异硫氰酸荧光素-人血清白蛋白标记物化学发光反应的研究

采用反相流动注射分析方法,研究了异硫氰酸荧光素（FITC）－人血清白蛋白（HSA）标记物的化学发光性能和反应的最佳条件,建立了化学发光测定人血清白蛋白的新方法。体系的化学发光强度与人血清白蛋白的含量在0．08－16μg/mL内呈线性关系,方法的检出限为0．04μg/mL。讨论了蛋白质标记物化学发光性增强的原因。     

荧光素-牛血清白蛋白的化学发光反应研究

研究了在碱性介质和阳离子表面活性剂CTMAB存在下,NaClO氧化荧光素-牛血清白蛋白的化学发光行为和化学发光反应的条件,提出了反相流动注射化学发光测定牛血清白蛋白的新方法.该法测定牛血清白蛋白的线性范围为0.02～6.4 μg/mL,检出限为0.005μg/mL.     

偶氮胂Ⅲ与牛血清白蛋白作用的分光光度研究

本文研究了溶液基本条件如酸度和离子强度等对偶氮胂Ⅲ－牛血清白蛋白分子复合物形成的影响。在pH2．0条件下，标准工作曲线的线性范围为0～60mg／L；桑德尔灵敏度为0．15μg／cm2。采用平衡透析法、双波长法及摩尔比法测定了pH2．0时牛血清白蛋白对偶氮胂Ⅲ的最大结合数。结果表明有两类结合，第一类结合的最大结合数为30～40；结合常数约106mol－1L.     

某些变色酸双偶氮染料-蛋白质体系的共振瑞利散射及其分析应用

在PH3．4－4．0的缓冲溶液中， 偶氮胂M（AAM）、偶氮氯膦Ⅲ（CPAⅢ）和氯磺酚S（CSPS）等变色酸双偶氮染料及蛋白质本身的共振瑞利散射（RRS）均十分微弱，但这些染料与蛋白质结合形成复合物时能使RRS急剧增强，在400－470nm的范围内呈现高的散射强度，其最大散射波大均位于470nm处，并且散射强度分别在0．36mg/L（CPAⅢ体系）、0－3．8mg/L(AAM体系）和0－4．8mg/L(CSPS体系）的范围内与牛血清白蛋白（BSA）的浓度成正比，方法具有高灵敏度，对于BSA的检出限（σ=3时）分别为18．5μg/L（CPAⅢ）、13．6μg/L（CSPS）和27．9μg/L（AAM）。考察了共存物质的影响，表明方法具有较好的选择性，此法可用于人血清中蛋白质的测定。     

葡萄糖的流动注射化学发光法测定

葡萄糖在浓盐酸中降解后,其产物羟甲糖醛可与Ce(Ⅵ）反应产生化学发光,罗丹明6G对该反应有较强的增敏作用。据此,建立了流动注射化学发光测定葡萄糖的新方法。该法的线性范围为0．2－90mg/L,检出限为0．08mg/L,相对标准偏差(n=11,ρ=10.0mg/L）为1．0％。方法用于血清中葡萄糖含量的测定,结果与标准方法一致,回收率为96％－106％。     

流动注射化学发光法测定尼莫地平

利用尼莫地平对ce（Ⅳ)-Na2SO3化学发光体系的抑制作用,建立了流动注射—化学发光法测定尼莫地平的新方法。化学发光强度与尼莫地平浓度在0．5～90mg/L范围内呈线性关系,线性范围为0．5～10mg/L时,r=0．9990;线性范围为10～90mg/L时,r=0．9968。回收率在98．3％～103．2％范围内;检出限为0．085mg/L。     

PAN-蛋白质络合物的极谱吸附波及其应用

在0.05 mol/L HAc溶液中,PAN-牛血清白蛋白/人血清白蛋白络合物在-0.58 V(vs.SCE)处产生一灵敏吸附还原峰,峰电位较之游离PAN还原峰负约0.28 V,峰电流与牛血清白蛋白、人血清白蛋白浓度在0.1～12 mg/L,0.1～11 mg/L范围内呈线性关系;检测限均为0.05 mg/L。运用该法测定了人血清样品蛋白质含量。     

血清白蛋白的铜(Ⅱ)-乙酰丙酮络合吸附波法测定

在pH6．8的磷酸盐缓冲溶液中,血清白蛋白与铜(Ⅱ)-乙酰丙酮络合物反应作用生成一种在汞电极上吸附性很弱的铜(Ⅱ)-血清白蛋白惰性络合物,使铜(Ⅱ)-乙酰丙酮络合物在-0．28V(vs．SCE)络合吸附波还原峰电流降低,电流降低值与1～30mg/L范围内牛血清白蛋白(BSA)或1～32mg/L范围内人血清白蛋白(HSA)呈线性关系;检出限分别为0．5和0．6mg/L。运用该法测定了人血清样品中蛋白质含量,结果满意。     

铁氢化钾化学发光体系测定利福平的研究

基于在NaOH碱性介质中，铁氰化钾可以直接氧化利福平产生化学发光这一现象，结合流动注射分析技术，提出了一种直接利用化学发光测定利福平的新方法。该方法测定利福平的线性范围为0．1-30mg/L，检出限为0．06mg/L，相对标准偏差为3．0％(n＝11，ρ(利福平)＝1．5mg/L)，方法已成功地用于胶囊及滴眼液利福平样品的分析。     

反相流动注射化学发光法测定草甘膦

在酸性介质中,草甘膦与过量的NO2^-反应生成稳定的N－亚硝胺,而剩余的NO2^-快速氧化亚铁氰化钾为铁氰化钾,与鲁米诺－铁氰化钾化学 光反应相偶合,据此,建立了反相流动注射化学发光法测定草甘膦的新方法,该方法的线性范围为0．10－5．00mg/L^-1,检出限为0．05mg.L^01,相对标准偏差为0．6％,该方法用于废水中草甘膦的测定,回收率为96－106％。     

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.