肿瘤病房医用直线加速器对周围环境电离辐射的调查分析

通过对医院肿瘤病房医用直线加速器机房周围环境的电离辐射监测调查 ,并计算分析各相关人群的年有效剂量当量 ,结果低于《辐射防护规定》(GB870 3- 88)中的标准限值。表明医用直线加速器机房的辐射防护设施设计是安全合理的 ,具有重要的现实意义 ,该辐射防护设施具有推广价值。     

Fatty acids composition of Caenorhabditis elegans using accurate mass GCMS-QTOF

The free living nematode Caenorhabditis elegans is a proven model organism for lipid metabolism research. Total lipids of C. elegans were extracted using chloroform and methanol in 2:1 ratio (v/v). Fatty acids composition of the extracted total lipids was converted to their corresponding fatty acids methyl esters (FAMEs) and analyzed by gas chromatography/accurate mass quadrupole time of flight mass spectrometry using both electron ionization and chemical ionization techniques. Twenty-eight fatty acids consisting of 12 to 22 carbon atoms were identified, 65% of them were unsaturated. Fatty acids containing 12 to17 carbons were mostly saturated with stearic acid (18:0) as the major constituent. Several branched-chain fatty acids were identified. Methyl-14-methylhexadecanoate (iso- 17:0) was the major identified branched fatty acid. This is the first report to detect the intact molecular parent ions of the identified fatty acids in C. elegans using chemical ionization compared to electron ionization which produced fragmentations of the FAMEs.     

单光子/光电子在线质谱实时分析聚氯乙烯热分解/燃烧产物

实验室研制了低能光电子磁场增强电离(MEPEI)和单光子电离(SPI)复合电离源,该电离源具有电离化合物范围宽、碎片离子少、质谱图简单等优点,结合飞行时间质谱(TOF-MS)实现了聚氯乙烯(PVC)热分解/燃烧产物的在线分析.针对不同的目标化合物,MEPEI/SPI复合电离源通过调节电离区电场强度,可以快速在SPI和SPI-MEPEI之间切换.PVC热分解/燃烧产物中电离能大于光子能量(10.60 eV)的HCl和CO2(12.74 eV、13.77 eV)利用MEPEI模式电离;而烯烃、二氯乙烯、苯系物、氯苯、苯乙烯、茚满及萘系物等可通过SPI-MEPEI复合模式电离.通过实时监测PVC主要燃烧产物的信号强度随温度的变化趋势可推断出,PVC燃烧产物主要是通过两种机制生成:①250～370℃时,PVC发生脱氯及分子内环化反应,产生大量的HCl、苯和萘;②380～510℃时,PVC发生分子间交联反应,生成烷基芳烃,如甲苯和二甲苯/乙苯等.实验结果表明,SPI/SPI-MEPEI复合离子源TOF-MS分析速度快,应用范围广,在在线分析中具有广泛的应用前景.     

The structure of the fire fighting foam surfactant Forafac®1157 and its biological and photolytic transformation products

For several decades, perfluorooctane sulfonate (PFOS) has widely been used as a fluorinated surfactant in aqueous film forming foams used as hydrocarbon fuel fire extinguishers. Due to concerns regarding its environmental persistence and toxicological effects, PFOS has recently been replaced by novel fluorinated surfactants such as Forafac®1157, developed by the DuPont company. The major component of Forafac®1157 is a 6:2 fluorotelomer sulfonamide alkylbetaine (6:2 FTAB), and a link between the trade name and the exact chemical structure is presented here to the scientific community for the first time. In the present work, the structure of the 6:2 FTAB was elucidated by ¹H, ¹³C and ¹⁹F nuclear magnetic resonance spectroscopy and high-resolution mass spectrometry. Moreover, its major metabolites from blue mussel (Mytilus edulis) and turbot (Scophthalmus maximus) and its photolytic transformation products were identified. Contrary to what has earlier been observed for PFOS, the 6:2 FTAB was extensively metabolized by blue mussel and turbot exposed to Forafac®1157. The major metabolite was a deacetylated betaine species, from which mono- and di-demethylated metabolites also were formed. Another abundant metabolite was the 6:2 fluorotelomer sulfonamide. In another experiment, Forafac®1157 was subjected to UV-light induced photolysis. The experimental conditions aimed to simulate Arctic conditions and the deacetylated species was again the primary transformation product of 6:2 FTAB. A 6:2 fluorotelomer sulfonamide was also formed along with a non-identified transformation product. The environmental presence of most of the metabolites and transformation products was qualitatively demonstrated by analysis of soil samples taken in close proximity to an airport fire training facility.     

氧活性粒子氧化NO生成HNO_3

采用强电离介质阻挡放电方法制取高浓度氧活性粒子(O+2、O3)并注入气体外排烟道中,实现O+2、O3氧化NO转化成资源酸(HNO3)的等离子化学反应。描述强电离放电的氧活性粒子产生器,讨论烟道中O+2、O3氧化NO成HNO3等离子体反应机制,分析回收酸液的NO-2、NO-3离子种类及浓度。考察强电离放电等离子体源的输入功率、水体积百分比、气体温度、气体流速对NOx氧化率的影响。氧化率为97.2%的最佳实验条件是:O+2浓度为1.38×1010个/cm3,O3浓度为210 mg/L,烟气温度为65℃,H2O体积浓度为5.6%,停留时间为0.94 s。     

Corynebacterium glutamicum as an indicator for environmental cobalt and silver stress–A proteome analysis

Cobalt and silver are toxic for cells, but mechanisms of this toxicity are largely unknown. Analysis of Corynebacterium glutamicum proteome from cells grown in control and cobalt or silver enriched media was performed by two dimensional gel electrophoresis (2DE) followed by mass spectrometry. Our results indicate that the cell adapted to cobalt stress by inducing five defense mechanisms: Scavenging of free radicals, promotion of the generation of energy, reparation of DNA, reparation and biogenesis of Fe-S cluster proteins and supporting and reparation of cell wall. In response to the detoxification of Ag⁺ many proteins were up-regulated, which involved reparation of damaged DNA, minimizing the toxic effect of reactive oxygen species (ROS) and energy generation. Overexpression of proteins involved in cell wall biosynthesis (1,4-alpha-glucan branching enzyme and nucleoside-diphosphate-sugar epimerase) upon cobalt stress and induction of proteins involved in energy metabolism (2-methylcitrate dehydratase and 1, 2-methylcitrate synthase) upon silver demonstrate the potential of these enzymes as biomarkers of sub-lethal Ag⁺ and Co toxicity.     

Development and application of LC–APCI–MS method for biomonitoring of animal and human exposure to imidacloprid

Imidacloprid (IMI) is a relatively new neuro-active neonicotinoid insecticide and nowadays one of the largest selling insecticides worldwide. In the present study a LC–APCI–MS based method was developed and validated for the quantification of imidacloprid and its main metabolite 6-chloronicotinic acid (6-CINA) in urine and hair specimens. The method was tested in biomonitoring of intentionally exposed animals and subsequently applied for biomonitoring of Cretan urban and rural population.     

Factors influencing on the bioaccessibility of polybrominated diphenyl ethers in size-specific dust from air conditioner filters

Size-specific concentrations and bioaccessibility of polybrominated diphenyl ethers (PBDEs) in dust from air conditioner filters were measured, and the factors influencing the PBDE bioaccessibility were determined. Generally, the PBDE concentrations increased with decreasing dust particle size, and BDE209 (deca-BDE) was generally the predominant congener. The bioaccessibility ranged from 20.3% to 50.8% for tri- to hepta-BDEs, and from 5.1% to 13.9% for BDE209 in dust fractions of varied particle size. The bioaccessibility of most PBDE congeners decreased with increasing dust particle size. The way of being of PBDE (adsorbed to dust surface or incorporated into polymers) in dust significantly influenced the bioaccessibility. There was a significant negative correlation between the tri- to hepta-BDE bioaccessibility and organic matter (OM) contents in dust. Furthermore, tri- to hepta-BDE bioaccessibility increased with increasing polarity of OMs, while with decreasing aromaticity of OMs. The tri- to hepta-BDE bioaccessibility significantly positively correlated with the surface areas and pore volumes of dust. Using multiple linear regression analysis, it was found that the OM contents and pore volumes of dust were the most important factors to influence the tri- to hepta-BDE bioaccessibility and they could be used to estimate the bioaccessibility of tri- to hepta-BDEs according to the following equation: bioaccessibility (%) = 45.05 − 0.49 × OM% + 1.79 × pore volume. However, BDE209 bioaccessibility did not correlate to any of these factors.     

Method optimization to measure polybrominated diphenyl ether (PBDE) concentrations in soils of Bratislava, Slovakia

We modified an analytical method to determine polybrominated diphenyl ethers (PBDEs) in urban soils of Bratislava (Slovakia). Gel permeation chromatography (GPC) introduced as a clean-up step for soil extracts substantially reduced matrix enhancements when PBDEs were measured with gas chromatography-negative chemical ionization-mass spectrometry (GC-NCI-MS). The resulting method proved to be accurate, precise, and showed low detection limits. The sum of 15 PBDE concentrations in surface horizons of Bratislava soils ranged from 87 to 627 pg g⁻¹. PBDE concentrations were mostly higher in surface than deeper horizons probably because of atmospheric deposition and lack of substantial vertical transport. Lower brominated PBDEs undergo more soil-atmosphere exchanges or are more scavenged and transferred with litter fall to the soil organic matter than higher brominated ones as suggested by the correlation between lower brominated PBDEs and soil organic C (C_org) concentrations.     

Wood-Specific Polycyclic Aromatic Hydrocarbon (PAH) Patterns in Soot Using Gas Chromatography-Atmospheric Pressure Laser Ionization-Mass Spectrometry (GC-APLI-MS)

If organic matter is burnt, the combustion of wood produces the highest amounts of polycyclic aromatic hydrocarbons (PAHs) compared with other fossil energy sources such as oil, coal, or gas. Emissions from wood combustion are increasingly of special interest due to the rising use of wood as a renewable energy source in residential heating in Europe. To the authors' knowledge, reproducible wood-specific PAH patterns in soot were identified for the first time by use of a sampling interval of only 5 min in this study. The short sampling interval was enabled by the very sensitive analytical method of gas chromatography–atmospheric pressure laser ionization–mass spectrometry (GC-APLI-MS) applied. The analysis of 40 PAH of soot from wood logs of spruce, pine, larch (softwood) and beech, birch, oak (hardwood), and wood pellets, as well as wood briquettes, showed 13.46–250.62 mg/kg for ∑40 PAH and 10.75–177.94 mg/kg for the U.S. Environmental Protection Agency PAH standard (without acenaphthylene and anthracene). Highest concentrations occurred in the samples from birch with bark, beech, and wood briquettes. Indeno[1,2,3-cd]pyrene, naphthalene, and alkylated naphthalenes were also detected. Significant concentrations of the very toxic dibenzopyrenes (up to 11.30 mg/kg) are reported. Softwood soot contained highest amounts of 2–4-ring PAH, followed by hardwood which is in accordance with the presence of highest amounts of abietic acid in softwood, a known precursor of retene and phenanthrene. PAH in soot from five spruce samples from different locations show a mean ∑40 PAH concentration of 13.46 mg/kg (n = 5, minimum 8.03, maximum 23.32 mg/kg, SD = 5.65) and exhibited a typical pattern that differed from all other wood soot samples. The distributions of alkylated naphthalenes of the spruce samples show a bell-shape distribution in contrast to the alkylated phenanthrenes/anthracenes of all samples (except the wood pellets), showing a slope distribution. The data indicate that wood-specific PAH patterns exist and under the applied conditions, spruce logs produced the least toxic soot.