二次微分简易示波伏安法用于大豆甙元及其衍生物清除超氧阴离子自由基的研究

用二次微分简易示波伏安法研究了大豆甙元及其衍生物3′-大豆甙元磺酸钠对邻苯三酚自氧化产生超氧阴离子自由基(O2^- .)的清除作用，并计算了两种抗氧化剂对O2^- .清除作用的IC50。试验结果表明，大豆甙元和3′-大豆甙元磺酸钠对O2^- .。均有一定的清除作用，清除能力3′-大豆甙元磺酸钠大于大豆甙元，其原因与3′-大豆甙元磺酸钠分子的共轭程度高和分子内氢键的形成有关。与检测自由基的其它方法相比，该方法用于某些化学反应检测有其独特的优越性。     

3’-大豆甙元磺酸钠的电化学行为及应用研究

采用线性扫描伏安法、循环伏安法和常规脉冲伏安法电化学手段详细研究了改 性药物3’-大豆甙元磺酸钠(3’-daidzein sulfonic sodium,Dss)在pHl．0—6． 2的水溶液中的电化学行为.在不同pH范围内得到了Das的三个还原波．研究证实， 在pH＜3．2条件下所获得的Pcl，Pc2波分别为质子化的Dss的单电子不可逆吸附还 原波及还原中间体自由基的单电子单质子不可逆吸附还原波；在3．2＜pH＜6.2条 件下所获得的Pc3波，属于Dss后随质子化的单电子不可逆吸附还原波，而还原中间 体自由基的单电子波被氢波掩盖．测得在单分子层饱和吸附的条件下，每一个Dss 分子所占汞电极面积为0.664nm^2.此外，通过邻苯三酚自氧化产生活性氧自由基再 还原，对Dss清除活性氧自由基能力进行了研究，从电化学角度对其药理机制进行 了探讨，研究证实Dss具有较强的抗氧化性，是一种有效的活性氧自由基清除剂．     

DPPH法测定人参四君子汤与党参四君子汤及其不同组分清除自由基的能力

应用DPPH法对"四君子汤"人参方与党参方进行清除自由基活性实验;并对二者进行石油醚层、乙酸乙酯层、正丁醇层以及水层有效部位提取从而确定各有效部位层清除[DPPH·]的能力.结果显示党参方和人参方"四君子汤"在清除自由基能力上存在较大的差异,党参方"四君子汤"清除自由基能力优于人参方;二者在其水煎液中起到主要抗氧化作用的物质都集中在乙酸乙酯层中,值得进一步研究.     

洋葱色素的提取及抗氧化活性的测定

分别用芬顿（Fenton）反应法和1，1-二苯-2-苦肼基（DPPH）法测定了洋葱色素的抗氧化作用。结果表明，洋葱色素对羟自由基和DPPH自由基均有一定的清除作用，其清除率大小依次为42．4％，58．2％。洋葱色素是十分具有开发利用价值的天然色素。     

脂肪二胺桥联受阻酚的合成及抗氧化活性研究

以脂肪二胺为桥联基,通过与β-(3,5-二叔丁基-4-羟基苯基)丙酰氯酰胺化缩合反应,合成了4种脂肪二胺桥联受阻酚.核磁氢谱和质谱证实了脂肪二胺桥联受阻酚的化学结构,采用DPPH法和测氧法对脂肪二胺桥联受阻酚的抗氧化活性进行了研究.结果表明脂肪二胺桥联受阻酚对含氮自由基DPPH和过氧自由基ROO均具有良好的抗氧化活性.随着受阻酚桥联基的增长,受阻酚清除自由基的活性均下降,但随着受阻酚物质的量分数的增加,清除活性均增大,且桥联基对清除DPPH自由基活性的影响大于清除ROO自由基的活性.     

Enterobacter Cloacae Z0206细菌胞外富硒多糖的抗氧化活性

利用产多糖菌Enterobacter cloacae Z0206(E.cloacaeZ0206)的深层发酵法制备了E.cloacae Z0206细菌富硒多糖;测定了其还原能力和清除1,1-diphenyl-2-picrylhydrazyl(DPPH)自由基、超氧阴离子及羟自由基的能力.结果表明,通过深层富硒发酵、醇沉离心等制备富硒多糖SEPS的产量为9.28g/L,富硒量为2.314mg/g;E.cloacae Z0206富硒多糖对DPPH自由基和羟自由基具有较好的清除作用,在浓度为5g/L时对DPPH自由基和羟自由基的清除率分别为80.35%和84.26%,并具有较强的还原能力,但其对超氧阴离子自由基的清除能力较差.     

珠芽蓼黄酮类化合物清除DPPH·的作用

以六盘水市本地野生的珠芽蓼为原料,利用70%乙醇作为提取介质提取黄酮类化合物,并以抗坏血酸(VC)和维生素E(VE)为对照物,采用DPPH法研究珠芽蓼黄酮提取物对二苯代苦味肼基自由基(DPPH.)的清除作用。结果表明:珠芽蓼黄酮对DPPH.有较强的清除作用,在其质量浓度为368.94μg/mL时,其清除效果最好,清除率达88.96%,显著高于相同浓度下的VC和VE的清除率。珠芽蓼黄酮提取物是一种有前途的抗氧化剂。     

对位叠式循环方波伏安法：Ⅰ.简单可逆电极体系

本文提出叠式循环方波伏安法和对位叠式循环方波伏安法，对简单可逆电极体系的理论作了推导和验证，经对各种电流的比较，发位叠式循环方波伏安法有较多的优点。较之其它方波伏安法灵敏。     

氧化型谷胱甘肽对还原型谷胱甘肽清除自由基的协同作用

利用分光光度法和基质辅助飞行质谱法研究了谷胱甘肽对1,1-二苯基-2-苦肼基(DPPH)自由基的清除作用.通过比较不同浓度和不同配比的还原型谷胱甘肽(GSH)和氧化型谷胱甘肽(GSSG)以及Na2SeO3混合溶液的自由基清除率,发现GSH/GSSG的配比对自由基清除率有明显影响.当GSH/GSSG的配比大于50∶ 1时,自由基清除率比同浓度的GSH大,且自由基清除率随GSH和GSSG的绝对浓度的增加而明显增加,说明适量的GSSG可协同催化GSH清除自由基过程.质谱测定结果表明: 此协同作用与GSSG 参与自由基清除过程中的自由基反应有关.Na2SeO3对GSH的清除自由基的影响主要是通过与GSH反应生成GSSG来调控GSH/GSSG配比的结果.通过测定和分析一定配比的GSH+GSSG混合溶液与DPPH作用前后的质谱图,提出了少量的GSSG共存下,GSH催化清除DPPH自由基的作用机理.     

常规二脉冲叠加四阶跃微分伏安法

常用的脉冲技术,如阶梯伏安法、微分脉冲伏安法、方波伏安法等,都是利用电容电流的衰减比法拉第电流快得多的特点,通过延时,在脉冲后期采样.其共同缺点是损失一部分法拉第电流,而且由于延时,扫描速率也很难提高.本文首次提出一种新型常规二脉冲叠加的四阶跃伏安法,在每个脉冲周期中,电位都回到初始电位,通过在4个相互反对称电位阶跃上采样电流的差分和叠加组合,使正反向脉冲引起的电容电流相互抵消,不需要通过较长的延时而牺牲法拉第电流,从而可提高扫描速率和灵敏度.这种新的脉冲扫描技术同时具有常规脉冲和微分脉冲伏安法的特点,灵敏度和扫描速率均优于微分脉冲伏安法,并适合于吸附体系和固体电极的研究.     

Synthesis,characterization and antioxidant activities of highly functionalized cyclopentadienes catalyzed by ZnO-nanorod as economic and efficient heterogeneous nano catalyst

A three-component condensation was applied for the preparation of cyclopentadiene derivatives through the reaction of primary amines, alkyl propiolate and dialkyl acetylenedicarboxylate in the presence of catalytic amount of ZnO-nanorods (Zn-NR) under solvent-free conditions at 50℃. The method has proved to be synthetically green, simple, and effective with high atom economy and yield. The catalyst also revealed significant reusability. Moreover, the antioxidant activity and free radical scavenging capacity of the newly synthesized derivatives 4a, 4b, 4c, and 4d was screened using free radical scavenging 2,2-diphenyl-1-picrylhydrazyl (DPPH) and ferric reducing antioxidant power (FRAP) assays and compared with hydroxytoluene (BHT) and tert-butylhydroquinone (TBHQ). These compounds do not exhibit good DPPH radical scavenging, but they have a desirable FRAP.     

4种黄酮小分子对DPPH自由基的清除作用及构效关系研究

通过紫外可见光谱测定了4种黄酮小分子芦丁、牡荆素、山奈素、金丝桃苷对DPPH自由基的清除率、稳定性及半抑制浓度(IC50),并以常用的天然抗氧化剂抗坏血酸作为对照,考察了其抗氧化效果,探讨了黄酮类化合物的抗氧化性与结构的关系。结果表明：不同的抗氧化剂清除DPPH自由基达到平衡的时间不同,芦丁所需时间最长。4种黄酮小分子及抗坏血酸均对DPPH自由基有清除效果,并存在一定的量效关系。对DPPH自由基的清除能力从大到小依次为金丝桃苷、抗坏血酸、芦丁、山奈素、牡荆素。结构分析表明,B环邻二酚羟基是黄酮类化合物抗氧化所必需的基团,其羟甲基化及A环羟基糖苷化不利于黄酮类化合物的抗氧化活性。而C环3-OH的糖苷化对抗氧化活性有利,且单糖苷优于双糖苷。     

Comparison of the simple cyclic voltammetry (CV) and DPPH assays for the determination of antioxidant capacity of active principles

Antioxidant activity of a number of small (low molecular weight) natural compounds found in spices, condiments or drugs (gallic acid, sesamol, eugenol, thymol, carvacrol, vanillin, salicylaldehyde, limonene, geraniol, 4-hexylresorcinol, etc.) has been evaluated using electrochemical and DPPH? radical scavenging measurements. Structural analysis of the tested compound suggest a remarkable activity for phenol derivatives and the importance of the -R groups located on the phenolic ring in the molecule's ability to act as free radical scavenging as well as their influence in the electrochemical behavior. The voltammetric method can be used for the determination of the antioxidant capability in the same manner as the DPPH? radical scavenging because of the correlation found between oxidation potentials and anti-radical power (ARP = 1/EC??). Such electrochemical determination is fast and cheap and allows making measurements under a variety of experimental conditions. The accuracy of the electrochemical measurements is the same for all the compounds, irrespective of their scavenging activity, the opposite of what occurs in the DPPH? test.     

甜樱桃色素的提取及抗氧化活性

采用溶剂浸提法从成熟甜樱桃中提取了甜樱桃色素,并通过C18柱分离纯化,HPLC／光电二极管阵列检测器分析色素的主要成分,同时测定了甜樱桃色素体外清除二苯代苦味肼基自由基（DPPH）和羟基自由基的活性．结果表明,甜樱桃色素含有新绿原酸和对-香豆酰奎宁酸两个主要成分,对DPPH和·OH自由基具有较强的清除能力,且随色素浓度的增大而增强．研究认为,甜樱桃色素是一种具有良好抗氧化活性的功能性天然色素．     

Prenylated xanthones from the bark of Garcinia xanthochymus and their 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging activities

Garcinia xanthochymus has been widely used in traditional Chinese medicine for expelling worms and removing food toxins. Bioassay-guided fractionation of an EtOAc-soluble extract of G. xanthochymus stem bark led to the isolation of six new xanthones. Their structures were elucidated by spectroscopic methods, especially 2D-NMR techniques. Free-radical-scavenging activities of the isolated compounds were elucidated through DPPH method. Most of the isolated compounds showed considerable free radical scavenging activity on DPPH assay. Compound 1 exhibited effective antioxidant scavenging activity against DPPH radical with an IC?? value of 19.64 μM, and compound 6 showed the lowest activity among all the tested molecules, with an IC?? value of 66.88 μM. These findings support the notion that the plant genus Garcinia is a good source of bioactive compounds.     

Key role of chemical hardness to compare 2,2-diphenyl-1-picrylhydrazyl radical scavenging power of flavone and flavonol O-glycoside and C-glycoside derivatives

The antioxidant activities of flavonoids and their glycosides were measured with the 2,2-diphenyl-1-picrylhydrazyl radical (DPPH radical, DPPH(·)) scavenging method. The results show that free hydroxyl flavonoids are not necessarily more active than O-glycoside. Quercetin and kaempferol showed higher activity than apigenin. The C- and O-glycosides of flavonoids generally showed higher radical scavenging activity than aglycones; however, kaempferol C3-O-glycoside (astragalin) showed higher activity than kaempferol. In the radical scavenging activity of flavonoids, it was expected that OH substitutions at C3 and C5 and catechol substitution at C2 of B ring and intramolecular hydrogen bonding between OH at C5 and ketone at C3 would increase the activity; however, the reasons have yet to be clarified. We here show that the radical scavenging activities of flavonoids are controlled by their absolute hardness (η) and absolute electronegativity (χ) as a electronic state. Kaempferol and quercetin provide high radical scavenging activity since (i) OH substitutions at C3 and C5 strikingly decrease η of flavones, (ii) OH substitutions at C3 and C7 decrease χ and η of flavones, and (iii) phenol or o-catechol substitution at C2 of B ring decrease χ of flavones. The coordinate r(χ,?η) as the electron state must be small to increase the radical scavenging activity of flavonoids. The results show that chemically soft kaempferol and quercetin have higher DPPH radical scavenging activity than chemically hard genistein and daidzein.     

Antioxidant activities of extracts and metabolites isolated from the fungus Antrodia cinnamomea

Three different solvent partitions (n-hexane, ethyl acetate [EtOAc] and n-BuOH) of the culture broth from Antrodia cinnamomea were assayed with two different radical scavenging methods: 1,1-diphenyl-2-picrylhydrazyl (DPPH) free radical scavenging and superoxide radical scavenging (SOD) assay. The EtOAc layer exhibited the best antioxidant activity. Two major antioxidant metabolites were isolated from the active EtOAc layer. The antioxidant activities of compounds 1-6 were further evaluated by DPPH, SOD and trolox equivalent antioxidant capacity (TEAC) assays. Compounds 3 and 5 showed stronger free radical scavenging than the reference BHA, ED???=?1.36 and 34.24 μM. Compound 5 displayed moderate SOD activity (ED???=?310.0?μM), and its antioxidant capacity of TEAC value was 2.2 mM trolox equivalency.     

Salvia officinalis L. essential oils: effect of hydrodistillation time on the chemical composition, antioxidant and antimicrobial activities

Salvia officinalis L. oils were isolated from the plant's commercial dried aerial parts, by hydrodistillation, with different distillation times. The essential oils were analysed by gas chromatography and gas chromatography-mass spectrometry. The antioxidant ability was measured using a free radical scavenging activity assay using 2,2-diphenyl-1-picrylhydrazyl (DPPH), a thiobarbituric acid reactive substances (TBARS) assay, a deoxyribose assay for the scavenging of hydroxyl radical, an assay for site-specific actions and a 5-lipoxygenase assay. Antibacterial activity was determined by the agar diffusion method. 1,8-Cineole, α-pinene and camphor were the dominant components of all the essential oils. The different hydrodistillation times did not affect the oil yield nor the relative amount of the oil components. The time of hydrodistillation influenced the antioxidant activity. With the DPPH method, the oils isolated for 2 and 3 h were stronger free radical scavengers, while with the TBARS method, the highest antioxidant values were obtained in the oils isolated for 30 min, 2 and 3 h. Hydroxyl radical scavenging and lipoxygenase activity assays showed the best results with oils isolated for 1 and 3 h. With the deoxyribose method, sage oils at concentrations <1000 mg L(-1) showed better activity than mannitol. The essential oil of S. officinalis showed very weak antimicrobial activity.     

Synthesis,conformational analysis and free radical scavenging activity of some new spiropyranoquinolinones

A series of novel spiroadamantyl- and spirocyclical substituted pyranoquinolin-2-ones were synthesized and the conformation of the pyran ring was investigated. The free radical scavenging activity of the synthesized compounds was determined by their interaction with the stable free radical 1,1-diphenyl-2-picrylhydrazyl (DPPH). All compounds tested scavenged the DPPH radical and among them derivatives possessing extended conjugation showed the highest activity.     

Screening and characterization of natural antioxidants in four Glycyrrhiza species by liquid chromatography coupled with electrospray ionization quadrupole time-of-flight tandem mass spectrometry

Licorice, derived from the dried roots and rhizomes of several species of genus Glycyrrhiza L. (Leguminosae family), has been traditionally used in herbal medicine for over 4000 years. In recent years, the interest in antioxidative constituents in licorice has greatly increased. In this work, a new method based on 1,1-diphenyl-2-picrylhydrazyl radical (DPPH) spiking test combined with HPLC coupled with electrospray ionization quadrupole time-of-flight tandem mass spectrometry (Q-TOF MS/MS) analysis was developed to screen and identify the antioxidants in licorice. The results of the method validation indicated that the developed method was reliable and repeatable. Compared with DPPH on-line method, the HPLC-Q-TOF MS/MS method combined with DPPH spiking test offered much higher sensitivity and resolution. Using this method, 35 radical scavengers were screened from four Glycyrrhiza species (G. inflata, G. glabra, G. pallidiflora and G. uralensis), and 21 of them were unambiguously or tentatively identified by HPLC-Q-TOF MS/MS. Among the 21 identified flavonoids, 10 compounds had been reported to possess antioxidative activities in the previous studies, and the radical scavenging activities of the other 11 compounds were reported for the first time. The effects of six purified flavonoids on DPPH radical and lipid peroxidation were evaluated for validation of the developed method. The results indicated that HPLC-Q-TOF MS/MS coupled with DPPH treatment is an efficient and powerful method to discover the potential antioxidative compounds from the complex natural product mixtures. In this study, the identified components with free radical scavenging activity, would help to explain the therapeutic benefit of licorice in the treatment of human disease associated with oxidative stress.