鲁米诺化学发光分析法研究进展

从化学发光反应机理和应用进展两个方面对鲁米诺-过氧化氢、鲁米诺-铁氰化钾、鲁米诺-碘化物、鲁米诺-高锰酸钾和鲁米诺-溶解氧等化学发光体系进行了综述;指出鲁米诺化学发光体系是应用最为广泛的一类化学发光体系,同时对鲁米诺化学发光分析法的发展方向进行了展望.     

溴酸钾-鲁米诺后化学发光法检测水中微量偏二甲肼

实验发现偏二甲肼(UDMH)在溴酸钾-鲁米诺化学发光反应体系中的后化学发光反应.在对这一后化学发光反应的动力学性质、发光条件,包括溴酸钾浓度、鲁米诺浓度、管长、流速和酸碱度条件等研究的基础上,建立了后化学发光反应法测定偏二甲肼的新方法,并讨论了其可能的反应机理.该方法的线性范围为1.0×10-7～1.0×10-5g/L...     

高碘酸钾-鲁米诺体系中一些后化学发光反应的研究

研究了葡醛内酯、盐酸美司坦和重酒石酸去甲肾上腺素等10种物质在高碘酸钾-鲁米诺体系中的后化学发光现象、后化学发光反应的动力学、化学发光光谱、荧光光谱以及其它相关性质, 提出了其可能的发光机理; 在优化的分析条件下建立了这10种物质的后化学发光分析方法, 初步构建了高碘酸钾-鲁米诺后化学发光分析体系.     

离子液体包裹纳米金修饰金电极用于鲁米诺电致化学发光的研究

室温离子液体是由有机阳离子和无机阴离子或有机阴离子组成的室温熔融盐,由于其优异的化学催化、生物催化和化学反应性能而在化学和工业方面受到广泛的关注和运用.离子液体也应用于合成纳米金属材料特别是纳米金~([1～3]),纳米金作为一种化学和生物催化性能良好的纳米金属材料也应用于鲁米诺的液相电致化学发光研究~([4]).本研究将巯基功能化离子液体应用于纳米金的合成,并将不同粒径的离子液体包裹的纳米金修饰金电极然后用于鲁米诺电极化学发光的研究.     

Ag(Ⅲ)-鲁米诺流动注射化学发光法用于茶饮料抗氧化活性的评价

以茶叶中常见的8种茶多酚化合物为研究对象,研究了三价银配合物[Ag(Ⅲ)]-鲁米诺流动注射化学发光法与2,2-联苯基-1-苦基肼基(DPP H)自由基清除法、邻苯三酚-碳酸盐-鲁米诺化学发光法和鲁米诺-过氧化氢化学发光法检测结果的相关性,并采用Ag(Ⅲ)-鲁米诺流动注射化学发光法评价了4种茶饮料的抗氧化活性.设置的仪器...     

流动注射化学发光法测定头孢他啶

在碱性条件下,头孢他啶对金纳米粒子催化高锰酸钾氧化鲁米诺化学发光体系的发光强度具有明显的增敏作用,基于此建立了一种测定头孢他啶的化学发光方法.在优化实验条件下,用该法测定头孢他啶的线性范围为3.0×10-5～5.0×10-2 g/L,检出限为1.0×10-5 g/L,相对标准偏差为2.0%(ρ=4.0×10-3 g/L...     

纳米粒子参与的鲁米诺化学发光及其分析应用

化学发光的基础理论和分析应用已经有多年的研究历史,但化学发光的研究多局限于分子和离子水平。纳米粒子由于其量子尺寸效应、表面能高以及比表面积大,因而常作为氧化还原反应的催化剂来放大反应信号。近年来,纳米粒子直接或者间接参与的化学发光拓展了化学发光的理论和应用研究范畴,己发现纳米粒子能够作为催化剂、还原剂、微尺度反应平台和能量接受体等参与化学发光反应。本文详细介绍了纳米粒子参与的鲁米诺化学发光体系,并重点评述了部分纳米粒子参与的鲁米诺化学发光与高效液相色谱、毛细管电泳等分离技术联用实例。纳米粒子作为一种新型化学发光响应单元,可提高鲁米诺化学发光反应的效率,对开发新的鲁米诺化学发光反应体系具有重要意义,已有关于金、铂、银、合金、半导体、磁性等纳米粒子参与的鲁米诺化学发光报道。除应用于环境、药品及食品等分析领域外,其在免疫分析方面也表现出巨大的应用潜力。最后,提出了纳米粒子参与鲁米诺化学发光体系研究目前存在的问题,并对其未来的发展方向进行了展望。     

纳米银增敏化学发光体系测定间苯二酚

采用柠檬酸钠包覆化学还原法制备纳米银粒子,将该纳米银粒子加入到碱性鲁米诺-铁氰化钾化学发光体系,体系的化学发光强度明显增强,而间苯二酚的加入能抑制该体系的化学发光,据此建立了流动注射化学发光法定量分析痕量间苯二酚的新方法.考察了鲁米诺、铁氰化钾、氢氧化钠以及纳米银浓度对化学发光体系的影响.在优化的实验条件下,该方法测定...     

流动注射化学发光法检测甲基嘧啶磷残留

研究发现,在碱性介质中甲基嘧啶磷能够有效增强鲁米诺-H2O2体系的化学发光。据此,结合流动注射分析法,建立了测定甲基嘧啶磷的流动注射化学发光分析方法,并对可能的反应机理进行了探讨。考察了甲基嘧啶磷-鲁米诺-H2O2体系的化学发光反应动力学以及反应体系pH、鲁米诺浓度、H2O2浓度、流速、进样体积等因素对化学发光的影响。结果表明:在最佳条件下,甲基嘧啶磷在5.0×10-8～1.0×10-5g/mL的浓度范围内与发光强度呈良好的线性关系,检出限(S/N=3)为2.5×10-8g/mL。将该体系应用于加标小麦样品测定,回收率为94.7%～113.0%,相对标准偏差为2.2%～3.6%。     

奇妙的化学发光:鲁米诺检测血迹*

鲁米诺是一种重要的化学发光试剂。在法庭科学领域,技术人员用鲁米诺试剂检测案发现场是否存在血迹,该场景也经常出现在一些涉及犯罪现场勘查的影视作品中。通过介绍化学发光的发现历程,鲁米诺化学发光的机理,以及鲁米诺在血迹检测中的应用,将有关化学发光的理论和应用等内容引入化学教育教学领域,能够有效开阔学生的科学视野。     

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.