蒽醌类化合物对大型蚤(Daphnia magna)的急性光致毒性研究

通过测定模拟光照和无光照条件下20种蒽醌类化合物对大型(Daphnia magna)的48h半数活动抑制浓度(EC50), 研究了该类化合物的光致毒性．比较了两种助溶剂(二甲基亚砜和丙酮)对这些化合物光致毒性的影响,初步讨论了光致毒性的机理．结果表明,所研究的助溶剂不影响这些化合物对大型潘的光致毒性．蒽醌类化合物因其取代基的不同(-NH2、-OH、-Cl、-Br、-NO2)、取代基位置的不同和取代基数目的不同,而表现出对大型潘光致毒性的不同．最低未占据分子轨道能(ELUMO)和最高占据分子轨道能(EHOMO)之间的能级差,可用于初步判断蒽醌类化合物 溞大型的潜在光致毒性．     

三维原子场全息作用矢量用于芳香类化合物的三维QSAR研究

采用新型的的三维原子场全息作用矢量(3D-HoVAIF)研究了200种芳香化合物的化学结构与其生物毒性的定量构效关系(QSAR).首先对芳香化合物进行了结构参数化表达,然后采用逐步回归(SMR)对变量进行筛选,建立了三维定量构效关系模型.其87个无氢键分子的模型和113个有氢键分子的模型的复相关系数和标准偏差分别为R2=0.801,SD=0.473和R2=0.929,SD=0.318.模型具有良好的稳定性和预测能力,证明了该三维原子场全息作用矢量在分子结构表征和生物毒性预测上的适用性.     

氟化酚对梨形四膜虫毒性的定量构效关系解析

应用Chem3D Ultra 7.0软件中的MOPAC半经验方法PM3,计算了16种氟化酚的19个量子化学和理化参数.采用PLS-VIP方法,筛选出影响氟化酚毒性的7个主要参数,即最低空轨道能量(ELUMO)、最高轨道能量与最低空轨道能量之差(△E)、分子总能量(ET)、最正H原子电荷(QH+)、羟基基团中氧原子的最负电荷(QO-)、connolly分子可及表面积(CAA)和connolly溶剂排斥体积(CSV),并据此建立模型对水生梨形四膜虫的急性毒性作定量构效关系研究.结果表明,氟化酚对梨形四膜虫的毒性作用表现为反应性毒性,ELUMO,QH+,ET对氟化酚的毒性作用有重要贡献,氟化酚对四膜虫急性毒性的大小与ELUMO、△E和ET呈负相关,而与QH+、QO-、CAA、CSV呈正相关,所得最优模型具有良好的预测效果(R2=0.961,F=344.8,P=2.92×10-11)和较高的稳定性(Q2cum=0.909).     

1-取代-2-氨基苯并咪唑化合物毒性和热力学性质的密度泛函理论研究

用密度泛函理论(DFT)B3LYP方法,在6-31G(d)基组水平上,对8个1-取代-2-氨基苯并咪唑化合物分子进行了全优化计算,得到其轨道能(ENHOMO、ENLUMO以及二者轨道能隙ΔE2)、原子电荷(Q)等量子化学参数,以及热能校正值Eth、恒容热容Cv、熵S等热力学性质,并计算了8种1-取代-2-氨基苯并咪唑化合物分子的电性拓扑状态指数Em。通过最佳变量子集回归建立这些化合物毒性的QSAR模型,以及热力学性质的QSPR模型。模型的相关系数R2和采用逐一剔除法得到的交叉验证相关系数R2cv均大于0.84和0.72,利用2个模型得到毒性的预测值与实验值的误差分别为0.11和0.20,3个热力学性质预测模型的误差分别为3.89%、4.03%和2.64%,吻合度较好,经检验证明所建模型具有良好的鲁棒性和预测能力。研究工作揭示了基团对毒性大小影响的变化规律、有利于对苯并咪唑类化合物在生态环境中的危害性进行评价,可为研发高效、低毒的苯并咪唑类新型药物提供理论依据。     

基于密度泛函理论揭示Cu~(2+)配位作用对头孢拉定水解反应的影响机制

基于密度泛函理论(DFT,Density functional theory),计算了水中Cu2+与抗生素头孢拉定的配位作用,发现Cu2+与头孢拉定可形成1∶1配合物,该配合物存在两种形态:Cu2+与头孢拉定分子支链氨基氮原子和羰基氧原子配位,同时结合一个水分子;Cu2+与羧基氧原子和内酰胺氧原子配位,同时结合两个水分子.结果表明,Cu2+的配位作用能增大头孢拉定水解反应位点正电荷量,降低水解前线分子轨道能级差和活化能,从而促进头孢拉定水解,该结果得到了实验证实.因此,DFT可用于预测Mn+配位作用对药物和个人护理用品(PPCPs,Pharmaceutical and personal care products)等有机污染物水解的影响,对于PPCPs类有机污染物的生态风险评价具有重要意义.     

采用实验和密度泛函理论计算揭示吸光性环境介质对多环芳烃光降解的影响机制

多环芳烃(PAHs)在环境中的光降解动力学受环境介质吸光组分的影响.为揭示介质吸光组分对PAHs光降解影响的内在机制,以吸光很弱的甲醇和吸光较强的丙酮和二甲基亚砜(DMSO)为模拟环境介质,考察不同吸光性溶剂介质对3种PAHs(菲、芘和苯并[a]芘)光解的影响;并采用密度泛函理论(DFT)计算,分析了溶剂分子光敏化能量/电子转移反应对PAHs光解的影响机制.结果表明,激发态的丙酮分子抑制了菲和芘的光解,而加快了苯并[a]芘的光解;激发态的DMSO分子抑制了菲的光解,促进了芘和苯并[a]芘的光解.过滤掉DMSO所吸收的部分光谱频段后,PAHs在DMSO中的光解速率与甲醇中的接近.DFT计算表明,激发态的丙酮或DMSO主要作为电子受体与PAHs发生光敏化电子转移反应,是影响PAHs光解的内在原因.     

腐殖酸与典型碳纳米材料协同光致产生活性氧物种的研究

采用电子自旋共振光谱(EPR)技术,分析腐殖酸在光照下对4种典型碳纳米材料诱导产生单线态氧(~1O_2)和羟基自由基(·OH)的影响。基于密度泛函理论计算4种典型碳纳米材料的前线轨道能,比较了它们分别经能量转移诱导产生~1O_2的能力以及经电子传递诱导产生·OH的能力。结果显示,4种不同形状的碳纳米材料(富勒烯、单壁碳纳米管、多壁碳纳米管以及石墨烯)悬浮液在紫外光照下均无~1O_2和·OH产生。与腐殖酸共同存在下,4种碳纳米材料均显著诱导~1O_2的产生,且富勒烯和石墨烯还能光致生成·OH。协同产生~1_O2的能力大小为:单壁碳纳米管富勒烯多壁碳纳米管石墨烯,协同产生·OH的能力大小为:石墨烯富勒烯。~1O_2的产生能力与碳纳米材料的能隙大小和颗粒聚集程度有关,而诱导产生·OH的能力主要取决于化学硬度。总之,我们的研究表明腐殖酸与碳纳米颗粒可协同产生活性氧物种。     

基于硫酸自由基氧化降解邻苯二甲酸二丁酯的密度泛函理论研究

用密度泛函理论(DFT)对邻苯二甲酸二丁酯(DBP)在零价铁活化过硫酸盐体系中的初始降解机理进行了研究.采用B3LYP杂化泛函对分子进行结构优化和振动分析,计算得到S_2O_8~(2-)的过氧键键能、键长分别为129.7 k J·mol~(-1)和1.476;活化产生SO_4~-·的亲电性是过硫酸盐的5—6倍,氧化还原电位也提高到+2.40 V.DBP的分子结构通过偶极矩和IR、UV-Vis光谱的特征峰得以确认;前线轨道、福井函数、双描述符的分析结果表明DBP中的C1—C11键易受SO_4~-·攻击;原子电荷、定量分子表面分析与C—H键解离能的计算结果说明抽H反应发生的次序为:C30C36C21C17C18C31,并利用Evans-Polanyi相关性预测抽H反应活化能的相对大小.基于以上结果,得到DBP与SO-4·初始反应的4条路径.     

多环芳烃光解活性的量子化学研究

应用量子化学从头算HF／6-311 G(d)和B3LYP／6-311 G(d)方法计算了16种PAHs的多种量子化学参数,选取六种参数为分子结构的描述符,采用最小二乘法对16种PAHs的光解半衰期进行逐步多元线性回归分析,得到两个PAHs光解半衰期的QSAR模型,模型具有较高的相关系数,可有效地用于预测PAHs的光解半衰期,结果表明,HF方法所得模型优于B3LYP方法所得的模型,所得模型与基于半经验PM3算法的QSAR模型相比较,HF从头算方法所建立的QSAR模型比半经验PM3算法的结果要好,在所考查的诸多参数中,分子最高占有轨道特征值EHOMO对PAHs光解半衰期起着决定作用,最后,运用所得模型预测了3种PAHs的光解半衰期。     

含氮有机污染物在超临界水氧化(SCWO)中去除的QSAR模型

超临界水氧化（SCWO）作为一项高效的去除水体中有机污染物的技术已得到了广泛的应用.为了更好地理解含氮有机物污染物在SCWO中总氮（TN）去除的规律,本研究以定量构效关系（QSAR）模型为方法,构建了41种含氮有机污染物在SCWO中TN%与有机污染物分子量子化学参数之间的QSAR模型.其最优QSAR模型结果为TN%=84.20-374.34f（-）_n-99.74E_gap+1.80μ+180.498f（+）_n,模型的验证结果表明,所建的最优QSAR模型对于预测TN%展现了良好的稳定性和预测能力.模型中量子化学参数分析结果表明,亲核及亲电攻击福井指数、偶极矩以及分子的前线轨道能量差是影响含氮有机污染物分子在SCWO中TN去除的内在量子因素,该模型的建立可为含氮有机污染物在SCWO中TN的去除效果和规律研究提供初始评估.     

Ecotoxicity of polycyclic aromatic hydrocarbons, aromatic amines, and nitroarenes through molecular properties

Air, marine, and terrestrial pollution are continuously critical issues to be solved in environmental sciences. Particularly with the recent disaster in the Mexico Gulf and the risk of oil spills from the continuous offshore drilling activities in the North Sea, ecotoxicological profiling requires great attention. Fjord ecosystems are particularly neglected marine ecosystems, which require better surveillance and ecotoxicological profiling. In this context, this study focuses on exploring three potential indicators for aquatic stress [polycyclic aromatic hydrocarbons (PAHs), aromatic amines (AAs), and nitroarenes (NAs)] by the study of their molecular and sub-molecular properties. The results show that the aromatic amine, 4-aminobiphenyl, gains a particularly reactive electronic potential, which can be summarized as a large change in LUMO+2 and HOMO?1 electron orbitals upon metabolic activation in the organism. This change in orbitals increases the overall electrostatic energy of the molecule, inducing a high affinity for DNA-adduct formation. Electronic analysis on nitroarenes shows in addition why 1,6-dinitropyrene is more stable than 1,8-dinitropyrene, and how the electrons favor nitrenium activation on the 6th and 8th carbon. Further analysis shows also that PAHs have a present correlation with hormonal similarity, and that their resemblance to estrogen can be correlated to mutagenicity, contributing to increased ecotoxicity. The electronic analysis of these three types of fossil pollutants shows how their toxicity is exerted from the electronic level and which structural features that determine the level of reactivity and toxicity. The summation of the background and electronic properties of these molecular toxins elucidates that PAHs, aromatic amines, and nitroarenes are all of equal importance as stress indicators for fjord systems, with particular emphasis on PAHs, which also exert hormonal structural similarities as a probable base of their carcinogenic mechanisms.     

UVR-induced toxicity of sludge and polycyclic aromatic hydrocarbons on seed germination and seedling growth of Triticum aestivum L.

The depletion of the ozone layer and enhancement of solar radiation may exert an adverse influence on the ecosystem. Phototoxicity of sludge and polycyclic aromatic hydrocarbons (PAHs) under ultraviolet radiation (UVR) to seedling was studied. Seeds of wheat (Triticum aestivum) were planted in sludge and PAHs (anthracene (An), benzo(a)pyrene (BaP) and pyrene (Py)) with and without UVR. Toxicity of sludge increased in the presence of UVR in wheat. UVB radiation was found to be more hazardous than UVA radiation. Results demonstrated that An, BaP and Py induced phototoxicity at various concentrations (1–10?µg/mL) under UVA (1.5?mW/cm²) or UVB (1.08?J/cm²) exposure. The pattern of phototoxicity was An?>?Py?>?BaP to shoot length, root length, and fresh weight; chlorophyll, protein content, enzyme activity of catalase and α-amylase were reduced while the activity of superoxide dismutase and starch was enhanced. Reduction in seedling growth and biochemical parameters may be related to less photosynthesis, less nutritional uptake, and distortion of root cap. Thus, the synergistic effect may be due to alterations in photosynthesis, phytohormones, or nutritional uptake.     

汾河流域水系和表层沉积物中多环芳烃的空间变化规律及其生态风险研究

本研究在汾河流域上、中、下游及其部分支流布设29个采样点,对其水体和表层沉积物多环芳烃(PAHs)的空间分布规律及生态风险进行了分析和讨论。结果表明,汾河流域水相中丰水期PAHs总量浓度范围是0.530~16.002μg·L~(-1),平均浓度为(2.738±3.078)μg·L~(-1),枯水期PAHs总量浓度范围是0.588~12.916μg·L~(-1),均值为(2.762±3.132)μg·L~(-1)。就空间分布而言,汾河流域整体呈现上游污染较轻,中下游污染严重的特点。PAHs的组成规律显示,丰水期和枯水期PAHs含量均以低环(2~3环)为主,不同采样期低环PAHs所占比例分别为96.5%和90.4%。与其他15个研究地区水体PAHs含量比较,汾河流域水体中PAHs污染程度的国内外对比处于中等到较高程度的污染。丰水期和枯水期水体中PAHs来源于石油源和植物、木材、煤的燃烧,主要受到流域煤化工、燃煤电厂排放污染物的影响。地表水健康风险评价结果显示,汾河流域丰水期和枯水期分别有13.8%和20.7%的点位存在一定的健康风险。汾河流域沉积相中16种PAHs平均浓度为(3.774±1.987)μg·g-1,其污染主要集中在流域中下游地区。PAHs的组成规律显示,PAHs含量集中在低环(2~3环),约占总量的75%左右。与本研究提到的河流、湖泊及港口沉积物中PAHs含量比较,汾河流域沉积物中PAHs污染程度仍处于中等偏高的污染水平。丰水期沉积相中PAHs以燃烧源和石油源为主,部分来自典型石油类产品的输入。表层沉积物生态风险评价结果显示,对于提出的12种PAHs的生态风险的效应区间低值(ERL值)或效应区间中值(ERM值)以及苯并(b)荧蒽(Bb F)和苯并(k)荧蒽(Bk F)这2类没有最低安全值的PAHs化合物来说,汾河上、中、下游流域均有采样点的PAHs可能存在着对生物的潜在生态风险。通过本研究可全面地了解该流域多环芳烃的空间分布规律及其可能的来源,并且为汾河流域多环芳烃污染的控制和生态风险评价提供科学依据。     

Comparative quantitative structure–activity relationship (QSAR) study on acute toxicity of triazole fungicides to zebrafish

We employed two-dimensional quantitative structure–activity relationship (2D-QSAR) and hologram QSAR (HQSAR) methods to quantitatively investigate the mechanism and active site of toxicity for Danio rerio exposed to triazole fungicides. Our results showed that 2D-QSAR models constructed using the energy of the lowest unoccupied molecular orbit, the net C atom charges, the octanol–water partition coefficient and the molecular shape factor had higher predictive abilities. HQSAR models containing the fragment distinctions atoms (As), bonds (Bs), chirality (Ch) and donors and acceptors (D&A) had higher reliability. It was found that 2D-QSAR results explaining the toxicity mechanism were consistent with HQSAR. In summary, the hydrophobicity and shape/size of the molecule were the important factors influencing the toxic effect of these chemicals against D. rerio. In addition, electron exchange may occur between these fungicides and the target. The study provided a method to evaluate the environmental risk of chemicals with a similar structure, based on the QSAR models obtained.     

Molecular modeling in environmental science∗

Quantum mechanic computer models are often used in chemistry to predict properties of molecules and to simulate reaction pathways. Such models calculate bond lengths, bond angles, dihedral angles, the energy of the molecular‐orbitals (MO's), the dipole moment, the ionisation potential, and the heat of formation. These results lead to detailed information on electronic structures like bond orders, electronic charges and levels of frontier orbitals (HOMO, LUMO).

It is possible to calculate properties of ground state molecules as well as ionic and radicalic structures, or reaction intermediates and other compounds with very short lifetimes.

From the exact knowledge of electronic structure, frontier orbitals, and reaction intermediates it is possible to predict stability of chemicals in the environment but also of fictive chemicals, which are not yet synthesized. Some authors have shown that there are correlations between electronic structure and toxicity.

The most interesting models for environmental chemistry are semiempirical models, such as MINDO, MNDO or MOPAC. Theses programs are able to handle molecules with 30 and more heavy atoms (all elements without hydrogen), and it is possible to install them on main frame computers (CPU‐time several minutes to hours) and on personal computers, with coprocessors (CPU‐time several hours to a few days).

Normally the molecule is read in from a Z‐matrix (a matrix of polar coordinates of atoms connected in the molecule) and with symmetry data. Furthermore, programs are available which create a Z‐matrix from the molecular structure plotted on the screen with a mouse.     

含氯苯酚类化合物结构表征与毒性预测

将有机化合物中的不同非氢原子及非氢原子之间的关系参数化得到新的结构描述符,运用该描述符对部分含氯苯酚类化合物分子结构进行了参数化表征。采用偏最小二乘回归(PLS)方法构建了化合物结构与毒性(-lg IC50)之间的关系模型,模型的建模相关系数(R2)为0.948,"留一法"交互检验的相关系数(Q2)为0.922,标准偏差(SD)为0.184。结果表明结构描述符能较好地表征化合物分子结构特征,所建模型稳定性好、预测能力强,对于酚类化合物QSAR研究具有一定的参考价值。     

2种毒性评估方法对PAHs污染场地人体健康风险的比较研究

毒性评估是人体健康风险评价的重要部分,目前主要存在2种方法,一种基于PAHs相对于苯并[a]芘(BaP)的毒性当量因子,采用Ba P致癌斜率因子参数(方法 1),另一种直接采用各PAHs致癌斜率因子和非致癌参考剂量等参数(方法 2)。然而2种毒性评估方法得到的风险及修复量是否存在差异以及引起差异的原因等问题鲜有讨论。针对苏南某焦化厂PAHs污染土壤,采用分层土壤健康风险评价模型,对比了2种毒性评估方法确定的PAHs风险、修复目标污染物及土方量的差异,并对引起差异的关键因素进行探讨。结果表明:对于0.0~1.0 m表层土壤,方法 1和方法 2确定的致癌风险最大值分别1.48E-05和1.32E-05,均超过可接受致癌风险,修复土方量分别为27 846 m~3和28 667 m3,修复目标污染物均为Ba P和二苊烃(Acy)。对于1.0~3.0 m深层土壤,方法 1确定的致癌风险最大值为3.36E-08,低于可接受致癌风险,不需要修复;而方法 2确定的致癌风险最大值为3.73E-04,非致癌危害指数最大值为6.96E+01,分别超过可接受致癌风险和非致癌危害商,需要修复,修复目标污染物为萘(NaP),修复土方量为35 944 m~3。最终,方法 2确定的总修复土方量(64 611 m~3)为方法 1确定土方量(27 846 m~3)的2.45倍,而这种差异主要是由于方法 1低估了深层土壤中高挥发性PAH单体尤其是NaP的风险所致。因此,从保守角度建议采用方法 2进行PAHs风险评价。     

应用物种敏感性分布法对太湖沉积物中多环芳烃的生态风险分析

多环芳烃(PAHs)具有高的疏水性,在水体中优先分布于沉积物.采用物种敏感性分布法(SSDs法),依据水生生物慢性毒性数据计算5%物种危害浓度(HC5);并结合欧盟委员会风险评价技术导则(TGD)进而得到沉积物预测无效应浓度(PNEC-sed),以报道的太湖的沉积物中浓度数据作为预测环境浓度(PECsed);用商值法P...