耐尔蓝-十二烷基苯磺酸钠-蛋白质体系的荧光反应及其分析应用

研究了耐尔蓝-十二烷基苯磺酸钠体系的吸收光谱和荧光光谱特性，并以此体系建立了测定蛋白质的新型荧光探针。在优化实验条件下，对人血清白蛋白和γ-球蛋白测定的线性范围均为0．16mg/L，检出限分别为0．020mg/L和0．036mg/L。该方法用于人血清中总蛋白含量的测定，与临床测定结果相吻合。     

鲁米诺-过硫酸钠化学发光体系测定硝苯地平

过硫酸钠在碱性条件下能氧化鲁米诺产生微弱化学发光,硝苯地平能大大增强此发光。基于此．建立起了一种直接测定硝苯地平的流动注射化学发光方法。该方法线性范围为0．05～5．0mg／L;检出限为0．017mg/L;相对标准偏差为2．8％(硝苯地平0．5mg／L,n=11)。利用该方法测定了硝苯地平片剂含量,结果令人满意。     

灿烂甲酚蓝褪色光度法测定抗坏血酸

在pH2的HCl缓冲溶液和增敏剂对氨基苯磺酸存在下，抗坏血酸还原灿烂甲酚蓝并使之褪色，褪色反应的体系具有很好的稳定性。在最佳的反应条件下，建立了测定抗坏血酸的新方法，该方法的检出限为0．28mg/L，对0．40mg/L的抗坏血酸测定的RSD为1．2％(n＝11)，线性范围为0．24-32mg/L，方法可应用于药品、合成样品中抗坏血酸的测定。     

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。     

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％。     

阻抑反应动力学光度法测定微量钙

提出了测定微量钙的阻抑反应动力学光度法。在0．012mol/L硫酸中,KBrO3氧化偶氮氯磷Ⅲ褪色,Ca^2 可阻抑该褪色反应的速度。最大吸收波长为550nm,Ca^2 浓度在0－1．4mg/L范围内与ΔSA呈线性关系,检出限0．0042mg/L。方法准确,灵敏,简便,用于直接测定水样中的微量钙,获得满意的结果。     

废水中痕量酚的流动注射停流-催化光度法测定

基于在硫酸介质中痕量酚对溴酸钾氧化罗丹明B反应的催化作用,建立了测定痕量酚的快速、简便的流动注射流－催化光度分析的新方法。该方法的线性范围为0．60－4．00mg/L,检出限为0．1mg/L,进样频率为34／h。11次重得测定的相对标准偏差小于2．0％。该法用于废水中酚的测定,并与4－氨基安替比林比色法对照,结果满意。     

高效液相色谱法同时测定甲基托布津和扑海因

提出了一种同时测定甲基托布津和扑海因的高效液相色谱法,方法的线性范围,相对标准偏差和检测限分别为：甲基托布津：1．0－40.0mg/L,0．7％,1．0mg/L,扎海因：0．25－125．0mg/L.0.6%,0.25mg/L,本方法用于保鲜剂中扑海因和甲基托布津含量及甜瓜中残留量的测定,取得了很好的结果。     

靛蓝胭脂红—高磺酸钾—草酸钠催化光度法测定钢中微量钒

研究了在1mol/L磷酸介质中,钒（V）对KIO4氧化靛蓝胭脂红褪色反应的催化作用及草酸钠的活化作用,建立了一种测定钒的方法,是酸钠时该体系为准零级反应,表观活化能为76．7kJ/mol,在22度时钒量在0－5mg/L范围内与ΔA呈线性,检出限为0．1mg/L。在草酸钠存在下则为准一级反应,表观活化能力为60．1kJ/mol,钒量在0－mg/L范围内与lg(A0/A)呈线性,检出限为0．02mg/L,提高介质酸度,可显著降低反应温度,在NaF及尿素存在下,大多数常见离子无干扰。本法简便快速,选择性和灵敏度较高,用于钢中微量钒的直接测定,结果满意。     

测定驱油体系中碱度的流动注射分光光度法

采用流动注射分析技术，以酸碱指示剂－－间硝基酚溶液作载流，实现了三元复合驱油体系中碱的测定；该法可测定10－600mg/L NaOH(强碱），20－1400mg/L Na2CO3(弱碱）；方法的检出限为0．5mg/L NaOH,1mg/L,Na2CO3；对含量为200mg/L的样品测定6次的相对标准偏差为0.6%(NaOH),0.5%(Na2CO3);测定速率每小时达94个样；该法也适用于其它无机碱、有机碱的测定。     

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.