液晶型非标记免疫传感器检测天蚕素B

制备了一种基于液晶取向变化的非标记液晶型免疫传感器,用于检测天蚕素B。首先采用硅烷化试剂自组装膜法构建基底敏感膜诱导液晶分子呈均一垂直排列,再通过戊二醛交联法将天蚕素B固定到基底表面,当天蚕素B抗体与天蚕素B特异性结合后扰乱了液晶分子的取向,使液晶膜的颜色和亮度发生变化,以此实现对天蚕素B的检测,检测限可达0.1 ng/m L。本方法具有灵敏度高、特异性好、非标记和操作简单等优点。     

声表面波分子印迹技术检测甲基膦酸二甲酯的研究

以分子印迹(MIP)电聚合的成膜方法,在声表面波(SAW)双通道延迟线上制备了对甲基膦酸二甲酯(DMMP)有选择性的分子印迹薄膜(纳米级),并证实了分子印迹的明显效果,所研制的声表面波分子印迹传感器／(SAW—MIP)对甲基膦酸二甲酯的检出限为5mg／m^3。     

基于液晶取向变化检测有机胺化合物的方法

采用旋涂法在玻璃基底表面制备4-三乙氧基硅基丁腈有机膜.有机膜表面采用丝绒布进行摩擦和5％乙酸水溶液改性处理后成为特异敏感膜.将此敏感膜的载玻片面对面贴合后,在其间组装液晶E7分子膜,表征液晶分子排列状态;采用挥发法在敏感膜表面组装液晶膜,制备成了检测目标物的复合材料.采用此种材料对甲胺、乙胺和二乙胺等有机胺化合物及实验室常见干扰气体进行检测,发现只有有机胺化合物会对材料的液晶分子排列状态产生影响,导致液晶膜的亮度发生改变,从而实现对目标物的特异检测.对有机胺化合物检测过程中,其响应速率为V甲胺＜V乙胺＜V二乙胺,恢复速率为:V乙胺＜V乙胺＜V甲胺;刘乙胺的检出限为0.46 mg/m3.本方法具有较高的检测灵敏度,抗干扰能力较强且操作简单,可发展为现场检测有机胺化合物的新技术.     

非标记液晶型免疫传感器检测赭曲霉素A

研制了一种基于液晶取向改变的非标记液晶型免疫传感器,并用于检测赭曲霉素A(0TA).采用戊二醛交联法将OTA同定在由自组装膜修饰的玻璃肇底表面.自组装膜能诱导液晶分子垂直排列,而连接OTA抗体后则扰乱了液晶分子取向的有序排列,导致液晶分子在化学敏感膜表面的取向发生变化,使光学信号的亮度及色彩发生变化,以此实现对OTA的...     

对-叔丁基杯[4]芳烃衍生物自组装分子在声表面波传感器中检测有机磷

杯芳烃;自组装;分子印迹;声表面波传感器;甲基膦酸二甲酯;沙林;检测     

乙基纤维素粘度对甲基膦酸二甲酯检测的影响

石英晶体微天平(QCM)作为一种质量敏感型传感器已广泛用于气体检测、气体成分分析、环境监测、免疫分析、军事化学等领域[1],其原理是依靠晶体表面涂覆的膜材料吸附气体的量所引起的频率变化来实现的,因而其性能很大程度上取决于膜材料的特性.乙基纤维素已用于化学战剂及其模拟剂的检测[2-3],但尚未见有文献对其粘度影响进行具体研究.本文在前期工作基础上[3],详细研究了不同粘度的乙基纤维素作为QCM膜材料对甲基膦酸二甲酯(DMMP)检测的影响,为传感器及膜材料在军事化学中的应用提供了方法和依据.     

压电晶体微天平阵列传感器识别毒剂的研究

压电晶体微天平(QCM)阵列传感器在毒剂侦检领域具有广泛的应用前景。本研究建立了QCM阵列传感器毒剂检测系统,以氢键酸性共聚硅氧烷(BSP3)、聚表氯醇(PECH)和乙基纤维素(ECEL)为膜材料制备了对毒剂敏感的QCM阵列传感器,对沙林、芥子气、甲基膦酸二甲酯进行了定量检测,并结合模式识别方法对检测结果进行了分析处理,识别率达到98%以上,为探索QCM阵列传感器对毒剂的定性定量分析提供了方法依据。     

基于制备接枝型分子印迹膜构建农药电位型电化学传感器及其检测性能研究

基于分子设计,以氯甲基化聚砜(CMPSF)为基膜,阴离子单体对苯乙烯磺酸钠(SSS)为功能单体,N,N'-亚甲基双丙烯酰胺(MBA)为交联剂,在表面引发体系-NH2/S2O2-8的作用下,采用"接枝聚合与分子印迹同步进行"的分子表面印迹新技术,制备了接枝型农药抗蚜威分子印迹膜(MIM)。采用红外光谱(FITR)和光学显微镜(OM)对该分子印迹膜进行表征,通过等温结合实验与竞争吸附实验,考察了抗蚜威分子印迹膜的分子识别性能与机理。以该印迹膜作为敏感膜,构建了抗蚜威电位型传感器,并对其检测性能进行了考察。结果表明,所制备的接枝型印迹膜对模板抗蚜威分子具有特异的识别选择性和优良的结合亲和性,结合容量高达92μg/cm2,相对于分子结构与抗蚜威相似的阿特拉津,印迹膜对抗蚜威的选择性系数为4.537。在p H 4.0的水介质中,传感器膜电极的电位响应与抗蚜威浓度对数在1.0×10-6~1.0×10-3mol/L范围内呈良好的线性关系(r=0.999 9),其检出限为2.5×10-8mol/L;以抗蚜威分子印迹膜为敏感膜所构建的电位型传感器,其构建过程简捷,检测灵敏准确,电位响应快速(t10 s)。     

氟化衍生-固相萃取对水中痕量膦酸的GC-MS检测EI北大核心CSCD

针对水中痕量(<1 mg/L)甲基膦酸类化合物进行了GC-MS定性分析检测研究。建立了固相萃取结合氟化物衍生的方法进行样品制备。采用600MHz核磁对氟化物衍生效率进行分析,衍生效率大于99%。采用气相色谱-电子轰击电离质谱(GC-EI/MS)、气相色谱-化学源负电离质谱(GC-NCI/MS)以及气相色谱-选择离子扫描质谱(GC-SIM-MS)分析方法对5种标准物质沙林、梭曼原体以及甲基膦酸异丙酯、甲基膦酸乙酯、甲基膦酸的衍生化产物进行了分析,检出限分别为10,50,0.2,0.1,0.05μg/L,方法的相对标准偏差小于7%。     

氟化衍生-固相萃取对水中痕量膦酸的GC-MS检测

针对水中痕量(1 mg/L)甲基膦酸类化合物进行了GC-MS定性分析检测研究。建立了固相萃取结合氟化物衍生的方法进行样品制备。采用600MHz核磁对氟化物衍生效率进行分析,衍生效率大于99%。采用气相色谱-电子轰击电离质谱(GC-EI/MS)、气相色谱-化学源负电离质谱(GC-NCI/MS)以及气相色谱-选择离子扫描质谱(GC-SIM-MS)分析方法对5种标准物质沙林、梭曼原体以及甲基膦酸异丙酯、甲基膦酸乙酯、甲基膦酸的衍生化产物进行了分析,检出限分别为10,50,0.2,0.1,0.05μg/L,方法的相对标准偏差小于7%。     

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.     

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.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

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.