血清蛋白-荧光素复合物单扫极谱波与应用

在0．08mol／L的HAc中，荧光素与牛血清白蛋白(BSA)或人血清白蛋白(HSA)相互作用形成复合物。复合物使荧光素在-0．58V(vs．SCE)处的还原峰电流增大，峰电流的增大值与加入的BSA或HSA的浓度在一定的范围内呈线性关系。BSA在2—24μg／mL范围内呈线性关系，检出限为1μg／mL；HSA在2—22μg／mL范围里呈线性关系，检出限为0．8μg／mL。应用该法测定了人血清蛋白样品，结果令人满意。     

刚果红与血清白蛋白相互作用的极谱分析

在pH4．7HAc-NaAc缓冲溶液中，刚果红与蛋白质(BSA或HSA)作用形成络合物，使刚果红-0．35V(vs SCE)的还原峰电流下降，峰电流的降低值同所加的BSA或HSA质量浓度在一定范围内呈线性关系；BSA和HSA的线性范围分别为0．5～12mg／L和0．5～11mg／L，检出限分别为0．25和0．20mg／L；运用该法测定了人血清白蛋白样品，结果令人满意。     

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。     

氰基乙基-5-氯尿嘧啶核苷探针测定蛋白质的同步荧光法研究

基于核苷类药物中间体氰基乙基-5-氯尿嘧啶(CECU)与血清白蛋白相互作用生成复合物,导致血清白蛋白的内源荧光产生特异性变化,而建立了以氰基乙基-5-氯尿嘧啶为荧光探针,用固定波长同步荧光光谱技术测定人血清白蛋白(HSA)和牛血清白蛋白(BSA)的新方法。结果表明,在最佳实验条件下,体系的荧光强度与人血清白蛋白和牛血清白蛋白分别在2.76~497μg/mL和3.90~507μg/mL范围内呈良好的线性关系,检出限分别为1.64和1.72μg/mL(n=11)。该方法灵敏度高、稳定时间长、选择性好、线性范围宽。方法已用于血清样品中蛋白质的快速测定。     

同步荧光光谱法测定蛋白质

在模拟生理条件下,由于核苷类药物中间体氰基乙基尿嘧啶(CEU)与血清白蛋白相互作用,血清白蛋白的内源荧光发生特异性变化,且体系的同步荧光强度和溶液中血清白蛋白的浓度呈线性关系,据此提出以氰基乙基尿嘧啶为探针,用固定波长同步荧光光谱法测定人血清白蛋白(HSA)和牛血清白蛋白(BSA)的方法.在最佳试验条件下,体系的荧光强度与HSA和BSA的质量浓度分别在1.38～496.2 mg·L-1和1.56～624.0 mg·L-1范围内呈线性关系,检出限(3S/N)分别为0.045 mg·L-1和0.051 mg·L-1.方法应用于人血清及牛血清中HSA及BSA的测定,并以此样品为基体分别加入HSA及BSA标准溶液作回收试验,测得回收率在95.1%～102.5%之间,相对标准偏差(n=6)在0.43%～2.72%之间.     

表面活性剂和染料探针共振光散射法测定蛋白质

在pH为2.1的Britton-Robinson缓冲溶液中,蛋白质与十二烷基磺酸钠和吖啶红作用形成聚集体,导致体系产生较大的共振散射光(RLS)强度,并且RLS的增强程度与蛋白质的浓度呈线性关系,据此建立了测定蛋白质含量的方法.人血清白蛋白(HSA)和牛血清白蛋白(BSA)分别在0.03～3.0μg/mL和0.2～7.0μg/mL的浓度范围内与增强的共振光散射强度有良好的线性关系,相应的检测限分别为0.0119μg/mL和0.026μg/mL.对体系的反应机理进行了讨论.将方法用于人血清中蛋白质含量的测定,并将分析结果与考马斯亮蓝法进行了对照.t-检验证明,两种方法无显著性差异.     

蛋白质衍生物在锑(Ⅲ)和氢氧化钠溶液中的极谱吸附波与应用

研究了在碱性溶液中的锑(Ⅲ) 蛋白质衍生物的极谱吸附波,提出一种灵敏的蛋白质测定的新方法。含有巯基或二硫键的蛋白质与0.08mol LNaOH、4.0×10-4mol L锑(Ⅲ)的混合溶液在沸水浴中反应8min,反应产物在单扫描极谱上于-0.74V(vs.SCE)处产生一个尖锐的、灵敏的吸附还原波。峰电流与牛血清白蛋白(BSA)、人血清白蛋白(HSA)的浓度均在3.0×10-9～4.5×10-6mol L范围内呈线性关系,BSA、HSA检出限均为7.5×10-10mol L;与溶菌酶(Lyso)的浓度在1.4×10-8～2.1×10-5mol L范围内呈线性关系,Lyso的检出限为3.5×10-9mol L。方法已应用于人血清样品中蛋白质的直接测定。     

微乳液体系共振光散射法测定蛋白质

在酸性条件下,十二烷基磺酸钠微乳液与牛血清白蛋白(BSA)形成离子缔合物,使其共振散射光强度增强。研究了相应的光谱特征、影响因素及反应条件。在最佳实验条件下,BSA在0~5.0μg/mL范围内与散射光强度呈线性关系。方法的检出限为0.08μg/mL,可用于人血清样品中蛋白质的测定。     

新型花菁染料-蛋白质散射体系的研究与应用

基于蛋白质对花菁染料的共振散射效应,以新型水溶性碳菁染料(1,1′-丙磺酸-3,3,3′,3′-四甲基吲哚三次甲基碳菁-5,5′-二磺酸钾)为探针,建立了一种新的蛋白质共振散射检测体系.在最优条件下,蛋白质对该碳菁染料具有明显的散射增强作用,散射强度与蛋白质浓度成良好的线性关系,牛血清蛋白BSA和人血清蛋白HSA线性响应范围分别为0.20～15.0μg/mL和0.50～10.0μg/mL,检测灵敏度(3σ/K)为0.05、0.10μg/mL.测定了BSA血清合成样品,回收率94.5%～104.0%;测定HSA血清合成样品,回收率95.6%～103.0%,测定相对标准偏差为1.1%～1.9%,测定较为稳定、准确.     

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。     

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。     

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.     

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.     

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。     

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.     

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。