基于尼古丁对胆碱氧化酶的抑制作用测定尼古丁的研究

基于尼古丁对胆碱氧化酶(CHOD)的抑制作用,将胆碱氧化酶电极用于微量尼古丁的测定。酶电极制作中,先在铂电极表面修饰一层壳聚糖膜,再用戊二醛交联CHOD。采用这种酶固定化方法,电极在4. 0×10-6 ~ 3×10-3 mol/L胆碱的浓度范围呈线性关系。探讨了工作电位、pH、底物浓度等实验条件对酶电极性能及抑制过程中响应电流的影响,测定了电极的重现性、干扰及使用寿命。电极检测尼古丁的线性范围为1. 5×10-5 ~3×10-3 mol/L;检出限为1. 25×10-5 mol/L。将电极用于实际样品烟草中尼古丁回收率的测定,结果良好。     

香蕉组织膜草酸电极的研究

将香焦组织与氧电极偶合,制成了草酸生物组织电极。在静态和流动条件下,测得电极的线性响应范围分别为8.8×10~(-5)～6.3×10~(-4)mol/L和5.0×10~(-5)～1.8×10~(-3)mol/L,二者的相关系数均为0.9998。研究了介质条件、pH、温度、流速、取样量和固定化等条件的影响。测定了电极的选择性和使用寿命等性能。计算了该实验条件下酶反应的米氏常数。采用静态法和流动注射法测得7份草酸标液的平均回收率分别为98.4％和98.9％。电极已用于一些食品中草酸的测定,所得结果与文献报道基本一致。     

毛细管电泳-电化学检测测定茶叶中咖啡因、表儿茶素和抗坏血酸

高效毛细管电泳电化学检测同时测定了6种茶叶中的咖啡因、表儿茶素和抗坏血酸的含量,考察了实验参数对分离、检测的影响。在最佳实验条件下,以300 靘直径的碳圆盘电极为检测电极,检测电极为1.20 V(vs.SCE),在25 mmol/L硼酸盐25 mmol/L磷酸盐(pH 7.6)的混合运行缓冲液中,上述各组分在16 min内能完全分离。咖啡因、表儿茶素和抗坏血酸在2×10-3mol/L～１×10-5 mol/L、5×10-5mol/L～5×10-7mol/L、2×10-4 mol/L～1×10-5mol/L范围内呈线性关系,检测下限分别为6×10-6mol/L、4×10-7mol/L和1×10-6mol/L。该法直接用于茶叶中咖啡因、表儿茶素和抗坏血酸的测定,结果令人满意。     

Nafion修饰玻碳电极伏安法测定痕量铟

报道了一种用Nafion修饰玻碳电极测定痕量铟的新方法。研究了Na-fion膜的有关特性和测定的条件,当富集时间为5 min时,峰电流与In(Ⅲ)浓度在1×10-9~1×10-7mol/L的范围呈良好的线性关系,检出限为1.46×10-10mol/L。该法用于实际水样中痕量铟的测定,平均回收率为98.4%。     

伏安型植物组织生物微电极的研究——茄子组织碳糊微电极的研究

茄子组织生物微电极在儿茶酚测定中表现出了较高的生物催化活性,而对抗坏血酸测定则为稳态响应,这表明该电极能有效地消除抗坏血酸的干扰。该电极的灵敏度高,重现性好,对多巴胺测定的线性范围为5.8×10~(-6)～6.5×10~(-4)mol/L,检出下限为:2.9×10~(-6)mol/L。     

就地镀铜旋转圆盘玻碳电极上阳极溶出测定砷(Ⅳ)

在铜或硒存在下利用悬汞电极阴极溶出测定砷已见报道,但使用玻碳电极进行砷的测定尚属少见。砷的阳极溶出法因汞电极中汞的氧化干扰而无法进行。本实验采用就地镀铜玻碳电极作工作电极成功地进行砷的阳极溶出法测定。 (一)操作步骤加入适量的砷、铜及硫酸溶液到50ml容量瓶中使砷的最终浓度为1.0×10~(-7)mol/L-9.0×10~(-6)mol/L,铜(Ⅱ)为4.0×10~(-6)mol/L,硫酸为0.6mol/L。将溶液转入石英电解池中,通氮除氧5min,在-0.60V沉     

铜膜差分脉冲阳极溶出伏安法测定药物中铋的含量

研究了铜膜电极代替汞膜电极测定重金属铋的差分脉冲溶出伏安法。实验了同位镀膜法测定铋的条件。在最佳实验条件下,Bi3+浓度在5×10-8~2×10-5mol/L范围内,其溶出峰峰高与浓度呈线性关系,检出限达到1×10-8mol/L。测定了一些药物中铋的含量,结果准确。     

醋酸纤维素为母体的稀土离子选择性电极的研制

醋酸纤维素为母体的稀土离子选择电极,制备容易,使用方便,可以测定混合稀土,电极的线性范围为1.2×10~(-1)～1×10~(-5)mol/L,适宜的pH范围较宽,测定结果令人满意。     

四硫富瓦烯为介体的碳纤维束葡萄糖氧化酶微电极的研究

本文研究了一种将电子介体四硫富瓦烯(TTF,Tetrathiafulalene)引入葡萄糖氧化酶微电极的新方法,制成了TTF为介体的碳纤维束葡萄糖氧化酶微电极。该电极制作简单,响应迅速、灵敏,电极寿命可达15天。葡萄糖浓度在1。0×10~(-4)～1.5×10~(-3)mol/L范围内有线性关系。检出限为7×10~(-5)mol/L。用于人体血样中葡萄糖测定获得满意结果。     

异烟肼在多壁碳纳米管修饰电极上的电化学行为及电化学测定

报道了一种测定异烟肼的化学修饰电极和电分析方法。与裸玻碳电极相比,多壁碳纳米管修饰玻碳电极显著提高异烟肼的氧化峰电流。优化了底液、pH值、修饰剂量、富集电位和富集时间等测定条件,建立了一种直接测定异烟肼的高灵敏度电分析方法。该方法测定异烟肼的线性范围为4×10-7~5×10-5mol/L;富集60 s后的检出限为1.5×10-7mol/L;对5×10-6mol/L的异烟肼平行测定10次的相对标准偏差为4.9%。此方法成功用于异烟肼片剂和血清中异烟肼含量的测定。     

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.