Development and validation of an analytical methodology for the determination of p,p′-DDT, p,p′-DDE and p,p′-DDD in fish oil pills

An analytical methodology was proposed and validated to be applied to the determination of p,p′-DDT and its metabolites p,p′-DDE and p,p′-DDD in fish oil. The analytical procedure presented in this paper involves a single-step clean up process prior to the analysis. A solution of 1,2,3,4-tetrachloronaphtalene was used as internal standard.The analytical technique used was gas chromatography coupled to an electron capture detector. Details on the validation process are provided.The limits of detection ranged from 2.6 to 4.7 pg μL^− 1. The BCR 598 standard reference material (cod liver oil) was used to evaluate the performance of the methodology with satisfactory recoveries for all the compounds.The analytes were determined in three different fish oil pills sold in Spain as a supplementary vitamin support. The sum of p,p′-DDT and metabolites was from 13.2 to 51.3 ng g^− 1, the dominant compound being p,p′-DDE.     

DDT在土壤和农业生态系统中的行为研究Ⅰ．DDT在亚热带旱地及水田中的残留和代谢动态研究

１９８９年冬和１９９０年夏在广州分别选取旱地和淹水大田，用有机玻璃管（ＰＶＣ）进行表面处理，并模拟农业生态，研究ＤＤＴ在土壤环境中的残留和去向。结果表明：ＤＤＴ的消失率较大，经２３６天，在旱田中的消失率为５３．３２％，Ｔ＿（５０）为２１５天；在水田中的消失率为６３．７８％，Ｔ＿（５０）为１６１天。淋溶的损失很少，在ＰＶＣ下层的残留量旱田为６．９４％，水田为１．５１％。经簿层层析（ＴＬＣ）和放射自显影（ＡＲＧ）鉴定，ＤＤＴ代谢物出现的顺序是ＤＤＤ（处理后第１４天）、ＤＤＡ（处理后２８天），随时间的增加而增加．ＤＤＴ在亚热带环境中的快速消失。与较强的太阳紫外线辐射、较高的温度和较低的有机质含量引起的光、热分解、生物降解和挥发作用的结果有关。     

Analytical chemistry of the persistent organic pollutants identified in the Stockholm Convention: A review

Persistent organic pollutants (POPs) are major environmental concern due to their persistence, long-range transportability, bio-accumulation and potentially adverse effects on living organisms. Analytical chemistry plays an essential role in the measurement of POPs and provides important information on their distribution and environmental transformations. Much effort has been devoted during the last two decades to the development of faster, safer, more reliable and more sensitive analytical techniques for these pollutants. Since the Stockholm Convention (SC) on POPs was adopted 12 years ago, analytical methods have been extensively developed. This review article introduces recent analytical techniques and applications for the determination of POPs in environmental and biota samples, and summarizes the extraction, separation and instrumental analyses of the halogenated POPs. Also, this review covers important aspects for the analyses of SC POPs (e.g. lipid determination and quality assurance/quality control (QA/QC)), and finally discusses future trends for improving the POPs analyses and for potential new POPs.     

Simple and surprisingly effective one-step extraction-cleanup by soxflo for DDT and its metabolites from environmental samples

A pilot study found that DDT breakdown at the GC inlet was extensive in extracts from some--but not all--samples with high organic carbon contents. However, DDT losses could be prevented with a one-step extraction-cleanup in the Soxflo instrument with dichloromethane and charcoal. This dry-column procedure took 1 h at room temperature. It was tested on spiked soil and peat samples and validated with certified soil and sediment reference materials. Spike recoveries from freshly spiked samples ranged from 79 to 111% at 20-4000 microg/kg concentrations. Recoveries from the real-world CRMs were 99.7-100.2% of DDT, 89.7-90.4% of DDD and 89.6-107.9% of DDE. It was concluded that charcoal cleanups should be used routinely during surveys for environmental DDX pollution in order to mitigate against unpredictable matrix-enhanced breakdown in the GC.     

江汉大学附属医院1999～2001年抗高血压药应用分析

目的 :分析 1999～ 2 0 0 1年抗高血压药在医院所占药品消耗金额的比重。方法 :计算抗高血压药物的DDD值 (限定日剂量 )、用药频度、每日治疗费用。结果 :3年来口服抗高血压药品种经营数额发生了一些变化 ,品种金额最大的是络活喜 ;钙拮抗剂使用量居前列 ,其次为ACEI类。结论 :(1)控制医药费增长应注意药品的总金额和每日治疗费用 ;(2 )有必要研制和开发国产药品 ,三年中抗高血压药金额近 1/ 3用在少数新、特、进口药品上 ;(3 )防治高血压十分重要     

Gas Chromatographic Enantiomer Separation of Atropisomeric PCBs Using Modified Cyclodextrins as Chiral Phases

Columns containing different types of cyclodextrin derivatives have been evaluated for chiral gas chromatographic separation of atropisomeric PCBs, o,p´‐DDT and o,p´‐DDD. Separation was attempted on columns containing mixed chiral selectors, and the performance of two closely related selectors was also examined. The cyclodextrins were: permethylated‐β‐CD (PM‐β‐CD), heptakis(2,3‐di‐O‐methyl‐6‐O‐tert‐butyldimethylsilyl)‐β‐CD (2,3‐M‐6‐TBDMS‐β‐CD), heptakis(2,3‐di‐O‐methyl‐6‐O‐tert‐hexyldimethylsilyl)‐β‐CD (2,3‐M‐6‐THDMS‐β‐CD), and heptakis(2,3‐di‐O‐ethyl‐6‐O‐tert‐hexyldimethylsilyl)‐β‐cyclodextrin (2,3‐E‐6‐THDMS‐β‐CD). The cyclodextrins were dissolved in OV‐1701 or in a dimethylsiloxane/silarylene copolymer containing 5% phenyl in the backbone. The application of mixed chiral selectors led to improved separations, however; at most eleven PCB congeners were separated on a single column. Chiral resolution of o,p´‐DDD was achieved. The use of a dimethylsiloxane/silarylene copolymer as a matrix for the cyclodextrins is a promising approach. With such a matrix, blocking of the CD cavities by silicone substituent groups can be avoided, and a reasonable CD solubility can be provided. The selectivity of heptakis(2,3‐di‐O‐ethyl‐6‐O‐tert‐hexyldimethylsilyl)‐β‐CD and heptakis(2,3‐di‐O‐methyl‐6‐O‐tert‐hexyldimethylsilyl)‐β‐CD was quite different, the former selector could separate four congeners, while the latter separated ten congeners.     

Electrochemical Reduction of 4,4′‐(2,2,2‐Trichloroethane‐1,1‐diyl)‐ bis(chlorobenzene) (DDT) and 4,4′‐(2,2‐Dichloroethane‐1,1‐diyl)‐ bis(chlorobenzene) (DDD) at Carbon Cathodes in Dimethylformamide

In dimethylformamide containing tetramethylammonium tetrafluoroborate, cyclic voltammograms for reduction of 4,4′‐(2,2,2‐trichloroethane‐1,1‐diyl)bis(chlorobenzene) (DDT) at a glassy carbon cathode exhibit five waves, whereas three waves are observed for the reduction of 4,4′‐(2,2‐dichloroethane‐1,1‐diyl)bis(chlorobenzene) (DDD). Bulk electrolyses of DDT and DDD afford 4,4′‐(ethene‐1,1‐diyl)bis(chlorobenzene) (DDNU) as principal product (67–94%), together with 4,4′‐(2‐chloroethene‐1,1‐diyl)bis(chlorobenzene) (DDMU), 1‐chloro‐4‐styrylbenzene, and traces of both 1,1‐diphenylethane and 4,4′‐(ethane‐1,1‐diyl)bis(chlorobenzene) (DDO). For electrolyses of DDT and DDD, the coulometric n values are essentially 4 and 2, respectively. When DDT is reduced in the presence of a large excess of D₂O, the resulting DDNU and DDMU are almost fully deuterated, indicating that reductive cleavage of the carbon–chlorine bonds of DDT is a two‐electron process that involves carbanion intermediates. A mechanistic scheme is proposed to account for the formation of the various products.     

Coupled DDD–FEM modeling on the mechanical behavior of microlayered metallic multilayer film at elevated temperature

To investigate the mechanical behavior of the microlayered metallic thin films (MMMFs) at elevated temperature, an enhanced discrete-continuous model (DCM), which couples rather than superposes the two-dimensional climb/glide-enabled discrete dislocation dynamics (2D-DDD) with the linearly elastic finite element method (FEM), is developed in this study. In the present coupling scheme, two especial treatments are made. One is to solve how the plastic strain captured by the DDD module is transferred properly to the FEM module as an eigen-strain; the other is to answer how the stress field computationally obtained by the FEM module is transferred accurately to the DDD module to drive those discrete dislocations moving correctly. With these two especial treatments, the interactions between adjacent dislocations and between dislocation pile-ups and inter-phase boundaries (IBs), which are crucial to the strengthening effect in MMMFs, are carefully taken into account. After verified by comparing the computationally predicted results with the theoretical solutions for a dislocation residing in a homogeneous material and nearby a bi-material interface, this 2D-DDD/FEM coupling scheme is used to model the tensile mechanical behaviors of MMMFs at elevated temperature. The strengthening mechanism of MMMFs and the layer thickness effect are studied in detail, with special attentions to the influence of dislocation climb on them.     

循证医学方法研究氟哌噻吨/美利曲辛治疗抑郁症的临床应用

目的运用循证医学方法探讨氟哌噻吨/美利曲辛的临床应用现状和发展趋势.方法采用销售金额与用药频度(DDDs)排序法对2003～2006年我院常用12种抗抑郁药有关数据进行统计分析;并将其分析结果与采用循证医学方法所收集有关氟哌噻吨/美利曲辛治疗抑郁症的临床资料进行系统分析。结果氟哌噻吨/美利曲辛的用药金额及用药频度(DDDs)逐年提高,且在所有查证资料中均属于临床首选药物之一.结论氟哌噻吨/美利曲辛发展前景广阔。我国制药企业应加快开发国产药品,以满足患者需要并降低治疗费用。