以国产微晶纤维素膜作固体基质五种多环芳烃的室温磷光法研究

本文考察了10种国产纤维素膜用于多环芳烃固体基质室温磷光(SS-RTP)的可行性。实验表明:MN-C和MN-P两种型号的微晶纤维素膜用于多环芳烃的SS-RTP是适宜的。阴离子交换纤维素膜、CM-纤维素膜和聚酰胺-6膜也能诱导出多环芳烃的RTP来,但其性能逊于前两种。故本文应用MN-C和MN-P两种微晶纤维素膜基质考察了五种多环芳烃的RTP特征,并建立了它们的SS-RTP新方法。并与用滤纸作基质的实验结果进行了比较,表明两种新的固体基质的RTP性能优于滤纸基质。     

沸石上萘的催化破环反应

沸石上萘的催化破环反应朱建华刘琳胡玉海曹洁明须沁华（南京大学化学化工学院化学系，南京２１００９３）关键词沸石催化剂，ＨＭＳ中孔分子筛，萘，多环芳烃，催化裂解，环境保护分类号Ｏ６４３／Ｘ５当前，治理大工业生产带来的环境污染已经成为全球关注的课题，也是...     

Some Conversions of Thiazoline Carboxylic Acid Esters

We have carried out solvolysis of the previously described ethyl esters of 3-methyl(aryl)-4-methyl-2-thioxothiazoline-5-carboxylic acids, leading to the corresponding acids without breaking down the heterocycle. We synthesized a series of novel esters from the latter by treatment with dimethyl sulfate or reactive halides. Of these, only in the case of the ethyl ester of 3,4-dimethyl-2-thioxothiazoline-5-carboxylic acid did we obtain the hydrazinolysis product (the hydrazide), from which we synthesized novel hydrazones by treatment with aldehydes and ketones.     

芳亚甲基丙二腈、芳亚甲基氰乙酰胺的固相合成

芳醛和丙二腈、氰乙酰胺在NH4Ac催化下经固相反应高产率的得到芳亚甲基丙 二腈和芳亚甲基氰乙酰胺。     

微波辅助萃取-气相色谱-质谱法测定大气可吸入颗粒物中痕量多环芳烃

建立了微波辅助萃取－气相色谱－质谱联用测定大气可吸入颗粒物中痕量多环芳烃（PAHs）的分析方法，优化了萃取时间、溶剂用量、微波辐射功率等微波萃取条件，并与超声波萃取方法进行了对照研究。结果表明：除了苊、芴外，微波萃取方法的回收率在85％－130％之间；方法的检出限在0.002-0.016μg/m^3之间。通过实际样品中PAHs的分析表明，该法快速、溶剂用量小，满足痕量分析的要求。     

Semiempirical calculation of electronic spectra of organic compounds by using the improved method of new-γ electron repulsion integral. Part 2. Polycyclic aromatic hydrocarbons (PAHs)

Excitation energies of 123 polycyclic aromatic hydrocarbons were calculated by incorporating the improved method of new-γ for the two-center electron repulsion integral into two semiempirical molecular orbital methods (CNDO/S and INDO/S). This variable method well reproduced experimental excitation energies of them. The average error of the improvement is about 0.162 (CNDO/S) or 0.237 eV (INDO/S) though the average error without the improvement is about 0.541 (CNDO/S) or 0.536 eV (INDO/S). The improvement was useful for the calculations of other organic compounds including hetero atoms, such as organic dye.     

新型氮芥和卤代烷基哌嗪芳香醛的合成

通过对Vilsmeier反应、烷基化反应和氯化反应的改进提出了以简单易得的苯胺和苯基哌嗪为原料制备氮芥和哌嗪芳香醛的方法. 采用该改进的方法合成了8个氮芥和哌嗪芳香醛, 其中7个为新化合物. 它们的结构均经质谱、红外光谱、核磁共振谱和元素分析确证.     

Existence of aromatic sp~2 C-H…O = C intramolecular interaction similar to hydrogen bond

A 'H NMR signal shifted drastically to down field (δ - 10.0) at the bay area and in dose proximity to C = O group for H-1 was observed through complete assignments of 1H NMR spectra for pyridino- and benzobenzanthrones. It is concluded that this phenomenon is due not only to the anisotropy effect of C=O plus aromatic ring current effect, but also to the electrostatic attraction of C-H (δ+)…O(δ-)=C interaction. The evidence for the sp2C-H…O = C intramolecular interaction similar to hydrogen bond has also been given by EI-MS and MS/MS (CID) spectroscopy and IR spectroscopy, as well as MNDO-PM3 calculations. This new kind of interaction might be called 'quasi-hydrogen bond'.     

The correlation between molecular polarizability of PAHs and their retention data on various stationary phases in reversed-phase HPLC

Summary The equation for the potential energy of interactions established for gas-liquid chromatography has been confirmed in reversed phase liquid chromatography. Equations derived for molecular polarizabilities of PAHs and their retention data have very high correlation coefficients. The results indicate that the inductive effect between solute and stationary phase is the main one and the dispersive effect is very small compared with the inductive effect but its contribution increases with the carbon chain length of the stationary phase.     

Vapor-particle partitioning of hydrocarbons in Western Mediterranean urban and marine atmospheres

An analytical procedure is described for a comprehensive determination of the composition of hydrocarbons in the atmosphere, based on: (a) aerosol filtration and subsequent adsorption of the vapor phase onto active charcoal and polyurethane foam; (b) GPC and HPLC fractionation of the extracts, and (c) analysis of the fractions by GC-MS under EI and NICI modes. Special emphasis is placed onn-alkanes, PAHs and their oxygenated derivatives.The characterization of samples collected in a coastal urban area (Barcelona city), and far away over the Western Mediterranean, at sea level and at 1100 m of altitude, revealed significant changes in the aerosol composition, mainly attributed to initial vapor-particle partitioning processes, influenced by ambient temperature variations, and to others taking place during long-range atmospheric transport, related with the different compound photoreactivities and with an unexplained source-decoupling phenomenon.