Ring-opening metathesis polymerization for the preparation of norbornene-based weak cation-exchange monolithic capillary columns

Functionalized monolithic columns were prepared via ring-opening metathesis polymerization (ROMP) within silanized fused silica capillaries with an internal diameter of 200 μm by in situ grafting. This procedure is conducted in two steps, the first of which is the formation of the basic monolithic structure by polymerization of norborn-2-ene (NBE) and 1,4,4a,5,8,8a-hexahydro-1,4,5,8-exo,endo-dimethanonaphthalene (DMN-H6) in a porogenic system (toluene and 2-propanol) using RuCl₂(PCy₃)₂(CHPh) as ROMP initiator. In the second step the still active initiator sites located on the surface of the structure-forming microglobules were used as receptor groups for the attachment (“grafting”) of functional groups onto the monolithic backbone by flushing the monolith with 7-oxanorborn-2-ene-5,6-carboxylic anhydride (ONDCA). Functionalization conditions were first defined that did not damage the backbone of low polymer content (20%) monoliths allowing high-throughput chromatographic separations. Variation of the functionalization conditions was then shown to provide a means of controlling the degree of functionalization and resulting ion-exchange capacity. The maximum level of in situ ONDCA grafting was obtained by a 3 h polymerization in toluene at 40 °C. The weak cation-exchange monoliths obtained provided good separation of a standard peptide mixture comprising four synthetic peptides designed specifically for the evaluation of cation-exchange columns. An equivalent separation was also achieved using the lowest capacity column studied, indicative of a high degree of robustness of the functionalization procedure. As well as demonstrably bearing ionic functional groups enabling analyte separation in the cation-exchange mode, the columns exhibited additional hydrophobic characteristics which influenced the separation process. The functionalized monoliths thus represent useful tools for mixed-mode separations.     

Cation-exchange fabric prepared by electron beam-induced graft copolymerization of binary monomer mixture

Applying the electron-beam preirradiation method in air the cation - exchange fabric (CEF) containing sulfonic acid (R-SO₃H) groups was prepared by graft copolymerization of sodium styrenesulfonate with acrylic acid onto non woven polypropylene fabric. The effect of reaction conditions on the grafting yield and reaction mechanism was examined. The ion-exchange properties towards Cu(II) and Co(II) ions of the CEF were investigated depending on the form of the CEF and a pH of the solution. It was found that the synthesized CEF contains both strong acid groups (R-SO₃H) and weak acid (R-COOH) groups in almost equal proportion. The utilization of the CEF in Na₊ form allows to make the best use of its ion-exchange capacity.     

阳离子交换分离—最小二乘法分光光度同时测定矿石中铌钽

用酒石酸、盐酸混合液作洗脱剂,阳离子交换树脂将矿石中的铌和钽与其它金属元素分离,洗下的铌、钽在盐酸—酒石酸介质中用5-Br-PADAP显色,用最小二乘法处理混合液的分光光度数据,建立浓度与吸光度间的最小二乘法数学模型。文中还对铌钽矿石进行分析,同时与二波长联合分光光度法     

醋酸甲酯催化水解本征动力学的研究

以阳离子交换树脂为催化剂 ,对醋酸甲酯催化水解本征动力学进行研究 ,并建立了消除催化剂包内扩散的本征动力学模型     

AG50W-x8树脂分离去除钡的多原子离子对电感耦合等离子体质谱法测定稀土元素的质谱干扰

采用AG50W－x8阳离子交换树脂,以HNO3作为梯度淋洗剂,可有效地分离Ba和稀土元素,实验表明：以2mol/L HNO3淋洗时,99．5％的Ba被分离去除;以5mol/L HNO3淋洗时,稀土的回收率在96－110％之间。标准参考物质的分析结果显示测定值与标准值十分接近,表明AG50W－x8阳离子交换树脂分离可有效地去除Ba元素的多原子离子（BaO^ ,BaOH^ )对ICP－MS法测定稀土元素测定的质谱干扰,该方法准确,可靠。同时,为准确测定Eu提供了一条新的途径。     

Transmembrane potentials in systems containing 18-crown-6

Electric potentials of MK-40 cation-exchange membrane, which is immersed in aqueous solutions of KCl, RbCl, and macrocyclic polyether 18-crown-6, have been measured. The possibility of preliminary calculations of biionic and multiionic potentials from equilibrium constants of ionic exchange and electrochemical mobilities of cations in the sulfo cationite is demonstrated.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1489–1490, August, 1995.     

强酸阳离子交换树脂在水中的热稳定性

通过在水中加热不同结构的磺化苯乙烯－二乙烯苯共聚物，研究了常见凝胶型和大孔型强酸阳离子交换树脂在１７０℃和１９０℃水介质中的热稳定性。     

Thermodynamics of ion exchange of H<Superscript>+</Superscript> by Na<Superscript>+</Superscript> or NH<Subscript>4</Subscript><Superscript>+</Superscript> on ion-exchange resins based on <Emphasis Type="Italic">C</Emphasis>-tetramethylcalix[4]resorcinarene

The corrected selectivity coefficients of the ion exchange H⁺-Na⁺ and H⁺-NH₄ ⁺ on ion-exchange resins based on C-tetramethylcalix[4]resorcinarene were calculated from the experimental data obtained from studying ion-exchange equilibria. The preference of the ion-exchange resins for cations increases in the sequence: Na⁺ < NH₄ ⁺ < < H⁺, and the ion-exchange resin based on (2-furyl)hydroxymethyltetramethylcalix[4]resorcinarene has a higher preference for ammonium cations. According to the results of microcalorimetric measurements, the exchange H⁺-Na⁺ on this ion-exchange resin is accompanied by the highest change in the differential enthalpy. It follows from the quantum-chemical calculations that the introduction of a (2-furyl)hydroxymethyl group into the structure of the polymer induces additional electrostatic interactions between an ammonium cation and an elementary unit of the ion-exchange resin.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2560–2563, December, 2004.     

碱性药物在硫醚嵌入苯磺酸硅胶固定相上的色谱行为

混合模式色谱（MMC）在复杂样品的分离分析方面具有独到的优势,相比于单一模式色谱,MMC受到多种作用控制,保留机理更为复杂。利用巯基-烯点击化学方法分别制备了单配体和双配体两种硫醚嵌入苯磺酸硅胶固定相,通过改变pH、离子强度和有机溶剂强度等流动相条件,以4种碱性药物为模型,对其保留机理进行了探讨。结果表明,两种固定相都具有反相和离子交换的混合保留机理。通过改变流动相中盐浓度、考察溶质保留因子与盐浓度倒数的关系,证明了反相、单纯离子交换和反相协同离子交换三种作用形式的保留模型更为合理。定量研究表明,在两个固定相上,由单纯离子交换和反相协同离子交换构成的总离子交换作用占主导,各作用占比与溶质、流动相组成、固定相配体的类型及其比例等密切相关,并且协同作用对溶质的保留和分离选择性影响很大。混合模式色谱保留机理的研究对于新型固定相设计和复杂体系的分离优化具有重要理论指导意义。     

Cation-exchange reaction with accompanying current discharge

When a cation-exchange membrane swollen with propylene carbonate was placed in tight contact with lithium foil, an ion-exchange reaction of lithium ions with the cation-exchange membrane occurred. The assembly exhibited properties of a lithium cell (3.0-3.2 V without load). The ion-exchange capacity of various cation-exchange membranes and their degree of swelling with propylene carbonte were related to the capacity of the formed lithium cell. A discharge current of 0.32 mA was observed through a 3 cm² cell. Analysis of lithium ions in the membrane phase after discharge revealed that the ion-exchange reaction of lithium ions with the cation-exchange groups of the membrane was directly related to the current discharge of the cell. However, the formed lithium cell showed high self-discharge.