新型N-甲基马蹄金素衍生物的合成及抗乙肝病毒活性

以L-苯丙氨酸甲酯盐酸盐为原料,依次经缩合、还原、甲基化和催化氢化反应制得N-甲基-L-苯丙氨醇（4）; 4依次与N-Fmoc-L-苯丙氨酸（5a）或N-Fmoc-L-酪氨酸（5b）经缩合和脱Fmoc反应制得游离氨基化合物7a或7b; 7a(7b)与多种苯甲酸衍生物反应合成了20个新型的N-甲基马蹄金素衍生物（8a～8t）,其结构经¹H NMR, ¹³C NMR和MS（ESI）表征。以2.2.15细胞模型进行了初步的抗乙肝病毒（HBV）活性评价。结果表明：化合物8n和8o显示出一定的抗HBV活性,IC₅₀分别为52.5 μmol·L^-1和49.2 μmol·L^-1。     

新型六氢吡啶-2,3-并吲哚化合物的合成及其抗肿瘤活性

以3-取代氧化吲哚与丙烯酸酯为原料,经Michael加成反应制得中间体--3-丙酸酯取代氧化吲哚（3a~3d）; 3a~3d与甲胺发生酰胺化反应制得3 丙酰胺取代氧化吲哚（4a~4d）; 4a~4d用氢化铝锂还原-环化,合成了4个六氢吡啶-2,3-并吲哚化合物(5a~5d）; 5a和5b用氢化铝锂还原合成了2个六氢吡啶-2,3-并吲哚化合物（6a和6b）, 5a～5d, 6a和6b均为新化合物,总产率42%～61%,其结构经¹H NMR, ¹³C NMR和HR-ESI-MS表征。采用MTT法研究了5a～5d, 6a和6b对人肺癌细胞（A549）,人前列腺（PC-3）和人白血病细胞（K562）的体外抗肿瘤活性。结果表明：5b对A549, PC 3和K562的抑制活性均较好,其IC₅₀分别为27.2μmol·L^-1, 37.5 μmol·L^-1和21.7 μmol·L^-1。     

新型7-(2-羟亚胺-2-苯基)-乙氧基白杨素的合成及活性研究

以天然产物白杨素为原料,与多种α-溴代苯乙酮反应制得6种7-(2-羰基-2-苯基)乙氧基白杨素衍生物(2a~2f); 2a~2f与盐酸羟胺进行肟化反应,合成了6种新型的Z-构型7-(2-羟亚胺-2-苯基)乙氧基白杨素衍生物（3a～3f）,其结构经¹H NMR, ¹³C NMR, IR和HR-MS(ESI)表征。采用MTT法测试了3a~3f对人宫颈癌细胞株Hela和人胃癌细胞SGC-7901的体外抑制活性。结果表明：化合物3b和3e对Hela的抑制作用较好,IC₅₀分别为18.2和17.4 μmol·L-1。     

新型2,6,9-三取代嘌呤衍生物的合成及抗血小板凝集活性

以9-乙酰氧基乙基-2-丙硫基-6-氯嘌呤化合物(1)为原料,经烷胺化和玻沃-布兰还原制得2-(6-烷氨基-2-丙硫基-9H-嘌呤-9-基)乙醇(2a~2d); 2a~2d与二苄基磷酰氯反应制得2-(6-烷氨基-2-丙硫基-9H-嘌呤-9-基)乙基二苄基磷酸酯(3a~3d); 3a~3d与三甲基溴硅烷反应合成了2-(6-烷氨基-2-丙硫基-9H-嘌呤-9-基)乙基磷酸二氢酯化合物(4a~4d)，化合物3与化合物4均为新化合物，其结构经¹H NMR, ¹³C NMR, ³¹P NMR, IR和HR-MS（ESI）表征。研究了3a~3d, 4a~4d的抗血小板凝集活性。结果表明：含有磷酸基团的嘌呤化合物活性明显优于不含磷酸基团嘌呤化合物的活性,其中4b活性最好，抗血小板凝集活性为17.79%。     

大黄素衍生物的合成及抗癌活性

通过对大黄素的C6位进行化学修饰, 设计合成了7个含氮杂环的大黄素衍生物和3个含季铵盐基团的大黄素衍生物. 通过红外光谱、 ¹H NMR和质谱表征了所制备化合物的结构, 并测试了它们对白血病细胞Molt-4和淋巴瘤细胞CA46的体外抑制活性. 其中化合物8, 9a+9b, 20a, 20b和20c均显示出比大黄素更高的抗癌活性, 表明苯并咪唑基团和季铵盐基团是大黄素提高抗癌活性的有效药效团.     

新型双环吡啶类化合物的合成及其抗血小板活性

以卤代物(1a~1d、 5a~5j)为起始原料,经硫脲盐酸盐(2a~2d)、磺酸钠(6a~6e)或磺酸(6f~6j)的氯代和氨解反应,制得相应的磺酰胺片段(4a~4d、 8a~8j)。 1-Boc-4-甲基-4-哌啶甲酸(9)脱保护基后与吡啶类化合物(11)发生亲核取代反应制得中间体1-（3-氰基-5-氧代-5,7-二氢呋喃[3,4-b]吡啶-2-基）-4-甲基哌啶-4-羧酸(12); 12与磺酰胺片段发生缩合反应合成了相应的双环吡啶类化合物(13a～13n),其结构经¹H NMR, ¹³C NMR和MS(ESI)表征。采用比浊法血小板聚集试验研究了13a～13n对人源血小板聚集的抑制作用。结果表明：13c和13g具有一定的抗血小板聚集活性,其中化合物13g的IC₅₀值为44.08 μM。      

新型16-E-苯亚甲基甾体衍生物的合成及其抗癌活性

以雄烯二酮为底物,通过2,3-二氯-5,6-二氰基-1,4-苯醌脱氢和羟醛缩合反应合成了一系列新的16-E-苯亚甲基甾体衍生物（4a~4k）,其结构经¹H NMR, ¹³C NMR和HR-MS(ESI)表征。并采用MTT法考察了化合物对人体宫颈癌细胞（Hela）和乳腺癌细胞（MCF-7）的增殖抑制活性。结果表明：浓度为30 μg·mL^-1时,化合物4b具有较强的抑制MCF-7细胞增殖的活性,抑制率46%。     

新型汉防己甲素衍生物的合成及其生物活性

以汉防己甲素为原料,经溴代反应制得关键中间体5-溴汉防己甲素(2); 2与硼酸衍生物经Suzuki反应合成了6个新型的汉防己甲素衍生物(4a~4f),其结构经¹H NMR, ¹³C NMR和ESI-MS表征。采用CCK-8法初步考察了4a~4f对人早幼粒白血病细胞(HL60)和人肺癌细胞(A549)的抑制活性;并采用MTT法对活性较好的化合物进行复筛。采用酶联免疫吸附法考察4a~4f对多种受体酪氨酸激酶的抑制活性。结果表明：4b, 4c和4e对HL60和A549有一定的抑制活性; 4b和4c对受体酪氨酸激酶FGFR1的抑制活性大于50%。     

含氮芥和蒽环的新型α,β-不饱和酮的合成、表征与抗肿瘤活性

为获得含氮芥和蒽环的α,β-不饱和酮衍生物及其体外抗肿瘤效果，结合Vilsmeier-Haack反应和羟醛缩合反应合成了两种新型含氮芥和蒽环的α,β-不饱和酮(1a和1b),其结构经¹H NMR、¹³C NMR、 MS(ESI)和紫外和荧光光谱表征。采用MTT法检测了1a和1b对肺癌细胞A549、肾癌细胞786-O、宫颈癌细胞Hela和乳腺癌细胞MDA-MB-231增殖的抑制活性；采用细胞划痕实验检测了1a对Hela细胞转移的影响；采用流式细胞仪(PI染色)检测了1a对Hela细胞周期的影响。结果表明：1a和1b对4种肿瘤细胞均有良好的抗增殖活性，其中1a的活性略高于1b;1a能有效抑制Hela细胞转移，并使Hela细胞周期阻滞在S期。     

新型含三氟甲基喹唑啉衍生物的设计合成及抗肿瘤活性研究

为了从喹唑啉衍生物中寻找高活性的抗肿瘤分子,以2-氨基苯甲酰胺为原料,经过三氟乙酰化、环化、氯代以及偶联反应等,合成了21个2-三氟甲基喹唑啉类化合物,并通过¹H NMR、¹³C NMR、¹⁹F NMR进行结构确证。采用四唑盐（MTT）法评价目标化合物的体外抗肿瘤活性,结果表明,部分所合成的喹唑啉衍生物对人前列腺癌细胞（PC3、LNCaP）、人慢性髓系白血病细胞（K562）、宫颈癌细胞（Hela）以及人肺癌细胞（A549）具有抗增殖活性,其中活性较好的化合物5a和5b在5μmol/L时对LNCaP细胞增殖的抑制活性分别为61.7%、62.8%。此外N-甲基化产物5a和5b的体外抗肿瘤活性较原型化合物（4a和4b）显著提高,这为该类化合物的深入研究提供了参考依据。     

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.     

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。     

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.

     

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。