     

Polymorphism of Alpha-Synuclein Amyloid Fibrils Depends on Ionic Strength and Protein Concentration

Protein aggregate formation is linked with multiple amyloidoses, including Alzheimer‘s and Parkinson‘s diseases. Currently, the understanding of such fibrillar structure formation and propagation is still not sufficient, the outcome of which is a lack of potent, anti-amyloid drugs. The environmental conditions used during in vitro protein aggregation assays play an important role in determining both the aggregation kinetic parameters, as well as resulting fibril structure. In the case of alpha-synuclein, ionic strength has been shown as a crucial factor in its amyloid aggregation. In this work, we examine a large sample size of alpha-synuclein aggregation reactions under thirty different ionic strength and protein concentration combinations and determine the resulting fibril structural variations using their dye-binding properties, secondary structure and morphology. We show that both ionic strength and protein concentration determine the structural variability of alpha-synuclein amyloid fibrils and that sometimes even identical conditions can result in up to four distinct types of aggregates.     

不同平均分子量及其分布烷基芳基磺酸盐的制备与性能

以直链α烯烃、苯、甲苯、混和二甲苯等为原料,采用原位离子液体催化烷基化反应分别合成出不同碳数的直链烷基苯、烷基甲苯和烷基二甲苯,经降膜式磺化、中和反应、提纯等方法制得不同相对分子质量的烷基芳基磺酸盐,其纯度均大于97.0%,仪器分析证明了其结构与设计相符。不同平均分子量、不同分布形式的磺酸盐体系降低油水界面张力能力不同;平均分子量为432、递增分布和反正态分布体系与碱、聚合物组成的三元复合体系在人造岩心上,室内模拟驱油可在水驱基础上提高采收率22%以上。     

Nanostructure and properties of proton‐conducting sulfonated poly(ether ether ketone) (SPEEK) and zirconia–SPEEK hybrid membranes for direct alcohol fuel cells: effect of the nature of swelling solvent and incorporation of heteropolyacid

The influence, on membrane nanostructure and properties, of water or ethanol as swelling solvent of sulfonated poly(ether ether ketone) (SPEEK) and zirconia–SPEEK hybrid membranes prepared using the sol–gel process has been investigated. Independent of the solvent, small‐angle X‐ray scattering measurements reveal the existence of a two‐level hierarchical structure in SPEEK of greater sulfonation level, consisting of solvent‐swelled spatially correlated primary SO₃H‐rich ionic clusters of around 15 Å in size, forming larger secondary aggregates well dispersed in the PEEK matrix. The size of the primary nanodomains and the connectivity between domains are determining parameters for protonic conductivity, solvent swelling ability and permeability of the membranes. For both SPEEK and zirconia–SPEEK membranes containing ethanol, the pronounced affinity of ethanol molecules with SPEEK leads to an increase in the size of ionic clusters and of the number of connecting channels between clusters compared to membranes containing water. This promotes solvent swelling and proton conductivity. The increase in permeability to water induced by incorporation of ethanol in place of water in both polymeric and hybrid membranes is less in the hybrid membranes. This result suggests that the potential use of zirconia–SPEEK hybrid membranes in direct alcohol fuel cells is more promising than that of pure SPEEK, due not only to the less probable alcohol and water penetration in the membranes associated with their lower permeability, but also to the fact that an eventual penetration of alcohol in hybrid membranes should reduce the risk of cathode flooding compared to zirconia‐free SPEEK membranes. Copyright © 2011 Society of Chemical Industry