聚L-白氨酸修饰电极伏安法测定痕量多巴胺的研究

用循环伏安法制备了聚L-白氨酸修饰玻碳电极,研究了多巴胺在聚L-白氨酸修饰玻碳电极上的电化学行为,建立了循环伏安法测定痕量多巴胺的新方法。实验结果表明,在pH 6.0的磷酸盐缓冲溶液中,多巴胺在聚L-白氨酸修饰玻碳电极上产生一对灵敏的氧化还原峰,峰电位分别为Epa=0.281V,Epc=0.170 V(相对Ag/AgCl电极)。峰电流与多巴胺的浓度在5.0×10-8~5.0×10-4mol/L的范围内有线性关系,检出限为5.0×10-9mol/L。对1.0×10-5mol/L多巴胺溶液平行测定9次,其相对标准偏差为4.0%。已用于针剂中多巴胺的测定。     

碳糊电极吸附伏安法测定痕量钒

研究了钒 荧光镓(LMG)络合物在碳糊电极上的吸附伏安行为,发现其在+0.81V(vs.SCE)的阳极二次导数峰电流与钒(V)的浓度在一定范围内呈线性关系。在pH=4.3的0.26mol/L的HAc NH4Ac缓冲溶液中,于+0.4V富集,从+0.4至+1.4V以300mV/s线性扫描,方法线性范围为4.0×10-9～1.0×10-7mol/L(5.0×10-7mol/LLMG)和1.0×10-7～1.2×10-6mol/L(2.0×10-6mol/LLMG),检出限为1.0×10-9mol/L(S/N=3)。该法用于煤飞灰,粉煤灰和水样中钒的测定,结果满意。     

核黄素的微分脉冲溶出伏安分析

采用循环伏安法和微分脉冲溶出伏安法,对核黄素在裸金电极和巯基化合物分子自组装膜修饰金电极上的电化学行为进行了研究,发现在pH4.8的B-R缓冲溶液中,核黄素在裸金电极和分子自组装膜修饰金电极上均于-0.35V左右产生一对可逆的氧化还原峰。核黄素在裸金电极和谷胱甘肽、三巯基丙酸、二巯基苯丙咪唑分子自组装膜修饰金电极上,其浓度分别在3.0×10-7～2.3×10-4mol/L、1.05×10-6～2.0×10-4mol/L、2.1×10-6～2.08×10-4mol/L、1.05×10-6～2.0×10-4mol/L范围内与微分脉冲伏安峰峰电流之间有良好的线性关系,其相关系数分别为0.9932、0.9909、0.9857、0.9832,核黄素的检出限为2.1×10-7mol/L、5.2×10-7mol/L、8.6×10-7mol/L、5.2×10-7mol/L。对浓度为1.0×10-5mol/L的核黄素进行10次平行测定,所得峰电流的相对标准偏差为2.0%。将该方法用于核黄素片剂和复合维生素B片剂的测定,结果令人满意。     

氟罗沙星的电化学特性研究

本文报道测定氟罗沙星(FLRX)的新方法。在0.05 mol/L KH2PO4 NaOH(pH=7.12)缓冲溶液中,FLRX Cu(Ⅱ)络合物在-0.36 V(vs.SCE)处产生一个灵敏的不可逆吸附还原峰。峰电流ip 与氟罗沙星浓度在5.0×10-8~4.0×10-6 mol/L范围内呈良好的线性关系,检测下限可达3.0×10-8 mol/L。络合物性质和电极反应机理研究表明,络合物组成比为:Cu(Ⅱ)∶FLRX=1∶2,是以Cu(Ⅱ)为中心原子,四个O为配位原子的螯合物。其电极过程为具有吸附性的不可逆还原过程。     

去肾上腺素在L-半胱氨酸修饰金电极上的电化学行为及其分析研究

应用循环伏安法(CV)和方波伏安法(SWV)研究了去甲肾上腺素(NE)在L-半胱氨酸自组装膜修饰金电极(L-Cys/Au)上的电化学行为。结果表明:在pH7.0的磷酸盐缓冲溶液中,L-Cys/Au对去甲肾上腺素具有明显的电催化作用。由方波伏安法测定的氧化峰电流在NE浓度1.0×10-6~4.0×10-5mol/L和6.0×10-5~4.0×10-4mol/L范围内分段呈线性关系,相关系数分别为0.9941和0.9962,检出限为5.0×10-7mol/L。已用于分析针剂样品。     

苯巴比妥的二次微分简易示波伏安法测定

利用苯巴比妥的示波特性 ,分别建立了在0.2mol/LKOH和1.0×10-4mol/LCd2 +-0.1mol/L硼砂底液中直接和间接测定苯巴比妥的二次微分简易示波伏安法 ;直接测定和间接测定的线性范围分别为1.0×10 -5mol/L～1.0×10 -4mol/L和4.0×10 -6mol/L～8.0×10 -5mol/L ;检出限分别为8×10 -6mol/L和2×10 -6mol/L;在直接测定中 ,对6.000×10 -5mol/L苯巴比妥进行10次测定的RSD为4.5 % ;间接测定中 ,对2.000×10 -5mol/L苯巴比妥进行10次测定的RSD为2.6 % ;这一研究表明对于一些在示波分析中灵敏度不高或本身没有示波活性的药物 ,可以利用其与金属离子生成沉淀的方法间接测定 ,从而提高药物测定的灵敏度、拓宽示波分析应用领域     

吡柔比星的伏安行为及其应用

吡柔比星在 0 .1 mol/L HAc- Na Ac缓冲溶液 (p H4.3)中 ,出现一灵敏的示波极谱导数还原峰 ,峰电位为 - 0 .39V(vs.SCE) ,峰电流与吡柔比星浓度在 2 .0× 1 0 -7～ 4.0× 1 0 -6mol/L范围内成正比。检出限为 1 .0× 1 0 -8mol/L。用于病人尿样的测定。用线性扫描和循环伏安法研究体系的性质。体系属具有吸附性的可逆过程。     

酪氨酸、脯氨酸和组氨酸的示波极谱连续测定

提出了用示波极谱法连续测定酪氨酸 ( Tyr)、脯氨酸 ( Pro)、组氨酸( His) 3种氨基酸的新方法。在 p H9.2硼酸缓冲溶液中 ,上述 3种氨基酸与镍发生配位反应 ,用示波极谱仪进行单扫描时 ,出现 3组灵敏度和分辨率均很高的二阶导数波谱 ,峰电位分别为 :Tyr - 1 .0 4 V,Pro - 1 .2 0 V,His - 1 .34V。酪氨酸、脯氨酸、组氨酸的峰电流与浓度分别在 2 .0× 1 0 -5～ 3.0× 1 0 -4 mol/L,3.2× 1 0 -6～ 2 .2× 1 0 -4 mol/L,4.0× 1 0 -5～ 2 .5× 1 0 -4 mol/L的范围内呈线性关系。该法已用于复方氨基酸注射液中酪氨酸、脯氨酸、组氨酸含量的测定。     

青霉素 V钾的二次微分简易示波伏安法测定

利用青霉素 V钾在 pH=7的 KH2PO4-Na2HPO4缓冲溶液中产生切口的示波特性 , 提出了一种药片中青霉素 V钾的测定方法 - - 二次微分简易示波伏安法 ; 校正曲线的线性范围为 2.0× 10-5～ 2.0× 10-4 mol/L, 检出限为 8× 10-6 mol/L; 对 7.0× 10-5 mol/L青霉素 V钾 8次测定结果的相对标准偏差为 1.6% ; 实验结果表明该法具有分析速度快、仪器装置简单以及药片中的淀粉等物质不干扰测定的优点 .     

方波伏安法测定酚酞片含量

研究了酚酞在0.5 mol/L氨水-氯化铵缓冲溶液(pH 10)介质中汞膜电极上的电化学行为,并依此建立了酚酞含量的方波伏安法测定.酚酞于-0.98 V(VS.Ag/AgCl)处出现一灵敏的阴极还原峰,峰高与酚酞的浓度在3.0×10-7-5.0×10-5mol/L范围内有良好的线性关系.方法的最低检出限为1.0×10-7mol/L,方法用于酚酞片中酚酞含量的测定,结果满意.     

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.     

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.     

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.     

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.