固定化肌红蛋白在水-乙醇混合溶液中的类酶活性电化学

用琼脂糖将肌红蛋白(Mb)固定到玻碳电极(GC)表面,制备了Mb-琼脂糖膜修饰电极。包埋在琼脂糖膜中的Mb在缓冲溶液和乙醇混合溶液中与电极直接传递电子,得到一对对称的Mb辅基血红素Fe(III)/Fe(II)电对的可逆氧化还原峰。其式电势随缓冲溶液pH值增加而负移,且呈线性关系,这说明Mb的电子传递过程伴随有质子的转移。在缓冲溶液和乙醇混合溶液中,固定化肌红蛋白表现出类似细胞色素P450的催化活性,能快速催化还原氯乙烷(六氯乙烷、五氯乙烷、四氯乙烷)脱氯,Mb-琼脂糖膜修饰电极具有较好的稳定性和重现性,可用于这些物质的定量检测。     

琼脂糖水凝胶固定化血红素蛋白质的电化学研究

利用琼脂糖（agarose）水凝胶将肌红蛋白（Mb）、血红蛋白（Hb）、辣根过氧化物酶（HRP）和过氧化氢酶（Cat）4种血红素蛋白质固定在裂解石墨电极表面,形成稳定的血红素蛋白质-agarose膜修饰电极。在agarose膜中,Mb、Hb、HRP和Cat直接与电极传递电子。4种血红素蛋白质的式电势都随溶液pH的增加而负移且呈线性关系,表明电子传递过程伴随着质子转移。     

电化学研究铝及其纳米Al13对谷胱甘肽还原酶活性的影响

采用滴涂法制备了碳纳米管(MWNTs)/壳聚糖(CHIT)修饰玻碳电极(GCE),较为明显的使还原型辅酶Ⅱ( NADPH)在裸GCE上的氧化电势从700 mV降低到修饰电极上的380mV,并且明显增大了催化电流.氧化电流与NADPH浓度在0.08～2.60 mmol/L范围内呈线性关系;检出限为18.3 μmol/L.利用此修饰电极,采用计时电流i-t法,在谷胱甘肽还原酶(GR)催化“氧化型谷胱甘肽+ NADPH”生成“还原型谷胱甘肽+NADP+”反应中,通过检测NADPH在电极上催化电流的变化情况,分析了不同酸度和浓度下的Al3+和nanoAl13的加入对GR酶促反应初速率V0、米氏常数Km及反应最大速率Vmax的影响.     

魔芋多糖固定化肌红蛋白的直接电化学与电催化

用魔芋多糖(KGM)和N,N-二甲基甲酰胺(DMF)的加合物,将肌红蛋白(Mb)固定在玻碳电极(GCE)上,制备了稳定的Mb-KGM-DMF/GCE修饰电极,并研究了Mb在修饰电极上的直接电化学行为和电催化性能。该电极在pH=7.0的磷酸盐缓冲溶液(PBS)中,-0.38 V(E0′)处有一对氧化还原峰,峰电位差ΔEp=70 mV,该峰正是Mb中血红素辅基FeⅢ/FeⅡ电对的氧化还原特征峰。在0.2~9.0 V/s扫速的范围内,氧化还原峰峰电流大小和扫描速率成正比,呈现出表面控制行为。在pH为5.0~12.0的范围内,式电位和pH值呈线性关系,表明电子传递过程伴随着质子转移。同时,Mb-KGM-DMF/GCE修饰电极表现出良好的电催化性能,对氧、H2O2有显著的催化作用。在4.70~75.0μmol/L的范围内,其催化峰电流大小与H2O2的浓度有良好的线性关系,其线性回归方程i=0.127 0.093C,r=0.9989,表观米氏常数为80.8μmol/L。     

血红素蛋白质-琼脂糖膜修饰电极的表征和电催化特性

利用琼脂糖(agarose)水凝胶将肌红蛋白(Mb)、血红蛋白(Hb)、辣根过氧化物酶(HRP)和过氧化氢酶(Cat)4种血红素蛋白质固定在裂解石墨电极表面,形成稳定的血红素蛋白质-agarose膜修饰电极.用紫外-可见和红外光谱及原子力显微法对血红素蛋白质-琼脂糖膜修饰电极进行了表征.紫外-可见和红外光谱显示,在琼脂糖凝胶中,血红素蛋白质保持原始构象.溶液的pH(3.0～10.0)可逆地改变血红素蛋白质的构象,从而影响其光谱性质.原子力显微图象表明血红素蛋白质与agarose水凝胶之间存在较强的作用.研究了血红素蛋白质催化还原O2、H2O2的机理.稳定的血红素蛋白质-agarose修饰电极能运用于H2O2的定量测定.     

基于石墨烯修饰电极测定蔬菜中残余对硫磷的研究

制备了石墨烯薄膜修饰玻碳电极,并通过循环伏安法研究了对硫磷(PT)在该修饰电极上的电化学行为。对支持电解质、溶液pH值等实验条件进行了优化。结果表明,在0.1mol/L的乙酸-乙酸钠缓冲溶液(pH=5.0)中,PT在石墨烯薄膜修饰电极上具有良好的电化学响应,对比裸玻碳电极,PT的氧化峰峰电流显著提高,表明修饰膜对PT的电化学氧化具有一定的催化作用。PT的氧化峰电流及其浓度分别在1.0×10-7~1.0×10-6 mol/L范围内和3.0×10-6~1.0×10-5 mol/L范围内呈良好的线性关系,线性相关系数分别是0.9956和0.9874,检出限为1.0×10-8 mol/L。将该修饰电极应用于小白菜中残留PT的测量,结果比较满意。     

血红蛋白在二维纳米金Langmuir—Blodgett单层膜修饰电极上的直接电化学

利用Langmuir-Blodgett(LB)技术在氧化铟锡(ITO)电极上制备了分散均匀的二维纳米金单层膜,并将血红蛋白(Hb)直接固定于该修饰电极表面,研究了Hb在电极上的直接电化学行为.实验结果表明:纳米金可以改善Hb和电极间的直接电子传递,提高电子传递效率.Hb/Nano-Au修饰电极在pH 5.0～9.0范围内的式电位与溶液pH呈线性关系,斜率为-57 mV/pH,说明Hb的电子传递过程伴随质子转移;该修饰电极对H2O2具有良好的催化作用,在0.1 mol/L pH 7.0 的磷酸盐缓冲溶液(PBS)中,H2O2在2.5×10-6～4.1×10-4 mol/L浓度范围内与响应电流呈良好的线性关系,检出限为6.2×10-7 mol/L;其异相电子转移速率常数为0.66 s-1,米氏常数为0.20 mmol/L.     

电沉积普鲁士蓝/壳聚糖修饰金电极的电化学研究

应用控制电位电解法在金电极上进行了普鲁士蓝(PB)/壳聚糖(CS)修饰膜的电沉积。在pH2、溶液组成为2.5 mmol/L FeCl3 2.5 mmol/L K3[Fe(CN)6] 0.01%CS 0.01 mol/L HCl和0.1 mol/L KCl的溶液中,于0.4 V(vs.SCE)电沉积300 s,获得性能理想的沉积膜。对修饰膜进行了红外和显微表征,结果表明,PB和CS同时沉积在电极上,且膜结构较纯PB沉积膜粗糙,修饰量大,具有更强的空间结构性。研究了PB/CS/金修饰电极(PB/CS/Au/CME)的电化学行为,该电极在中性(pH7.0~8.0)条件下性能比纯PB修饰膜更稳定,具有良好的电化学活性和对H2O2的电催化性能。氧化峰电流与H2O2浓度在1×10-6~5×10-3mol/L范围内呈良好线性关系,为研制基于酶催化反应的电化学生物传感器奠定了良好基础。     

咖啡酸玻碳修饰电极对烟酰胺腺嘌呤二核苷酸的电催化氧化

研究了咖啡酸修饰电极的制备、性质及对NADH的电催化作用。修饰电极在0．1mol/L PBS缓冲溶液中(pH7．0)于0．0～ 050V(vs.Ag／AgCl)电位范围内呈现一对氧化还原峰，式量电位(E^0‘‘)为 0．250V(vs．Ag／AgCl)。E^0‘‘随pH增加而朝负方向移动，pH在5．0～8．0范围内，其线性回归方程为E^0‘‘=0．6233-0．05996pH，R=0．9969。表观电极反应速率常数(Kb)为12．3s^-1。电极反应的电子数为2且有2个质子参与。该修饰电极对NADH的氧化具有很好的电催化作用。NADH浓度在0．1—6．0mmol／L．范围内与峰电流呈现良好的线性关系。文中对电催化过程进行了探讨。     

HPLC／CoPC修饰电极安培检测大鼠心肌线粒体中谷胱甘肽的研究

研究了钴酞菁修饰电极的修饰方法及其电化学性质。它可以催化氧化谷胱甘肽,降低ＧＳＨ的过电位。以ＣｏＰＣ何尝修饰电极为工作电极的安培薄层化学检测器,与高压认相色谱联用,在工作电极电位为＋０．８Ｖ时,ＧＳＨ的浓度在３．０＊１０＾－６ｍｏｌ／Ｌ－１．０＊１０＾－３ｍｏｌ／Ｌ浓度范围内与峰电流呈良好的线性关系,线性相关系数为０．９９９１,检出限为１．０＊１０＾－３ｍｏｌ／Ｌ浓度范围内与峰电流呈良好的线性关系     

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%.     

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.     

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.     

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.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.     

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.