基于Fe3O4@Au复合纳米粒子标记抗体的电化学免疫方法用于水体中大肠杆菌的检测

合成了Fe₃O₄@Au复合纳米粒子作为辣根过氧化酶标记抗体的载体, 并将该复合纳米粒子标记物应用于电化学放大免疫分析. 将电子媒介体硫堇聚合在玻碳电极表面, 以纳米金作为固定大肠杆菌抗体的基底, 通过辣根过氧化酶催化溶液中H₂O₂产生的电流信号来测定大肠杆菌. 实验结果表明, 该方法对水体中大肠杆菌检测的线性范围为50～1×10⁵ cfu/mL, 检出限为20 cfu/mL. 对过富集后的实际水样进行测定, 该法结果表明, 对水体中大肠杆菌的检测灵敏度达到2 cfu/mL.     

碳纳米管/纳米金修饰金电极上柔红霉素电化学行为的研究

将碳纳米管与纳米金结合修饰在金电极上制成修饰电极,并用于柔红霉素(DNR)的电化学行为研究和检测.在4.4 mmol/L磷酸盐缓冲溶液(pH=5.81)中,DNR在碳纳米管-纳米金/Au电极上有一对灵敏的氧化还原峰.还原峰电流与DNR的浓度在3.2×10-8～1.0×10-6mol/L和1.0× 10-6～2.2× 1...     

邻苯二酚在金纳米粒子-碳纳米管复合修饰电极上的电化学行为

用循环伏安法研究了在pH7.0的磷酸盐支持电解质中,在-1.0～1.0 V(vs.SCE)电位范围内,邻苯二酚在金纳米粒子-碳纳米管复合修饰电极上的电化学行为,发现金纳米粒子-碳纳米管复合膜对邻苯二酚的电化学反应具有非常明显的电催化作用,催化效果强于单独的金纳米粒子或碳纳米管修饰电极。邻苯二酚在该修饰电极上的电化学反应受到表面吸附过程控制。可利用该修饰电极对对苯二酚、邻苯二酚和间苯二酚进行同时测定。邻苯二酚在4.0×10-5～1.0×10-3mol.L-1范围内呈线性,检出限(3S/N)达到1.0×10-5mol.L-1。     

基于二硫化钼/纳米金和硫堇/纳米金信号放大的雌二醇电化学适配体传感器

构建了一种新型的基于二硫化钼/纳米金和硫堇/纳米金信号放大的检测17β-雌二醇的电化学适配体传感器. 利用巯基自组装技术将17β-雌二醇的适配体探针DNA固定在二硫化钼/纳米金修饰玻碳电极表面, 与末端带巯基的部分互补DNA链杂交, 将硫堇/纳米金电化学指示剂自组装在杂交后的双链DNA上, 制备了17β-雌二醇电化学适配体传感器. 二硫化钼/纳米金复合材料增加了电极的有效表面积和DNA探针的固定量. 纳米金作为信号物质载体负载硫堇, 实现了电化学指示剂的信号放大. 加入目标物17β-雌二醇后, 目标物与适配体DNA特异性结合, 导致互补DNA链脱落, 双链上结合的硫堇/纳米金电化学指示剂数量减少, 电化学信号降低. 实验结果表明, 在1.0×10 ^-14~5.0×10 ^-12 mol/L范围内17β-雌二醇浓度与峰电流的线性关系良好, 检出限为4.2×10 ^-15 mol/L(S/N=3). 该传感器可望用于其它环境激素类物质的检测.     

石墨烯-金纳米粒子复合膜修饰电极的制备及对双酚A的测定

采用电化学还原技术,通过一步电沉积制备了石墨烯-金纳米粒子复合膜修饰电极(ERGO-Au/GCE).采用透射电子显微镜(TEM)和循环伏安(CV)法对修饰电极进行了表征,并研究了双酚A(BPA)在该修饰电极上的电化学行为.结果表明,所制备的复合物修饰电极对双酚A有明显的电催化效果.在p H=6.0的磷酸盐缓冲溶液中,双酚A在0.3~1.0 V扫描电位范围内有1个不可逆的氧化还原峰出现.在优化的条件下,双酚A的浓度在3.00×10-8~1.30×10-5mol/L范围内与其氧化峰电流呈线性关系,检出限为1.0×10-8mol/L(S/N=3).将该修饰电极用于饮用水和塑料制品中双酚A含量的测定,回收率为96.4%~103.5%.     

基于纳米金修饰硼化钴纳米片的电化学免疫传感器用于检测人绒毛膜促性腺激素

开发了一种基于金纳米颗粒修饰硼化钴纳米片(AuNPs/CoB)阵列的电化学免疫传感器用于定量检测血清中的人绒毛膜促性腺激素(hCG)。通过电沉积与电聚合的方法构建硫堇/金纳米颗粒/硼化钴纳米片阵列,hCG抗体通过Au—N键或肽键偶联到硫堇/金纳米颗粒/硼化钴纳米片(Thi/AuNPs/CoB)阵列上形成免疫探针。金纳米颗粒修饰的硼化钴纳米片催化还原硫堇产生响应电流,实现对hCG的检测。构建的电化学免疫传感器具有高选择性和良好的稳定性,线性检测范围为10～5.0×10⁴ pg/mL,检出限(S/N=3)为2.8 pg/mL。实验结果表明,此电化学免疫传感器可应用于血清中hCG的检测,为早期妊娠和妇科疾病的临床诊断提供了一种简单可靠的评价方法。     

硫化银纳米球负载金纳米粒子信号放大的大肠杆菌O157:H7电化学免疫传感器

设计了一种利用碳纳米管作为基底固定材料以及硫化银纳米球负载金纳米粒子做为电化学标记信号的无酶免疫传感器,用于检测大肠杆菌O157:H7。同时引入具有信号放大功能的硫化银纳米球负载金纳米粒子作为标记物,并采用示差脉冲伏安法对金纳米粒子进行检测,其产生的电化学信号在一定范围内与大肠杆菌O157:H7的浓度呈线性关系。在最优条件下,该传感器线性范围为:1×10~3~1×10~7cfu/m L,检出限为4×10~2cfu/m L,并且具有良好的精密度和稳定性。该免疫传感器可以用于大肠杆菌O157:H7的快速检测。     

免标记电化学免疫传感器用于微囊藻毒素-LR的灵敏检测

采用纳米金作为抗体的固定基质,同时以硫堇为电活性指示剂,构建了一种免标记的电化学免疫传感器用于微囊藻毒素-LR(MC-LR)的灵敏检测。将萘酚修饰到金电极表面,通过静电作用将硫堇捕获。加入纳米金与硫堇的氨基结合,抗体将通过与纳米金作用而固定到电极表面。通过MC-LR与其相应抗体的特异性结合作用阻碍硫堇的电子传递,实现MC-LR的电化学检测。在最优实验条件下,MC-LR的质量浓度与电信号在5~100μg/L范围内呈良好的线性关系,检出限为0.71μg/L,可满足饮用水检测需求,能够用于实际水样中M C-LR的测定。     

纳米金与磁性纳米复合物构建电流型免疫传感器的研究

制备了易于磁性分离、硫堇(Thi)包覆的四氧化三铁(Fe3O4)纳米复合物。通过静电吸附作用,将萘酚(Nafion)、Thi包覆的Fe3O4复合纳米粒子层层修饰到玻碳电极表面,再利用Thi分子中的氨基吸附纳米金,最后固载甲胎蛋白抗体,从而制得灵敏度高、稳定性好的无试剂电流型甲胎蛋白免疫传感器。实验通过透射电子显微镜(TEM)对该复合纳米粒子进行表征,并用循环伏安法考察了电极的电化学特性。结果表明,Fe3O4/Thi复合纳米粒子修饰的电极在实验过程中呈现出良好的氧化还原活性,其检测范围为0.05～20μg/L,检出限为0.03μg/L。     

DNA电化学生物传感器在转基因植物特定序列基因检测中的应用

在玻碳电极(GCE)上采用循环伏安法电聚合硫堇(PTh)得到PTh/GCE修饰电极,并利用聚硫堇层共价结合和静电作用吸附金纳米粒子(AuNP′s)制得AuNP′s/PTh/GCE修饰电极。然后通过将ss-DNA/AuNP′s/PTh修饰电极置于cDNA杂交液中,于42℃杂交制得ds-DNA/AuNP′s/PTh修饰玻碳电极,实现了脱氧核糖核酸(DNA)探针在AuNP′s/PTh修饰的玻碳电极上的固定,制得DNA电化学生物传感器。在[Fe(CN)6]3-/4-溶液中采用微分脉冲伏安法(DPV)及交流阻抗谱技术(EIS)对DNA的固定和杂交进行了表征。试验结果表明:在1.0×10-10～1.0×10-6mol.L-1的浓度范围内,该传感器可对转基因植物外源基因草丁膦乙酰转移酶基因(PAT基因)片段进行检测,检出限(3s)为3.2×10-11mol.L-1。     

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.