奎宁修饰的纳米铑簇合物催化丙酮酸乙酯对映选择性加氢反应研究

研究了奎宁作手性修饰剂修饰的负载型纳米铑簇合物催化剂 (Rh/ PVP-γ-Al2 O3)催化丙酮酸乙酯不对称氢化反应 ,在该反应中手性修饰剂奎宁不仅具有手性诱导作用 ,而且还有明显加速反应的作用 ;载体γ-Al2 O3在促进提高催化剂活性和对映选择性方面也有很重要的影响 .在优化的反应条件 [2 0℃ ,7.0 MPaH2 ,c(奎宁 ) =3 .86× 1 0 - 3mol/ L,四氢呋喃作溶剂 ]下 ,丙酮酸乙酯不对称加氢的转化频率 (TOF)为871 h- 1 ,对映选择性达到了 5 4.7% ;反应温度降低到 3℃时 ,对映选择性达到 5 9.2 % .     

三正辛胺修饰电极伏安测定痕量金的研究

用化学修饰电极伏安测定痕量金,Kalcher K等曾采用阴离子交换剂碳糊修饰电极及打萨宗碳糊修饰电极检测100～300μg/L的金。本文采用三正辛胺(TOA)修饰玻碳电极,在1.5 mol/L介质中,Au(Ⅲ)在+0.16 V(vs SCE)处有一灵敏的不可逆还原峰。检出限为0.1μg/L。灵敏度比文献方法高千倍。Au(Ⅲ)浓度在5×10~(-7)～5×10~(-9)mol/L范围内峰高与浓度     

Effect of electrode membrane surface ratio and thickness on lead electrode potential

Summary The lead ion selective electrode (ISE) consisting of PbS-Ag₂S is normally used with a membrane surface of outer layer areaA _o) and inner layer area (A _i) at unity (A _o=A _i). Partial covering of one surface area with an insulating material and keeping the other surface layer intact resulted in different ratios of membrane surface areas exposed to lead solutions. The potential linearly increased with increasing theA _o/A _i ratio and decreased with decreasing theA _o/A _i ratio. The lead ISE potential increased linearly with increasing the membrane thickness, but which required much longer time for a stable potential.

---

Wirkung von Oberflächenverhältnis und Dicke der Elektrodenmembran auf das Potential einer Bleielektrode

Zusammenfassung Die aus PbS-Ag₂S bestehende spezifische Bleiionen-Elektrode wird üblicherweise mit einem Oberflächenverhältnis der Außenfläche (A _o) und der Innenfläche (A _i) mitA _o=A _i verwendet. Durch teilweise Abdeckung einer Oberfläche mit isolierendem Material, ohne daß die andere Oberfläche verändert wird, ergaben sich verschiedene Verhältnisse der mit der Bleilösung in Berührung stehenden Oberflächen. Mit dem VerhältnisA _o/A _i stieg das Potential linear an bzw. es fiel mit diesem Verhältnis ab. Das Potential der spezifischen Bleielektrode stieg mit der Dicke der Membran, stabilisierte sich aber wesentlich langsamer.

     

铕（Ⅲ）—β—二酮—4,5—二氮芴—9—酮三元配合物的合成

铕（Ⅲ）┐β┐二酮┐４，５┐二氮芴┐９┐酮三元配合物的合成成义祥徐端钧＊徐元植（浙江大学化学系杭州３１００２７）关键词铕，β－二酮，二氮芴酮，三元配合物，合成，荧光光谱１９９７－０３－３１收稿，１９９７－０７－１５修回噻吩甲酰三氟丙酮（ＴＴＡ）和苯甲...     

Interaction between Metal in Metallo Enzyme and Small Biological Molecules

ＩｎｔｅｒａｃｔｉｏｎｂｅｔｗｅｅｎＭｅｔａｌｉｎＭｅｔａｌｌｏＥｎｚｙｍｅａｎｄＳｍａｌｌＢｉｏｌｏｇｉｃａｌＭｏｌｅｃｕｌｅｓ￥ＨｕＪｉｅ－Ｈａｎ；ＳｈｕＺａｎ－Ｙｏｎｇ；ＴａｏＬｉ－Ｍｅｉ；ＣｈｅｎｇＧｕｏ－Ｂａｏ（ＤａｌｉａｎＩｎｓｔｉｔｕｔ...     

果蔬中L—抗坏血酸的示波计时电位K3Fe（CN）6滴定法研究

本文报导的方法是在南京大学高鸿教授研究的K_3Fe(CN)_6示波极谱滴定法(在PH8的K_2HPO_4—KH_2PO_4—KBr底液中,用0.04660mol/LK_3Fe(CN)_6标准溶液对纯抗坏血酸测定)的基础上,考虑到L—抗坏血酸(以下简称V_e)在碱性、中性介质中稳定性差,如用于V_e含量很微的果蔬测定,对结果影响大。本文改为H_2C_2O_4—KBr的酸性介质作底液,用     

Enhanced Kinetic Isotope Effect of the Phosphate-Catalyzed Proton Exchange in N,N'-Dimethylurea

The concerted mechanism of phosphate-catalyzed proton exchange in N,N'-dimethylurea has been studied. Kinetic data were measured using the technigue of NMR line-shape analysis. A significant kinetic isotope effect was observed for the concerted proton transfer in N,N'-dimethylurea and is attributed to the tunnelling effect.     

力加寿片薄层色谱鉴别研究

力加寿片是由人参皂甙、白芍、刺五加、淫羊藿、灵芝、维生素E醋酸酯(简称维E)等组成的抗衰老药。由于处方中成分复杂,相互干扰,样品必须经过色谱前预处理及薄层条件优选方可望获得重现性、灵敏度、准确性较好的层析结果。本文介绍了力加寿片样品预处     

The solubility products of some slightly soluble lead salts and the potentiometric titration of molybdate, tungstate, perrhenate and fluoride with use of a lead ion-selective electrode

The conditional solubility products of lead molybdate, lead tungstate and lead perrhenate were found to be 1.2 +/- 0.3 x 10(-13), 8.4 +/- 0.1 x 10(-11) and 6.9 +/- 0.8 x 10(-9), respectively. In the case of lead perrhenate, the conditional stepwise formation constants for PbReO(+)(4) and Pb(ReO(4))(2) were found to be 1.2 +/- 0.1 x 10(5) and 1.2 +/- 0.2 x 10(3), respectively. Conditions for the potentiometric titration of molybdate, tungstate, perrhenate and fluoride with lead were established. The precipitates obtained during the titration of molybdate, perrhenate and fluoride mixtures have been proved to be physical mixtures of lead molybdate, perrhenate, fluoride and hydroxide, by infrared spectrometry. The pK(sp)-values of the lead salts of chromate, molybdate and tungstate are shown to increase linearly with increasing atomic number or electronegativity of the Group VI metal ion.