加速溶剂萃取-色谱质谱联用法测定土壤中的多环芳烃

采用加速溶剂萃取-色谱质谱联用法测定土壤中的多环芳烃.土壤样品与无水硫酸钠(质量比为1:2) 混合后,再加适量中性氧化铝,用丙酮-二氯甲烷(体积比为1:1)在加速溶剂萃取仪上以10.3 Mpa、80℃提取10 min,用色谱进行分离,质谱检测器进行分析,土壤中16种多环芳烃的回收率为76.9%～101.4%,测定结果的相对标准偏差为1.6%～15.8%(n=7).     

SOLUBILITIES OF POLYCYCLIC AROMATIC HYDROCARBONS AND DI-REGION THEORY

By using the relationship equation of Partition coefficients with water solubilities for polycyclic aromatic hydrocarbons (PAHs), we have estimated the solubilities of PAHs. In addition the high-performance liquid chromatograph (HPLC) method has been used for the indirect determination of solubilities of PAHs. t3ased on the di-region theory, We have studied the relationship of the solubilities of PAHs with carcinogenicity and introduced the solubility parameter into the di-region theory equation. The calculated carcinogenicity of PAHs from the obtained equation shows little difference from that calculated from Dai Qianhuan's equation.     

南四湖水中多环芳烃的分析及分布研究

采用固相萃取结合气相色谱-质谱(GC-MS)方法对南四湖水中13种多环芳烃进行了分析。南四湖水中检出的多环芳烃以二环、三环为主,检出的6种多环芳烃中相对含量较高的是菲、芴和苊,多环芳烃总浓度范围为0.004~3.53μg/L。入湖河口各点浓度比湖内点位低,上级湖的入湖河口含量高于下级湖的入湖河口,且湖内各点位多环芳烃的含量按湖水流向逐渐降低。     

利用GC/MS测定海洋中贻贝、牡蛎体内的多环芳烃

应用毛细管柱气相色谱／质谱（GC／MS）联用技术对贻贝,牡蛎体内的几种多环芳烃含量进行了分析研究,贻贝,牡蛎样品经超声提取,层析分离后,由GC／MS测定,采用选择性离子检测模式,定性,定量检出了几种多环芳烃。     

TRIPLET STATES OF POLYCYCLIC AROMATIC HYDROCARBONS IN FLUID SOLUTION AND IN THE SOLID STATE

Abstract— –Triplet states of several large polycyclic aromatic hydrocarbons together with their lifetimes have been determined both in fluid solution and in the solid state using a spectrophoto-metric technique.
Excited states and lifetimes of some solid charge transfer complexes between the hydrocarbons and chloranil have been examined.
The assignment of the ¹ B _b states of some of the hydrocarbons have been made from the energies of the triplet states.     

ELECTROGENERATED CHEMILUMINESCENCE OF SEVERAL POLYCYCLIC AROMATIC HYDROCARBONS

Abstract Electrogenerated chemiluminescence (eel) of several polycyclic aromatic hydrocarbons (PAH) (-)/triphenylamine (TPA) derivative (+) mixed systems has been studied at a platinum wire electrode in acetonitrile (ACN) and tetrahydrofuran (THF) solutions using tetra- n -butylammonium perchlorate (TBAP) as a supporting electrolyte, and the results are reported. Exciplexes, as well as the lowest singlet excited state of PAH, are identified as emitting species in these eel systems. The results shown by the temperature and pulse duration dependencies on eel intensities indicate that exciplexes are formed directly from solvent separated ion pairs. The interaction of PAH in their excited states with several donor molecules is discussed based on eel and fluorescence quenching results.     

RATE PARAMETERS FOR THE QUENCHING OF SINGLET OXYGEN BY WATER-SOLUBLE AND LIPID-SOLUBLE SUBSTRATES IN AQUEOUS AND MICELLAR SYSTEMS

Abstract— The laser flash photolysis method has been used to determine the bimolecular rate constants for the reaction between O₂(¹Δ₉) and several lipid-soluble and water-soluble substrates. Values for lipid-soluble substrates have been obtained using aqueous dispersions of surfactants above the critical micelle concentration with 1,3 diphenylisobenzofuran as monitor of singlet oxygen. Under these conditions the hydrophobic substances are solubilized by the micellar phase. For substrates which are water-soluble, 9,10-anthracene dipropionic acid disodium salt was used as singlet oxygen monitor. For several substances, the values obtained are comparable to the values found in homogeneous nonaqueous solutions. In cases where significant differences have been found these have been rationalized according to the individual case. The only major unexpected result concerned β-carotene which, in micellar dispersion, failed to react at all with O₂(¹Δ₉) This may be due to multi-molecular aggregations occurring in the polar medium. The work described herein shows clearly that, under appropriate conditions, singlet oxygen kinetics can be effectively followed in aqueous solutions by time resolved methods. The indiscriminate use of β-carotene as a quencher of O₂(¹Δ₉)in mainly aqueous media is questioned.     

THE MEDIUM EFFECTS IN THE SULPHONATION OF POLYCYCLIC AROMATIC HYDROCARBONS

Abstract

Both the relative reactivities and the initial isomer distributions in the sulphonation of polycyclic hydrocarbons were found to be strongly dependent on the composition of reaction medium.     

伊敏煤田伍牧场矿区煤中多环芳烃分布特征

伊敏煤田伍牧场矿区储藏着丰富的煤层，有从褐煤至瘦煤连续变化的系列煤样。对该煤系样品索氏抽提物中芳烃馏分进行ＧＣ／ＭＳ分析，取得从萘系至ｍ／ｅ４９６分子量的一个系列的芳烃分布数据。煤中多环芳 鉴定是通过气相色谱的保留指数，质量色变和质谱多个方面考证而定出本系列样品中５７个化合物的同系物。     

QUENCHING OF PYRENE FLUORESCENCE BY TRYPTOPHAN IN MICELLAR SOLUTIONS

Deactivation of excited pyrene incorporated to cationic (cetyltrimethylammonium chloride), anionic (sodium dodecyl sulfate) and neutral (Triton X-100) micelles by tryptophan has been investigated over a wide pH range. Data obtained allow an estimation of the tryptophan association to the micelles, of the tryptophan apparent p K in the micellar solutions, and of the dynamics of tryptophan incorporation to the micellar pseudophase. In particular, the data obtained at pH 7 allow an estimation of the effect of the micellar charge upon the binding capacity of the tryptophan zwitterion.     

QUENCHING OF FLUORESCENCE OF AROMATIC HYDROCARBONS BY PROTONS IN CAFFEINE- SOLUBILIZED AQUEOUS SOLUTION. INTRACOMPLEX ENERGY TRANSFER

The fluorescence of pyrene and five other aromatic hydrocarbons solubilized with caffeine in aqueous solution was quenched by 0.001–1mol dm^?3 sulfuric acid; this quenching did not occur in the absence of caffeine. Exceptionally a non-alternative hydrocarbon, fluoranthene, showed an increase of the fluorescence intensity by the acid. The observed quenching rate was explained by the rate of energy transfer from the aromatic molecules to protonated caffeine in the complex.     

THE PHOTODYNAMIC IMMOBILIZATION OF ARTEMIA SALINA NAUPLII BY POLYCYCLIC AROMATIC HYDROCARBONS AND ITS RELATIONSHIP TO CARCINOGENIC ACTIVITY

Abstract— The rates of the photosensitized immobilization of the nauplii of the crustacean Artemia salina were measured as a function of irradiation time and the amount of light absorbed by the sensitizers. The nauplii were incubated in the dark in dilute solutions of the sensitizers for periods of 2 and 22 h prior to irradiation. Nineteen carcinogenic and 22 noncarcinogenic polycyclic aromatic hydrocarbons were used as sensitizers. Relative photodynamic activities (RPA) were determined from the rates of immobilization using benz[ c ]acridine as a standard (RPA = 1). High RPA was restricted to carcinogenic compounds with 4 and 5 fused rings, compounds with 6 or more fused rings had low RPA regardless of their carcinogenic activities. The correlation of RPA with carcinogenic activity was excellent ( P = 0.006 and 0.009 for the 2 and 22 h dark incubations, respectively). It is suggested that carcinogenesis by polycyclic aromatics may result from sublethal photodynamic effects.     

二烷基苯胺在饱和烷烃中对蒽和芘的荧光淬灭

研究了1,3-双(N-苯基-N-甲胺基)丙烷(DMA-AMD)、N-甲基-N-乙基苯胺(MEA)和二甲基苯胺(DMA)在正戊烷、甲基环己烷和正十六烷中对蒽和芘的荧光淬灭。荧光淬灭的同时有相应的激基复合物形成。发现DMA-AMD是一种比MEA或DMA都更为有效的淬灭剂,但生成的激基复合物的荧光效率很低。结果可用DMA-AMD内的另一个苯胺基与激基复合物产生分子内的淬灭来说明。这些苯胺的双分子淬灭速度常数取决于溶剂的粘度,而且在粘稠的烷烃中可以超过理论上扩散控制的限度。     

四氯化碳液相催化加氢反应动力学的研究

氯氟烃的生产工艺中 ,甲烷氯化生产甲烷氯化物是其中重要的一步 ,因此必然伴有大量的四氯化碳生成。由于氯氟烃和四氯化碳的臭氧破坏系数(ＯＤＰ)值比较高[1] ,为了保护人类赖以生存的环境 ,根据“蒙特利尔公约”规定 ,我国目前已经禁止出口四氯化碳 ,对氯氟烃的出口也采取了许可证制度 ,并进行限制生产 ,准备逐步淘汰 ,因此对于大量四氯化碳和氯氟烃的处理成了人们普遍关注的一个重要问题。目前把大量的四氯化碳和氯氟烃转化为相应消耗臭氧指数较低的化合物则是比较现实的途径 ,选择性催化加氢脱氯就是其中一种有效的方法。四氯化碳催化加…     

TEMPERATURE AND VISCOSITY DEPENDENCE OF FLUORESCENCE QUENCHING BY OXYGEN IN MODEL SYSTEMS

Abstract— The bimolecular rate constant, k _q, for the quenching of the fluorescence of pyrenebutyric acid and naphthaleneacetic acid by molecular oxygen has been studied as a function of temperature and viscosity, η. Fluorescence lifetime measurements were used to monitor the degree of quenching. Glycerol-water and sucrose-water mixtures were used to increase the bulk viscosity. Plots of log k _q vs log η show deviations from Stokes-Einstein behavior, but the data are consistent with the patterns that have been observed for other diffusion limited reactions. This work provides background information, regarding the viscosity dependence of oxygen quenching reactions, which is essential for the correct interpretation of oxygen quenching/viscosity dependence studies with more complex systems (i.e. quenching of tryptophan residues in proteins).     

GC-MS法测定焦化厂气溶胶中多环芳烃

利用气相色谱-质谱(GC-MS),电子轰击离子化(EI)法测定焦化厂气溶胶中多环芳烃的含量。超声波抽提气溶胶样品,用GC-MS的选择离子监测(SIM)方式测定EPA提出的优先监测的16种多环芳烃的含量。该法的检出限为0.167pg·m~(-3),PAHs的回收率为85.1％～110.5％,相对标准偏差为4.62％～19.4％。应用该法测定气溶胶中PAHs获得满意的结果。     

FLUORESCENCE QUENCHING OF PYRENE DERIVATIVES BY NITROXIDES IN MICROHETEROGENEOUS SYSTEMS

Abstract Fluorescence quenching of pyrene derivatives by 2,2,6,6-tetramethylpiperidinyl-1-oxy (TEMPO), 4-oxo-2,2,6,6-tetramethylpiperidinyl-1-oxy and 4-hydroxy-2,2,6,6-tetramethylpiperidinyl-1-oxy has been measured in homogeneous solvents and microheterogeneous systems: cetyltrimethylammonium chloride micelles, large unilamellar vesicles of dioctadecyldimethylammonium chloride and dipalmitoylphosphatidylcholine (DPPC) and rat liver microsomes. The extent of intraaggregate quenching is mostly determined by the quencher incorporation to the micro-phases. In particular, it is observed that quenching by TEMPO in vesicles is considerably faster when the bilayer is in the liquid crystalline state. This significant increase in quenching rate with the melting of the bilayer is not observed for the other TEMPO derivatives, indicating that the effect of the lipid organization upon the solubility is related to the hydrophobicity of the solute. The data obtained in rat liver microsomes at 37°C show a pattern very similar to that observed in DPPC vesicles in the liquid crystalline state.     

PHOTODISSOCIATION OF CARBON TETRACHLORIDE SENSITIZED BY NAPHTHALENE DERIVATIVES-I. RADICAL-CHAIN REACTION IN THE SYSTEM NAPHTHALENE-METHANOL-CARBON TETRACHLORIDE

Abstract— Irradiation of naphthalene in methanol in the presence of carbon tetrachloride with light of 313 nm wavelength forms hydrochloric acid, chloroform, and formaldehyde as the main products. The quantum yields of these products are larger than 1 (up to 50 , depending on the concentrations of reactants and sensitizer and on temperature). The quantum yield for the disappearance of the sensitizer naphthalene is smaller than 0.3. From these results it is concluded that the products are built up by a chain reaction with CC1₃ and CH₂OH radicals as intermediates.     

QUENCHING OF EXCITED TRIPLET LUMIFLAVIN BY LUMIFLAVIN RADICALS FORMED IN ITS T-T REACTION

Abstract— Reactions of the triplet state of lumiflavin (³LF) in water adjusted at pH 7.2 were reexamined by means of a Xe-flash photolysis and a laser photolysis. Measurements of the decay of ³LF were made on solutions of LF ranging in the concentration from 4 to 61 times 10^-6 mol/dm³. A one-electron reduced and a one-electron oxidized species of lumiflavin (LF^- and LF⁺) were produced in the first decay stage of ³LF with a high efficiency (0.6 ± 0.1) in a bimolecular triplet-triplet reaction. The product radicals (LFH^- and LF⁺) quench ³LF very efficiently (3 ± 0.8 × 10⁹ mol^-1dm³ s^-1) compared with LF in the ground state (> 2 × 10⁷ dm³ mol^-1).