甲磺基铝酞菁与爱尔新蓝的缔合作用在核酸定量中的应用

阴离子荧光染料四磺基铝酞菁与阳离子荧光染料爱尔新蓝的缔合作用，使四磺基铝酞菁发生荧光猝灭，而当核酸存在时，染料缔合平衡受到影响而导致四磺基铝酞菁的荧光恢复。根据这一原理，建立了核酸定量测定的新方法。方法具有很高的灵敏度和较好的选择性，其线性范围为0-200цg/L；检测限分别为1.8цg/L(SMDNA)、2.0цg/L(CTDNA)、5.4цg/L（酵母RNA）。将方法用于实际样品金黄色葡萄球菌中DNA含量的测定，获得满意结果。     

以四磺基铝酞菁-牛血清白蛋白为底物的荧光恢复均相法测定胃蛋白酶

酸性介质中,红区荧光探针四磺基铝酞菁(AlS4Pc)的荧光被白蛋白显著猝灭,加入胃蛋白酶后,体系荧光明显回复。基于此现象,建立了荧光恢复均相测定胃蛋白酶的新方法。考察了各种影响因素,在最佳实验条件(pH2.5、反应温度50℃、反应时间1h)下,本方法的线性范围为0.04～4mg/L,检出限为20μg/L。用本方法测定实际样品中胃蛋白酶,取得了满意的结果。     

荧光各向异性法研究酸度对四磺基铝酞菁与牛血清白蛋白相互作用的影响

对酞菁类化合物与白蛋白相互作用的研究有助于了解其在血液中的存在形式,从而探索其光敏作用机制[1].荧光各向异性法是研究小分子与蛋白质相互作用的有力工具[2].本文将荧光各向异性的原理和方法应用于由光敏剂四磺基铝酞菁(AlS4Pc)与牛血清白蛋白(BSA)组成的体系,考察了AlS4Pc的荧光各向异性随酸度变化的规律.结果表明,BSA对AlS4Pc有较强的结合能力,提示血清白蛋白对酞菁类光敏剂可起到储存和转运的作用.1　实验部分1.1　试剂及仪器　四磺基铝酞菁的合成与纯化参照文献[3]方法进行.产物经聚酰胺层析、紫外可见吸收光谱、荧光光谱、红…     

新型空间链取代四-(6-氨基己酸磺肽基)铝酞菁配合物的合成及其光物理性质

高锰酸钾降解2-萘酚-6-磺酸钠合成了"分子碎片"4-磺酸钾基邻苯二甲酸(1)。1在钼酸铵催化下,用固相法合成了四-磺酸铝酞菁(2)。采用氨基转化的方法,2经磺酰氯化和Hinsberg磺酰胺化反应分别合成了四-磺酰氯铝酞菁(3)和新型空间链取代四-(6-氨基己酸磺肽基)铝酞菁(4)。1～4结构经1HNMR,IR,MS和元素分析表征,并对4的光物理性质进行了初步研究。     

用四磺基铝酞菁直接测定血清中白蛋白

以红区荧光染料四磺基铝酞菁（ＡｌＳ４Ｐｃ）为探针建立了荧光猝灭法测定白蛋白的新方法。考察了各种影响因素。厚佳实验条件下,该方法的线性区间０．１０－４．５ｍｇ／Ｌ,检测限为４０μｇ／Ｌ。将该方法用于人血清样品中白蛋白的直接测定并与临床方法（溴甲酚绿法）比较,二者符合良好。     

模拟酶催化荧光反应测定核酸

痕量核酸对meso-四-(3-N-甲基吡啶基)卟啉合锰(Mn-TMPyP)催化H2O2氧化对-羟基苯乙酸(p-HPA)的荧光反应产生增强作用,且增强程度与核酸浓度之间有良好韵线性关系,据此建立了测定核酸的高灵敏的荧光分析方法。在最佳条件下,测定小牛胸腺DNA和酵母RNA的线性范围分别是2．0-150μg/L和5．0-100μg／L;检出限分别为0．6和1．6μg/L。对50μg／L CT DNA作7次平行测定,相对标准偏差为1．6％。本法已应用于锯缘青蟹样品中核酸含量的测定,所得结果与紫外吸收法一致。     

四磺化铁酞菁-阿尔新蓝8GX-对-羟基苯乙酸-H2O2催化荧光反应体系在核酸定量中的应用

阳离子荧光染料阿尔新蓝8GX与阴离子荧光染料四磺化铁酞菁发生缔合作用，使四磺化铁酞菁的荧光猝灭，当核酸存在时，削弱了离子缔合作用使四磺化铁酞菁的荧光恢复。荧光增强的程度与核酸的量成线性关系，据此实现了对核酸的定量测定。     

反相离子对高效液相色谱法分离测定钪、锡和铝

 以 1,2 二苯乙烯 4,4′ 双 (1 偶氮 ) 3,4 二羟基苯 2 ,2′ 二磺酸铵 (芪唑 )为柱前衍生试剂 ,采用反相离子对高效液相色谱法分离和测定钪、锡和铝。在C18柱上 ,用含 2 0mmol/LHAc NaAc缓冲溶液 (pH 6 0 )和 10mmol/L十二烷基磺酸钠的甲醇水溶液作流动相 ,检测波长 5 0 0nm ,同时分离测定了钪、锡和铝的络合物。钪、锡和铝的检出限分别为 0 9μg/L ,1 0 μg/L和 1 2 μg/L ,此方法用于矿石样品分析获得满意结果。     

负载空间链四(6-氨基己酸磺酰基)铝氯酞菁聚合物纳米粒子的合成及其离体光动力活性

以四磺酸铝氯酞菁1为原料,采用氨基转化法,经磺酰氯化和Hinsberg磺酰胺化反应合成四磺酰铝氯酞菁2和四(6-氨基己酸磺酰基)铝氯酞菁3,产物结构经元素分析,IR,1HNMR和MS-ESI表征。3在磷酸盐缓冲溶液中与两亲嵌段共聚物聚乙二醇-聚-L-赖氨酸(PEG-b-PLL)通过静电自组装,形成负载3的聚合物纳米粒子3/m。原子力显微镜(AFM)和透射电子显微镜(TEM)表明3/m具有球形核壳结构,直径约为10～20 nm。紫外-可见吸收光谱和荧光光谱法研究了3/m的光物理性质。通过对不同孵育时间的人脐带血内皮细胞(HUVEC)摄取药代动力学测定3/m细胞摄取率和MTT法评价3/m的离体光动力活性,相对自由酞菁3,3/m的细胞摄取率大大提高,且提前1 h达到最高浓度,而且细胞抑制率明显增大,约为3的2倍。     

蝶呤类化合物的荧光性能研究

研究了蝶呤类化合物的天然荧光特性。着重考察了新蝶呤、生物蝶呤、黄蝶呤和蝶呤在 p H7.7磷酸盐缓冲溶液条件下的荧光光谱及各种因素对其荧光强度的影响。在最佳实验条件下 ,四种蝶呤类化合物的线性范围为 :蝶呤 0 .6～ 2 .8μg/m L,新蝶呤 0～ 2 .6μg/m L,生物蝶呤 0～ 2 .4μg/m L,黄蝶呤 0～ 6.0 μg/m L,检出限依次为 :4.2 9× 1 0 - 7g/m L,6.71× 1 0 - 8g/m L,5.79× 1 0 - 9g/m L和 1 .75× 1 0 - 8g/m L     

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.