溶胶-凝胶-HBsAb膜免疫传感器的研制与应用

采用溶胶-凝胶(Sol-gel)技术,成功地将乙肝表面抗体(HBsAb)包埋于Sol-gel中,再滴涂于铂盘电极表面,制成溶胶-凝胶-HBsAb膜非标记免疫传感器.根据抗原与抗体特异性结合形成的免疫复合物使敏感膜有效扩散截面积减小的特性,提出了利用铁氰化钾作为氧化还原探针间接检测乙肝表面抗原(HBsAg)的新方法.用循环伏安法(CV)对电极逐层修饰过程进行了表征,并探讨了对HBsAg定量检测的可行性及其响应机理.采用差示脉冲伏安法(DPV)检测人体血清中的HBsAg.线性范围5～320μg/L,线性相关系数r=0.997.该传感器响应迅速,灵敏度高,稳定性好.于4℃干态保存14d,其响应信号基本不变.将其用于108例临床血清检验,与酶联免疫吸附法(ELISA)的符合率为87.5％.     

溶胶-凝胶非标记免疫传感器检测乙肝表面抗原

采用溶胶 凝胶 (sol gel)技术包埋乙肝表面抗体 (HBsAb) ,涂布于金盘电极表面 ,构成sol gel HBsAb/Au非标记免疫传感器 ,用于检测人血清中乙肝表面抗原 (HBsAg)。该传感器对HBsAg的电位响应遵循Nernst方程 ,在 1～ 330 μg/L浓度范围内 ,传感器的电位响应值ΔE与HBsAg浓度C的对数呈线性关系 ,线性回归方程为ΔE =1 8.1 7+79.84lgC。响应时间为 3min。癌胚抗原、甲胎蛋白等对测定无明显影响。对于HBsAg阴性血清 ,电位响应值ΔE <30mV ,而对于阳性血清则ΔE >30mV ,据此 ,作为临床判别的依据。对1 0 0例临床血清分别用传感器和酶联免疫法 (ELISA)进行双盲检验 ,两法的符合率为 86 %。     

表面等离子体子共振生物传感器用于乙肝表面抗原的测定

运用自行研制的表面等离子体子共振（SPR）生物传感器，采用自组装成膜技 术并以戊二醛作偶联剂，在传感片表面修饰HBsAg单克隆抗体，将其用于乙肝表面 抗原（HBsAg)的检测。实验结果表明SPR生物传感器对HBsAg的检出限为0.06ng/mL 。与传统的酶联免疫吸附试验（ELISA）相比，SPR生物传感器的检出灵敏度明显高 于ELISA法。用该SPR生物传感器对HBsAg质控血清与纯化的HBsAg溶液进行比较检测 ，结果表明该SPR生物传感器对HBsAg具有好的特异选择性。     

微型IgG免疫传感器的制备及其对人免疫球蛋白G的响应

以硅烷醇-戊二醛交联法在Ag电极表面制备的抗Igc膜电极为敏感器件,配以Ag／AgCl参比电极制备成微Igc免疫传感器。传感器基于免疫反应的原理,通过其电动势的变化对Igc的Nemst响应,测定人免疫球蛋白（hIgc）的含量。采用两种抗Igc膜电极的传感器,对hIgc的响应时间均小于6min;线性范围在0．20-2．0μg／L,检出限为0．1μL。直接检测健康人血清中hIgc的相对标准偏差为6．2％（n=5）;加标回收率为93％-108％。以0．012moL／L盐酸为再生液,传感器可重复使用,对Igc的活性在4℃可保持30d。     

用于乙肝表面抗原检测的压电免疫传感器的研制

研制了一种用于乙肝表面抗原（ＨＢｓＡｇ）检测的新型传感器———石英压电免疫传感器。采用聚乙烯亚胺粘附和戊二醛交联法在金电极上固定抗体蛋白，对固定化过程进行了监测。ＨＢｓＡｇ含量的检测范围为１～４０ｍｇ／Ｌ。使用过的电极用０２ｍｏｌ／Ｌ乙醇胺（ｐＨ＝８）解吸，可重复使用。将此传感器用于实际血清样品的检测，与酶联免疫吸附法所得结果吻合。     

热敏相分离荧光免疫分析乙肝表面抗原的新方法

以N-异丙基丙烯酰胺为单体,将水溶性热敏高分子聚异丙基丙烯酰胺(PNIP)和抗体偶联,用异硫氰酸荧光素标记羊抗人乙肝表面抗原抗体,建立了夹心型热敏相分离荧光免疫分析乙肝表面抗原(HBsAg)的新方法.评价了抗体在PNIP上的固定效率和非特异性吸附情况.HBsAg在0.5～100μg/mL范围内与体系荧光强度呈良好的线性关系,检出限为10ng/mLHBsAg.该方法既具有均相免疫分析的快速性,又有固相免疫分析的高灵敏度.用于乙肝病人血清中HBsAg水平的测定,结果令人满意.     

基于双层纳米金修饰的高灵敏电位型乙肝表面抗原免疫传感器研究

基于电沉积和层层自组装技术，提出了一种新的生物分子固定化方法，研制成一种高灵敏电位型乙肝表面抗原免疫传感器。利用L-半胱胺酸（LCys）的双官能团结合双层纳米金，从而通过比表面积大，生物相容性好的纳米金胶吸附大量抗体，同时用聚乙烯醇缩丁醛（PVB）薄膜的笼效应把乙肝表面抗体（HBsAb）和纳米金固定在玻碳电极上，从而制得了高灵敏度、高稳定性的电位型免疫传感器。采用循环伏安法（CV）对电极的层层自组装过程进行了考察，并对该免疫传感器的性能进行了详细的研究。该免疫传感器线性范围是8．5～256．0ng／mL，线性相关系数为0．9978，灵敏度为89．0，检出限为3．1ng／mL。已用于病人的血清样品分析。     

新表面抗原定量 检测试剂面市

不久前,全球体外诊断的领导者罗氏诊断宣布,用于预测患者对乙肝治疗应答的新型HBsAg定量检测试剂正式在中国上市。据了解,HBsAg定量检测用于检测慢性乙肝患者体内的乙肝表面抗原的浓度（HBsAg）,反映机体对抗乙肝病毒的免疫应答状态,有助于优化慢性乙肝的治疗管理。     

对氟苯酚-H_2O_2-HRP体系酶联荧光免疫分析研究ⅣF~--Zr-8-羟基喹啉-5-磺酸荧光法测定人血清中乙肝表面抗原和E抗体

将Ｚｒ－８－羟基喹啉－５－磺酸荧光体系与对氟苯酚为底物的酶促反应相偶合，建立了一种测定辣根过氧化物酶（ＨＲＰ）及其标记物的新方法．测定ＨＲＰ的线性范围为０．０３１～３１ｍＵ／ｍＬ，检出限（３σ）为０．００７ｍＵ／ｍＬ．用于测定人血清中乙肝表面抗原和Ｅ抗体，结果令人满意．     

对氟苯酚—H2O2—HRP体系酶联荧光免疫分析研究：IV,F^—Zr—8羟基喹…

将Ｚｒ－８羟基喹啉－５－磺酸荧光体系与对氟苯酚为底物的酶促反应相偶合，建立了一种测定辣根过氧化物酶（ＨＲＰ）及其标记物的新方法，测定ＨＲＰ的线性范围为０．０３１～３１ｍＵ／ｍＬ，检出限（３σ）为０．００７ｍＵ／ｍＬ．用于测定人血清中乙肝表面抗原和Ｅ抗体。结果令人满意.     

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.     

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.     

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.