污水中18种类固醇激素化合物的痕量分析

采用HLB固相萃取柱和超高效液相色谱-串联质谱法(UPLC - MS/MS),在多反应监测(MRM)模式下建立了污水处理厂进出水样中18种类固醇激素(群勃龙、诺龙、雄烯二酮、睾酮、炔诺酮、甲基睾酮、孕酮、康力龙、羟孕酮、泼尼松、氢化泼尼松、六甲强龙、醋酸甲地孕酮、安宫黄体酮、倍他米松、地塞米松、醋酸泼尼松龙和醋酸氢化可...     

加压毛细管电色谱-紫外检测法分析糖皮质激素及其在头发检测中的应用

采用反相加压毛细管电色谱与紫外检测联用技术,建立了一种高效、简便的糖皮质激素分析方法,适用于头发中糖皮质激素的检测。使用C18反相色谱柱,流动相为pH 8.0, 1.5 mmol/L的Tris-乙腈(65:35, v/v),检测波长为245 nm、分离电压为~10 kV、反压为10.5 MPa、泵流速为0.05 mL/min,进行等度洗脱,倍他米松、地塞米松、泼尼松、泼尼松龙、醋酸泼尼松龙、醋酸氢化可的松、醋酸可的松、皮质脂酮等8种激素在20 min内实现快速分离。各组分的质量浓度线性范围达到3个数量级,检出限(S/N=3)在μg/g水平,迁移时间和峰面积的相对标准偏差(RSD)分别小于4.8%和7.4%。将所建立方法应用于头发样品分析,检测前采用蛋白酶水解提取和净化处理样品,不同浓度糖皮质激素的回收率为71%～85%。该研究为糖皮质激素药物暴露监测以及压力检测提供了新手段,有望用于滥用药物的控制和临床诊断。     

铁卟啉催化酮和二甲亚砜以及醋酸铵的环化反应:吡啶的一步合成（英文）

发展了一种在铁卟啉催化下酮和二甲亚砜(DMSO)以及醋酸铵的环化反应,该反应利用DMSO作为碳源来合成不对称和对称的吡啶化合物,多种酮能够很好地和DMSO反应产生吡啶化合物,产率在30%到85%之间.该方法利用非贵金属和简单酮类化合物来合成吡啶,条件温和,操作简单.在初步的控制实验基础上,提出了该反应可能的机理.     

反相高效液相色谱法同时测定动物血浆中泰乐松注射液的多种组分

研究了用反相高效液相色谱法分析动物血中泰乐松注射液中三种组分氯霉素、醋酸氢化泼尼松和酒石酸泰乐菌素浓度的方法，，血药由甲醇－氯仿混合液提取，采用ＯＤＳ柱，以甲醇－腈－醋酸钠溶液为流动相，可变波长检测。     

二醋酸碘苯在含氮杂环化合物中的合成应用:1,2-苯基-1H-苯并眯唑类衍生物的合成

通过使用二醋酸碘苯(IBD)氧化N,N'-二芳基苄基脒,合成了一系列取代苯并咪唑.该反应条件温和,操作简便.产物结构通过1H NMR,13C NMR,MS,IR进行了确定.根据实验结果对该反应提出了可能的反应机理.     

高效液相色谱-荧光检测法测定牛奶中氯霉素的残留量

建立了对牛奶中氯霉素的残留量进行检测的高效液相色谱-荧光检测方法。氯霉素还原后在温和条件下与荧光胺发生衍生化反应,采用十八烷基键合硅胶固定相,以乙腈/四氢呋喃/0.02 mol/L醋酸钠-醋酸缓冲液(pH 6.0)(体积比为16∶8∶76)为流动相,流速1.0 mL/min,柱温40 ℃,荧光检测激发波长为410 nm,发射波长为508 nm。在上述实验条件下,氯霉素检测的线性范围为0.4~800 μg/L (r2=0.9999),检出限为0.2　μg/L。当空白样品中氯霉素添加水平为2~40 μg/L时,该方法的回收率为66.6%~92.8%,相对标准偏差为4.5%~9.4%。该方法适用于牛奶中氯霉素痕量残留的监测,具有干扰小、选择性好、灵敏度高等优点。     

咔唑-9-乙氧基碳酰肼柱前衍生中性糖的高效液相色谱分析

采用一种新型紫外、荧光衍生试剂咔唑-9-乙氧基碳酰肼(EEOC-Hydrazlde)对5种中性糖(乳糖,甘露糖,葡萄糖,鼠李糖和山梨糖)进行柱前衍生,并通过紫外、荧光检测的方法进行高效液相色谱(HPLC)分析。结果表明：反应温度65℃,时间6．5h,醋酸含量为3．5％(V／V)的条件下,衍生产率可达最大。衍生物的激发和发射波长为λex／λem=293／360nm,紫外检测波长254nm。检出限范围15-60fmol。该方法具有检测灵敏度高,衍生化反应简单,适合糖类化合物的分析。     

离子液体和β-环糊精修饰反向微乳毛细管电动色谱分析化妆品中的激素

建立了以离子液体和β-环糊精为添加剂的反向微乳毛细管电泳(MEEKC)法分离测定化妆品中丙酸氟替卡松、曲安奈德、醋酸可的松、地塞米松、氢化可的松和泼尼松6种激素的方法.在优化的实验条件下,6种物质于12min内达到基线分离,丙酸氟替卡松在2.0～200mg/L范围内线性关系良好,其它组分在2.0 ～ 500mg/L范围内线性关系良好,检出限(S/N =3)分别为0.75、0.81、0.66、0.68、0.74、0.86 mg/L.方法用于化妆品样品测定,加标回收率在93.5％～105％之间,RSD均小于4.3％(n=3).     

活性炭在醋酸水溶液中对醋酸的吸附实验条件探索

通过活性炭在醋酸水溶液中对醋酸的吸附实验 ,确定合适的醋酸水溶液浓度范围和振荡时间等实验条件 ,该实验条件随实验温度变化而不同。用SA310 0表面积分析仪测定活性炭的比表面积 ,并与该方法测定的活性炭比表面积数值进行比较 ,分析了该实验方法产生误差的原因     

相转移催化合成药物有机中间体乙氧基苯的研究

乙氧基苯是一种重要的有机合成中间体,应用于农药、染料、化学试剂,药品如非那西丁、氢化可的松、醋酸泼尼松等的合成,本文研究了利用相转移催化反应在不同的催化剂反应条件下,合成中间体乙氧基苯,在氢氧化钠存在下,苯酚与硫酸二乙酯于60-65℃反应3h条件下合成乙氧基苯,产品产率达90%以上。对不同的催化剂的使用和反应时间进行了条件优化,对产品乙氧基苯的IR谱图、NMR谱图进行了确认和详细的分析.     

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.     

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。     

Acid hydrolysis of carboxymethylcellulose of low degree of substitution

Cotton cellulose was swollen in a sodium hydroxide solution and carboxymethylated by a two-bath method for different periods of time for each process. The kinetics of acid hydrolysis and the crystallinity of the swollen and carboxymethylated samples were measured. The proportion of broken bonds, rate constants for hydrolysis, and permeability of cellulose to hydrolyzing agents were calculated. The susceptibility of glycosidic linkages to acid hydrolysis was improved by carboxymethylation more than by swelling in alkali. The increased accessibility of carboxymethylcellulose to acid was regarded as a consequence of increased intra-and intercrystalline swelling and of the glycosidic bonds' weakness caused by the electron-attracting carboxymethyl group on the C-6 position.     

恶臭嗅辨实验室建设探讨

针对恶臭测试的环境影响问题,提出了解决的实例方案,并对方案的要点及优缺点进行讨论,此方案在实际操作中具有较好的效果。     

氯氧化镁生成热的研究

用氧化镁氯化镁水溶液制备了8水合氯氧化镁[nMg(OH)2·MgCl2·8H2O], 并测定了其在盐酸中的溶解热, 实验结果表明, 氯氧化镁溶解热与n值呈线性关系, 根据溶解热求出5Mg(OH)2·MgCl2·8H2O和3Mg(OH)2·MgCl2·8H2O的生成热分别为-7727.1和5888.1kJ·mol^1^-。     

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.

     

Estimation of Kinetic Parameters of Thermal Oxidation of Ilmenite

The aim of the presented work was the investigation of thermal oxidation of ilmenite in static air atmosphere. The investigations were carried out by use of a derivatograph (MOM, Hungary). The changes of crystallographic structure of investigated samples were identified by X-ray diffractometry on Philips PW-1710 diffractometer. In temperature above 500°C appears structure of hematite Fe₂O₃. On the basis of the thermogravimetric measurements, the contracting area and contracting volume models were found as the best fitting experimental data. This revised version was published online in August 2006 with corrections to the Cover Date.     

Mechanism of action of base-catalyzed oxygenation of phenol derivatives

Cyclopropyl derivative of 2,6-di-tert-butylphenol is synthesized as a probe to investigate the mechanism of base-catalyzed autooxidation of phenol derivatives. Our study indicates that one electron reduction of molecular oxygen from phenolate gives phenoxyl radical 3, a key intermediate of autooxidation. The coupling of phenoxyl radical and superoxide radical gives peroxylate anion 4 and produces the final epoxy alcohol adduct 6.     

Synthesis of phenolic components of Grains of Paradise

Two vanilloids, (5E)-8-(4-hydroxy-3-methoxyphenyl)oct-5-en-4-one (1) and 4-[3-hydroxydecyl]-2-methoxyphenol (2), isolated from the dried seeds of Grains of Paradise (Aframomum melegueta), were synthesized; the latter compound was made as the S-enantiomer and the material derived from the seeds was found to be a 1:1.7 mixture of the R and S isomers. The synthetic route used should allow the preparation of analogs having extended alkyl chains and consequently different lipophilicity, and 3, a homolog of 2, was also prepared.     

解决能源问题的新途径——光解水制氢的研究

面对日益枯竭的能源危机,氢能是一种洁净、最有前景的替代能源。目前在各种制氢的方法中光催化分解水制氢的研究最多,光解水过程中催化剂最关键,本文对利用太阳能光解水的途径、提高光催化反应效率以及光催化剂的开发研究进行了综述。