毛细管电泳-柱端安培检测测定莲子心中荷叶碱、芦丁和金丝桃甙的含量

采用毛细管电泳-柱端安培检测测定莲子心中荷叶碱、芦丁和金丝桃甙的含量．研究了检测电位、运行缓冲液浓度和pH值,分离电压和进样时间对分离和检测的影响．以微碳圆盘电极（Ф=0.5ram）为工作电极,检测电位为＋0．95V（vs．Ag／AgCl）,pH为7．25的50mmol／L Na2B4O7和100mmol／L NaH2PO4缓冲液为运行液,当分离电压为15kV时,3种分析物在15min内完全分离．荷叶碱、芦丁和金丝桃甙的检出限（S／N=3）分别为0．02μg／mL、0．05μg／mL和0．04μg／mL．该方法已成功地应用于莲子心中上述3种活性成分的测定．     

毛细管电泳-电化学发光法测定石蒜鳞茎中的石蒜碱

建立了毛细管电泳-电化学发光(CE-ECL)检测石蒜碱的方法。探讨了检测电位、分离缓冲液pH和浓度、分离电压、进样电压及进样时间等因素对石蒜碱分离检测的影响。在最佳实验条件下,石蒜碱含量在0.03~2μg/mL范围内与其峰面积呈良好的线性关系,相关系数为0.9995,检出限为0.005μg/mL(S/N=3)。对0.8μg/mL石蒜碱进行7次平行实验,其迁移时间、峰高和峰面积的RSD分别为1.7%,5.2%和5.6%。方法应用于石蒜鳞茎中石蒜碱的测定,加标回收率为92.2%~98.6%。     

生物合成纳米金与MWCNTs/L-Cys复合修饰玻碳电极测定左旋多巴

利用荷叶萃取液生物合成纳米金,并与多壁碳纳米管/L-半胱氨酸复合成修饰电极材料,研究了左旋多巴在该修饰电极上的电化学行为.在0.2 mol/L乙酸-乙酸钠体系(pH=2.6)中,氧化峰电流与左旋多巴浓度在0.6~40μmol/L及60~120μmol/L范围内呈良好的线性关系,检出限达5.2×10-8mol/L.实验结果表明,生物合成纳米金复合多壁碳纳米管/L-半胱氨酸修饰电极具有良好的稳定性和高灵敏度,对实际样品测定的回收率在91.2%~102.5%之间.     

电化学传感分析复方金银花药剂中木犀草素含量

采用循环伏安法制备了聚多巴胺修饰电极，并在NaOH溶液中进行电化学活化，得到木犀草素电化学传感器。通过循环伏安法探讨了木犀草素在传感界面的电化学反应机理。结果显示，活化后的多巴胺修饰电极对木犀草素具有显著的电催化作用，氧化峰电流较裸电极增强了91.7%。在最佳条件下，通过微分脉冲伏安法，建立了木犀草素氧化峰电流与浓度的标准工作曲线，线性范围为0.10～200.00μmol/L，检出限为31.65 nmol/L。将该传感器应用于市售金银花颗粒样品和金银花露样品中木犀草素测定，根据反向延伸法，计算得样品中木犀草素含量分别为297μg/g和2.15μg/mL；标准加入法回收率分别为98.5%～115.0%和93.6%～111.5%。     

毛细管电泳电化学检测法测定马钱子中的士的宁和马钱子碱

用毛细管电泳电化学检测法测定了马钱子中的士的宁和马钱子碱.以BR缓冲溶液(35 mmol/L混酸用180 mmol/L NaOH调节至pH 6.50)为电泳液,分离电压为6 kV,检测电位为0.95 V,士的宁和马钱子碱在30 min内得到了良好分离.士的宁和马钱子碱浓度分别在0.35～35.00 μg/mL和0.40(40.00 μg/mL内具有良好的线性关系,检测限分别为0.08μg/mL和0.15μg/mL.应用于马钱子样品的测定.     

Nafion修饰铂电极电化学还原法测定溶液中的一氧化氮

采用电化学还原法对溶液中一氧化氮（ＮＯ）进行测定，研究对比了电化学氧化和电化学还原对ＮＯ检测的选择性和灵敏度，同时研究了工作电极表面修饰膜厚度、工作电极在被测溶液中的吸附时间，扫描速度对峰电流及峰电位的影响，证明电化学还原法选择性好，方法检出限为６μｍｏｌ／Ｌ，线性范围１０￣８００μｍｏｌ／Ｌ。     

血清蛋白-荧光素复合物单扫极谱波与应用

在0．08mol／L的HAc中，荧光素与牛血清白蛋白(BSA)或人血清白蛋白(HSA)相互作用形成复合物。复合物使荧光素在-0．58V(vs．SCE)处的还原峰电流增大，峰电流的增大值与加入的BSA或HSA的浓度在一定的范围内呈线性关系。BSA在2—24μg／mL范围内呈线性关系，检出限为1μg／mL；HSA在2—22μg／mL范围里呈线性关系，检出限为0．8μg／mL。应用该法测定了人血清蛋白样品，结果令人满意。     

离子色谱-在线柱后电化学衍生-荧光法测定酪氨酸

采用自制电解池作为电化学衍生装置,建立了离子色谱一电化学衍生一荧光法测定饮料中的酪氨酸。在碱性淋洗液作用下,酪氨酸在阴离子交换柱上被分离,到达自制电解池的阳极室,在阳极上被氧化,氧化后的产物因具有较强的荧光而被荧光检测器检测。离子化试剂既可以做色谱分离所需的淋洗液,又可以作为电化学反应优良的支持电解液,因此,离子色谱和电化学衍生具有较好的兼容性。最佳的实验条件为：淋洗液NaOH（10mmol／L）＋乙腈（ACN,1＋9）,流动相流速1．0mL／min,电解池电压1．0V,激发／发射波长320／420NM。在优化的实验条件下,酪氨酸的线性范围为0．01～10mg／L,检出限为1．2μg／L（信噪比S／N=3）。50μg／L的酪氨酸标准溶液进样7次,得到的色谱峰面积相对标准偏差为2．5％。方法具有快速,灵敏和选择性好的特点,并成功用于饮料中酪氨酸的测定。     

植物激素吲哚乙酸电化学生物传感器的研究

本文提出了以绿豆芽叶片组织-二茂铁修饰的碳糊电板(LFMCE)作为植物激素吲哚乙酸传感器的研制，探讨了影响电极性能的因素，初步研究了吲哚乙酸氧化酶处于最优活性的基本条件。实验表明，此电极在NaH2PO4-Na2HPO4(pH5．8)缓冲溶液中对植物生长素有良好的电催化作用，氧化峰电位约在0.42V左右。用循环伏安法测得的氧化峰电流变化值与吲哚乙酸浓度在8-l60μg／mL范围内呈良好的线性关系，检测下限为4．2μg／mL，相关系数为0．9984，在样品回收率的测定中取得满意结果。     

单扫描示波极谱法测定药物中的苯妥英钠

建立了测定苯妥英钠的新方法。在0．016mol／L B-R(pH 7．0)缓冲溶液中,本妥英钠产生一还原波,峰电位为-1．18V。该还原波二阶导数峰电流与苯妥英钠浓度呈线性,线性范围为2．5～50μg／mL,检出限为2．0μg／mL。该方法用于片剂中笨妥英钠含量的测定,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%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

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.     

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.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.