双酚A及其类似物对斑马鱼胚胎及幼鱼的毒性效应

为探讨双酚A及其类似物对鱼类早期生长发育的毒性效应,研究了双酚A及其7种类似物对斑马鱼胚胎及仔鱼的毒性效应。通过对胚胎的孵化率、心率、仔鱼体长等指标进行测定分析,结果显示:(1)双酚A及其7种类似物都可使斑马鱼胚胎出现心包水肿、卵黄囊肿、脊柱弯曲和尾部弯曲等症状。(2)综合考虑斑马鱼78 hpf胚胎心率、120 hpf胚胎孵化率及7 dpf仔鱼体长抑制率等指标,8种受试物中双酚P(BPP)的毒性最大,其次是双酚AP(BPAP)、双酚AF(BPAF)、双酚Z(BPZ),然后是双酚A(BPA)、双酚B(BPB)、双酚F(BPF),双酚S(BPS)的毒性最小,每种受试物的浓度与受精卵的孵化率、仔鱼心率呈明显负相关关系,与体长抑制率呈明显正相关关系。8种受试物毒性与辛醇-水分配系数(log K_(OW))呈正相关关系,log K_(OW)越大毒性则越大。     

Development of quantitative structure-property relationship model for predicting the field sampling rate ( R s ) of Chemcatcher passive sampler

Passive sampling technology has been considered as a promising tool to measure the concentration of environmental contaminants. With this technology, sampling rate (Rs) is an important parameter. However, as experimental methods employed to obtain the Rs value of a given compound were time-consuming, laborious, and expensive. A cost-effective method for deriving Rs is urgent. In addition, considering the great dependence of Rs value on water matrix properties, the laboratory measured Rs may not be a good alternative for field Rs. Thus, obtaining the field Rs is very necessary. In this study, a multiparameter quantitative structure-property relationship (QSPR) model was constructed for predicting the field Rs of 91 polar to semi-polar organic compounds. The determination coefficient (R2Train), leave-one-out cross-validated coefficient (Q2LOO), bootstrap coefficient (Q2BOOT), and root mean square error (RMSETrain) of the training set were 0.772, 0.706, 0.769, and 0.230, respectively, while the external validation coefficient (Q2EXT) and RMSEEXT of the validation set were 0.641 and 0.253, respectively. According to the acceptable criteria (Q2 > 0.600, R2 > 0.700), the model had good robustness, goodness-of-fit, and predictive performances. Therefore, we could use the model to fill the data gap for substances within the applicability domain on their missing Rs value.     

Toward rational design of amines for CO2 capture: Substituent effect on kinetic process for the reaction of monoethanolamine with CO2

Amines have been considered as promising candidates for post-combustion CO₂ capture. A mechanistic understanding for the chemical processes involved in the capture and release of CO₂ is important for the rational design of amines. In this study, the structural effects of amines on the kinetic competition among three typical products (carbamates, carbamic acids and bicarbonate) from amines + CO₂ were investigated, in contrast to previous thermodynamic studies to tune the reaction of amines with CO₂ based on desirable reaction enthalpy and reaction stoichiometry. We used a quantum chemical method to calculate the activation energies (E_a) for the reactions of a range of substituted monoethanolamines with CO₂ covering three pathways to the three products. The results indicate that the formation of carbamates is the most favorable, among the three considered products. In addition, we found that the E_a values for all pathways linearly correlate with pK_a of amines, and more importantly, the kinetic competition between carbamate and bicarbonate absorption pathways varies with pK_a of the amines, i.e. stronger basicity results in less difference in E_a. These results highlight the importance of the consideration of kinetic competition among different reaction pathways in amine design.     

双酚A类似物雌激素干扰效应的定量结构-活性关系模型

由于双酚A(BPA)具有内分泌干扰等毒性效应,有些国家已经开始限制其在部分工业品生产中使用。一些双酚A类似物因用于替代BPA而被大量使用。因其与双酚A具有相似的分子结构,双酚A类似物是否也具有内分泌干扰等毒性效应受到越来越多的关注。采用逐步多元线性回归(MLR)方法,构建了可预测双酚A类似物雌激素效应的定量结构-活性关系模型。模型的决定系数R~2=0.899,去一法交叉验证系数Q_(LOO)~2=0.868,Bootstrapping验证系数Q_(BOOT)~2=0.755,均方根误差RMSE=0.339,表明模型具有较好的拟合优度、稳健性;验证集决定系数Q_(EXT)~2=0.921,外部验证系数Q_(EXT)~2=0.810,均方根误差RMSE=0.638,表明模型具有较好的预测能力。采用欧几里德距离方法和Wil iams图表征了模型应用域,依据分子描述符对模型进行了机理解释,并用所建模型,填补了22种其他双酚A类似物缺失的雌激素干扰效应数据。     

乙腈溶剂中单壁碳纳米管与常见有机化合物的相互作用

以单壁碳纳米管(SWCNTs)为固定相,采用高压匀浆法,制备HPLC色谱柱.测定乙腈相中18种有机化合物在SWCNTs色谱柱上的保留因子,研究SWCNTs与化合物的相互作用.结果表明,有机化合物取代基的种类和个数、杂原子的个数影响乙腈相中有机化合物与SWCNTs的相互作用.采用线性溶解能关系(LSER)定量表征SWCNTs与有机化合物的相互作用,所构建的LSER模型具有较强的拟合能力(R2=0.844)和稳健性(Q2LOO=0.768),发现π-/n-电子对作用和空穴/弥散作用是控制SWCNTs与有机化合物相互作用的主要因素.     

有机污染物生物降解性预测模型

生物降解性是评估污染物环境持久性的重要依据,也是化学品是否获准生产及进入市场的评价指标。采用17位生物降解领域专家评估的生物降解等级数据,通过功能树(FT)算法建立了包含15个分子结构参数的初级生物降解和最终生物降解预测模型。外部验证结果表明,模型具有较好的预测准确性,初级生物降解性加权准确度(weighted accuracy,WA):训练集WA=84.1%,验证集WA=78.9%;最终生物降解性WA:训练集WA=91.0%;验证集WA=83.6%。预测正确性对化合物的杠杆值作图,表征了生物降解性模型的应用域。     

可用于表征可电离化合物离子化影响的描述符研究进展

在人为有意生产的化学品或无意识产生的化学品中,可电离有机化合物(IOCs)均占有较大比重.在环境水体、生理或实验pH条件下,IOCs可解离为分子和离子形态.研究表明,IOCs的分子和离子形态均对其表观物理化学、环境归趋和行为、生态和健康毒性效应参数具有不可忽视的影响,因而在开展IOCs相关实验或理论研究时不应忽略离子化的影响.在构建IOCs相关预测模型时,核心是如何表征离子化的影响.本文从描述符入手,总结了可用于表征IOCs离子化影响的4类描述符,即酸碱解离常数(pKa)及其衍生参数(分子态和离子态的比例分数(δ分子和δ离子))、考虑离子化影响的分配系数包括正辛醇-水分布系数(logDow(pH))和进行形态修正的脂质体-水分配系数(logDlip/w(pH))、考虑离子参数的多参数线性自由能关系(离子描述符J+和J-)、基于形态修正的量化参数,并展望了表征IOCs离子化影响的未来研究重点.     

构建基于GHS标准的黑头呆鱼(Pimephales promelas)急性毒性二元分类模型

鱼类急性毒性参数是进行化学品生态风险评估、分类标签等工作不可或缺的毒性指标。本文选取634个有机化学品对黑头呆鱼(Pimephales promelas)的急性毒性数据,并依据"全球化学品统一分类和标签制度"(GHS)中推荐的分类标准,将急性毒性值小于和大于100 mg·L-1的物质分别划分为有毒物质和无毒物质。以分类结果为建模指标,构建了基于欧几里德距离的K最近邻(k NN)二元分类模型。评估结果表明,模型训练集和验证集的预测准确度(Q)、敏感性(Sn)和特异性(Sp)参数均大于0.7,说明模型具有较好的预测能力。因而,在化学品分类标签工作中,可使用该模型预测缺失的鱼类急性毒性类别。     

Study on a novel pneumatic stratified vibration sorting method of waste plastic films

Journal of Material Cycles and Waste Management - Waste plastic films introduce serious pollution and need to be separated and collected for recycling. Aiming at highly efficient sorting of waste...     

地震灾害下市政管网消防供水能力可靠度评估

提出了一种地震后管网的消防供水能力可靠度评估方法,考虑地震后管网破损的随机性与火灾发生位置的随机性,采用蒙特卡罗模拟生成管网震损场景,基于管网低压状态对不同位置火灾进行了消防供水能力评估。在管网不同位置依次生成火灾场景,对每个场景进行消防供水能力评估,同时基于我国消防用水量,构建了消防供水能力可靠度评价指标。将所提出方法应用于云南省某旅游古镇并与传统GIRAFFE方法进行比较,结果表明：传统方法高估了管网整体消防供水能力,尤其在震级较小时,会显著高估枝状管网区域的消防供水能力。