色氨酸及其肽对cis-syn型1,3-二甲基尿嘧啶二聚体的光敏化裂解作用

通过荧光猝灭实验和测定二聚体裂解程度的辐照实验研究色氨酸(Trp)及其二肽色氨酰酪氨酸(Trp-Tyr)和色氨酰苯丙氨酸(Trp-Phe)对cis-syn型1,3-二甲基尿嘧啶二聚体(DMUD)的光敏化裂解作用.结果表明,色氨酸及其二肽在较强光(λ＞290 nm)辐照下,主要通过双光子电离生成的水合电子(eaq)导致二聚体裂解,其次,通过激发单重态与二聚体间的电子转移导致二聚体裂解Trp-Tyr因其氧化电位(Eox)低,除以上二途径外,另有一导致二聚体裂解的可能途径:色氨酸残基激发三重态与二聚体间的电子转移光敏化二聚体裂解.     

可见光促进下N-芳基丙烯酰胺甲基化合成3-甲基-3-乙基氧化吲哚

以过氧化苯甲酸叔丁酯为氧化剂,在可见光促进下通过N-芳基取代的丙烯酰胺类化合物的串联自由基加成/环化反应,实现了3-甲基-3-乙基氧化吲哚类化合物的合成.该反应具有反应条件温和、底物普适性较广等优势.     

漆酶对共基质体系下吲哚的去除研究

采用漆酶对低浓度单基质吲哚及与苯酚共存下低浓度吲哚进行去除实验。结果表明,与单基质相比,含有苯酚的体系中,漆酶对吲哚的去除效果更好;漆酶不仅可以同时去除共基质中的苯酚和吲哚,苯酚的存在还促进了漆酶对吲哚的去除;共基质体系中,苯酚浓度与吲哚的去除率有较好的线性相关性,苯酚的中间产物可能与漆酶组成了新的介体系统,促进了吲哚的氧化;与单基质相比,共基质体系中漆酶对吲哚的去除有两个较优的pH值,分别为3.5和6.5,且苯酚的加入可以减小漆酶的用量。     

2—氯酚水溶液的氧化降解的机理研究

利用脉冲辐解技术对2-氯酚稀水溶液在多种条件下的脉冲辐解进行了详细研究。对瞬态光谱中的主要吸收作了归属,并初步考察了这些瞬态粒子的生长、衰减动力学。实验表明2-氯酚与·OH的反应符合假一级动力学,2-氯酚与·OH自由基的反应途径与pH值有关:在中性条件下·OH与2-氯酚主要生成较为稳定的羟基加成物;在酸性条件下,同时生成了羟基加成物和氢加成物,且羟基加成物可发生H~+催化的脱H_2O反应,生成氯酚氧基;在碱性条件,2-氯酚阴离子的羟基加成物不稳定,可进一步脱HCI和OH-而生成氯代酚氧基阴离子和半醌自由基阴离子,同时2-氯酚阴离子与·OH还可直接发生电子转移,形成氯代酚氧基阴离子。     

β-(1,2)-萘醌电化学行为研究

研究邻萘醌类母核化合物β-(1,2)-萘醌在乙腈体系的电化学行为.结果表明,β-(1,2)-萘醌的电化学还原过程并非如1,4-对苯醌乙腈体系的简单的两步单电子过程,推测可能存在后行化学反应.同时运用现场红外光谱电化学技术观察到其氧化还原过程均存在半醌自由基中间体在一定电位下的生成、继而消去的现象.     

2-吲哚乙酸乙酯的合成

丙二酸二乙酯在醇溶液中,与氢氧化钾皂化得到丙二酸单乙酯钾盐,然后在N,N’-羰基二咪唑(CDI)作用下,与2-硝基苯乙酸进行亲核加成得到4-(2-硝基苯基)-乙酰乙酸乙酯,再经三氯化钛的催化还原环化制得医药中间体2-吲哚乙酸乙酯,收率达72.2%。     

气相苯丙氨酸手性转变基元反应过渡态的电子激发特征

用密度泛函理论(DFT)中的B3LYP方法, 在6-311+G(2df)基组水平上优化气相条件下苯丙氨酸(Phe)分子的几何构型, 分析Phe分子体系手性转变过程中各基元反应中间体和过渡态的特征, 在PBE0/def2-TZVP下, 用含时密度泛函理论(TDDFT)方法得到气相条件下Phe分子体系手性转变过程中某过渡态在电子激发过程中的激发态特性. 结果表明： 根据Δr指数和空穴-电子指数的电子激发特征判据, 可有效指认较明显的激发态特征, 并直接给出基元反应中过渡态分子体系激发特征的判断结果.     

气相苯丙氨酸手性转变基元反应过渡态的电子激发特征

用密度泛函理论(DFT)中的B3LYP方法, 在6-311+G(2df)基组水平上优化气相条件下苯丙氨酸(Phe)分子的几何构型, 分析Phe分子体系手性转变过程中各基元反应中间体和过渡态的特征, 在PBE0/def2-TZVP下, 用含时密度泛函理论(TDDFT)方法得到气相条件下Phe分子体系手性转变过程中某过渡态在电子激发过程中的激发态特性. 结果表明： 根据Δr指数和空穴-电子指数的电子激发特征判据, 可有效指认较明显的激发态特征, 并直接给出基元反应中过渡态分子体系激发特征的判断结果.     

ABTS强化HRP/H2O2体系降解吲哚的效能与机制

针对辣根过氧化物酶催化过氧化氢(HRP/H₂O₂)体系存在对污染物降解速度慢的问题,采用2,2′-联氮-双-3-乙基苯并噻唑啉-6-磺酸(ABTS)作为电子转移体,强化HRP/H₂O₂体系降解吲哚,对不同pH值、ABTS浓度和常见共存水体成分的吲哚降解效能进行研究.通过高效液相色谱-四级杆-飞行时间质谱仪及发光细菌毒性实验,考察吲哚的降解产物及毒性变化.结果表明：在pH值为5.0～11.0的范围内,ABTS可显著强化HRP/H₂O₂体系降解吲哚,且强化效能随ABTS浓度的增加而增加;常见共存水体成分对吲哚的降解均无显著影响;检测到5种吲哚降解产物,其生物毒性相较于吲哚有所下降.     

左旋多巴与脯氨酸或谷氨酸构成的环二肽的合成及其DPPH自由基清除活性测试

采用缩丙酮保护的左旋多巴(L-DOPA)的儿茶酚基,在常温下以哌啶催化直链二肽甲酯并使其发生分子内环化反应,制备了L-Pro、L-Glu或D-Glu与L-DOPA形成的环二肽;该保护方式成功地规避了微波辐射法所引起的氨基酸消旋和高温回流法对氨基酸侧链保护的限制.缩丙酮保护的环二肽中间产物在常温下稳定,适合长期保存;同时它可以在95%三氟乙酸中高效快速地去保护而生成目标环二肽,方便使用.在所制备的三种环二肽中,cyclo(L-DOPA-L-Glu)表现出最好的1,1-二苯基-2-三硝基苯肼(DPPH)自由基清除活性(IC_(50),18.93μmol·L~(-1)),优于丹参素.     

Photosensitized splitting of cis-syn 1,3-dimethyluracil dimer by tryptophan and its peptides

Photosensitized splitting of cis-syn 1,3-dimethyluracil dimer by tryptophan (Trp) and its peptides (Trp-Tyr and Trp-Phe) is studied by fluorescence quenching experiments and irradiation experiments.It reveals that 1,3-dimethyluracil dimer is mainly split by e?-?aq resulting from two-photon ionization of Trp and its peptides under irradiation with light (λ>290 nm).Moreover,the excited singlet state of Trp and its peptides can transfer an electron to the dimer,which splits and gives two pyrimidines.In addition,because of its lower oxidative potential,the excited triplet state of Trp-Tyr can also split the dimer via transfering an electron to the dimer.     

Electron transfer reactions of piperidine aminoxyl radicals

This review article summarizes the electron transfer reactions of piperidine aminoxyl radicals. Electrochemical studies revealed the single electron transfer nature of piperidine aminoxyl radicals. In solution, piperidine aminoxyl radicals serve as single electron transfer oxidation reagent to react with various biologically interesting molecules such as glutathione, cysteine, ascorbic acid, and amines. The reaction product distribution, reaction kinetics, intermediates, and the reaction features in biological mimic environments including micelles and cyclodextrins were investigated. Oxoammonium salts, the one-electron transfer oxidation products of piperidine aminoxyl radicals, are agents of organic synthesis to selectively generate ketones or di-ketones from alcohols or ketones bearing α-methylene group under mild conditions. The new reactions of oxoammonium salts with aromatic amines, phenols, heterocycles including phenothiazines, papaverine, and bilirubin are also illustrated.     

Pulse radiolysis studies of functionally substituted imidazolium-based ionic liquids

The reactions of imidazolium-based ionic liquids having different substituent groups on the ring with hydrated electrons (eaq-),hydroxyl radicals (·OH),and sulfate anion radicals (SO4·-) were investigated using nanosecond pulse radiolysis techniques.The spectra of these ionic liquids on reaction with eaq-all exhibited a similar peak at about 320 nm,and a typical peak for eaq-in aqueous ionic liquid solutions.The reaction rate constants for 1,3-disubstituted imidazolium-based ionic liquid hexafluorophosphates (BMIPF 6) with eaq-were deduced to be 10 10 L mol-1s-1,however the values were lower for trisubstituted ionic liquids.For example,the rate constant for 1-butyl-2,3-dimethylimidazolium tetrafluoroborate (BMMIBF 4) was 5.5×10 9 L mol-1s-1.Imidazolium-based ionic liquids reacted with hydroxyl radicals via adducts to produce a mixture of isomeric OH adducts,and the pk a value of the OH adducts was deduced to be 8.4±0.4 for 1-butyl-3-methylimdazolium tetrafluoroborate (BMIBF 4).Moreover,imidazolium cations were also oxidized by SO4·-to produce bivalent cation radicals,which exhibit a peak at 320 nm,and these rate constants are of the same order of magnitude,i.e.,10 9 L mol-1s-1,except that for 1-(2-hydroxyethyl)-3-methylimdazolium tetrafluoroborate with SO4·-(k=2.8×10 8 L mol-1 s-1).Theoretical calculations were carried out to estimate the structures of the products of reduction by eaq- and the results were related to the experimental data.     

Photoionization of aromatic amino acid at different pH values

The photoioization of aromatic amino acid in solutions of different pH values were investigated by 248 nm laser flash photolysis. The results showed that the photoionizations of tyrosine and tryptophan were affected by pH value of solution, but phenylalanine was not. The ionization was in favor of monophotonic process at high pH value and of biphotonic process at low pH value. The mechanisms of pH effect on photoionization of tyrosine and tryptophan were the deprotonation of phenolic hydroxyl group and the deprotonation of＞NH on the indole ring respectively. Our results explain the discrepancy of values for the yield of hydrated electron obtained by other investigators.     

（光）助电-Fenton降解有机染料罗丹明B

以高纯石墨电极为阴极,铁片为阳极,Na2SO4溶液为支持电解质,通过阳极氧化提供Fe^2＋/Fe^3＋和阴极还原溶解氧转化为H2O2而形成Fenton体系,以降解有机染料罗丹明B（RhodamineB,RhB）为探针反应,研究了外加电压、铁电极面积（电荷密度）、极间距、电解质溶液浓度及外加紫外光照射（300 nm〈λ〈380n m）等因素对RhB降解反应的影响.结果表明：外加电压为7 V,铁片面积为3 cm^2（电荷密度为0.045 A/cm^2）,电极之间距离为4 cm,Na2SO4质量浓度为10 g/L时,反应100 min后RhB褪色完全.采用过氧化物酶催化反应吸光光度法和苯甲酸荧光分析法分别跟踪测定RhB降解反应过程中H2O2和羟基自由基（·OH）,表明RhB降解过程涉及·OH历程.通过分析测定RhB降解过程TOC变化和红外光谱分析,表明染料降解反应不仅仅为简单褪色而且深度氧化,180 min矿化率为73.0%.     

黄瓜多糖抗氧化活性研究

建立了热水提取、乙醇沉淀、Sevage法除蛋白、有机溶剂分离精制提取黄瓜多糖的方法,并用蒽酮-硫酸比色法测定其含量;采用超氧阴离子自由基、羟基自由基、二苯代苦味肼基自由基（DPPH·）体系,对黄瓜多糖的抗氧化活性进行了研究,结果表明：黄瓜多糖对DPPH·、·OH and O2^-·具有较强的清除能力,与其浓度呈线性关系。     

<Emphasis Type="Italic">In situ</Emphasis> generation and detection of methyl radical by voltammetry

The chemistry of free radicals is one of the advanced subjects of fundamental sciences such as biomedicine, environment protection, new energy sources and new material. The detection technique of free radicals is an essential tool for studying free radicals. Methyl radical is one of the representatives of alkyl radicals and the studies on it attract more attention. The current approaches to obtaining methyl radical are based on pulse radiolysis of organic substances that contain the methyl gro…     

紫外光照射下钴钼杂多酸降解有机染料SRB

制备了不同配比的钴钼杂多酸（CoMox Heteropoly acids,CoMox）,在紫外光（λ≤387 nm）照射下,以有机染料酸性桃红（Sulforhodamine B,SRB）的光催化降解为探针反应,研究了CoMox杂多酸不同配比及用量和体系介质pH值对其降解行为的影响.结果表明,最佳配比的钴钼杂多酸为CoMo12,在pH=3.0,CoMo12用量为1.0 g/L时,对SRB降解效果最好.在紫外光照射下,CoMo12活化O2,3.5 h内SRB脱色率达到96%.通过紫外-可见吸收光谱（UV-vis absorption spectrum）,红外光谱（FTIR）和总有机碳（TOC）测定分析钴钼杂多酸对SRB的降解特性,同时采用苯甲酸荧光光度法跟踪测定降解过程中产生的活性氧化物种,表明CoMo12多酸对SRB的光催化降解过程主要涉及.OH氧化历程.     

猪血浆巯基蛋白酶抑制剂的分离纯化及性质研究

用(NH_4)_2SO_4分段盐析,DEAE-纤维素离子交换和Papain—Sepharose亲和层析,从猪血浆纯化了一种巯基蛋白酶抑制剂(SUlfhydryl proteinase inhibitor;简称SPI);纯化倍数为54.36倍.经高pH、低PH不连续电泳呈一条区带.含糖量为7.77％;PI为4.80.氨基酸组成分析表明,猪血SPI富含酸性氨基酸、芳香族氨基酸和含硫氨基酸.用SDS-PAGE和SephadexG-100层析,测得分子量为130000d和131000d,由两个分子量略有差别的亚基组成.对木瓜蛋白酶有强烈抑制作用,对胰蛋白酶无作用。α-螺旋结构含量高。     

高级氧化技术研究现状及其发展趋势

 中国面临环境保护的重大压力,高级氧化技术(AOT)是解决环境污染的理想绿色技术,而高级氧化技术是指·OH制备以及诱发一系列的攻击污染物及微生物反应,从源头上解决了治理污染过程中再污染的问题。高级氧化技术规模制备·OH是其标志性核心关键问题。基于此,学术界进行了一系列羟基自由基制备研究工作。本文介绍了在水中制备·OH的方法,主要介绍O₃/H₂O₂、O₃/UV、H₂O₂/UV、Fenton、光催化氧化、电子辐射和水激励等方法;也介绍了在气体中制备·OH的方法,主要有脉冲电晕放电法、电子束和强电离放电法等。强电离放电法有望同时解决在水、气中规模制备·OH过程中存在的问题。