含多芳香环嵌段聚合物PS-b-PAH对碳纳米管的修饰

以芘丁酸为原料通过酯化反应制备了含芘丁单元的苯乙烯基单体,再利用原子转移自由基聚合法(ATRP)合成了分子量可控的嵌段聚合物PS-b-PAH,采用凝胶渗透色谱(GPC)、核磁共振(1H-NMR)等测试手段对产物进行了表征。采用聚合物对碳纳米管表面修饰,比较了聚苯乙烯PS和嵌段聚合物PS-b-PAH修饰碳纳米管后在THF溶剂中的分散情况。结果表明,PS和嵌段聚合物修饰碳纳米管可提高碳管在THF的分散性,PS和嵌段聚合物PS-b-PAH修饰后碳管在THF中的溶解性分别为0.28 g/L,0.332 g/L。

The expression of PAH-DNA adducts in lung tissues of Xuanwei female lung cancer patients

Objective:The coal-fired pollution in Xuanwei area has been considered to be local main reason for high incidence of female lung cancers.The aim of the study was to investigate the expression of PAH-DNA adducts in lung tissues of Xuanwei female lung cancer patients, and to explore the relationship between the large number of coal-fired pollution PAHs materials and the high incidence of Xuanwei female lung cancers.Methods:We totally collected each 20 cases of Xuanwei female lung cancer patients, Xuanwei male lung cancer patients, non-Xuanwei female lung cancer patients and collected each 10 cases of Xuanwei, non-Xuanwei female patients with benign lung lesions.The cancer tissues, adjacent cancer tissues and normal lung tissues were collected in lung cancer patients and only the normal tissues were collected in benign lung lesion patients.There were total 80 cases and 200 tissues.Using immunofluorescence, we detected the expression of PAH-DNA adducts in each group.Image pro-plus 6.0 software was used to analyze the images and did part quantified analysis.SPSS 13.0 statistical software was used to analyze the data.Results:The positive expressions of PAH-DNA adducts in lung cancer tissues, adjacent cancer tissues and normal lung tissues of Xuanwei female lung cancer patients were 90%, 80% and 65%, respectively.They were higher than the positive expressions of PAH-DNA adducts in Xuanwei male lung cancer patients (35%, 30% and 30%) and non-Xuanwei female lung cancer patients (20%, 15% and 10%; P<0.01).The expression of PAH-DNA adducts in lung tissues of Xuanwei female benign lung lesion patients (70%) was higher than that in non-Xuanwei female benign lung lesion patients (10%).With the direction changing from cancer tissues, adjacent cancer tissues to normal lung tissues, the expression of PAH-DNA adducts was decreased but had no statistical difference (P>0.05).Conclusion:The expression of PAH-DNA adducts in lung tissues of Xuanwei females was higher than that in Xuanwei males and non-Xuanwei females.

Polycyclic aromatic hydrocarbon formation under simulated coal seam pyrolysis conditions

Coal seam pyrolysis occurs during coal seam fires and during underground coal gasification. This is an important source of polycyclic aromatic hydrocarbon （PAH） emission in China. Pyrolysis in a coal seam was simulated in a tubular furnace. The 16 US Environmental Protection Agency priority controlled PAHs were analyzed by HPLC. The effects of temperature, heating rate, pyrolysis atmosphere, and coal size were investigated. The results indicate that the 3-ring PAHs AcP and AcPy are the main species in the pyrolysis gas. The 2-ring NaP and the 4-ring Pyr are also of concern. Increasing temperature caused the total PAH yield to go through a minimum. The lowest value was obtained at the temperature of 600℃. Higher heating rates promote PAH formation, especially formation of the lower molecular weight PAHs. The typical heating rate in a coal seam, 5 ℃/min, results in intermediate yields of PAHs. The total PAHs yield in an atmosphere of N2 is about 1.81 times that seen without added N2, which indicates that an air flow through the coal seam accelerates the formation of PAHs. An increase in coal particle size reduces the total PAHs emission but promotes the formation of 5- and f-ring PAHs.

Characterization of Average Molecular Structure of Heavy Oil Fractions by ~1H Nuclear Magnetic Resonance and X-ray Diffraction

The chemical structure of heavy oil fractions obtained by liquid-solid adsorption chromatography was character-ized by 1 H nuclear magnetic resonance and X-ray diffraction.The molecular weight and molecular formula of asphaltene molecules were estimated by combining 1 H nuclear magnetic resonance and X-ray diffraction analyses,and were also ob-tained from vapor pressure osmometry and elemental analysis.Heteroatoms,such as S,N,and O atoms,were considered in the construction of average molecular structure of heavy oils.Two important structural parameters were proposed,including the number of alkyl chain substituents to aromatic rings and the number of total rings with heteroatoms.Ultimately,the av-erage molecular structures of polycyclic aromatics,heavy resins and asphaltene molecules were constructed.The number of α-,β-,γ-,and aromatic hydrogen atoms of the constructed average molecular structures fits well with the number of hydro-gen atoms derived from the experimental spectral data.

Vapor-Liquid Equilibrium of Toluene-Polycyclic Aromatic Hydrocarbon System in Sub- and Supercritical State

The phase behaviors of toluene/polycyclic aromatic hydrocarbon mixture systems were investigated with a continuous-flow type apparatus at 573.2, 598.2, 623.2 and 648.2 K, while the pressure changed from 1 to 5MPa. The pseudo-binary phase behaviors were predicted with the Peng-Robinson equation of state with interaction parameters between toluene and pseudo-components considered. The phase diagrams of the system have been classified following the category of phase boundary diagram models. The extraction selectivity and efficiency of tolu-ene as a solvent was discussed by comparing with that of hexane. The prediction model for selectivity was also suggested.

Use of antioxidant enzymes of clam Ruditapesphilippinarum as biomarker to polycyclic aromatic hydrocarbon pollution

The typical organic pollutant polycyclic aromatic hydrocarbon(PAH) anthracene was selected as a contaminant to investigate its eff ects on the activities of superoxide dismutase(SOD), catalase(CAT) and glutathione peroxidase(GSH-Px) in the clam Ruditapes philippinarum. The results show that SOD, CAT and GSH-Px had diff erent induction and inhibition reactions to anthracene stress, and that three diff erent organs in R. philippinarum(visceral mass, muscle tissue and mantle) had diff erent sensitivities to anthracene stress. This study suggest that SOD activities of the visceral mass, CAT activitities of the mantle and the visceral mass, and GSH-Px activity of the muscle tissue could be used as sensitive indicators of anthracene stress in R. philippinarum.

Levels and statistical analysis of aerosol phase PAHs over Qingdao alongshore

Atmospheric concentrations of polycyclic aromatic hydrocarbons (PAHs) were measured during various seasons at six different cities/locations in Qingdao alongshore. The annual average PAHs concentration ranged from 16 ng/m3 (at a clean com- pared site) to 308 ng/m3 (in an industry site). The average total particulate PAHs concentration was 74.5 ng/m3 with a higher concentration of particulate PAHs in winter. Based on a year-round dataset, the sources of PAHs in the air of Qingdao were drawn by principal factor analysis and correlation analysis. The results indicated that vehicle emissions and oil burning were the main source of PAHs in Qingdao alongshore.

A 200-Year Record of Polycyclic Aromatic Hydrocarbons Contamination in an Ombrotrophic Peatland in Great Hinggan Mountain, Northeast China

Peat bogs are regarded as one of the faithful archives of atmospheric polycyclic aromatic hydrocarbons(PAHs) deposition, and a large number of studies on PAHs accumulation in peatlands have been reported in Europe and North America. Comparatively little information is available on peat chronological records of atmospheric PAHs flux in China. We investigated the concentrations and historical accumulation rates of PAHs(AR PAHs) through geochemical analysis of three 210Pb-dated ombrotrophic peat cores from Great Hinggan Mountain, northeast China. Eight USEPA priority PAHs were detected and they are naphthalene(Nap), acenaphthylene(Acl), acenaphthene(Ace), fluorence(Flu), phenanthrene(Phe), anthracene(Ant), fluoranthene(Fla) and pyrene(Pyr), respectively. The average total eight PAHs(tPAHs) concentrations are 135.98- 262.43 μg kg-1 and the average AR tPAHs over the last two centuries are 96.45- 135.98 μg m-2 yr-1. The Ace, Acl and Phe account for 30.93- 54.04%, 25.29- 35.81%, and 9.14- 19.84% of the tPAHs, respectively, and have significant positive correlations with the tPAH. As a result, they are regarded as the iconic compounds of PAHs pollution in this area. A ca.200-yr atmospheric PAHs contamination history was reconstructed from the temporal sequences of bothconcentration and AR tPAHs, suggesting the variation of local environmental pollution. The main sources of the PAHs are identified by two isomer ratios as petrogenic origin including oil extraction and refining process as well as their combustions for industrial development. In addition, the contribution of coal combustion for industrial activities and resident heating could not be ignored. But prior to 1860, the undeveloped industry and most of agricultural activities might mainly account for the low level of PAHs, although it could infer a long-range input of atmospheric PAHs from other industrial areas. Therefore, there is a global implication to study longterm PAHs pollution records and all the results will provide practical significance in formulating policies to achieve sustainable and healthy development.

The Study of Pollution of PAHs （Polycyclic Aromatic Hydrocarbons） in AI-Hilla River, Iraq by Using Bioindicator Freshwater Crab （Sesarma boulengeri Caiman）

The present study was used freshwater Crab （Sesarma boulengeri Caiman） as bioindicator to measured the PAHs levels in AI-Hilla River, Iraq, during the period from March 2010 to February 2011. Crab samples were collected from two sites on the AI-Hilla River. Sixteen of PAils compounds were identified seasonally in these samples. High mean value was （72.06 μg/g）, recorded by Dibenzo （a, h） anthracene （DbA） in Site 1 and low mean value was （0.36 μg/g） recorded by Anthracene （Ant） in Site 2. The study showed a clear variation in PAHs concentration independent from the seasons and locations. Site 1 recorded high value of HMW （high molecular weight） and LMW （low molecular weight） more than Site 2. The present study revealed that all PAHs compounds were from Pyrogenic Origin. Seven carcinogenic PAHs （cPAHs） were recorded in crab tissues that were collected from the AI-Hilla River. The TEF （toxicity equivalency factor） was calculated to toxicity equivalent crab concentration. From the results, the fresh water Crab Sesarma boulengeri is a good bioindicator to water pollution by PAHs.

Chemical Effects of CO2 Concentration on Soot Formation in Jet-stirred/Plug-flow Reactor

Soot formation was investigated numerically with CO2 addition in a jet-stirred/plug-flow reactor （JSR/PFR） C2H4/OJN2 reactor （C/O ratio of 2.2） at atmospheric pressure. An updated Kazakov mechanism empha- sizes the effect of the O2/CO2 atmosphere instead of an O2/N2 one in the premixed flame. The soot formation was taken into account in the JSR/PFR for C2H4/O2/N2. The effects of CO2 addition on soot formation in different C2H4/O2/CO2/N2 atmospheres were studied, with special emphasis on the chemical effect. The simulation shows that the endothermic reaction CO2 ＋ H - CO ＋ OH is responsible of the reduction of hydrocarbon intermediates in the CO2 added combustion through the supplementary formation of hydroxyl radicals. The competition of CO2 for H radical through the above forward reaction with the single most important chain branching reaction H ＋ O2, ＇ O ＋ OH reduces significantly the fuel burning rate. The chemical effects of CO2 cause a significant increase in residence time and mole fractions of CO and OH, significant decreases in some intermediates （H, C2H2）, polycyclic aromatic hydrocarbons （PAHs, C6H6 and CI6H10, etc.） and soot volume fraction. The CO2 addition will leads to a decrease by only about 5% to 20% of the maximum mole fractions of some C3 to Clo hydrocarbon intermediates. The sensitivity analysis and reaction-path analysis results show that C2H4 reaction path and products are altered due to the CO2 addition.

Potential of the White-Rot Fungus Pleurotus pulmonarius F043 for Degradation and Transformation of Fluoranthene

Fluoranthene, a four-ring polycyclic aromatic hydrocarbon that is possible genotoxic in nature, has been used as an indicator for assessing polycyclic aromatic hydrocarbon （PAH）-containing pollutants. Microbial degradation is one of the promising methods in removing up PAH-contaminated environments. White-rot fungi have showed the ability to degrade a wide range of PAHs. This study aimed to investigate enzyme production, fungal biomass, and glucose utilization during the biodegradation process of fiuoranthene by a white-rot fungus Pleurotus pulmonarius F043 and to identify the metabolites produced in the degradation process. The extracellular ligninolytic enzyme system of the fungi, producing laccases and peroxidases, was directly linked to the biodegradation of fiuoranthene. The production of ligninolytic enzymes during fluoranthene degradation was related to an increase in the biomass of Pleurotus pulmonarius F043. Fluoranthene removal decreased with an increase in fluoranthene concentrations. The highest biomass production of Pleurotus pulmonarius F043 （〉 4 400 mg L-1） was found in the 10 mg L-1 fluoranthene culture after 30 d of incubation. Two fluoranthene metabolites, naphthalene-l,8-dicarboxylic acid and phthalic acid, were found in the process of fluoranthene degradation. Laccase was revealed as the major enzyme that played an important role in degradation process. Suitable conditions must be found to promote a successful fungal biotransformation augmentation in liquid culture.