α-生育酚中性自由基的EPR考察

众所周知,维生素E又称生育酚,它有α-、β-、γ-和δ-四种构型,其中最重要的是α-生育酚(简记为α-TH).近年来,对α-TH的研究十分活跃,应用电子顺磁共振(EPR)技术进行研究的报导正日益受到重视.在本研究中我们采用EPR技术对α-TH在引发剂二叔丁基过氧化物(Di-tert-butyl peroxide,DBPO)或偶氮二异庚腈(2,2-azo-(2,4-dimethylvaleronitrile,ADVN)中和在γ-氧化铝(γ-Al_2O_3)或硅酸铝(SiO_2/Al_2O_3)表面上,其酚羟基中的氢被夺去后生     

脂肪酶催化水解反应纯化α-生育酚琥珀酸酯

α-生育酚琥珀酸酯（α-tocopherol succinate）是天然维生素E的衍生物，它是由琥珀酸与α-生育酚的β-色酮环的6位羟基成酯而形成的化合物（图1），由于丧失了自由的羟基而不具有维生素E的抗氧化活性，在空气中较为稳定，因其可保护α-生育酚的6位羟基，使α-生育酚在储存和运输中稳定性增加，而广泛用于α-生育酚的运输和储存。     

阳离子表面活性剂增敏碳糊电极电化学测定维生素E胶丸中维生素E的含量

以硝酸作氧化剂,将非电活性的维生素E氧化为具有电活性的醌型化合物-生育酚红,采用循环伏安法研究了生育酚红在碳糊电极上的电化学行为,探讨了阳离子表面活性剂的增敏效果、电极反应机理和表面活性剂的增敏机制。试验结果表明:在乙醇-硝酸(69+31)电解质溶液中,在一定量的阳离子表面活性剂十八烷基三甲基氯化铵存在时,生育酚红在碳糊电极上,具有一对可逆的氧化还原峰,峰电位差为30 mV,维生素E的浓度在1.6×10~(-8)～4.0×10~(-6)mol·L~(-1)范围内与其峰电流呈线性关系,检出限(3S/N)为4.0×10~(-9)mol·L~(-1)。该阳极溶出伏安法应用于分析维生素E药品,回收率在92.9%～110.2%之间。     

生物抗氧化剂的研究——Ⅲ.维生素E在十二烷基硫酸钠胶束中对亚油酸自动氧化的促氧化作用

本文研究了维生素E(α-生育酚)在含有过氧化亚油酸的亚油酸中的反应,发现在乙醇溶液中没有明显的反应发生,但在十二烷基硫酸钠胶束中,维生素E迅速与过氧化亚油酸反应并引发亚油酸的过氧化,吸收氧气,用紫外光谱、高效液相色谱、顺磁共振技术对反应的动力学进行了仔细的研究,证明反应的中间体是α-生育酚自由基,反应的主要产物是α-生育醌,反应机理为α-生育酚及α-生育酚自由基与过氧化亚油酸发生两步连续双分子反应,速率常数分别为2.93和6.21mol/L~(-1)·S~(-1),讨论了反应的胶束效应。     

用联谱技术鉴定维生素E同系物的结构

本文介绍从精炼植物油副产物中提取的天然维生素E(生育酚)进行高效液相色谱的分析、分离条件的研究。用φ8×300mm的硅胶柱进行了维生E同系物各组分纯样的制备。用质谱与核磁共振波谱仪对同系物各组分进行了结构鉴定。按经验公式计算的化学位移值与实测化学位移值,基本一致。确定了由精炼植物油副产物中得到的维生素E同系物主要含有α-、β-、γ-及δ-维生素E。     

气质联用法测定化妆品中的VE

维生素E(α-生育酚)和它的衍生物醋酸α-生育酚是维生素E的同类物,由于具有促进人体血液循环,保护皮肤水分,防止皮肤色素沉着,防皱等作用,且又是很好的抗氧化剂,近年来,维生素E及其同类物广泛用于化妆品中[1],故在化妆品的分析中常需对该类物质进行分析和测定.目前,国内外所使用的测定方法有HPLC和GC法[2-4],但样品前处理过程繁琐,且因化妆品成分复杂,尤其是W/O型护肤膏霜中,含和维生素E有相同保留时间的物质,需用其它方法进一步进行确证[3].本文采用GC-MS-SIM法来测定化妆品中的维生素E,不仅大大简化了样品前处理,且灵敏度高,选择性强,较好地解决了HPLC及GC法测定化妆品中VE含量所遇到的一系列问题.     

离子液体BMIMPF6修饰碳糊电极电化学测定维生素E

用疏水性离子液体1-丁基-3-甲基咪唑六氟磷酸([BMIM]PF6)作粘合剂制备了离子液体修饰碳糊电极(IL/CPE)。采用循环伏安法(CV)研究了维生素E(vitamin E,VE)的氧化产物生育酚红在IL/CPE和未修饰碳糊电极(CPE)上的电化学行为,结果表明生育酚红在IL/CPE上氧化过程更易于进行,峰电流响应ip也明显增加,表明IL/CPE对生育酚红的氧化还原反应具有良好的电催化作用。同时测定了电极过程的动力学参数:电荷转移系数α=0.8746,扩散系数D=1.65×10-3cm2/s,电极反应速率常数kf=6.64×10-2cm/s。采用方波伏安法(SWV)发现生育酚红氧化峰电流与其浓度在1.53×10-4mol/L～8.39×10-7mol/L范围内呈线性关系,检出限为1.58×10-8mol/L。该法可用于VE实际样品的分析测定。     

SIM法快速测定植物油中的α-生育酚

本文就气相色谱/质谱/计算机联用中的SIM法用于测定植物油及其副产物中的α-生育酚(维生素E)作了初步研究,摸索最佳的实验条件,建立了一种快速、简便的分析方法。     

磷钼酸催化合成DL-α-生育酚

以磷钼酸(H3PMo12O40)为催化剂,通过2,3,5-三甲基氢醌与异植醇在室温下缩合得到DL-α-生育酚(维生素E),发现H3PMo12O40是合成DL-α-生育酚的一种高活性、易于分离和能够重复使用的催化剂。     

正相高效液相色谱法测定维生素E保留时间稳定性的提高

维生素E有许多同系物,其中以4种生育酚异构体（即α-,β-、γ-、δ-生育酚）的活性最高,其主要的生理功能是抗氧化作用。维生素E的定量方法有分光光度法、薄层层析法、荧光法、气相色谱法和高效液相色谱（HPLC）法等,其中HPLC法因具有快速、准确、样品处理简单以及分辨率高等优点而成为维生素E测定的首选方法。HPLC法测定维生素E既可以采用正相HPLC法也可以采用反相HPLC法。从近年发表的文献看,反相HPLC法的应用比正相HPLC法更普遍一些,这是由于反相HPLC法在实际应用中具有色谱柱性能稳定、保留时间恒定和色谱柱平衡快速等优点。但反相HPLC法测定维生素时维生素E与某些亲脂性化合物反应生成部分沉淀造成色谱峰峰形明显变差。     

Electrochemical oxidation of 2-thiouracil at pyrolytic graphite electrode

2-Thiouracil has been studied in phosphate buffers of pH 1.95-11.08 using linear and cyclic sweep voltammetry, coulometry, controlled potential electrolysis and spectral studies. One well-defined oxidation peak I(a) in the pH range 1.95-11.08 was noticed. The number of electrons involved in peak I(a) was found to be four in a thin layer cell whereas under exhaustive electrolysis condition oxidation was found to involve six electrons. A reduction peak II(c) (2e, 2H(+)) is noticed in the reverse sweep. Spectral studies during oxidation were carried out at different pH. Kinetic studies indicated that the decay of the UV-absorbing intermediate is a first order reaction. The products of the electrooxidation have been characterized and a tentative EC mechanism has been suggested for the oxidation of 2-thiouracil.     

Investigation into phenoxonium cations produced during the electrochemical oxidation of chroman-6-ol and dihydrobenzofuran-5-ol substituted compounds

A series of chroman-6-ol and dihydrobenzofuran-5-ol based compounds with structures similar to vitamin E were examined by cyclic voltammetry and controlled potential electrolysis. The compounds displayed characteristic voltammetric features that enabled their electrochemical behavior to be interpreted in relation to the oxidation mechanism for vitamin E. The electrochemical experiments indicated the presence of several oxidized species: cation radicals, phenoxyl radicals, phenoxonium ions, hemiketals, and p-quinones, whose lifetimes varied depending on the extent of methylation of the aromatic ring (R(1), R(2), R(3)) and the nature of substituents R(4) and R(5).     

Electrochemical reduction of 1-([(4-halophenyl)imino]methyl)-2-naphthols in aprotic media.

The electrochemical reduction of 1-([(4-halophenyl)imino]methyl)-2-naphthols on graphite electrodes was studied using cyclic voltammetry, chronoamperometry, constant-potential coulometry and preparative constant-potential electrolysis techniques. The data revealed that the reduction on graphite was irreversible and followed an EC mechanism. The diffusion coefficients and the number of electrons transferred were determined using the chronoamperometric Cottrell slope and the ultramicro disc Pt-electrode steady-state current. The number of electrons was also determined by bulk electrolysis. The compounds were subjected to constant-potential preparative electrolysis and the electrolysis products were purified and identified by spectroscopic methods. Based on these findings, a mechanism for the electro-reduction process is proposed.     

The study of the electrochemical oxidation mechanism of diphenylamine derivatives in dipolar aprotic solvents: II. The electrochemical oxidation of 4-aminodiphenylamine in acetonitrile

The electrochemical oxidation of 4-aminodiphenylamine was investigated in acetonitrile. Voltammetry at a rotating Pt electrode, controlled potential electrolysis and cyclic voltammetry were the techniques followed. The oxidation occurred in two steps, the first involves the complete oxidation of one molecule through an ECE mechanism. The ejected proton—in the follow-up reaction—is received by the other molecule which undergoes oxidation at the potential of the second step. This result was confirmed from the effect of acid and base addition on the oxidation patterns.     

Electrochemical oxidation of C4-vanillin- and C4-isovanillin-1,4-dihydropyridines in aprotic medium: Reactivity towards free radicals

This work reports the electrochemical oxidation of two new synthetic C4-vanillin and -isovanillin-1,4-dihydropyridines in aprotic medium. Its reactivity with alkylperoxyl radicals ABAP-derived at pH 7.4 is also studied. Voltammetry, coulometry, controlled-potential electrolysis, UV–visible spectroscopy and GC–MS techniques were employed to collect data that permitted us to study its oxidation. Effect of TBA-OH addition on the oxidation was electrochemically and spectroscopically followed. In aprotic medium, the oxidation mechanism involves the formation of the pyridine derivative, which was generated by controlled-potential electrolysis (CPE) at 1270 mV and identified by GC–MS technique as the final product of the electrolysis. Spectroelectrochemical experiments also support the formation of the pyridine derivative from the oxidation of both 1,4-dihydropyridines. Direct reactivity of synthesized compounds towards alkylperoxyl radicals ABAP-derived was determined. Results reveal that the inclusion of vanillin radical or its positional isomer, isovanillin in the 4-position of the dihydropyridine ring produced a significant positive effect on the reactivity towards alkylperoxyl radicals, even compared with commercial dihydropyridine drugs with a well-known antioxidant ability. Scavenging mechanism involves the electron-transfer and the formation of a pyridine derivative, which was identified by GC–MS.     

New tetrakis(4-aminophenyl)ethenes: synthesis and electrochemical investigations

Four novel functional conjugated tetraarylamines containing a tetraphenylenecore were synthesized via Ni-catalyzed aryl amination followed by McMurry olefination. Their electrochemical properties were studied by cyclic voltammetry, coulometry, and electrolysis monitored by UV-vis spectroscopy, and discussed with regard to those of the known tetrakis(dimethylaminophenyl)ethane.     

Electrochemical Oxidation of Desipramine Drug in the Presence of 4,6‐Dimethylpyrimidine‐2‐thiol Nucleophile in Aqueous Acidic Medium

Electrochemical oxidation of desipramine (DES) has been studied in the presence of 4,6‐dimethylpyrimidine‐2‐thiol (DMPT) as nucleophile in acidic medium by means of cyclic voltammetry, controlled‐potential electrolysis and spectroscopic data, as diagnostic techniques. Voltammetric studies of electro‐oxidation of desipramine were realized in a range of pH 1.0 to 8.0 in the absence and presence of DMPT. The results indicate the participation of the product of electrochemical oxidation of desipramine in the reaction with DMPT with ECEC electrochemical mechanism. However, the voltammetry and coulometry results imply existence of a catalytic (EC′) electrochemical mechanism in parallel with ECEC electrochemical mechanism. The product has been characterized by IR, ¹H NMR, ¹³C NMR and MS methods.     

Electrochemical Investigation on Porphyrazines with Peripheral Crown-Ether Groups

 In this study, the electrochemical properties of novel porphyrazines with eight crown ether substituents appending on the periphery through flexible chains were investigated by using cyclic voltammetry and controlled potential coulometry. Cyclic voltammetry measurements showed that the metal free porphyrazine gave all of the six possible redox reactions of common porphyrazine derivatives. Cobalt porphyrazine exhibited a metal-based reduction and a metal-based oxidation processes followed by two ligand-based reduction and two oxidation processes. I _p vs. ν^1/2 plots of redox processes of the two compounds indicated the diffusional mass transfer mechanism of the complexes. Copper porphyrazine gave an oxidation process having adsorption properties and three reduction reactions. The variations of peak current ratios of electrochemical reactions for all three complexes with scan rate showed that electron transfer processes of complexes were followed by reversible or irreversible chemical reactions. Aggregation and sandwich adduct formation properties of complexes were determined by CV measurements. Peak potentials of redox processes for all complexes were shifted towards positive potentials by addition of alkali metal cations. Addition of K⁺ formed sandwich type adducts with 15-crown-macrocycles diminishing aggregation of planar molecules by intramolecular rather than intermolecular complexation.     

Electrosynthesis of symmetric and highly conjugated benzofuran via a unique ECECCC electrochemical mechanism: evidence for predominance of electrochemical oxidation versus intramolecular cyclization

Electrochemical oxidation of hydroquinone, catechol, and some of their monosubstituted derivatives has been studied in the presence of 3-hydroxy-1H-phenalen-1-one (2) as a nucleophile in water/acetonitrile (80/20) solutions using cyclic voltammetry and controlled-potential coulometry methods. The results revealed that quinones derived from oxidation of hydroquinones and catechols participate in Michael addition reactions with 2. The formed adducts convert to the corresponding benzofuran derivatives via different mechanisms. In this work, we derived a variety of products with good yields using controlled potential electrochemical oxidation at a graphite electrode in an undivided cell.     

Electrochemical Investigation on Porphyrazines with Peripheral Crown-Ether Groups

Summary.  In this study, the electrochemical properties of novel porphyrazines with eight crown ether substituents appending on the periphery through flexible chains were investigated by using cyclic voltammetry and controlled potential coulometry. Cyclic voltammetry measurements showed that the metal free porphyrazine gave all of the six possible redox reactions of common porphyrazine derivatives. Cobalt porphyrazine exhibited a metal-based reduction and a metal-based oxidation processes followed by two ligand-based reduction and two oxidation processes. I _p vs. ν^1/2 plots of redox processes of the two compounds indicated the diffusional mass transfer mechanism of the complexes. Copper porphyrazine gave an oxidation process having adsorption properties and three reduction reactions. The variations of peak current ratios of electrochemical reactions for all three complexes with scan rate showed that electron transfer processes of complexes were followed by reversible or irreversible chemical reactions. Aggregation and sandwich adduct formation properties of complexes were determined by CV measurements. Peak potentials of redox processes for all complexes were shifted towards positive potentials by addition of alkali metal cations. Addition of K⁺ formed sandwich type adducts with 15-crown-macrocycles diminishing aggregation of planar molecules by intramolecular rather than intermolecular complexation. Corresponding author. E-mail: ahmetg@itu.edu.tr Received May 23, 2002; accepted (revised) May 31, 2002