新型有机污染物降解机理的量子化学计算与分子模拟

Organic pollutants are a large group of chemicals,which are existing widely, performing complicated behaviors and causing serious environmental problems. Many of them are carcinogens, teratogens, mutagens and/or endocrine disrupters. Degradation is their common process in the environment, also is the critical step for pollution control and remediation. After their degradation in different natural media, organic pollutants may be transformed to non- or low-toxic products. However, they may also form the secondary pollutants, which are more dangerous and stable than the original ones. In this proposal, degradation mechanisms of emerging organic pollutants will be studied by using quantum chemical calculation and molecular simulation as well as experimental test. The chemical structures, reaction routes, transformation processes and intermediate products will be discussed from the molecular level, to clarify the main degradation pathways, rate-determining steps and the major degradation products. The chemical structures of emerging organic pollutants will be related to their macroscopic behavior in the environment, to establish the model predicting the degradation properties. Such studies are important to better understand their reactivities, degradation mechanisms, removal regulations, and to further understand their potential to form the secondary pollutants. The proposed research will hopefully provide both methods and theories to evaluate the environmental effects of organic pollutants, and to control and remediate their contaminations.

有机污染物是环境中量大、面广、危害严重、环境行为复杂的一类化学物质。许多有机污染物具有致癌、致畸、致突变效应及环境内分泌干扰效应。降解既是有机污染物的典型环境行为，也是污染控制与修复的基本方法。有机污染物在各种环境介质中降解，转化成安全无毒或毒性较低的产物，但也可能生成毒性更强、更稳定的二次污染物。本项目拟采用量子化学计算/分子模拟方法并辅以适当的实验验证研究新型有机污染物的降解机理。从分子水平上探讨其结构信息、反应路径、转化过程、中间产物等；查清速控步骤、主要降解产物；将新型有机污染物结构与其宏观的环境行为进行关联，建立降解性能预测模型；寻找更为高效的降解剂或降解酶。这些研究对更好地理解新型有机污染物在环境中的反应活性、清除规律，以及进一步理解由其形成二次污染物的潜能无疑具有深远的科学意义。期望通过本项目的研究，为评估新型有机污染物对环境的影响及污染控制与修复提供研究方法和理论依据。

本项目发展了描述环境效应的电子结构理论模型及描述开放型反应体系的动力学模型，采用量子化学计算或量子化学/分子力学组合方法，辅以适当的实验验证，明确了多溴联苯醚等典型新型有机污染物的化学降解及在生物酶作用下的降解机理，建立了新型有机污染物化学降解与生物酶降解预测模型，构建了有机污染物致癌性预测模型和急性毒性预测模型。本项目共发表论文90篇，SCI论文85篇(目标为40~50篇)，影响因子在5.0以上的SCI论文10篇，影响因子在3.0以上的SCI论文51篇(目标为20篇)。其中在《美国科学院院刊》(PNAS)上发表论文1篇，在环境领域顶级期刊Environ. Sci. Technol.上发表论文3篇，在“Nature Index”期刊Water Res.上发表文章1篇。发表在Enviorn. Sci. Technol.上的论文被美国化学会以图片形式新闻报道，发表在Catal. Sci. Technol.上的论文被编辑评价为“highest-quality work”，并作为亮点文章当选期刊正封面。研究成果获得计算机软件著作权两项。在本项目的资助培育下，项目负责人张庆竹教授获得了山东省泰山学者特聘专家人才称号。张庆竹教授获得了2016年度山东省高等科学技术奖一等奖一项(排名第一)，2018年度山东省高等科学技术奖三等奖一项(排名第一)。