微阀进样和固定化试剂化学发光微流动注射芯片的研究

设计了一种将微注样阀和发光试剂均集成化的微流动注射化学发光芯片。利用luminolK3Fe(CN)6H2O2化学发光体系,研究了这种芯片的分析特性。该芯片测定H2O2的线性范围为2×10-5～8×10-9mol/L;检出限为3.6×10-9mol/L;相对标准偏差RSD=4.4%(c=1×10-6mol/L,n=11)。与常规的流动注射化学发光分析法相比,该芯片具有简单、快速、灵敏度高、耗样量少等特点,并结合酶促反应成功地用于人体血清中葡萄糖的测定。     

Ru(bipy)_3~(2+)-CO_3~(2-)-SO_3~(2-)-KClO_3体系化学发光法测定空气中的二氧化硫

提出了 Ru(bipy) 2 +3 - CO2 -3 - SO2 -3 - KCl O3 体系化学发光法测定溶液中亚硫酸盐的方法。SO2 -3 浓度与化学发光强度在 1 .0× 1 0 - 7～ 1 .0× 1 0 - 4mol/L 范围内成正比 ,检出限为 8.76× 1 0 - 8mol/L,对 1 .0× 1 0 - 4mol/L SO2 - 3 溶液 6次测定的相对标准偏差为 2 .9%。该法用三乙醇胺作为吸收液 ,成功地用于测定空气中二氧化硫的含量 ,结果满意。     

锰C-抗坏血酸甲醛-化学发光体系的研究

实验观察到锰 氧化抗坏血酸可以产生弱的化学发光 ,甲醛对这一化学发光反应有较强的增敏作用 ,据此建立了测定抗坏血酸的流动注射化学发光分析法。方法的检出限为 2× 1 0 -8mol/L抗坏血酸 ;线性响应范围为 6 .0× 1 0 -8～ 2 .0× 1 0 -5mol/L。对 1 .0× 1 0 -6mol/L的抗坏血酸进行 1 1次测定 ,相对标准偏差为 2 3%。该方法已成功应用于维生素C针剂和片剂中抗坏血酸含量的测定 ,结果与药典方法测得值一致     

流动注射化学发光发测定葡萄糖

β-D-葡萄糖的检测是临床化学的常规分析项目 .化学发光分析法测定葡萄糖具有线性范围宽、灵敏度高等优点[1～ 3] .我们曾研究了鲁米诺 ( L uminol) -KIO4 -H2 O2 化学发光反应体系[4 ] ,发现 H2 O2 浓度在 2 .0× 1 0 - 7～ 6.0× 1 0 - 4mol/L范围内与发光强度有良好的线性关系 .本文将生成 H2 O2 的葡萄糖 -葡萄糖氧化酶 ( GOD)的酶促反应与鲁米诺 -KIO4 -H2 O2 的化学发光反应相偶合 ,结合流动注射技术 ,建立了一种流动注射化学发光测定葡萄糖的新方法 .方法的线性范围为 0 .6～ 1 1 0 mg/L ,相关系数为 0 .9997,检出限为 0 .0…     

毛细管电泳-间接化学发光法检测染发剂中苯二酚异构体和苯酚

根据某些酚类化合物在碱性条件下具有能猝灭鲁米诺-铁氰化钾体系化学发光信号的特性,建立了毛细管电泳-间接化学发光分离检测苯二酚异构体和苯酚的新方法.电泳缓冲溶液选用7.5 mmol/L Na2B4O7-2.5 mmol/L Na2HPO4.在优化的化学发光和电泳条件下,对苯二酚、间苯二酚、邻苯二酚和苯酚在10 min内可直接实现分离,其检出限(S/N=3)分别为2.9×10-8 mol/L、3.7×10-7 mol/L、8.4×10-8 mol/L和4.4×10-6 mol/L;相对标准偏差(RSD)为2.5%～4.8%(n=5).通过对不同染发剂实际样品进行分离分析研究,证明该方法可以用于实际染发剂样品的分析测定,结果令人满意.     

锰(Ⅳ)-安乃近-甲醛化学发光体系的研究

实验发现锰(Ⅳ)氧化安乃近可以产生弱的化学发光,甲醛对这一化学发光反应有较强的增敏作用。据此建立了测定安乃近的流动注射化学发光分析法。在最优化的条件下,测定安乃近的线性范围为6 0×10-7～1 0×10-5mol/L,检出限为2×10-7mol/L安乃近。对1.0×10-6mol/L安乃近进行11次测定,相对标准偏差为3.4%。该方法已应用于针剂中安乃近的测定,其结果与药典方法测得值一致。     

诺氟沙星的铽敏化化学发光法研究与应用

本文根据 Tb3+能显著增强 Ce ( ) - SO2 - 3- NFLX体系的化学发光 ,建立了流动注射铽敏化化学发光测定诺氟沙星的新方法。本法的线性范围为 9.0× 1 0 - 9～ 1 .0× 1 0 - 6 mol/L,检出限为 4.5× 1 0 - 11mol/L。利用该法测定了诺氟沙星胶囊中诺氟沙星的含量 ,并对血清和尿样进行了回收率测定 ,回收率在 1 0 0 .4%～ 1 0 5 .7% ,结果令人满意。     

L-酪氨酸-高锰酸钾-硫酸化学发光体系研究

在硫酸介质中 ,L -酪氨酸与高锰酸钾反应能产生较强的化学发光 ,据此建立了测定 L -酪氨酸的分析方法。该法线性范围为 4.0× 1 0 - 6 ～ 2 .8× 1 0 - 5mol/L;检出限为 8.8× 1 0 - 7mol/L;对 1 .0× 1 0 - 5mol/L 的 L-酪氨酸进行连续1 0次平行测定 ,相对标准偏差为 2 .7%。该法已应用于测定医用氨基酸注射液中的 L-酪氨酸。     

反向流动注射化学发光法测定二邻苯二甲酰亚胺甲基二磺酸基酞菁锌

在碱性介质中 ,二邻苯二甲酰亚胺甲基二磺酸基酞菁锌 (简写为ZnPcS2 P2 )可增强Luminol H2 O2 CTAB体系的化学发光 ,据此建立了测定ZnPcS2 P2含量的反向流动注射化学发光分析新方法。用该法测定ZnPcS2 P2 ,其范围为 2 .5× 1 0 - 7～ 1 .0× 1 0 - 8mol/L ,检测限为 9× 1 0 - 9mol/L ,对 1 .0× 1 0 - 7mol/L的Zn PcS2 P2 溶液进行 9次平行测定 ,其相对标准偏差为 1 .2 %。本法有一定的选择性 ,与分光光度法相比 ,灵敏度提高了 1～ 2个数量级。     

高锰酸钾-甲醛-碘化学发光法测定碘

在酸性条件下 ,高锰酸钾氧化甲醛产生很强的化学发光。当该体系中有碘离子存在时 ,化学发光强度受到一定的抑制 ,据此 ,建立了新的碘离子的化学发光分析方法。该方法对碘离子检出限为 7.87× 1 0 - 7mol/L,线性范围为 2 .44× 1 0 - 6～ 7.87× 1 0 - 3mol/L,用于食品中碘含量的测定 ,结果满意     

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.