Ion-exchange selectivity of a network calixarene-containing polymer obtained by the template synthesis on Na<Superscript>+</Superscript>, K<Superscript>+</Superscript>, and Ba<Superscript>2+</Superscript> matrices

The ion-exchange equilibrium in network polymers obtained from cis-2,8,14,20-tetraphenyl-4,6,10,12,16,18,22,24-octahydroxycalix[4]arene by template synthesis on cations Na⁺, K⁺, and Ba²⁺ as matrices was studied. The selectivity coefficients of ion exchanges Ba²⁺-H⁺, Na⁺-H⁺, K⁺-H⁺, Na⁺-K⁺, and Na⁺-NH₄ ⁺ were determined. The template synthesis enhanced the affinity of the polymers to matrix-forming cations by 6–8 kJ mol⁻¹. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1919–1922, August, 2005.     

Synthesis of a Tweezer—like Bis（Phenylthiapropoxy）calix[4]—arene as a Cation／π Enhanced Sensor for Ion—Selective Electrodes

Two novel 25,27-dihydroxy-26,28-bis(3-phenylthiapropxy)-calix[4]arene(3) and 25,27-dihydroxy-26,28-bis(3-phenylthiapropoxy)-5,11,17,23-tetra-tert-butylcalix[4] arene (4) were synthesized for the evaluation of their ion-selectivity in ion-selective electrodes(ISEs).ISEs based on 3 and 4 as neutral ionophores were prepared,and their selectivity coefficients for Ag^ (lg KAg,M^pot)were investigated against other alkali metal,alkaline-earth metal,aluminum,thallium(Ⅰ）,Lead and some transition metal ions using the separate solution method (SSM).These ISEs showed excellent Ag^ seletivity over most of the interfering cations examined,except for Hg^2 and Fe^2 having relative smaller interference(lg KAg,M^pot≤-2.1).     

Phase transfer catalytic system with the third liquid phase

Phase transfer catalysis, a technique to bring the reactants in two immiscible phases together by adding a phase transfer agent, has been employed in the production of fine chemicals and pharmaceuticals in the last few decades. The third liquid phase (catalytic phase) may be formed when phase transfer catalysts (PTC), cannot be dissolved in either organic or aqueous phase. The third phase catalytic systems have the following three advantages, that is, (1) high activity (2) repeated use and (3) separation between the organic phase and the aqueous phase. It is expected that simple new processes can be constructed by applying these three advantages.     

纳米微晶Y_2Sn_(2-x)FexO_(7-δ)的制备及其催化选择性能研究

采用共沉淀并加法制备了Ｂ位掺杂烧绿石型稀土复合氧化物纳米微晶Ｙ２Ｓｎ２－ｘＦｅｘＯ７－δ（ｘ＝００～１０）。制备的纳米微晶属于立方晶系，Ｆｄ３ｍ，晶胞参数与掺杂量呈线性关系。通过Ｍｓｂａｕｅｒ、ＴＧＤＴＡ，气相色谱和γ射线辐照等技术研究了纳米微晶对ＣＯ的催化选择性能。结果表明，纳米微晶对ＣＯ的催化选择性明显高于一般粉料对ＣＯ的选择性；纳米微晶对ＣＯ的选择性与掺杂量有关；未辐照的纳米微晶，当掺杂量ｘ＝０６时，其对ＣＯ的选择性为最高，辐照后的纳米微晶，当掺杂量ｘ＝０４时，其对ＣＯ的选择性为最高     

Organomineral sorbents based on clinoptilolite-containing tuffs

The anion-exchange properties of a new organomineral sorbent obtained by modification of clinoptilolite-containing tuffs by polyhexamethyleneguanidine have been studied after different periods of storage (time after synthesis) and numbers of sorption-regeneration cycles. The sorbent can be used as a cation- and an anion-exchanger simultaneously. Selectivity coefficients (exchange constants) for F^–, SO₄ ^2–, and HPO₄ ^2– ionsvs. Cl^– ions on modified clinoptilolite-containing tuffs have been determined. The modification improves the mechanical properties of clinoptilolite tuffs.For part 1, see Ref. 1.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1554–1556, September, 1994.     

Chloride distribution coefficient on strongly basic anion-exchange resin: Dependence on co-ion in alkali fluoride solutions

Summary The dependence of the chloride distribution coefficient on the co-ion of solutions of different alkali fluorides, MF, up to 11M is tested on the strongly basic anion-exchange resin AG1-X10. Under the same experimental conditions the distribution coefficient decreases in the following order for M⁺: Na⁺>K⁺>Rb⁺>Cs⁺. This can be explained by the different co-ion-chloride interactions. The consequence of this interaction for a chromatographic separation of chloride is shown with 5M KF and CsF solutions, used as eluants. Depending on the fluoride concentration, the distribution coefficient passes through a minimum value to increase again at higher electrolyte concentration. The non-exchange electrolyte in the resin phase is responsible for this effect. In addition, the bromide and the iodide distribution coefficients up to 10M KF solutions are determined. One results is that the selectivity coefficient between halide ions increases at higher electrolyte concentrations.     

催化剂和供氢剂对渣油模型化合物裂化反应选择性的影响

供氢剂与分散性催化剂协同作用对于传统的煤液化体系和渣油加氢裂化体系非常重要。通过活化分子氢及煤分子，使液化反应在较低的温度下进行以减少副反应，继而提高氢转移效率，增加液体产物产率。供氢剂和催化剂起促进煤分子裂化的作用。将供氢剂与催化剂的协同作用应用于渣油加     

Facial selectivity of the Ireland-Claisen rearrangement of allylic esters of 2-methyl and 2-methoxycyclopentanecarboxylic acids

Ketene silylacetals derived from prenyl and (Z)- and (E)-crotyl 2-methylcyclopentanecarboxylates (9) were subjected to the Ireland-Claisen rearrangement. All three substrates rearranged with complete facial selectivity, but the (Z)- and (E)-crotyl systems gave a mixture comprised of the same diastereomers of 1-(1-methyl-2-propenyl)-2-methylcyclopentanecarboxylic acid (14) in ratios of 2:1 and 1:2, respectively. In contrast, the ketene silylacetals prepared from allyl and prenyl 2-methoxycyclopentanecarboxylates (22) underwent rearrangements with both facial stereochemistries.     

微波辐射-酶耦合催化(MIECC)反应

将微波辐射用于非水相酶催化可以获得很多有别于常规加热下的反应结果.本文讨论了微波的非热效应在酶促反应中的表现,探讨了微波辐射对酶的结构、构象、活性及酶催化反应动力学的影响,以及微波辐射-酶耦合催化对反应的对映选择性、底物专一性、前手性选择性和区域选择性的影响.在大多数场合,适当的微波辐射不会损伤酶活而且可以提高反应速率,而对酶特异性的影响则不一而论.     

Detectability enhancement of spectrophotometric detectors by the use of multidimensional gas chromatography

Multidimensional gas chromatography (2D GC) is demonstrated as a way to improve limits of detectability of spectrophotometric detectors. UV and IR detectors are generally less sensitive than mass spectrometers or other GC detectors. This has placed some limitations on the useful capabilities provided by spectrophotometric detectors, such as the ability to provide structure‐related information for a particular analyte. In this paper, we report results from interfacing a 2D GC instrument to a UV detector. Symmetry factor and the ratio of retention time divided by peak width did not show deterioration of the quality of chromatography when a megabore column was used with this detector. Furthermore, an increase in the limits of detectability over that attainable in a single‐column system was realized by using the 2D GC system. However, the low flow (1 mL/min) imposed by the use of a microbore column (250 μm ID) caused significant tailing when the UV detector was used.