OH自由基引发的甲烷光化学氧化体系中有机过氧化物的研究

在１．０１３２５×１０＾５Ｐａ,２９８Ｋ,Ｏ２－Ｎ２气氛下,采用长光路付立叶红外光谱仪跟踪反应进程,高压液相色谱仪测定反应产物中有机过氧化物,研究了ＯＨ自由基基引发的甲烷光化学反应体系,证实反应产物中有Ｈ２Ｏ２、甲基过氧化氢（ＣＨ３Ｏ２Ｈ,ＭＨＰ）和过氧甲醚（ＣＨ３Ｏ２ＣＨ３）,并发现羟甲基过氧化氢（ＨＯＣＨ２ＯＯＨ,ＨＭＨＰ）和一未知有机过氧化物,ＨＭＨＰ的发现表明ＣＨ４氧化过程中可能存在过氧甲     

正相液体色谱法测定ppt量级的硒

硒作为生命必需的微量元素,其有关研究报告日见增多。在我国,已经报道了由区域环境低硒引起的大骨节病、克山病、以及区域性癌症。相关研究工作包括我国低硒带的成因、硒的生物地球化学循环、地方病病因的探讨。由于中国低硒带内环境样品硒含量低,其中饮水中硒的总量一般低于0.1ppb,形态分析中的组成部分含量甚至低于0.01ppb,因     

有机酸、碱类污染物分配系数的测定及相关性研究

用反相高效液相色谱(RHPLC)法及振荡法测定了42种环境中常见的有机酸、碱类污染物的分配系数,两种方法的测定值与文献值吻合较好,但RHPLC法快速、准确、样品用量少、测定范围宽、且对样品纯度要求低.测定了苯酚类化合物在环己烷/水、四氯化碳/水、氯仿/水、和苯/水体系中的分配系数,并建立了这四种体系与正辛醇/水体系分配系数的相关方程.     

水中几种有机污染物的SPE-HPLC联用测定技术

酚类及硝基苯是水中一类重要的优先控制污染物。通过对固相萃取 (SPE)技术与高效液相色谱 (HPLC)联用技术的研究 ,得出对于含酚类及硝基苯的水样采用 2 0 0mg的键合硅胶C1 8柱在水样pH值为 3 .0和过柱水样为 40mL时可得到较好的萃取及测定结果 ,从而提出一种对水中酚类物质及硝基苯测定具有灵敏度高、准确性好的分析方法。     

HPLC测定大气中的光气

报道了用０．２５％的苯胺溶液吸收大气中的光气，所形成的１，３－二苯基脲衍生物以高效液相色谱分析。方法回收率为９８．１％￣１００．８％，最低检出浓度为１．７×１０＾－４ｍｇ／ｍ＾３，线性范围为０．１￣３４０ｎｇ，相对标准偏差为１．２３％。     

Toxicity tests with luminescent photobacteria and quantitative structure activity relationships for nitroparaffins

EC₅₀ values of different nitroparaffins were determined by a photobacterium phosphoreum toxicity test. Octanol/water partition coefficients were determined by a reversed phase HPLC method. From these experimental data quantitative structure activity relationships were deduced which point to a dependence of toxicity on a “form factor” that includes the number of methyl and methylene groups in a molecule. The hypothesis will be formulated that the specific effects depend on the number of methylgroups and an equation for specific effects is given.     

A new approach to graphical and numerical analysis of links between plant chemotaxonomy and secondary metabolism from HPLC data smoothed by a simplex mixture design

Summary. HPLC analysis of secondary metabolites represents an efficient tool for the studying of plant chemical diversity under different aspects: chemotaxonomy, metabolomics, adaptative responses to ecological factors, etc. Statistical analyses of HPLC databases, e.g. correlation analysis between HPLC peaks, can reliably provide information on the similarity/dissimilarity degrees between the chemical compounds. The similarities, corresponding to positive correlations, can be interpreted in terms of analogies between chemical structures, synchronic metabolisms or co-evolution of two compounds under certain environment conditions, etc. . In terms of metabolism, positive correlations can translate precursor-product relationships between compounds; negative correlations can be indicative of competitive processes between two compounds for a common precursor(s), enzyme(s) or substrate(s). Furthermore, the correlation analysis under a metabolic aspect can help to understand the biochemical origins of an observed polymorphism in a plant species. With the aim of showing this, we present a new approach based on a simplex mixture design, Scheffé matrix, which provides a correlation network making it possible to graphically visualise and to numerically model the metabolic trends between HPLC peaks. The principle of the approach consisted in mixing individual HPLC profiles representative of different phenotypes, then from a complete mixture set, a series of average profiles were calculated to provide a new database with a small variability. Several iterations of the mixture design provided a smoothed final database from which the relationships between the secondary metabolites were graphically and numerically analysed. These relationships were scale-dependent, namely either deterministic or systematic: the first consisted of a monotonic global trend covering the whole variation field of each metabolites’ pair; the second consisted of repetitive monotonic variations which gradually attenuated or intensified along a global trend. This new metabolomic approach was illustrated from 404 individual plants of Astragalus caprinus (Leguminoseae), belonging to four chemical phenotypes (chemotypes) on the basis of flavonoids analysed in their leaves. After smoothing, the relationships between flavonoids were numerically fitted using linear or polynomial models; therefore the co-response coefficients were easily interpreted in terms of metabolic affinities or competitions between flavonoids which would be responsible of the observed chemical polymorphism (the four chemotypes). The statistical validation of the approach was carried out by comparing Pearson correlations to Spearman correlations calculated from the smoothed and the crude HPLC database, respectively. Moreover, the signs of the smoothed relationships were finely supported by analogies and differences between the chemical structures of flavonoids, leading to fluent interpretation in relation to the pathway architecture.     

鱼体中单甲脒农药的测定

本文介绍了单甲脒农药在鱼体中残留量的测定方法.鱼样经石油醚提取,液-液分配后用高效液相色谱法测定.方法对单甲脒的最低检出浓度为0.05mg·kg~(-1),最低检出限为3×10~(-7)g,平均添加回收率为96.38±3.56%.     

Determination of polycyclic aromatic hydrocarbons in dry tea

Twenty-eight different tea samples sold in the United States were evaluated using high-performance liquid chromatography (HPLC) with fluorescence detection (FLD) for their contamination with polycyclic aromatic hydrocarbons (PAHs). Many PAHs exhibit carcinogenic, mutagenic, and teratogenic properties and have been related to several kinds of cancer in man and experimental animals. The presence of PAHs in environmental samples such as water, sediments, and particulate air has been extensively studied, but food samples have received little attention. Eighteen PAHs congeners were analyzed, with percentage recovery higher than 85%. Contamination expressed as the sum of the 18 analyzed PAHs was between 101 and 1337 μg/kg on dry mass and the average contents in all of the 28 examined samples was 300 μg/kg on dry mass. Seven of the congeners were found in all samples with wide ranges of concentrations as follows: fluorene (7–48 μg/kg), anthracene (1–31 μg/kg), pyrene (1–970 μg/kg), benzo(a)anthracene (1–18 μg/kg) chrysene (17–365 μg/kg), benzo(a)pyrene (1–29 μg/kg), and indeno(1,2,3-cd)pyrene (4–119 μg/kg). The two most toxic congeners benzo(a)pyrene and dibenzo(a,h)anthracene were found at high concentrations only in Earl Grey Twinnings, Earl Grey Harney& Sons Fine Teas, and Chai Ultra Spice Black Tea Twinnings. Six PAH congeners are considered as suspected carcinogens (U.S.EPA), formed the basis of the estimation of the toxic equivalent (TEQ), Chai Ultra-Spice Black Tea Twinnings had the highest TEQ (110.9) followed by two grey tea samples, Earl Grey Harney & Sons Fine Tea (57.7) and Earl Grey Twinnings (54.5). Decaffeinated grey teas had the lowest TEQs, decaffeinated Earl Grey Bigelow (9.4) and Green Tea Honey Lemon Decaffeinated Lipton (9.6).     

乙腈盐析萃取HPLC-PDA同时测定水中11种苯胺类化合物

通过对色谱分析和样品萃取条件的选择和优化，建立了同时分析水中11种苯胺类化合物的HPLC方法。样品经乙腈盐析萃取后直接进样分析，采用 ODS色谱柱，以乙腈-水为流动相进行梯度洗脱，用PDA检测。结果表明，11种苯胺类化合物在0.20~100mg/L范围内其浓度和检测信号呈良好的线性关系，方法检出限为0.002~0.007mg/L，地表水和废水样品加标回收率为81.6%~97.4%，相对标准偏差为1.5%~5.5%。