2,6-二乙氧基-β-环糊精对铕(Ⅲ)-强力霉素络合物包合作用的研究及其分析应用

在pH=9.4的NH4Cl-NH3*H2O 的缓冲溶液条件下,强力霉素能与铕(Ⅲ)生成二元络合物并发射出铕(Ⅲ)位于612 nm处的特征荧光,加入2,6-二乙氧基-β-环糊精后,体系的荧光强度显著增强,且增强的荧光强度与强力霉素的浓度呈线性关系,据此建立了荧光分光光度法测量强力霉素的方法.在最佳实验条件下,测量的线性范围和检出限分别为6.2×10-8～1.3×10-5 mol/L和1.4×10-8 mol/L.本方法曾用于血样和尿样中强力霉素的测定.本研究讨论了荧光增强的机理.     

2,6-二乙氧基-β-环糊精对铕（Ⅲ）-强力霉素络合物包合作用的研究及其分析应用

在pH=9.4的NH4Cl-NH3·H2O的缓冲溶液条件下,强力霉素能与铕(Ⅲ)生成二元络合物并发射出铕(Ⅲ)位于612 nm处的特征荧光,加入2,6-二乙氧基-β-环糊精后,体系的荧光强度显著增强,且增强的荧光强度与强力霉素的浓度呈线性关系,据此建立了荧光分光光度法测量强力霉素的方法。在最佳实验条件下,测量的线性范围和检出限分别为6.2×10-8~1.3×10-5mol/L和1.4×10-8mol/L。本方法曾用于血样和尿样中强力霉素的测定。本研究讨论了荧光增强的机理。     

荧光光度法研究修饰β-环糊精与Eu(Ⅲ)-金霉素体系的相互作用及其应用

在pH=6.00的NH4Ac-HAc缓冲条件下,金霉素(CTC)能显著增强Eu(Ⅲ)位于波长618 nm处的特征荧光强度.加入修饰的β-环糊精后,体系的荧光强度进一步显著增强,据此建立了荧光分光光度法测量金霉素的方法.实验表明,修饰β-环糊精时,金霉素的线性范围为3.99×10-7～1.05×10-5mol/L,检出限...     

一种基于共振瑞利散射和荧光增强并对Fe~(3+)和Fe~(2+)具有高识别作用的荧光方法的研究

本文合成了4-甲基哌嗪-1,8-萘酰亚胺修饰的β-环糊精,该化合物对Fe3+和Fe2+展现出良好的选择性识别能力。当适量的氨水加入到该化合物水溶液中后,溶液体系的荧光被完全猝灭。然而,当Fe3+和Fe2+加入到该溶液体系后,520nm处的荧光信号和416nm处的共振瑞利散射峰均逐渐增强。Fe3+和Fe2+引起的荧光强度和共振瑞利散射强度比值的差异可用于鉴别Fe3+和Fe2+,同时,该方法还展现了较高的灵敏度。本文建立的方法对Fe3+检测的线性范围为1.5×10-5~2.2×10-5mol/L,检测限为1.1×10-5mol/L;对Fe2+检测的线性范围为0.5×10-5~4.2×10-5mol/L,检测限为0.6×10-5mol/L。     

（英）一种基于共振瑞利散射和荧光增强并对Fe3 和 Fe2 具有高识别作用的荧光方法的研究

本文合成了4-甲基哌嗪-1,8-萘酰亚胺修饰的β-环糊精,该化合物对Fe3+和Fe2+展现出良好的选择性识别能力。当适量的氨水加入到该化合物水溶液中后,溶液体系的荧光被完全猝灭。然而,当Fe3+和Fe2+加入到该溶液体系后,520nm处的荧光信号和416nm处的共振瑞利散射峰均逐渐增强。Fe3+和Fe2+引起的荧光强度和共振瑞利散射强度比值的差异可用于鉴别Fe3+和Fe2+,同时,该方法还展现了较高的灵敏度。本文建立的方法对Fe3+检测的线性范围为1.5×10-5~2.2×10-5mol/L,检测限为1.1×10-5mol/L;对Fe2+检测的线性范围为0.5×10-5~4.2×10-5mol/L,检测限为0.6×10-5mol/L。     

四环素-铕与卵磷脂的相互作用及卵磷脂的测定

以四环素(TC)-Eu3 作为荧光探针,提出了新的荧光光度法测量卵磷脂(PC)。在pH 5.7的酸度条件下,扫描不同浓度的PC与TC-Eu3 的荧光光谱。通过优化实验条件,得到了测定PC的最佳条件。卵磷脂能使TC-Eu3 位于612 nm处的特征荧光显著增强且增强的荧光强度与PC的量成正比。测量的线性范围为4.0×10-7~1.4×10-5mol/L,检出限为3.9×10-8mol/L。该方法已用于实际样品的测定。     

巴洛沙星-Tb3+-ATP荧光体系的建立及其分析应用

在二元配合物巴洛沙星-Tb3+中加入ATP,Tb3+在其特征波长545 nm处的荧光强度增强,据此建立了新的巴洛沙星-Tb3+-ATP荧光体系.在最优化实验条件下,增强的荧光强度与ATP的浓度呈良好的线性关系,线性范围为2.0×10-6～3.0×10-5 mol/L,检出限为8.0×10-7 mol/L.详细的机理研究表明,ATP能与巴洛沙星-Tb3+形成大的三元络合物荧光体系.新建立的荧光体系成功地应用于ATP注射液中ATP的定量检测.对不同批次ATP注射液进行加标回收试验,回收率为101％～106％,测定结果的相对标准偏差为1.1％～1.9％(n=5).     

铕敏化荧光法测定甲磺酸帕苏沙星

稀土Eu3+能与甲磺酸帕苏沙星形成络合物,并发出Eu3+的特征荧光.加入表面活性剂SDBS能大大增强体系的荧光强度,由此建立了表面活性剂敏化的Eu3+荧光探针测定甲磺酸帕苏沙星的方法.最佳测定条件为最大激发和发射波长分别是332和618 nm;pH=7.5;Eu3+浓度为1.2×10-5 mol/L,SDBS浓度为3.0×10-5 mol/L.甲磺酸帕苏沙星浓度在3.0×10-8～2.0×10-6 mol/L范围内与荧光强度线性关系良好,r=0.9993;检出限为1.0×10-9 mol/L.该方法用于甲磺酸帕苏沙星注射剂和人体血清以及尿样中的甲磺酸帕苏沙星的含量测定,结果令人满意.     

表面活性剂敏化的铽离子荧光探针对氧氟沙星的测定

稀土Tb3 +能与氧氟沙星形成络合物 ,并发出Tb3 +的特征荧光 ;加入表面活性剂SDBS能大大增强体系的荧光强度 ,由此建立了表面活性剂敏化的Tb3 +荧光探针测定氧氟沙星的方法。用 1cm石英比色池在激发波长为 30 0nm ,发射波长为 5 4 5nm处测定其荧光强度。在pH =5 .5～ 6 .5 ,Tb3 +浓度为 5 .0× 10 -5mol/L ,SDBS浓度为 5 .0× 10 -4mol/L的最佳测试条件下 ,氧氟沙星的浓度与体系的荧光强度呈线性关系 ,线性范围为 5 .0× 10 -8～ 2 .0× 10 -6mol/L ;检出限为 6 .0× 10 -9mol/L。该法可用于氧氟沙星药物的测定     

叶酸的能量转移荧光测定法及其应用

报道了一种灵敏检测叶酸的荧光新方法。 在叶酸-KMnO4-Eu3+-H2O2体系中,以pH=4.7的乙酸-乙酸钠（浓度为0.2 mol/L）为缓冲溶液,利用高锰酸钾和过氧化氢将叶酸氧化形成蝶呤-6-羧酸,与Eu3+配位成配合物,该配合物被激发后,蝶呤-6-羧酸通过分子内能量转移将吸收的能量传递到Eu3+,从而发射出Eu3+的特征荧光。 在4×10-8~4×10-5 mol/L范围内,Eu3+的荧光强度与叶酸的浓度呈线性关系,相关系数为0.9902,检测限达到1.2×10-8 mol/L。 用于实际样品中叶酸的检测,得到了满意的结果。     

利用手持技术改进测定乙醇分子结构实验

利用压强传感器代替排水集气法,改进测定乙醇分子结构实验的仪器装置,并探索最佳反应条件。另外,设计两个空白实验,结合压强变化曲线对实验误差进行相关讨论。     

光谱仪测试范围的扩展

由于石化行业的生产需要，其材质的使用具有多样性和广泛性，经常会出现顾客委托的测试样品的一个或几个元素跨越光谱仪现有测试程序测量范围的情况。本法通过对光谱仪测试原理的认识，根据光谱仪的测试能力及标样的采集，实现了一个或几个元素测量范围的扩展，并对其测量的影响因素进行了研究。     

Neutral diterpenoids of oleoresins of five species of conifers of Transcarpathia

The compositions of the neutral diterpenoids of the oleoresins of five species of conifers growing in the Transcarpathia have been studied. It has been found that the oleoresins ofAbies alba M.,Larix decidua M., andPicea excelsa L. contain more than 50% of neutral diterpenoids. The group and qualitative compositions of the oxygen-containing diterpenoids have been determined. In the oleoresins ofAbies alba,Picea excelsa, andPicea abies tertiary alcohols — cis-abienol and isocembrol — predominate, while inLarix decidua the main component is the hydroxy ester larixyl acetate. Primary alcohols related to the resin acids have been found in all the oleoresins investigated. Features of the distribution of diterpenoids according to the species of conifers have been revealed. The results obtained are necessary for the chemotaxonomy of conifers of the family Pinceae.Novosibirsk Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR. Translated from Khimiya Prirodynkh Soedinenii, No. 6, pp. 812–816, November–December, 1988.     

非那雄胺合成工艺改进

非那雄胺能抑制5α-还原酶的活性,明显降低二氢睾酮水平,是一种治疗良性前列腺增生的有效药品。该合成工艺以甾烯酮酸为原料,将其与氯化亚砜反应,无须分离即与叔丁胺反应得17β-酰胺化合物,再氧化开环,环合,氢化,脱氢合成了非那雄胺。经元素分析、IR、1HNMR、13CNMR、MS分析表征了其结构。该法无须使用昂贵的2,2-二吡啶二硫化物和剧毒药品苯亚硒酸酐,且以乙酸铵代替氨气,降低了对设备的要求和腐蚀,更适用于工业生产。     

Calculation of enthalpies of hydrogenation of hydrocarbons

Sets of hydrogen molecule equivalents have been developed which permit the calculation of hydrogenation of different types of carbon-carbon bonds from ab initio total energies (3-21G and 6-31G* basis sets, and, to a more limited extent, for MP2/6-31G* data) of reactants and products. The calculated enthalpies of hydrogenation are in good agreement with experiment for unstrained molecules, with average errors on the order of 2 kcal/mol. The 6-31G* equivalents allow the enthalpies for strained molecules to be calculated accurately, but the 3-21G equivalents do not. The equivalents for both basis sets have been tested by calculating the enthalpies of hydrogenation of carbon-carbon bonds in nitrogen- and oxygen-containing organic molecules, free radicals, and classical carbocations. The results are in good agreement with experiment in most cases.     

Neutral diterpenoids of oleoresins of five species of conifers of Transcarpathia

The compositions of the neutral diterpenoids of the oleoresins of five species of conifers growing in the Transcarpathia have been studied. It has been found that the oleoresins ofAbies alba M.,Larix decidua M., andPicea excelsa L. contain more than 50% of neutral diterpenoids. The group and qualitative compositions of the oxygen-containing diterpenoids have been determined. In the oleoresins ofAbies alba,Picea excelsa, andPicea abies tertiary alcohols — cis-abienol and isocembrol — predominate, while inLarix decidua the main component is the hydroxy ester larixyl acetate. Primary alcohols related to the resin acids have been found in all the oleoresins investigated. Features of the distribution of diterpenoids according to the species of conifers have been revealed. The results obtained are necessary for the chemotaxonomy of conifers of the family Pinceae.     

Influence of viscosity of medium on processes of oxygen quenching of excited states of mesoporphyrin

The oxygen quenching rate constants for singlet and triplet excited states of the dimethyl ester of mesoporphyrin IX increase with decreasing viscosity of the medium and reach a maximum at a viscosity of approximately 0.4 mPa·sec, after which the rate constants begin to decrease. The drop in rate constant with increasing fluidity of the medium may be related to a nonequilibrium character of the elementary act in the interaction of the reactants in the solvent cage. In viscous media such as isopropyl alcohol, isobutyl alcohol, and isoamyl alcohol, the reaction radius is greater than the sum of the radii of the reacting particles. The long-range character of these processes is due to the relatively weak dependence of the quenching probability on distance.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 2, pp. 161–167, March–April, 1989.     

Dichroism of absorption and polarization of phosphorescence of molecules of the closed form of nitrobenzospirothiopyran

The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted indolinospirobenzothiopyran were studied in oriented polyethylene films and in solutions with different polarity. An oscillator model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997.