癌胚抗原毛细管电泳-化学发光均相免疫分析

设计了一种测定人血清中癌胚抗原的毛细管电泳-化学发光检测均相免疫分析新方法。采用四苯硼酸钠增强luminol-H2O2-HRP体系化学发光的原理,化学发光检测经毛细管电泳分离的,用辣根过氧化物酶(HRP)标记的癌胚抗体及免疫复合物。测定癌胚抗原的线性范围2.0~80.0μg/L(R=0.9921),检出限为0.1μg/L(绝对检出限为0.75 fg)。     

流动注射化学发光同时检测甲胎蛋白和癌胚抗原

将包被有单克隆抗体的两个透明微型检测池串联在流动注射分析装置上,利用移动式微型检测池建立了一种能同时检测甲胎蛋白和癌胚抗原的流动注射化学发光免疫分析方法,为提高分析效率提供了一种有效途径.样品抗原和辣根过氧化物酶标记的相应抗体分别导入微管进行孵育,形成三明治式免疫夹心结构.在注入鲁米诺和H2O2后, 两微型检测池中分别形成较稳定的酶催化化学发光体系.通过切换检测池,使两个透明微型检测池中发生的酶促增强化学发光反应相继得到检测,从而实现两种待测物的同时检测.考察了一系列影响化学发光检测的参数,如免疫反应时间、鲁米诺和H2O2的浓度及反应介质的pH值.在最佳实验条件下,甲胎蛋白和癌胚抗原的检测线性范围分别为1.25～50.00 μg/L和1.25～40.00 μg/L,检出限分别为1.06和1.00 μg/L.对人血清实际样品进行了检测,取得了满意的结果.     

测定甲氨蝶呤的在线电生次氯酸根流动注射化学发光法

将在线恒电流电解产生ClO-与流动注射化学发光分析法结合, 基于甲氨蝶呤对ClO--鲁米诺体系化学发光的抑制作用, 建立了测定甲氨蝶呤流动注射化学发光新方法. 该法测定甲氨蝶呤质量浓度的线性范围为2×10 ～ 4×102 μg/L, 检出限为1×10 μg/L, 相对标准偏差为2.1%(8×10 μg/L, n=9), 已应用于片剂和针剂中甲氨蝶呤的测定. 该法具有简单、快捷、灵敏等特点.     

毛细管电泳-联吡啶钌电化学发光法对血浆中丁卡因与普鲁卡因的同时测定

建立了毛细管电泳-电致化学发光同时测定丁卡因和普鲁卡因的新方法.考察了毛细管电泳流动相和检测池中磷酸盐缓冲液pH和浓度、进样时间和电压、分离电压和检测电位等对丁卡因和普鲁卡因的分离以及联吡啶钌电致化学发光检测的影响.基于循环伏安法考察了丁卡因和普鲁卡因的电化学行为与发光机理.在优化的实验条件下,丁卡因和普鲁卡因的标准曲线分别在6.6 ～265.6 μmol/L和0.7 ～219.0 μmol/L范围内呈良好的线性,检出限(S/N=3)分别为1.9 μmol/L和0.2 μmol/L.对23 μmol/L丁卡因和15 μmol/L普鲁卡因的标准溶液连续测定5次,迁移时间的相对标准偏差(RSD)分别为0.13%、0.16%,电化学法发光强度的RSD分别为3.7%和4.9%.该方法已成功用于血浆中丁卡因和普鲁卡因的同时检测,平均回收率均为94%,相对标准偏差低于4%.     

毛细管电泳-化学发光法测定人血清中的异烟肼

基于碱性介质中异烟肼对laminol-K3Fe(CN)6化学发光体系的增敏作用,设计了一个经毛细管电泳(CE)分离,在线化学发光检测异烟肼的新方法.研究并优化了毛细管电泳分离及化学发光检测的条件.在优化的实验条件下,该方法测定异烟肼的线性范围为4.0×10-7～1.0×10-5g/mL(R2=0.9984),检出限(3σ)为1×10-8g/mL,对6.0×10-6g/mL的异烟肼进行6次平行测定,其相对标准偏差为4.0%.方法已用于血清中异烟肼的测定.     

毛细管电泳-电容耦合非接触电导法检测牛奶中金属离子和三聚氰胺

采用毛细管电泳-电容耦合非接触电导法检测牛奶中金属离子和三聚氰胺的含量.以20 mmol/L乳酸溶液为背景电解质,采用毛细管(50 μm×50 cm,有效长度40 cm),电导检测器的操作参数为180 kHz×8 V,对标准品和牛奶中K+, Ca2+和Na+的检出限为0.009～0.040 μg/g,对三聚氰胺的检出限为0.10～0.20 μg/g.本方法仪器简单,可以对牛奶中三聚氰胺及无光学活性的无机离子进行快速准确的检测.     

2-氨基-3-羟基吡啶-过氧化氢-辣根过氧化物酶伏安酶联免疫体系分析人血清癌胚抗原

以氮杂环化合物为电化学分析底物的2-氨基-3-羟基吡啶-H2O2-辣根过氧化物酶(HRP)伏安酶联免疫体系测定人血清癌胚抗原(CEA).HRP催化H2O2氧化2-氨基-3-羟基吡啶的酶促反应产物,在缓冲液中-0.36 V处产生一个灵敏的伏安还原峰,借助此峰可以测定游离的HRP,进而可用于以HRP为标记物的酶联免疫分析.对酶促反应条件和测定条件的优化反应条件为:以B-R缓冲液(pH 6.0)为反应介质,在10 mL总反应液中含有1.0 mL 0.2 mol/L B-R缓冲液、3.0 mL 8.0 mmol/L 2-氨基-3-羟基吡啶溶液以及1.5 mL 0.5 mmol/L H2O2溶液,反应温度37 ℃,反应时间30 min.最佳测定条件为:B-R缓冲液(pH 7.0)为支持电解质,在10 mL总测定溶液中含有5 mL上述总反应液、1.0 mL 0.2 mol/L B-R缓冲液.测定仪器条件:起始电位0.00 V,终止电位-0.80 V,电位扫描速度400 mV/s,滴汞静止时间7 s.在最佳的反应条件和测定条件下,新体系测定游离HRP的线性范围为4.0×10-4～1.0 μg/L; 对HRP的检出限为0.12 ng/L.新体系对CEA测定的线性范围为0.50～80.0 μg/L; 检出限为0.50 μg/L.为经典ELISA法的检出限的1/10.     

反向毛细管电泳高频电导法测定牛黄中的胆酸

建立了毛细管电泳高频电导法快速简便测定牛黄粉中胆酸的新方法.考察了电泳介质的种类、浓度、 pH值以及操作电压和进样时间对分离检测的影响.缓冲液为0.5 mmol/L Na3PO4 2 mmol/L Na2HPO4 0.2 mmol/L CTAB(pH 11.7), 分离电压为 -15 kV时可实现较好的分离和检测.胆酸的线性范围为75～200 μg/mL, 检出限为0.1 μg/mL.线性方程为y=0.6054ρ-4.14991, r=0.953.回收率为100.9%, RSD(n=5)=2.1%.     

胶束扫集毛细管电泳分离测定绿原酸和咖啡酸

采用胶束扫集毛细管电泳分离测定双黄连口服液中的绿原酸和咖啡酸.试验条件为:重力进样时间40 s;以20 mmol/L NaH_2PO_4,100 mmol/L 十二烷基磺酸钠(SDS)为电泳缓冲液(含体积分数15%甲醇,pH 2.20),分离电压-20 kV,检测波长214 nm,讨论了pH、SDS浓度、样品溶剂等对分离效果的影响.在优化条件下,绿原酸和咖啡酸的检出限分别达到1.02和0.168 μg/mL,线性范围分别为5.86～51.5 μg/mL和1.27～14.5 μg/mL.     

核黄素化学发光体系测定盐酸赛庚啶

核黄素是一种荧光试剂,本实验发现,核黄素也可以用作化学发光试剂.以核黄素为化学发光试剂, 构建了NCS-核黄素-盐酸赛庚啶化学发光新体系.利用此体系建立了测定盐酸赛庚啶的化学发光分析新方法.方法的线性范围为0.02～1.0 mg/L, 检出限为9.0 μg/L, 对浓度为01 mg/L盐酸赛庚啶溶液进行11次平行测定的相对标准偏差(RSD)为0.8%.此法已用于药品中盐酸赛庚啶含量的测定, 结果与药典测定结果一致.对化学发光反应的机理也进行了初步的探讨.     

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.     

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.     

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.     

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.     

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.     

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.