闭路循环动态针捕集/气相色谱-质谱法测定卷烟烟丝挥发性成分

建立了闭路循环动态针捕集/气相色谱-质谱测定卷烟烟丝中挥发性化学成分的方法,优化了采集模式、捕集与解吸条件,考察了动态针捕集(NT)的解吸率,并与固相微萃取方法进行了对比。结果表明,填充Carboxen1000的捕集针,在样品加热温度为80℃,以3 m L/min流速浸入式闭路循环捕集30 min,并在250℃下解吸5 min为最佳条件;在卷烟烟丝中共检出有机酸、酯、醛、醇类等45种化合物,其中相对标准偏差(RSD)小于5%的有27种,占化合物数量的60%。NT捕集方式的灵敏度、重复性均优于固相微萃取,更适用于卷烟烟丝中挥发性成分分析。     

榴莲中香气成分分析

报道了通过溶液萃取和吹扫－捕集,对榴莲的香气富集浓缩,并用ＧＣ－ＭＳ分析。结果表明：在其香气成分中,含有多种酯类、酮类、烃类和含硫化合物,其主要香气成分为３－羟基－丁酮－２和一些Ｃ４～Ｃ８的酯类。     

超临界流体色谱与气相色谱-质谱联用测定卷烟主流烟气中醛酮类化合物的研究

建立了一种卷烟主流烟气中醛酮类香气化合物的超临界流体色谱/气相色谱-质谱测定方法。将捕集卷烟主流烟气粒相物的剑桥滤片用超临界流体萃取醛酮类香气成分后,通过配备高效分离柱的超临界流体色谱(SFC)先对香气成分进行划段,分离后的各段馏分再用GC-MS分析。结果表明:经SFC分离后的各段化合物之间基本不重叠,解决了GC-MS峰容量有限的问题,且分离出的醛酮类香气成分数量远多于直接进样分析法;样品直接进样后经GC-MS分析仅鉴定出29种醛酮类化合物,其中醛类7种、酮类22种;而经SFC分段后再用GC-MS分析,可鉴定出57种醛酮类化合物,包括13种醛类和44种酮类。3种不同焦油量卷烟主流烟气中醛酮类化合物种类和含量存在较大差异,每种卷烟主流烟气中分别含有不同特有醛酮类化合物。该研究为卷烟主流烟气中醛酮类香气成分的测定提供了新方法。     

合欢鲜花香气挥发物成份研究

采用循环吹气吸附法捕集合欢鲜花头香,经溶剂冼脱后用GC/MS/DS联用技术和气相色谱双柱程序升温保留指数辅助定性分析鉴定出其中的25种成份,它们是单萜烯3种、芳烃1种、烯烃1种、含氮化合物2种、含氧化合物18种(其中醇8种、醛酮3种、酯5种、脂肪酸1种、环醚1种)。主要成份为反-氧化芳樟醇(呋喃型)、α-罗勒烯、顺-氧化芳樟醇(吡喃型)、芳樟醇、异戊醇和4-戊烯-2-酮。嗅觉鉴定的结果表明,合欢鲜花的主要赋香成份为反-氧化芳樟醇(呋喃型)、芳樟醇、异戊醇、α-罗勒烯和2,2,4-三甲基恶丁烷。     

微波辐射下无催化剂一锅法合成N-甲基十氢吖啶-1,8-二酮化合物

为了研究从简单易得的原料在无催化剂的条件下一锅法合成N-甲基十氢吖啶-1,8-二酮化合物，我们以各类醛（脂肪醛、芳香醛、二醛）、达咪酮或1,3-环己二酮和甲胺为原料，以乙二醇或水为溶剂，经微波辐射，一步反应得到了一系列N-甲基十氢吖啶-1,8-二酮化合物。反应时间从传统热反应的4-5小时缩短至2-10分钟，产率较高（56-95%），并且不需要使用催化剂。该反应后处理方便，只需要简单洗涤，环境友好，为合成此类化合物提供了一种简便、有效的合成方法。该方法不仅适用于一元脂肪醛、芳香醛，还适用于芳香二醛，因此可以合成含有一个或两个十氢吖啶结构单元的杂环化合物。     

醚取代芳香β－醛酮衍生物的合成及抗菌活性研究

鱼腥草素具广谱的抗菌活性,其药效团为β－醛酮结构。本文以对羟基苯乙酮为原料,通过Claisen缩合、加成、缩合得到12个芳香β－醛酮衍生物,所合成化合物经过红外、核磁、质谱进行了结构表征。对所合成的化合物进行了抑菌活性测试,初步构效关系表明,烷氧基胺席夫碱可能是活性基团,酮羰基的存在对提高抗菌活性有利,苯环上取代基对抗菌活性有重要影响。     

静态和动态收集与富集挥发性有机物的方法在法医中的应用

引言捕集和富集挥发性化合物近来已成为制备试样的一种标准方法,但很少用以取得法庭物证。在文献报导的几乎所有应用中,都是将小量挥发性化合物捕集在过量的吸附剂上,但在物证中挥发物的量很容易超过吸附剂的容量,使试样失去代表性。法庭分析工作者可以根据由下列四个参数的排列组合而得到的十六种情况来设计、使用和评价试样中挥发物的富集方法: 1.试样是由动态的“吹洗和捕集”还是由静态扩散来富集? 2.吸附剂容量是否足以定量捕集所有挥发性化合物?     

阔叶箬竹叶和箬竹叶中挥发油的提取及成分分析

采用水蒸气蒸馏法分别提取阔叶箬竹叶和箬竹叶中的挥发油,用乙醚作溶剂进行多次萃取,利用气相色谱-质谱(GC-MS)联用分析二者的化学成分并进行比较。从阔叶箬竹叶提取的挥发油中共鉴定出37种化合物,主要成分为叶醇、1-己醇、苯甲醇、己醛、2-乙基呋喃、β-紫罗兰酮等。从箬竹叶提取的挥发油中共鉴定出49种化合物,主要成分为叶醇、苯甲醇、β-紫罗兰酮、2-己烯醛、苯乙醇、2-甲氧基-4-乙烯基苯酚、2-乙基呋喃等。两种箬叶挥发油中相对含量最高的成分都为叶醇,都含有酮、醛、醇、酚、酯类化合物,且酮、醛、醇的含量明显高于其他成分。     

滤嘴对卷烟主流烟气中挥发性羰基化合物截留效率的测定

本文采用HPLC和GC分别对国内市场占有率较高的18种牌号卷烟主流烟气及其滤嘴中挥发性羰基化合物的含量进行了测定,并对滤嘴截留挥发性羰基化合物效率和机制进行了探讨。结果表明:卷烟主流烟气中挥发性羰基化合物含量高低的顺序是乙醛、丙酮、甲醛、丙稀醛、巴豆醛、丁酮和丁醛;滤嘴中挥发性羰基化合物含量高低的顺序是甲醛、丁酮、巴豆醛、丁醛、丙稀醛、丙酮和乙醛;滤嘴对羰基化合物截留效率高低的顺序是巴豆醛、丁酮、甲醛、丁醛、丙烯醛、丙酮和乙醛。二醋酸纤维丝束对挥发性羰基化合物的截留效率较聚丙烯丝束好。     

FeCl3催化羰基化合物与芳烃的还原Friedel-′Crafts烷基化反应

在二甲基氯硅烷作用下,FeCl3能催化羰基化合物（醛、酮）与芳烃及噻酚的还原Friedel—Crafts烷基化反应,在温和的条件下一步实现羰基化合物的还原和C—C键的构造．     

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。     

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.

     

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.     

Summary of development of the theory of stability of colloids and thin films

In this review, the research of the author in the field of colloidal systems is summarized. The factors influencing colloidal stability are systematized and analyzed. Examples are presented to illustrate the practical utilization of the theory of stability of colloids and thin films.This review was prepared on the basis of the works of the author, which were awarded the State Premium for 1991 in the field of science and technology, chemistry section.Institute of Physical Chemistry, Russian Academy of Sciences, 117915 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1708–1717, August, 1992.     

Study of hydration of two cements of different strengths

Main hydration products of two cement pastes, i.e. CSH-gel, portlandite (P) (and specific surface S) were studied by static heating, and by SEM, TEM and XRD, as a function of cement strength (C-33 and C-43) hydration time (th) and subsequent hydration in water vapour.Total change in mass on hydration and air drying, M_o, increased with strength of cement paste and with hydration time. Content of water escaping at 110 to 220°C, defined as water bound with low energy, mainly interlayer and hydrate water, was independent on cement strength but its content increased with (th). Content of chemically bound (zeolitic) water in CSH-gel, escaping at 220-400°C, was slightly dependent on strength and increased with (th). It was possibly derived from the dehydroxylation of CSH-gel and AFm phase. Portlandite water, escaping at 400-500°C, was independent on cement strength and was higher on longer hydration. Large P crystals were formed in the weaker cement paste C-33. Smaller crystals were formed in C-43 but they increased with (th). Carbonate formated on contact with air (calcite, vaterite and aragonite), decomposed in cement at 600-700^oC. It was high in pastes C-33(1 month) and C-43(1 month), i.e. 5.7 and 3.3%, respectively; it was less than 1% after 6 hydration months (low sensitivity to carbonation) in agreement with the XRD study showing carbonates in the air dry paste (1month), and its absence on prolonged hydration (6 months) and on acetone treatment. Water vapour treatment of (6 months) pastes or wetting-drying increased this sensitivity.Nanosized P-crystals, detected by TEM, could contribute to the cement strength; carbonate was observed on the rims of gel clusters.This revised version was published online in November 2005 with corrections to the Cover Date.     

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^-。     

Thermodynamics of the formation of oxosulfides of rare-earth elements

The enthalpies of solution of several oxosulfides of rare-earth elements and the high-temperature enthalpies of oxosulfides and oxosulfates of lanthanum and yttrium were measured using solution calorimetry and high-temperature microcalorimetry techniques. Standard enthalpies of formation and some thermodynamic properties of oxosulfides and oxosulfates were calculated. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2 pp. 294–297, February, 1997.     

探究“铁的锈蚀条件”实验创新设计

设计了铁的锈蚀实验,说明了铁钉的处理方法,增加了温度、酸、碱的影响条件,实现了铁跟蒸馏水及空气中氧气快速反应而生锈,使实验在5 min左右就能够得到准确的结果。