吖啶橙荧光猝灭法测定饮用水中痕量溴酸根

基于在盐酸介质中,一定量的溴化钾存在下,当溴酸根氧化吖啶橙时使其荧光猝灭,提出了荧光猝灭法测定饮用水中溴酸根的方法。在激发波长493 nm,发射波长528 nm条件下,体系的荧光强度降低值△F与溴酸根的质量浓度在10.0～560.0μg·L^-1范围内呈线性关系,方法检出限（3S/N）为3.03μg·L^-1。方法用于纯净水和桶装水中溴酸根的测定,回收率在94.0%～107%之间。     

罗丹明6G荧光猝灭法测定痕量肝素

在pH 8.0的缓冲体系中,肝素使得罗丹明6G的荧光发生明显猝灭,罗丹明6G的荧光猝灭程度在一定范围内与肝素的浓度成正比,据此建立了荧光猝灭法测定痕量肝素的方法,并对体系的荧光猝灭机理进行了讨论。体系的激发波长为482 nm,发射波长为560 nm,线性范围为0.05~3.0 mg/L,检出限为6.1μg/L。方法已应用于肝素钠注射液中肝素含量的测定。     

蛋白质对溴鼠灵的荧光增敏及分析应用

实验发现, 牛血清白蛋白可以大大增强杀鼠剂溴鼠灵的荧光. 利用荧光猝灭法考察了溴鼠灵和牛血清白蛋白的相互作用. 结果表明溴鼠灵对牛血清白蛋白的内源荧光有较强的猝灭作用, 两者形成了新的复合物, 属于静态荧光猝灭. 跟据荧光增敏现象, 建立了水溶液中测定溴鼠灵的荧光方法. 在优化实验条件下, 线性范围为5.0×10-8～4.0×10-7 mol/L和4.0×10-7～1.5×10-5 mol/L, 检出限为5.9×10-9 mol/L. 该方法用于渠水中微量溴鼠灵的测定, 回收率为94.1%～101.3%.     

2,3,7-三羟基-9-(2,4-二羟基)苯基荧光酮荧光猝灭法测定锰(Ⅱ)

在pH=9.33的NH3.H2O-NH4Cl缓冲介质中,于表面活性剂溴化十六烷基三甲铵(CTMAB)存在下,利用Mn(Ⅱ)与2,3,7-三羟基-9-(2,4-二羟基)苯基荧光酮(DHPF)形成Mn(Ⅱ)-DHPF-CTMAB三元配合物可产生荧光猝灭,建立了荧光猝灭法测定痕量Mn(Ⅱ)的新方法。该体系激发波长λex=520nm,发射波长λem=540nm,荧光猝灭值与Mn(Ⅱ)的含量在0～0.36μg/25mL范围内呈线性关系,检出限为0.02μg/25mL,在CTMAB存在下,配合物摩尔比Mn(Ⅱ)∶DHPF=1∶2。拟定方法用于测定尿样中微量锰的含量,结果满意。     

铁(Ⅲ)-过氧化氢-水杨基荧光酮-溴化十六烷基三甲铵荧光猝灭反应及其应用

在pH 3.1～5.2的HCl-NaAc缓冲介质中,溶液中的铁(Ⅲ)与过氧化氢(H2O2),水杨基荧光酮(SAF)和溴化十六烷基三甲铵(CTMAB)反应产生一多元混合络合物,使水杨基荧光酮溶液的荧光明显猝灭,据此建立了测定痕量铁的荧光猝灭分析法.该体系的激发波长λex=435.8 nm,发射波长λem=540 nm.铁的浓度在2～100 μg/L范围内有良好的线性关系;方法的检出限为0.41 μg/L.该方法灵敏度高,操作简便,用于天然水和人发样中微量铁的测定,结果满意.     

铜-硫堇同步荧光光谱行为研究及其应用

研究了Cu2+对硫堇(TH)荧光光谱的影响,发现Cu2+对TH的荧光有猝灭作用。为了消除瑞利散射的干扰,进一步考察了Cu2+对TH同步荧光(Δλ=4～12 nm)的猝灭情况,并确定λex为626 nm,λem为635 nm(Δλ=9 nm)为工作波长。在同步荧光猝灭度(ΔF)与Cu2+质量浓度(ρCu2+)之间呈良好的线性关系,并据此建立了测定Cu2+的新方法。Cu2+的线性范围0.0133～0.975μg/mL,检出限为0.004μg/mL,加标回收率为97.4%～104.2%。该方法可用于自来水和矿泉水中痕量铜的测定。     

荧光光度法测定纤维用亚麻原茎中微量铜

在KH2PO4-Na2HPO4介质中,乳化剂OP存在下,铜(Ⅱ)与水杨基荧光酮(SAF)形成配合物使荧光猝灭,由此建立了测定微量铜的荧光猝灭新方法.该体系的最大激发波长λex＝365 nm,最大发射波长λem＝526 nm.研究表明,该法Cu(Ⅱ)的含量在0.0～5.0 μg/25mL范围内与荧光猝灭程度(△F)呈线性关系,相关系数R2＝0.9993,检出限为1.28 μg/L.方法灵敏度高,选择性好,用于测定纤维用亚麻原茎中微量铜的测定,回收率在99.8％～101.5％之间.     

四溴荧光素荧光猝灭法测定司帕沙星

基于司帕沙星能够猝灭四溴荧光素的荧光且荧光猝灭程度与司帕沙星的量成正比,建立了一种测定微量司帕沙星的方法。在pH3．5的Clark—Lubs缓冲溶液中,四溴荧光素激发波长λex=485nm、发射波长λem=545nm,司帕沙星的质量浓度在0～2．0mg／L范围内符合比耳定律,方法检出限为42．7μg/L。已用于片剂及胶囊中司帕沙星的测定。6次平行测定回收率为93．8％～104．3％,相对标准偏差为1．1％～2．8％。     

N-邻羧基苯基-N-(2-氨己基)草酰胺荧光特性的研究及应用

研究了酸度、温度对不对称草酰胺：N-邻羧基苯基-N-（2-氨己基)草酰胺(OBZE)荧光特性的影响。测定了该试剂的荧光量子产率。在pH8．0～9．5的H3BO3-NaOH缓冲介质中，NO3^-能使OBZE荧光强度定量猝灭，据此建立了荧光猝灭法测定NO3^-的新体系。OBZE的激发波长为210nm，发射波长为395nm。荧光猝灭值与NO3^-在0．004～0．68mg／L呈范围内线性关系，方法的检出限为0．004mg／L。实验了多种干扰离子的影响，已用于水中硝酸根离子的测定。     

光谱法研究铬(Ⅵ)与血红蛋白的相互作用

运用荧光光谱、紫外光谱、CD光谱法研究了K₂Cr₂O₇与牛血红蛋白(BHb)的相互作用。紫外光谱表明,加入铬(Ⅵ)酸根离子后,BHb分子中Soret带的吸收持续降低, 峰位红移,说明铬(Ⅵ)酸根离子可能使部分血红素辅基从BHb的空腔中脱离出来,部分转变为高铁血红蛋白。荧光光谱表明,铬(Ⅵ)酸根离子与BHb形成基态复合物导致BHb内源荧光猝灭,猝灭机理主要为静态猝灭。测定了不同温度下该反应的热力学参数,表明上述作用过程是一个熵增加、自由能降低的自发分子间作用过程,铬(Ⅵ)酸根离子与BHb之间以氢键和范徳华力相互作用为主;并用同步荧光和CD光谱技术考察了铬(Ⅵ)对BHb结构的影响。     

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。     

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.     

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。     

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.     

Determination of heats of detonation and influence of components of composite explosives on heats of detonation of high explosives

The heats of detonation of 20 simple high explosives and explosive mixtures were determined by means of an adiabatic detonation calorimeter designed by the authors. The results indicated that the performance of the instrument was reliable and the experimental data were very accurate. For explosive mixtures, there was a linear accumulative relationship between the heats of detonation of the explosive mixture and its components. Accordingly, the heats of detonation of explosive mixtures could be calculated directly from the heats of detonation of simple explosives and the characteristic heats of other components. The experiments showed that the gold or brass shell of the cylindrical charge could be substituted by a thick-walled porcelain shell, which had the advantage of cheapness.

     

物质分配系数的测定实验改进

实验教学目的是从解决实际问题出发,以实验技术训练和实验设计思想培养为目标。介绍了将单一的物质分配系数测定实验改进为综合实验,提高了实验效果及实验资源利用率。     

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.     

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。