次甲基蓝-Mn2+-H2O2体系光度法测定中药的抗氧化性

提出了Mn^2 -H2O2一次甲基蓝分析新体系并用于羟自由基的测定：醋酸介质中,用Mn^2 与RQ反应,类似Fenton试剂产生羟自由基,羟自由基与次甲基蓝反应,使次甲基蓝褪色,用分光光度汁测定其吸光度的变化(△A664),可间接测定羟自由基的产生量．实验结果表明．△A664与次甲基蓝、MnSO4及H2O2呈量效关系．中药提取物可以清除溶液中的羟自由基,使次甲基蓝溶液的褪色程度降低,据此建立了一种测定中药对羟自由基清除率的新方法．测定了五倍子、诃子、金银花等11种中药的抗氧化性,结果满意。     

考马斯亮蓝G250褪色光度法测定Fenton反应产生的羟基自由基

在约0.008 mol.L-1硫酸介质中,Fenton反应产生的羟基自由基可使考马斯亮蓝G250(CBB G250)显著褪色。在CCB G250的吸收峰582 nm波长处测得的吸光度降低值(ΔA)与羟自由基(.OH)浓度在25 mg.L-1以下的范围内呈线性关系。根据Fenton反应及与方程式所示的化学计量关系,可用过氧化氢的浓度代表羟自由基浓度。用过氧化氢标准溶液对此反应体系作精密度试验,测得相对标准偏差(n=6)为0.6%。应用此方法对抗坏血酸等9种抗氧化剂的清除羟基自由基性能进行了测定。结果表明此方法可方便地应用于抗氧化剂的筛选。     

褪色光度法测定芬顿体系中产生的羟自由基

建立了检测Fenton反应产生羟自由基的新方法。在pH3．5条件下，经自由基与甲基紫发生反应使甲基紫褪色，在580nm处用分光光度计测定其△A值的变化，可间接测定羟自由基的生成量。通过对测定条件的研究，得到最佳实验条件。甲基紫光度法稳定性好，可作为一种简便的筛选羟自由基清除剂的方法。     

胭脂红酸褪色光度法检测H2O2-Fe2+产生的羟自由基

提出了Fe2 H2O2 胭脂红酸分析新体系,并用于羟自由基的测定。该法用Fenton反应产生羟自由基,并加入胭脂红酸显色剂,使胭脂红酸褪色,采用分光光度计测定其ΔA值的变化,可间接测定羟自由基的产生量。通过测定条件的研究,得出最佳实验条件,并对抗坏血酸等7种抗氧化剂的抗羟自由基氧化性能进行了比较。     

褪色光度法测定羟自由基及常见食物的抗氧化活性

在用稀硫酸调节至pH 4的溶液中,生物染色剂玫瑰桃红R能被由Fenton反应产生的羟自由基(·OH)氧化而褪色.根据在520 nm波长处所测得的吸光度的消褪的程度(△A=A0-A1),实现了羟自由基存在量的光度测定,应用此方法还测定了自由基消除率,作为选择清除剂的判据;还测定了几种常见食品的抗氧化活性.从方法的操作和所测得的结果证明该方法具有操作简单、方便且稳定而经济.     

药用百合提取液对羟自由基清除作用的研究

在Fenton反应产生羟自由基的稳定体系中,以溴邻苯三酚红为显色剂,用分光光度法测定吸光度的变化值,研究百合提取液在此体系中清除羟自由基的作用。通过常见抗氧化剂对羟自由基清除作用的对照试验表明,百合提取液对羟自由基有较好的清除效果,此法操作简便,稳定性好,测定快速,为开发百合复方保健品提供理论依据。     

亮绿褪色光度法检测Fenton反应产生的羟自由基

建立了Fg^2＋-H2O2-亮绿的分析新体系,并用于羟自由基的检测。该法利用Fenton反应产生羟自由基,并加入亮绿显色剂,羟自由基使亮绿褪色。在632nm处测其△A值的变化,可间接测定羟自由基的产生量。探讨了最佳实验条件,并对苯甲酸与丹参等中草药的抗羟自由基氧化性能作了比较,以验证本法的有效性,得到较好的清除结果。该法稳定,可作为一种简便的筛选抗氧化剂的方法。     

不同提取方法对红茶提取物抗氧化活性影响的研究

采取沸水浴法、回流法、微波法及超声波法探讨信阳红茶和印度红茶的抗氧化性,通过测定吸光度利用Fenton反应表征提取物对羟自由基的清除率.不同的提取方法对红茶抗氧化活性有一定的影响,羟自由基的清除率与红茶的抗氧化活性成正比.结果表明:信阳红茶沸水浴法提取率较高,印度红茶超声波法提取率较高.     

水杨基荧光酮荧光法测定钴（II）—过氧化氢系产生的羟自由基

本实验发现Co^2 与H2O2反应生羟自由基的产率比Fenton试剂的高100倍以上,采用水杨基荧光酮(salicyfluorone,SAF)-Co(II)-H2O2荧光法测定羟自由基的新体系,激发波长和发射波长为510nm和500nm,测定体系在反应前后的荧光变化,可间接测定羟自由基产生量,此法不需昂贵的仪器设备,方法灵敏,操作简单易行,清除率实难及ESR波谱法检测证明了该方法的准确可靠,对于医用筛选抗羟自由基药物及抗羟自由基机理研究等方面应用价值.     

H_2O_2-Co~(2+)产生的羟自由基的溴邻苯三酚红氧化法检测

提出了Co2 -H2O2-溴邻苯三酚红分析新体系并用于羟自由基的测定。该法用Co2 与H2O2 反应 ,类似Fenton试剂产生羟自由基 (·OH) ,并加入溴邻苯三酚红显色剂 ,使溴邻苯三酚红的颜色发生变化 ,采用紫外-可见分光光度计测定其ΔA值的变化 ,可间接测定羟自由基的产生量。通过测定条件的研究 ,得出最佳实验条件。结果表明 ,该法稳定性好 ,操作简便 ,测定快速 ,可作为一种简便的筛选抗氧化剂的方法。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.