线性扫描极谱法测定盐酸吡硫醇

用线性扫描极谱法研究盐酸吡硫醇的电化学行为,在pH 6.27的磷酸氢二钠-磷酸二氢钾缓冲溶液中,盐酸吡硫醇于-0.560V(vs·SCE)处产生一灵敏的吸附波,其一次微分线性扫描峰电流与盐酸吡硫醇质量浓度在0.10～100.0 mg·L-1范围内呈线性关系,检出限(3S/N)为0.07mg·L-1。对10.0mg·L-1盐酸吡硫醇溶液进行6次平行试验,相对标准偏差为0.82%,方法可用于片剂中盐酸吡硫醇含量的测定,所得结果与标示值相符。     

盐酸吡格列酮-乙基曙红荷移光度测定法

在pH 4.0的盐酸-乙酸钠缓冲介质中,吡格列酮(PGTZ)与乙基曙红(EE)之间发生荷移反应,形成离子缔合物,使溶液发生褪色现象,且在516 nm波长处测定时,溶液的褪色程度与盐酸吡格列酮的浓度在9.75 × 10-7～1.26×10-5mol·L-1范围内呈线性关系.表观摩尔吸光率(ε516)为6.44×104·mol-1·cm-1,检出限(3s/k)为3.25×10-7mol·L-1.方法用于市售药品中PGTZ含量的测定,所得结果与标示值及高效液相色谱法(HPLC)测得结果相符.以血浆及尿液样品为基体加入标准溶液作回收试验,测得其回收率在97.7%～103.3%之间,测定值的相对标准偏差(n=6)均小于2.5%.     

吡格列酮药典杂质5-羟基吡格列酮的一锅法合成

5-羟基吡格列酮是治疗糖尿病原料药吡格列酮及其制剂氧化降解研究的必备杂质,而其合成方法未见文献报道.本文以盐酸吡格列酮为起始原料,利用KHMDS/O2/P(OMe)3氧化体系,通过去质子化、氧气氧化和还原反应可"一锅法"合成克级规模的5-羟基吡格列酮.通过对反应所需的碱、还原剂、溶剂和温度等条件进行优化,确定最佳反应条...     

催化反应—导数示波极谱法测定痕量钨

在盐酸介质中，痕量钨对钛（Ⅲ）还原金莲花橙的缓慢反应有强烈催化作用，在ＮａＯＨ介质莲花橙Ｏ于－０．５０Ｖｖｓ．ＳＣＥ产生一灵敏的导数示波极谱波。据此，建立了一定检测限和测定范围分别为０．８ｎｇ／ｍＬ和１．６－８０ｍｇ／ｍＬＷ的催化反应－示波极谱新方法，用于钢和矿样中钨的测定，获得满意结果。     

催化动力学极谱法测定痕量钯的研究

研究了催化动力学极谱法测定痕量钯的方法，在盐酸介质中，钯催化次磷酸钠与钼酸铵反应生成磷钼蓝，用氨－氯化铵缓冲液调节溶液ｐＨ值为９．２６可抑制催化反应条件，并在单扫描示波极谱仪上于－１．２４Ｖ（ｖｓ．ＳＣＥ）产生一灵敏极谱波，导数波高与钯０．０５～１．０ｎｇ．ｍｌ＾－１呈线性关系，检出限为０．０３ｎｇ．ｍｌ＾－１，研究了极谱波性质及机理，证明其为吸附波，方法用于合成样及电镀废液中的钯测定，结果满意。     

用交流示波极谱测定难溶盐的溶度积

应用交流示波极谱测定了三种难溶银盐的溶度积,结果与用离子选择性电极测得的文献值相似,显示了交流示波极谱用作溶液中微观粒子的探测工具的可能性。     

某些酸性三苯甲烷染料与盐酸吡格列酮相互作用的分子光谱特点及其分析应用

溴甲酚绿;氯酚红;酚红;溴甲酚紫;盐酸吡格列酮;分光光度法     

盐酸-结晶紫底液中痕量碲的示波极谱测定

极谱法测定痕量碲已有不少文献发表,但在盐酸-结晶紫底液中,用示波极谱测定痕量碲的工作还未见有报道。我们发现,在盐酸-结晶紫底液中,碲有一清晰而又灵敏的导数波,峰电位约-0.9V(vs SCE),碲浓度在2.4—80ppb范围内与峰高成正比,碲浓度在80ppb—1ppm范围内与峰高的平方根成反     

超高效液相色谱-串联质谱法快速检测降糖类保健食品中的10种非法添加物

建立了超高效液相色谱-串联质谱快速检测降糖类保健食品中10种非法化学降糖药物(盐酸苯乙双胍、那格列奈、格列齐特、盐酸吡格列酮、盐酸罗格列酮、格列吡嗪、瑞格列奈、格列美脲、格列苯脲、格列喹酮)的方法。样品经甲醇超声提取,用Thermo Hypersil Gold色谱柱分离,采用三重四极杆质谱进行定性及定量分析。10种药物在1~1000μg/L范围内线性关系良好,检出限为0.1~1.5μg/L,在低、中、高3个添加水平范围内的平均回收率为82.5%~111.9%,相对标准偏差为2.1%~7.8%。     

盐酸吡格列酮的合成新方法研究

报道了治疗糖尿病药物盐酸吡格列酮的合成新方法.在六氢吡啶作用下,对羟基苯甲醛和2,4-噻唑烷二酮缩合生成5-[(4-羟苯基)亚甲基]-2,4-噻唑烷二酮,经钯炭催化氢化还原生成5-[(4-羟苯基)甲基]-2,4-噻唑烷二酮,再和氢氧化钾反应生成相应的钾盐,然后与5-乙基-2-羟乙基吡啶和甲基磺酰氯反应得到的磺酸酯作用生成吡格列酮,最后用盐酸酸化得到其盐酸盐.产品结构经1H NMR和IR确证.     

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.     

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。     

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。