氯代环醚系列化合物结构与急性毒性关系研究

由化学物质毒性效应登录(RTECS)1998年版光盘系统检索获得52种环醚和34种氯代环醚急性毒性数据.应用主成份分析法从11种分子描述符中选择出对急性毒性有明显影响的5种:氯原子数,取代苯环上氢的氯原子数,取代烷基氢的氯原子数,烷基数和氧原子数.通过样本学习集训练并优化神经网络结构、建模分类、预报,对于86个样本,低中和高剧两类毒性,正确分类率达到91%;而对于低、中、高、剧4类毒性,正确分类率达到80%.结果表明,氯代环醚的特殊结构具有很强的致毒作用.     

62种杂环芳胺结构与致变活性关系的神经网络研究

应用自适应分子结构描述符生成方法和神经网络数值模式,研究62种烹调食品过程中产生的杂环芳胺结构与致变活性间的关系。该模式预报结果与实验测定结果符合良好;致变剂、非致变剂和勉强有致变活性剂三类间正确分类率超过90％。通过6次自适应分子结构描述符选择迭代,得到５种特征分子描述符为：芳环碳原子取代甲基数、芳环氮原子取代甲基数、母体共轭环数、端环增活结构数和端环抑活结构数。其中,增活结构为具有共轭烯烃碎片结构;抑活结构具有短共轭烯烃结构或不具有共轭烯烃结构。最后,对该构效关系的起因进行了定性解释。     

含苯环化合物对发光菌急性毒性QSAR研究

文章通过将化合物中骨架非氢原子进行分类、参数化转换、构建非氢原子间的关系而得到新的结构描述符,并且将其用于28个含苯环类化合物的结构参数化表征。通过多元线性回归建立含苯环类化合物的分子结构与对发光菌急性毒性(-lg EC_(50))之间的关系模型,模型的相关系数为0.960,标准偏差为0.191。构建的模型可以用于含苯环类化合物对发光菌急性毒性的预测,为环境中的有毒化合物的定量结构-毒性关系研究提供参考。     

环境化学

X13 200500632 PCDFs的Ah受体结合能力的定量结构效应关系/ 李芳…(华中科技大学同济医学院环境医学研究所)//中国环境科学/中国环境科学学会.-2004, 24(3).-324-326 环图X-58 应用单苯环氯取代方法取G1-G1010个分子结构描述符,通过正向逐步线性回归方法构建对     

氯脂肪烃分子结构与对鼠急性毒性关系的专家系统研究

应用专家系统方法对１１０种氯脂肪烃和可能的对应烷烃的分子结构及对鼠急性毒性关系进行了研究。分子结构描述符取为：特殊构象结构，母体烃结构，取代氯原子数和分子含碳原子数。结果表明：对于四类活性正确分类率达到８２％以上，满足统计预报要求。     

多环芳烃在污泥与菜籽饼堆肥中的降解规律

研究了城市污泥和菜籽饼堆肥体系中16种多环芳烃(PAHs)在94 d内的降解演化过程.堆肥体系开始时16种PAHs的总浓度为1.792 mg·kg~(-1),堆肥结束后其总浓度为0.153 mg·kg~(-1).其总降解率为91.5% (p<0.05).堆肥过程中,堆体腐殖酸呈现先上升后下降,最后又稳步上升的趋势;与此同时,PAHs则呈现先下降后上升,最后又明显下降的趋势(第31～61 d).PAHs的微生物降解主要发生在堆肥的第16～31 d,但是苯环数≤3的PAHs降解过程与苯环数≥4的PAHs在堆肥第31～47 d存在差异:苯环数≤3的PAHs(除了菲)存在着一个持续的降解过程,但是苯环数≥4的PAHs和菲在堆肥第31～46 d表现出浓度的上升.这表明苯环数≥4的PAHs和菲存在强吸附作用,它们紧密的吸附使得微生物不易进行生物降解.PAHs化合物降解率与其相对分子质量之间存在正相关的关系,即相对分子质量越大的化合物其降解率越高,苯并(b)荧蒽例外.     

ToxCast化学品对CYP450异构酶抑制的QSAR研究

研究收集美国国立健康研究所化学基因组中心利用高通量筛选测定的1万多种化合物对5种细胞色素P450(CYP450)酶的抑制数据,利用随机森林法构建MOE 2D描述符的分类模型.采用五折交叉验证建模策略保证模型的预测能力.模型对1A2、2C9、2C19、2D6和3A4等酶抑制剂预测的正确分类率分别高达84.4%、82.5%、82.1%、78.4%和80.0%,结构分析表明,卤代(氯/氟)芳烃结构在抑制剂中出现概率显著高于非抑制剂.最后,利用上述模型对ToxCast项目954个化合物进行虚拟筛选.实例化合物分析验证了模型预测与实际效应的吻合程度.构建的模型可进一步对其它环境化学品的CYP450酶抑制活性进行预测,加快对化学品健康风险的初步筛选.     

基于分形维数权重的南水北调东线源头水质评价研究

水质评价问题的实质是对水质现状和各评价因素间的函数关系的逼近,是一种复杂的非线性问题.针对水质评价指标之间的非线性关系,提出了基于分形维数权重的水质评价方法.为有效地评估南水北调东线源头的水质现状,首先选取影响水质评价的7个主要因素,根据标准等级水体分类标准,采用在等级标准中随机内插的方法,得到50个标准等级样本,并根据样本综合评估值与经验等级之间的关系建立分形插值评价模型;最后,以长江江都市芒稻河断面2001—2008年的年平均水质监测数据为例对模型进行验证.结果表明,该方法可以通过分段函数得到每个样本的具体得分值,因而具有较高的分类精度,为水质评价提供了一种较好的新方法.     

密度泛函方法预测二英类化合物(PCDD/Fs)的正辛醇/水分配系数

在B3LYP/6-31G水平上全优化计算了多氯代二苯并—对-二英和多氯代二苯并呋喃(PCDD/Fs)系列物的分子结构;基于得到的分子结构描述符,依据修正的线性溶解能理论,分别建立了PCDDs和PCDFs的正辛醇/水分配系数的定量结构-性质关系模型(R2分别为0.985和0.966),并用交叉验证法对模型进行了验证(q2分别为0.983和0.936),用t-检验对各变量进行了检验.检验结果表明,模型的预测能力优于AM1法、单苯环氯取代指数法和拓扑量子方法得出的模型.     

环境化学

X1312田202618单苯环氯取代指数法预测二恶英类化合物PCDFs的正辛醇/水分配系数/黄俊…(清华大学环境科学与工程系,环境模拟与污染控制国家重点实验室)//环境科学研究/中国环科院一2(X)2,15(2).一1一5环图X一6 采用单苯环氯取代指数作为二恶英类化合物多氯代二苯并吠喃(PCDFs)的分子结构描述符,通过正向逐步线性回归方法建立了PCDf’s的正辛醇/水分配系数(l沙端,)与分子结构描述符之间的定量关系模型。与有关文献报道的模型相比,该模型不仅具有显著的相关性(n二sllhaj=0.571,SE二0.173抖,在a二0.仍时,F=38.翻7,p二0.戊C),而且对于分…     

Mutagenic activity of airborne particulate matter in indoor and outdoor environments

Research on mutagenic activity of airborne particulate matter has focused mainly on the outdoor environment, although far more time is spent indoors than outdoors. Most of these investigations were conducted on samples, collected in urban or industrial areas. Results may give the mutagenic potential of air samples; however, as the number of samples is often limited, the influence of various sources and processes on mutagenic activity of airborne particles is not assessed. This review deals with the interpretation of the variation in mutagenic activity of outdoor as well as indoor airborne particulate matter and their relationship. A comparison is made with the chemical and physical character of aerosols on the one hand and with general air pollution parameters on the other hand. Furthermore this paper briefly discusses the relevance of mutagenic principles on airborne particulate matter for human exposure.     

Determination of mutagenic activity of airborne particulates and of the benzo[α]pyrene concentrations in Athens atmosphere

The mutagenicity and benzo(α)pyrene (BαP) content of airborne particles (172 samples) from four locations in Athens was studied for 1 year starting February 1984. All the organic extracts of airborne particulate matter showed direct mutagenic activity. There was a good correlation between BαP concentration and mutagenicity in all samples. Higher values of mutagenic activity and BαP concentrations were found at the sites located in the center of the city than at the sites located in the industrial areas. The height of the sampling place has a negative effect on both measured pollution parameters. The higher percentage of biological and chemical parameters were associated with particles <3.3 μm in diameter. The mean yearly values of mutagenic activity of airborne particulates and BαP levels, were 1.9 rev m⁻³ and 2.6 ng m⁻³, respectively and can be grouped among the median, between the heavily and the lightly polluted cities of the world. Higher values of mutagenic activity were found during winter months. From the diurnal variation of mutagenic activity it was found that maximum value occurred during morning (0900–1100). The main source of mutagens seems to be the emissions from diesel powered engines and central heating.     

洗发香波诱发蝌蚪红细胞微核的研究

研究了１２种洗发香波对中华大蟾蜍蝌蚪红细胞微核的诱变效应。蝌蚪对各试验液中染毒７ｄ，采心脏血制片。结果表明，８种洗发香波能诱发蝌蚪红细胞微核率显著升高，其致变效应与洗发香波浓度及染毒时间有关。     

In vitro toxicity of particulate matter emissions from residential pellet combustion

Particulate matter emissions (PM₁₀) from the combustion, in a residential stove, of two commercial brands of certified (ENplus A1) pellets, a non-certified brand and laboratory made pellets of acacia were tested for their ability to induce ecotoxic, cytotoxic, and mutagenic responses in unicellular organisms and a human cell line. Ecotoxicity was evaluated through the Vibrio fischeri bioluminescence inhibition assay. Moreover, cytotoxicity was assessed at two time points (24- and 48-hr) through two complementary techniques in order to evaluate the cellular metabolic activity and membrane integrity of human lung epithelial cells A549. The Ames test using two Salmonella typhimurium strains (TA100 and TA98) was employed to assess the mutagenic potential of the polycyclic aromatic hydrocarbon fraction extracted from the PM₁₀ samples. Results obtained with the bioluminescent bacteria indicated that only particles from the combustion of acacia pellets were toxic. All samples induced impairment on the A549 cells metabolic activity, while no significant release of lactate dehydrogenase was recorded. PM₁₀ emissions from acacia pellets were the most cytotoxic, while samples from both certified pellets evoked significant cytotoxicity at lower doses. Cytotoxicity time-dependency was only observed for PM₁₀ from the combustion of acacia pellets and one of the brands of certified pellets. Mutagenic activity was not detected in both S. typhimurium strains. This study emphasises the role of the raw material for pellet manufacturing on the toxicological profile of PM emissions. Alternative raw materials should be deeply investigated before their use in pelletisation and combustion in residential appliances.     

兰州市交通要道颗粒物污染状况及其致突变活性的研究

采用现场监测，色－质联用分析以及小鼠骨髓微核试验方法，评价了兰州市交通要道颗粒物的污染状况，分析了颗粒提取物（PE）的有机组成及致突变活性。结果表明，兰州市总悬浮颗粒物（TSP）污染严重。颗粒提取物中含有近100种有机化合物，其中包括致癌性多环芳烃。微核试验显示PE具有致突变活性，对人群健康的影响不容忽视。     

应用分子全息QSAR技术预测硝基芳烃的遗传毒性

分子全息是一种新的分子结构表征技术，基于分子全息的结构．活性关系(HQSAR)技术具有高效、快速、预测能力高等优点，非常适合于分析大量数据样本．本文应用这一最新的QSAR技术，采用偏最小二乘回归技术，研究了54种硝基芳烃的致突变毒性，建立了QSAR定量预测模型．交叉验证和非交叉验证结果表明，模型具有良好的拟合效果和显著的预测能力，进一步的测试数据检验表明，模型具有高度的预测能力和很好的稳健性，可以用来对这一类典型的有毒有机污染物的毒性进行预测．     

The photo-oxidation of automobile emissions: measurements of the transformation products and their mutagenic activity

Dilute mixtures of automobile emissions (comprising 50% exhaust and 50% surrogate evaporative emissions) were irradiated in a 22.7 m³ smog chamber and tested for mutagenic activity by using a variant of the Ames test. The exhaust was taken from a single vehicle, a 1977 Ford Mustang equipped with a catalytic converter. Irradiated and nonirradiated gas-phase emissions were used in exposures of the bacteria, Salmonella typhimurium, strains TA100 and TA98. A single set of vehicular operating conditions was used to perform multiple exposures. The mutagenic activities of extracts from the particulate phase were also measured with the standard plate incorporation assay. (In most experiments only direct-acting mutagenic compounds were measured.) The gas-phase data for TA100 and TA98 showed increased activity for the irradiated emissions when compared to the nonirradiated mixture, which exhibited negligible activity with respect to the control values. The particulate phase for both the irradiated and nonirradiated mixtures showed negligible activity when results were compared to the control values for both strains. However, the experimental conditions limited the amount of extractable mass which could be collected in the particulate phase. The measured activities from the gas phase and particulate phase were converted to the number of revertants per cubic meter of effluent (i.e. the mutagenic density) to compare the contributions of each of these phases to the total mutagenic activity for each strain. Under the experimental conditions of this study, the mutagenic density of the gas-phase component of the irradiated mixture contributed approximately two orders of magnitude more of the total TA100 activity than did the particulate phase. For TA98 the gas-phase component contributed approximately one order of magnitude more. However, caution must be exercised in extrapolating these results to urban atmospheres heavily impacted by automotive emissions, because the bacterial mutagenicity assay was used as a screening method, and additional assays using mammalian systems have not yet been conducted. In addition, only limited number of conditions were able to be tested. The significance and limitations of the results are discussed.     

污灌区地下水中有机污染物的分离鉴定与致突变活性研究

应用XAD系列大孔网状树脂萃取富集法,结合GC、GC/MS/DS1的分离鉴定技术,研究了北京东郊污灌区深层(90m)和浅层(18m)地下水中的有机污染物。采用LSC-GC/MS/DS装置测定了地下水中的挥发性有机物,并对水样进行了Ames试验以检验水样的致突变活性。结果从深井水样中检出32种非挥发性有机物,未检出挥发性有机物,致突变试验阴性。浅井水样中同时检出非挥发性和挥发性有机物。两种菌株在所有试验条件下均呈现阳性致突变反应。