Activation of peroxyl and molecular oxygen using bis -benzimidazole diamide copper (II) compounds

New tetradentatebis-benzimidazole ligands have been synthesized and utilized to prepare copper (II) complexes. Some of these copper (II) complexes have been characterized structurally. The copper (II) in these complexes is found to possess varying geometries. A distorted octahedral geometry is found with a highly unsymmetrical bidentate nitrate group. An unusual polymeric one-dimensional structure is observed where copper (II) is in a distorted square pyramidal geometry with a monodentate nitrate ion, having long Cu-O bond, while a distorted triagonal bipyramidal geometry is found with two carbonyl O atoms and a Cl atom in the equatorial plane, and two benzimidazole imine N atoms occupy the axial position. These compounds are found to activate the cumylperoxyl group, and this has been utilized in the facile oxidation of aromatic alcohols to aldehydes, where they act as catalysts with large turnovers. The yields of the respective products vary from 32 to 65%. The role of molecular oxygen has been studied and an attempt has been made to identify the “active copper species”. Activation of molecular oxygen has also been observed and has been used for oxidative dealkylation of a hindered phenol, producing di-butyl quinones with yields of 20–25% and 10–12 fold catalytic turnover. Dihydroxybenzenes and substituted catechols are also readily oxidized to the corresponding quinones, in oxygen-saturated solvents. Yields of 84% have been observed with 34-fold catalyst turnover, with di-t-butylcatechol. The activity of these copper (II) —bis-benzmidazolediamide compounds is reminiscent of the functioning of copper centres in galactose oxidase, tyrosinase and catechol oxidase.     

甲基紫掺杂聚乙烯醇薄膜材料红光多重全息存储

甲基紫掺杂聚乙烯醇薄膜材料在两束相干光照射下生成相位光栅.当改变一束相干光光程,通过监测相位光栅的一级衍射信号强度的变化,可以检测相位光栅的生长和擦除过程.在此实验基础上,讨论了甲基紫掺杂聚乙烯醇薄膜材料多重全息存储的原理与结果.     

萃取浮选光度法测定微量钼的研究及应用

研究了用甲苯萃取浮选Mo(Ⅴ)—SCN~-—Kφ三元络合物的各种条件。在硫酸介质中,紫红色络合物最大吸收波长位于585nm,摩尔吸光系数为2.8×10~5l·mol~(-1)·cm~(-1),钼量在0—10μg/25ml范围内符合比耳定律。大量常见元素均不干扰,40倍的钨(Ⅵ)亦不干扰钼的测定,方法已应用于钨矿中微量钼的测定,其结果令人满意。     

Phenol biosensor based on electrochemically controlled integration of tyrosinase in a redox polymer

An amperometric biosensor for the detection of phenolic compounds was developed based on the immobilization of tyrosinase within an Os-complex functionalized electrodeposition polymer. Integration of tyrosinase within the redox polymer assures efficient catechol recycling between the enzyme and the polymer bound redox sites. The non-manual immobilization procedure improves the reproducibility of fabrication process, greatly reduces the desorption of the enzyme from the immobilization layer, and, most importantly prevents fast inactivation of the enzyme by its substrate due to fast redox cycling. A two-layer sensor architecture was developed involving ascorbic acid oxidase entrapped within an electrodeposition polymer in a second layer on top of the redox polymer/tyrosinase layer. Using this sensor architecture it was possible to eliminate the current interference arising from direct ascorbate oxidation up to a concentration of 630 μM ascorbic acid. The effects of the polymer thickness, the enzyme/polymer ratio, and the applied potential were evaluated with respect to optimal sensor properties. The sensitivity of the optimized sensors for catechol was 6.1 nA μM⁻¹ with a detection limit of 10 nM, and for phenol 0.15 nA μM⁻¹ with a detection limit of 100 nM.     

用硫化物沉淀法脱除甲基紫染料中的铜

在pH为2～3的硫酸介质中,缓慢加入稀硫化钠溶液,可以将甲基紫染料中的铜含量降至1000ug/g以下.本方法工艺简单,设备投资低,试剂用量少,经济效益高,是理想的甲基紫染料生产工艺改进方法.讨论了工业生产中的废料利用及治理环境污染等问题.对该方法已成功进行了工业放大实验.     

催化动力学电位法测定微量锰的研究

用结晶紫选择性电极（自制）以催化电位法对测定微量锰进行了研究。该方法测定标的线性范围为７～７４μｇ／Ｌ，对标准钢样中的锰含量测定结果满意，且操作方便。     

膨润土对结晶紫的吸附

用分光光度、显微电泳和ｘ－射线衍射等方法研究了膨润土对结晶紫的吸附；实验表明，钙型膨润土在吸收结晶紫溶液时，加入钠盐可明显改善吸附效果。     

溴化十二烷基吡啶和羟胺协同增敏显色反应的研究

系统地研究了钼－羟胺（ＨＹ）－邻苯二酚紫（ＰＶ）－溴化十二烷基吡啶（ＤＰＢ）体系的四元胶束混配物协同增敏显色反应。在ｐＨ４￣５的弱酸性条件下，Ｍｏ－ＰＶ二元配合物生成速率很慢，须加热才能完成，最大吸收波长λｍａｘ＝５１０ｎｍ，表观摩尔吸光系数εｍａｘ＝６．１×１０＾４Ｌ·ｍｏｌ＾－１·ｃｍ＾－１；Ｍｏ（Ⅵ）－ＰＶ－ＤＰＢ配合物在室温下缓慢形成１：１：１的配合物，最大吸收波长为５９０ｎｍ，表观摩尔吸     

在增溶剂存在下硫氰酸盐-结晶紫光度法测定微量钨

在明胶存在下,钨与硫氰酸盐和结晶紫生成可溶性三元缔合物,最大吸收波长为540nm,表现摩尔吸光系数为4.1×10~5 L·mol~(-1)·cm~(-1),钨在0～11μg/25ml范围内服从比尔定律。方法已用于测定岩石中微量钨。