银掺杂聚L-天冬氨酸修饰电极的制备及对肾上腺素的测定

利用循环伏安法,研究了银和L-天冬氨酸在玻碳电极表面电化学聚合的条件,制备了银掺杂聚L-天冬氨酸修饰电极。研究了肾上腺素在修饰电极上的电化学行为,建立了循环伏安法测定肾上腺素的新方法。在pH=3.5的磷酸盐缓冲溶液中,扫描速率为50mV/s时,肾上腺素在修饰电极上产生一对明显的氧化还原峰,峰电位分别为Epa=0.447V,Epc=0.387V。用循环伏安法测定时,氧化峰电流与肾上腺素浓度分别在8.00×10-8～1.00×10-5mol/L和1.00×10-5～1.00×10-4mol/L范围内呈良好的线性关系,检出限为8.0×10-9mol/L。     

肾上腺素在对甲苯磺酸修饰电极上的电化学行为

研究了对甲苯磺酸在玻碳电极上电化学聚合的条件及修饰电极的电化学特性, 发现该聚合膜对肾上腺素的电氧化有显著的催化作用, 在pH 7.0的磷酸盐缓冲溶液中, 搅拌富集40 s后, 用循环伏安法对肾上腺素进行了测定, 线性范围: 4.05×10-7～9.45×10-6 mol/L, 检出限为3.2×10-8 mol/L. 对2.0×10-6 mol/L肾上腺素平行测定7次相对标准偏差为2.4%. 该电极有效地排除了抗坏血酸的干扰, 具有良好的稳定性和重现性.     

聚L-丝氨酸修饰电极选择性测定去甲肾上腺素

用循环伏安法制备了聚L-丝氨酸修饰玻碳电极,研究了去甲肾上腺素在聚L-丝氨酸修饰玻碳电极上的电化学行为,建立了测定去甲肾上腺素的新方法。实验结果表明:在pH 6.0的磷酸盐缓冲溶液中,聚L-丝氨酸薄膜对去甲肾上腺素的电化学氧化具有明显的催化作用,利用循环伏安法测定其还原峰电流可排除抗坏血酸干扰。去甲肾上腺素检测线性范围为4.0×10-7~1.5×10-4mol/L;检出限为1.0×10-8mol/L。该修饰电极具有良好的灵敏度、选择性和稳定性,已用于针剂样品分析。     

去甲肾上腺素和抗坏血酸在导电聚合物膜修饰电极上的同时测定

采用循环伏安法研究去甲肾上腺素(NE)和抗坏血酸(AA)在4-(2-吡啶偶氮)间苯二酚(PAR)导电聚合膜修饰电极上的电化学行为;以差示脉冲伏安法(DPV)对二者进行测定,发现PAR修饰电极对NE和AA有很强电催化作用,明显增强了电极反应的可逆性及峰电流。在pH 6.0磷酸盐缓冲液(PBS)中,NE氧化峰电流与其浓度在6.25×10-7~6.25×10-5mol/L范围内呈良好的线性关系,AA氧化峰电流与其浓度在1.0×10-6~3.0×10-4mol/L范围内呈良好的线性关系,检出限分别为5.0×10-8mol/L和5.0×10-7mol/L。该PAR膜修饰电极可对NE和AA进行单独或同时的测定,并用于实际样品重酒石酸去甲肾上腺素针剂和维生素C针剂的检测。     

聚L-精氨酸修饰电极存在下同时测定多巴胺和肾上腺素

用循环伏安法制备了聚L-精氨酸修饰玻碳电极,研究了多巴胺和肾上腺素在修饰电极上的电化学行为,建立了同时测定多巴胺和肾上腺素的新方法。在pH7.5的磷酸盐缓冲溶液中,多巴胺在修饰电极上产生一对氧化还原峰,峰电位分别为0.276V和0.059V;肾上腺素在修饰电极上产生3个氧化峰和一个还原峰,峰电位分别为0.262V、0.121V、-0.126V和-0.316V(对Ag/AgCl电极)。多巴胺和肾上腺素同时存在时ΔEpc=375mV,用还原峰对多巴胺和肾上腺素同时测定的线性范围分别为8.0×10-7~5.0×10-4mol/L和5.0×10-7~5.0×10-5mol/L;检出限分别为3.0×10-7mol/L和1.0×10-7mol/L。大量的抗坏血酸和尿酸不干扰测定,用于人尿液中多巴胺和肾上腺素样品的同时测定,结果满意。     

去甲肾上腺素在3-氨基-5-巯基-1,2,4-三唑修饰金电极上的电化学行为及研究

本文通过自组装的方法制备了3-氨基-5-巯基-1,2,4-三唑(TA)修饰金电极。X射线光电子能谱表明,3-氨基-5-巯基-1,2,4-三唑是通过形成S-Au键而组装到Au电极表面。研究了去甲肾上腺素在该自组装膜电极上的电化学行为。实验结果表明:在pH 4.5的0.1 mol/L BR缓冲溶液中,膜电极对去甲肾上腺素的电化学氧化具有明显的催化作用,其氧化峰电流与去甲肾上腺素的浓度在2.0×10-6~1.9×10-4mol/L范围内呈良好线性关系。方法检出限为4.0×10-7mol/L。     

肾上腺素在聚对氨基吡啶化学修饰电极上的电化学行为及其吸附伏安法测定

报道了肾上腺素(EP)在聚对氨基吡啶(POAP)修饰电极上的电化学行为及其测定方法。POAP修饰电极对EP的氧化有良好的电催化作用。最佳条件下,氧化峰电流与EP的浓度在5×10-8～9×10-6mol L和9×10-6～9×10-5mol L范围内呈良好线性关系,相关系数分别为0.9990和0.9997,检出限为2.5×10-9mol L。该电极寿命已超过两年,已用于实际样品中EP的测定。     

聚赖氨酸修饰电极在抗坏血酸共存时测定肾上腺素

在pH8.0磷酸盐缓冲溶液(PBS)中利用循环伏安法制备了聚赖氨酸修饰电极,在pH4.0 PBS中,聚赖氨酸膜对肾上腺素(EP)的电化学氧化具有明显的催化作用.利用循环伏安法测定EP还原峰电流可排除抗坏血酸(AA)干扰.肾上腺素还原峰电流与其浓度分别在6.3×10-7mol/L~1.0×10-5 mol/L与1.0×10-5mol/L~1.2×10-4 mol/L范围内呈良好线性关系,相关系数分别为0.9978与0.9975,;检出限(S/N=3)为7.2×10-8mol/L.该方法具有良好的灵敏度、选择性,已用于针剂样品分析.     

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。     

肾上腺素在酸性品红修饰玻碳电极上的电化学行为

用酸性品红修饰电极,循环伏安法(CV)研究L-肾上腺素(EP)的电化学行为.研究了介质溶液、pH值、修饰剂用量、扫描速度、扫描电位等条件进行优化,修饰电极与裸电极相比,还原峰电流增强8倍.峰电流与EP在2.0×10-5～2.2×10-3mol/L浓度范围呈良好的线性关系,相关系数r为0.9909,检出限为9.58×10-5mol/L.对1.0×10-3mol/L的EP平行测定11次的RSD为5.4%,重复性好.方法可用于盐酸肾上腺素注射液中EP含量的测定,回收率在96.1%～113.0%,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%.     

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.     

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.     

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.     

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.     

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.