基于巯基自组装单层膜技术的补体C3压电免疫传感器的研究

本文采用自组装单层膜(SAMs)技术在压电石英晶振金电极表面组装巯基丙酸SAMs,以盐酸1-乙基-3-(3-二甲基氨基丙基)碳二亚胺(EDC)和N-羟基琥珀酰亚胺(NHS)作偶联剂共价固定补体C3抗体,研制了一种检测人血清中补体C3成分的压电免疫传感器。研究了巯基丙酸的自组装和抗体的固定化条件,考察了晶振固定抗体后的液相振荡行为和检测特性。并利用压电传感装置的实时监测功能,研究了巯基丙酸在金电极表面的自组装成膜过程和补体C3免疫反应动力学,获得了重要的动力学依据和参数。传感器检测补体C3的线性范围为2．34～23．2μg／mL。将传感器用于临床样品的检测,所得结果与酶联免疫吸附法基本一致。     

纳米金自组装膜的IgM压电免疫传感器的研究

利用等离子体聚合膜沉积技术和纳米金亚单层自组装技术设计传感器界面，用 于固定羊抗人M抗体，研制了一种新的M压电免疫传感器．先在石英品振上沉积正丁 胺等离子体聚合膜，通过戊二醛交联结合一半肮胺单层膜，利用膜上流基与纳米金 键合组装纳米金亚单层，得到可用于固定18kI抗体的界面，再以牛血清白蛋白 (BSA)和聚乙二醇(PEG)封闭晶振上的非特异性吸附位点．实验探讨了影响纳米金自 组装和抗体包被等主要实验参数和条件；考察了采用此固定化方法传感器的响应性 能，与戊二醛共价交联固定法和金电极表面直接吸附固定法进行了比较．结果表明 ，以纳米金单层作界面固定抗体时，具有传感界面不需活化、固定抗体的活性高、 检测时的非特异性吸附小、传感器能反复再生等优点．将传感器用于实际样品的检 测，结果令人满意．     

基于巯基自组装单层膜的日本血吸虫石英晶体微天平免疫传感器

应用自组装膜技术在压电石英晶振金电极表面自组装一带羧基的巯基丙酸单层膜,通过盐酸1-乙基-3-(3-二甲基氨基丙基)碳二亚胺及N-羟基琥珀酰亚胺共价固定32KD的日本血吸虫分子抗原(SjAg32),设计了石英晶振微天平免疫传感器,用于测定日本血吸虫抗体.比较了巯基自组装单层膜与HEMA-MMA共聚物涂层修饰的石英晶振在溶液中的振荡行为,发现巯基自组装单层膜修饰的石英晶振稳定快,且稳定性好.在优化条件下,测得IRS(49-2000)的滴度为1:1500.此外,对不同程度血吸虫感染的兔血清进行了测试,结果表明,该传感器能较好地定量区别血吸虫感染程度.     

压电免疫传感器在梅毒检测中的研究

用巯基丙酸(MPA)为基层物质在压电石英晶体表面形成单分子膜,经过N-乙基-N′-(3-二甲氨基)丙基碳化二亚胺盐酸(EDC)和N-羟基琥珀酰亚胺(NHS）活化后固定梅毒抗原TpAg,制成免疫传感器检测不同浓度的标准抗体溶液。并考察了传感器的响应特性和免疫反应动力学特性,结果表明这种免疫传感器是临床检测的有效工具,有巨大的应用潜力。     

基于电聚合膜和纳米金自组装的生物分子固定化新方法的研究

结合电聚合膜和纳米金自组装技术,提出了一种新的生物分子固定化方法,研制成一种检测抗胰蛋白酶的压电免疫传感器。通过在石英晶振金电极表面电聚合邻苯二胺膜,再在膜表面自组装一层纳米金粒．以静电吸附作用固定抗体(抗原),实现对相应抗原(抗体)的检测。利用扫描电镜技术,从形态上考察了晶振金电极上自组装纳米金后的表面形貌。研究了抗体的固定化条件,探讨了传感器的响应与再生性能结果表日月．这种固定化方法对所固定的生物分子的生物活性影响小,传感器的测定灵敏度高．响应性能和再生性能较好。     

一种高灵敏的压电免疫传感器用于高密度脂蛋白的测定

采用自组装单层膜(SAMs)技术在压电石英晶体的金电极表面组装巯基丙酸SAMs,以盐酸1-乙基-3-(3-二甲基氨基丙基)碳二亚胺(EDC)和N-羟基琥珀酰亚胺(NHS)作偶联剂,以共价键合方式固定高密度脂蛋白抗体,研制成一种高灵敏的压电免疫传感器用于检测人血清中低含量的高密度脂蛋白。利用压电装置的实时监测功能,考察了巯基丙酸在金电极表面的自组装成膜过程与机制;研究了晶振固定抗体及其反应结合抗原的液相振荡行为和传感特性。传感器采用初始速率法测定高密度脂蛋白的线性浓度范围为1.63~18.8 mg.L-1,检出限为0.82 mg.L-1。     

金表面抗原抗体的固定及其荧光法的测定

抗原或抗体的固定是制作免疫传感器的基础 .免疫传感器由固定于载体的具有识别作用的抗原或抗体以及指示免疫反应的换能器组成 .金表面自组装技术固定生物分子既可用电化学检测 ,也可用光学检测和质量检测 ,因而近年来用金表面自组装技术固定生物分子的研究越来越多 .其原理是利用金硫键固定含巯基的化合物 ,然后用偶联剂将生物分子连接固定在金表面 ,或者直接将有巯基的生物分子固定在金表面 [1,2 ] .本文报道了在金表面自组装技术固定兔 Ig G和山羊抗兔 Ig G的方法基础上 ,建立了抗体竞争法、夹心法和抗体过剩法测定兔 Ig G和山羊抗兔 …     

纳米增效的骨唾液蛋白压电免疫传感器阵列的研制

以AT切型10MHz双面镀金的石英晶体为换能器,结合纳米金颗粒(AuNPs)独特的物理化学特性,制作纳米压电免疫传感器阵列,用于临床检测血清骨唾液蛋白(BSP)。采用纳米金巯基自组装法固定抗体,通过免疫反应检测血清中BSP含量。考察了纳米金巯基自组装和巯基自组装两种抗体固定方法的固定效果,前者抗体固定量显著高于后者(P<0.05)。对稀释度为1:9～1:2的标准血清进行检测的结果显示,在该血清稀释度范围内,构建的BSP纳米压电免疫传感器阵列的准确度和灵敏度优于未使用AuNPs的传感器阵列。初步验证了乳腺癌患者和骨质疏松症患者的血清中BSP的含量均显著高于正常人(P<0.05)。使用AuNPs可以增加抗体的固定量,提高免疫反应的响应值;此传感器阵列具有结构简单、稳定性好、灵敏度高、特异性好等优点,可用于BSP的定量检测。     

基于微机电系统技术和纳米金自组装膜的安培型免疫传感器研究

基于微机电系统(MEMS)技术制备安培型免疫传感器,并利用基于硫醇单层膜的纳米金单层膜自组装技术设计传感器界面,用于固定人免疫球蛋白(IgG)抗体,研制了一种新型的安培型免疫传感器。采用MEMS技术,在硅片上制备微型的三电极系统以及SU-8反应池。基于自组装技术,先在金电极上自组装巯基乙胺单层膜,利用膜上氨基与纳米金共价结合组装纳米金单层膜,得到可用于固定抗体的界面。实验探讨了影响抗体固定的主要实验参数和条件;考察了采用此固定化方法传感器的响应性能,与金电极直接吸附固定法和戊二醛共价交联固定法进行了比较。对IgG检测的实验结果表明,采用纳米金自组装膜固定抗体,具有活性高、非特异性吸附小、检测线性范围宽等优点。并且,基于MEMS技术的安培型免疫传感器具有微型化、与集成电路工艺相兼容、易于实现传感器的阵列化和实时多参数检测等优点。     

血清样品中乙肝病毒的DNA电化学传感器检测

利用自组装单分子膜技术，将巯己基修饰的具有乙肝病毒(HBV)DNA序列特异性的单链DNA探针固定在金电极表面，制得DNA电化学传感器；以电活性的Hoechst 33258为指示剂，考察了该传感器对血清样品中乙肝病毒DNA的响应；探讨DNA电化学传感器在临床检测中的应用；将传感器法与荧光聚合酶链反应(PCR)法进行对比，两者的分析结果具有一致性。     

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.     

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.     

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.