电沉积Cu_2O在无酶葡萄糖传感器中的应用

采用电化学沉积法在玻碳电极表面制备了Cu_2O,利用X射线衍射(XRD)和扫描电镜(SEM)对Cu_2O的微观结构和表面形貌进行了表征,通过循环伏安法和计时电流法研究了Cu_2O对葡萄糖的电催化氧化性能。结果表明:该修饰电极对葡萄糖有良好催化作用,葡萄糖检测的线性范围为5.0μmol/L~6.23mmol/L,检测限(S/N=3)为0.4μmol/L。该传感器制备简单,稳定性和重复性好,可用于实际样品的测定。     

花瓣状铂-金-石墨烯纳米结构的制备及其在葡萄糖测定中的应用

利用氧化石墨烯(GO)、PtCl62-、AuCl4-作为前驱体,在-0.4 V条件下,采用一步电化学还原法对GO和金属前驱体进行同时还原,成功制备了花瓣状的Pt-Au-GO纳米结构;同时利用伏安法研究了该催化剂对葡萄糖氧化的电催化性能,结果表明,此纳米结构对葡萄糖氧化反应表现出很好的电催化性能;据此构建了无酶葡萄糖传感器,该传感器在较低的电位下(-0.1 V)对葡萄糖的线性检测范围为1.0~25.0 mmol/L,响应灵敏度为26.3μA cm-2(mmol/L)-1,检出限为4.0μmol/L(S/N=3),且传感器具有很好的重现性、稳定性和选择性,可用于实际样品的分析检测。     

聚茜素黄R膜修饰电极对尿酸电催化及对人尿中尿酸的检测

用电聚合的方法制备了聚茜素黄R膜修饰的玻碳电极,研究了尿酸在该电极上的电化学行为。结果表明,该修饰电极对尿酸的氧化具有良好的电催化能力。示差脉冲伏安法测定尿酸的氧化峰电流与其浓度在1.0×10-6～1.0×10-4mol/L范围内呈现良好的线性范围,检测限为8.6×10-7 mol/L(S/N=3)。本方法用于人尿液中尿酸含量的测定,结果令人满意。     

钯/碳纳米纤维复合材料修饰电极同时检测邻苯二酚和对苯二酚

利用电纺丝技术制得钯/碳纳米纤维复合材料(Pd/CNFs),并将其用于修饰玻碳电极Pd/CNF-GCE/CME.Pd/CNF-GCE/CME对邻苯二酚和对苯二酚的氧化还原反应具有较高的电催化活性,显著提高了二者电化学反应的可逆性.考察了支持电解质的酸度对邻苯二酚和对苯二酚电化学响应的影响,选用0.1 mol/L PBS(pH 8.0)作为支持电解质.用微分脉冲伏安(DPV)法对邻苯二酚和对苯二酚进行选择性检测:当混合溶液中存在50 μmol/L对苯二酚时,邻苯二酚的氧化峰电流与其浓度在1～90 μmol/L范围内呈线性关系,检出限为0.3 μmol/L(S/N=3);当存在50 μmol/L邻苯二酚时,对苯二酚的氧化峰电流与其浓度在2～100 μmol/L范围内呈线性关系,检出限为1.0 μmol/L.另外,此修饰电极具有较好的重现性和较强的抗干扰能力.将此修饰电极用于模拟水样中邻苯二酚和对苯二酚的测定,结果令人满意.     

基于聚多巴胺/铜微粒自组装多层膜的无酶葡萄糖传感器

利用多巴胺易于在电极表面发生自聚反应,且聚多巴胺膜中富含邻苯二酚等反应性基团,可通过二次反应实现电极表面的进一步功能化修饰的特点,在玻碳电极(GCE)表面,将多巴胺自聚膜(PDA)与铜微粒(Cu)进行层-层自组装,构建了无酶葡萄糖电化学传感器(GCE/(PDA/ Cu) n )。传感器的灵敏度可通过控制多层膜的组装层数进行调控。采用紫外-可见光谱跟踪表征了多层膜的组装过程,结果表明,多层膜的生长是逐步且均匀的过程。采用循环伏安法和电流-时间曲线法研究了修饰电极对葡萄糖的电催化氧化性能。对于GCE/(PDA/ Cu)4,检测葡萄糖的线性范围为0.5~9.0 mmol/ L,检出限为5.8μmol/ L(S/ N=3)。本传感器具有良好的重现性、稳定性和较强的抗干扰能力。将本传感器用于血清中葡萄糖的测定,结果令人满意。     

基于中空多孔金纳米/石墨烯复合纳米材料的葡萄糖氧化酶直接电化学及其生物传感研究

采用溶液相牺牲模板法制备中空多孔金纳米粒子（HPAuNPs）,并将该材料与还原氧化石墨烯（rGO）复合,用于葡萄糖氧化酶（GOx）在玻碳电极（GCE）表面的有效固定,构建GOx/HPAuNPs/rGO/GCE传感界面。利用扫描和透射电镜、X射线光电子能谱、X射线衍射谱、红外光谱及电化学等方法对材料的形貌与结构,GOx的固定化过程,以及传感器的直接电化学和电催化性能进行表征。结果表明,HPAuNPs和rGO的协同作用能有效促进GOx与电极之间的直接电子转移（DET）。基于GOx/HPAuNPs/rGO/GCE对葡萄糖的良好电催化性能,该方法有效实现了对葡萄糖的高灵敏度检测,其电流响应的线性范围为0.05～7.0 mmol/L,检出限（S/N=3）为16μmol/L。该传感器具有良好的选择性、重现性及稳定性,对实际样品血清中血糖的测定结果令人满意,回收率为98.0%～103%,相对标准偏差不大于5.0%。     

电化学沉积制备纳米结构铜电极及其葡萄糖检测性能

利用电化学沉积法制备了高电活性的纳米结构铜电极材料, 采用扫描电子显微镜和电化学方法分别对电极表面形貌和电化学性能进行了表征, 研究了实验参数对葡萄糖电氧化活性的影响. 结果表明, 改变沉积条件可以调控沉积铜的形貌及电催化活性. 在最佳条件下制备的铜纳米结构电极对葡萄糖检测的灵敏度为1310 μA·L/mmol, 检出限为5.0×10^-7 mol/L(S/N=3).     

金纳米粒子和钼氧化物复合膜修饰电极的制备及应用

利用循环伏安法将金纳米粒子和钼氧化物共同电沉积在玻碳电极表面,制备了金纳米粒子和钼氧化物复合膜修饰电极,利用SEM和XPS研究了MoOx/AuNPs复合膜的表面形态,并研究其修饰电极对葡萄糖的电催化氧化过程. 首次提出了阳极扫描极化反向催化伏安法,即在反向扫描过程中纯的催化氧化电流通过扣减背景电流的方法被提取出来. 显著提高电流测量灵敏度改善了信噪比. 制备的MoOx/AuNPs复合膜修饰电极在0.01-4.0 mmol/L对葡萄糖具有线性响应,电流灵敏度为2.35 mA·L/（mmol·cm2）,检测限为9.01 μmol/L（信噪比为3）.     

多贝斯在石墨烯修饰玻碳电极上的电化学行为及其测定

制备了石墨烯修饰玻碳电极（GN/GCE）。 在0.05 mol/L H2SO4溶液中,用循环伏安法研究了多贝斯在GN/GCE上的电化学行为。 结果表明,GN/GCE对多贝斯的氧化还原反应有明显的电催化作用。 建立了测定多贝斯的新方法,用微分脉冲伏安法测得多贝斯的氧化峰电流与其浓度在2.0×10-9~1.2×10-6 mol/L范围内呈线性关系,检出限为1.0×10-9 mol/L(S/N=3)。 该法可用于胶囊中多贝斯的测定,修饰电极有较好的稳定性和重新性。     

基于Nafion/碳纳米粒子修饰的葡萄糖传感器

采用滴涂法制备了Nafion/碳纳米粒子复合物修饰玻碳电极,该电极对H2O2具有良好的电催化氧化性能。还利用滴涂法制备了Nafion/碳纳米粒子复合物包裹的葡萄糖酶电化学生物传感器,该生物传感器对葡萄糖有着良好的电催化作用。应用该传感器对葡萄糖进行了检测,检测线性范围为2.0×10-6～6.0×10-3mol/L,检出限为1.6×10-6mol/L(S/N=3),实验结果表明该传感器具有良好的稳定性、重现性和抗干扰能力。对小鼠血清样品中的葡萄糖进行检测,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.     

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.