电化学方法简便测定芬顿反应产生的羟基自由基

1　引　　言由于羟基自由基的反应活性大、寿命短、存在浓度低 ,直接测定存在一定的难度。因此 ,建立快速、简便的测定方法 ,对自由基理论研究和抗氧化药物筛选有重要意义。水杨酸、2 脱氧 Ｄ 核糖和ＤＭＳＯ是测定羟基自由基常用的分子探针。其中 ,ＤＭＳＯ与羟基自由基反应 ,主要的生成物有甲基亚磺酸 (Ｉ)及甲醛 (ＩＩ)等。·ＯＨ +(ＣＨ3) 2 ＳＯＣＨ3ＳＯ2 Ｈ +·ＣＨ3(1)·ＣＨ3+Ｏ2 ＣＨ3ＯＯ· (2 )2ＣＨ3ＯＯ·ＨＣＨＯ(ＩＩ) +ＣＨ3ＯＨ +Ｏ2 (3)　　有报道通过测定上述反应生成的甲基亚磺酸或来间接定量测定羟基自由基 ,也有…     

Synthesis of Polymers Containing Free Radical Verdazyl

Abstract

In precediig papers the authors have reported on the syntheses of polvrners containing a neYi type of free rarlical verdazyl [1, 2] through the anionic polymerizatim cf vinyl verdazyl monomers [3, 4]. In tNs paper we wish to report on the synthesis of polymer verdazyl by the reaction of verdazyl having amino group I with copolymers of maieic annvdride.     

Graft Copolymers from Natural Polymers Using Free Radical Polymerization

The present research work deals with the surface modification of natural cellulosic polymers to develop novel materials for different applications. Natural cellulose-graft-poly (methyl acrylate) copolymers were prepared using the free radical induced graft copolymerization technique. Different reaction parameters were optimized to achieve the highest percentage of grafting of natural cellulose-graft-poly (methyl acrylate) copolymers. The natural cellulose graft copolymers were characterized by FT-IR, SEM, TGA, and physicochemical studies. For the evaluation of swelling and the physicochemical mechanism, swelling and chemical resistance studies were carried out in different solvents as well as chemicals.     

Hydroxy Functional Acrylates: Enzymatic Synthesis and Free Radical Polymerization

Hydroxy functional acrylates were prepared via transacylation of methyl acrylate with 1,2,6-hexanetriol catalyzed by Candida antarctica lipase B. Under the applied reaction conditions, 70% of the substrate was converted into hydroxy functional acrylates. In a subsequent step, after filtration of the enzyme, the monomer mixture containing methyl acrylate and the new monomers was polymerized via free radical polymerization resulting in a functional copolymer with M_n = 14500 g/mol.     

天然水体中可溶性有机质的自由基光化学行为

可溶性有机质在天然水体中广泛分布,是全球碳循环的重要组成部分。大部分的可溶性有机质含有苯环、羧基、羟基和羰基等发色团,能够吸收特定波长的太阳光,产生水合电子、单线态氧、羟基自由基等活性自由基,从而影响天然水体污染物的光化学转化以及降解过程。本文综述了20世纪90年代以来可溶性有机质的自由基光化学行为以及其在水体污染物转化中的作用方面的研究进展,并探讨了今后研究中应该关注的问题。     

A Simple Approach to the Synthesis of 1,4-Bis(arylsulfonyl)tetrahydropyrazine-2,5-diones

Summary.  The addition of triphenylphosphine to dimethyl acetylenedicarboxylate in the presence of arylsulfonylglycyl chlorides leads to 1,4-bis-arylsulfonyl-tetrahydropyrazine-2,5-diones and dimethyl (E)-2-chloro-2-butenedioate. Corresponding author. E-mail: isayavar@yahoo.com Received June 3, 2002; accepted June 10, 2002     

Synthesis of Functionally-Terminated Oligomers by Free Radical Ring-Opening Polymerization

Since free radical ring-opening polymerization made it possible to introduce functional groups, such as esters, carbonates, thioesters, and amides, into the backbone of an addition polymer, it was reasoned that simple hydrolysis of these copolymers would produce the desired oligomers that could be terminated with various combinations of hydroxyl, amino, thiol, and carboxy1 groups. Thus the copolymerization of 2-methylene-1,3-dioxepane and styrene (r1=0.021 and r2=22.6) gave a copolymer containing 10 mole-percent of an ester-containing unit with 100% ring opening at 120°C. Hydrolysis of this copolymer gave an oligomer terminated with a hydroxyl group and a carboxylie acid group. Similarly the copolymerization of 2-methylene-1,3-dioxepane and ethylene gave a series of biodegradable polyethylene copolymers containing 2.1 to 10.4% ester-containing units. Hydrolysis of these copolymers gave a series of ethylene oligomers with nine to forty-seven ethylene units and terminated with a hydroxyl group and a carboxylic acid group. By the same general method oligomers of various monomers that are terminated with a methylandno group and a carboxylic acid group from N-methyl-Z-methylene-1,3-oxazolidine and with a thiol group and a carboxyl group from Z-methylene-1,3-oxathiolane.     

羟基自由基辅助沸石分子筛合成的研究进展

作为化学工业中最重要的固体催化剂之一,沸石分子筛在不同的领域发挥着广泛的应用.随着消耗量的逐年增加,如何绿色高效地制备沸石分子筛材料已经成为了研究热点.羟基自由基是具有高活性的物种,能够促进分子筛初始凝胶中硅铝酸盐的解聚和再聚合,进而加速了分子筛的晶化过程.众多研究表明,除了能够加速沸石的结晶,羟基自由基在其合成过程中还有其他的作用.本综述从不同的产生方式入手,系统地介绍了羟基自由基在沸石合成中的作用,提出了该策略存在的问题,并对其发展前景进行了展望.     

Free Radical Hydrophosphorylation of Fluoroalkyl Vinyl Ethers: Synthesis of Fluoroalkyl Phosphonates

An effective method for the synthesis of dialkyl [2-(polyfluoroalkoxy)ethyl]phosphonates by free radical hydrophosphorylation of fluoroalkyl vinyl ethers with dialkyl (H)-phosphonates was developed. The reaction proceeds in the presence of catalytic amounts of azabisisobutyric acid dinitrile (AIBN) (150°C, 2 h, portionwise addition of AIBN) to afford the target fluoroalkyl phosphonates in up to 85% isolated yield.     

A Synthesis of Norbisabolide via a Synthon Prepared by a Free Radical Reaction

An improved synthesis of norbisabolide (1) is described starting from limonene. Free radical addition of acetic acid in the presence of manganese (III) acetate led to an ethylenic acid which is converted to (1) in acidic medium.     

Mimicking Non-Canonical Radical Cyclizations in the Synthesis of Dibenzocyclooctadiene Natural Products

Unique chemical structures that are often characteristic of biologically active natural products are often created by oxidative cyclizations. Many of these reactions are catalysed by ‘non-canonical’ or ‘thwarted’ iron oxygenases that appear to involve long-lived radicals. This perspective summarizes our group‘s efforts to mimic these biosynthetic transformations for the synthesis of highly oxidized dibenzocyclooctadiene lignan natural products using redox neutral photocatalysis. We describe the evolution of this research program, which hinges on the use of Okada's redox active ester, and show how multiple factors control the fate of the resulting radicals.     

α-Carbonyl Radical Cyclization for the Total Synthesis of Natural Products

Intramolecular radical cyclization reactions are now used routinely to synthesize carbocyclic and heterocyclicstructures. We have reported that α-carbonyl radicals 1, generated from the corresponding iodo ketones or enones,underwent intramolecular radical cyclization smoothly to afford products 2. [1,2]     

水杨酸甲酯清除羟基自由基活性的研究

利用脉冲辐解技术研究了水杨酸甲酯清除羟基自由基反应的瞬态吸收谱,测定了水杨酸甲酯与羟基自由基反应的表观速率常数。辅以常规检测方法,测定了水杨酸甲酯对羟基自由基的清除率。结果表明,水杨酸甲酯能快速有效清除羟基自由基。探讨了水杨酸甲酯清除羟基自由基的反应机制。     

一种长链结构稳态氮氧自由基的合成

从提高光稳定剂与聚合物的相容性及光稳定效能的目的出发,以受阻胺为原料,H2O2为氧化剂,合成了具有高分子长链结构的新型稳态氮氧自由基,其结构经IR,ESR,GPC及元素分析表征。     

几种天然黄酮类化合物对二苯代苦味肼自由基的清除作用

采用循环伏安法、示差脉冲伏安法对四种天然黄酮类化合物清除二苯代苦味肼自由基（DPPH）的能力进行了探讨.研究表明：此法可直接观测样品对DPPH的清除作用,而且灵敏度高、准确可靠,是一种检测自由基及物质对其清除作用的有效方法.     

N-乙烯基咔唑三羰基铬的合成和自由基聚合反应

合成一种新的金属铬有机单体N-乙烯基咔唑三羰基铬,经元素分析、IR和1HNMR确证和表征.研究结果表明,N-乙烯基咔唑三羰基铬能发生自由基聚合反应,得到结构单元含等物质的量铬的金属有机高分子,苯环及含氮给电子中心的共轭效应能在一定程度上弥补由Cr(CO)₃基团吸电子诱导效应引起的单体聚合活性的下降     

天然抗氧化剂茶多酚

抗氧化剂是指能防止或延缓食品成分氧化变质的食品添加剂.茶多酚是目前尚不能人工合成的纯天然、多功能、高效能的抗氧化剂和自由基净化剂,可用超临界CO2萃取法、离子沉淀提取法、树脂吸附分离法、有机溶剂萃取法提取.采用酒石酸亚铁比色法测定茶多酚含量.