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。     

蒽醌化合物的光解动力学及定量结构-性质关系

以高压汞灯为光源, 测定了15 种蒽醌化合物(ATQs)的光解速率常数(k), 讨论了取代基位置、数目及种类对ATQs 光解速率的影响.另外,选取9 种氨基蒽醌, 应用偏最小二乘(PLS)算法, 建立了关于k的定量结构-性质关系(QSPR)模型. 根据该模型, 决定k值大小的主要因素包括:分子生成热、H 原子所带最大正电荷、C 原子所带最大负电荷,以及分子最低未占据轨道与最高占据轨道能量差.     

多氯代苯并噻吩分子空间坐标指数与气相色谱保留时间的QSPR研究

运用Chem Office软件绘制37个多氯代苯并噻吩三维图,并得到对应的分子空间坐标Pi(xi,yi,zi)。以多氯代苯并噻吩分子的原子距离指数、分子空间特征指数、分子电性距离矢量、氯原子数为分子描述变量,采用多元线性回归和BP人工神经网络建立描述变量与多氯代苯并噻吩的气相色谱保留时间的QSPR模型。结果表明:多元线性回归建模相关系数R=0.9970,SD=2.1830,基于BP人工神经网络建立的模型R=0.9996,SD=0.3123。为多氯代苯并噻吩分子结构与物性的QSPR研究提供了新思路。     

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(-lgIC₅₀)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。     

Effects of changing climate on water and nitrogen availability with implications on the productivity of Norway spruce stands in Southern Finland

An integrated process-based model was used to study how the changing climate affects the availability of water and nitrogen, and consequently the dynamics of productivity of Norway spruce (Picea abies) on sites with different initial soil water conditions in southern Finland over a 100-year period. The sensitivity of the total stem volume growth in relation to short-term availability of water and nitrogen was also analyzed. We found that a high proportion (about 88–92%) of the total precipitation was lost in total evapotranspiration (incl. canopy evaporation (E_c), transpiration (E_t) and ground surface evaporation (E_g)), under both current and changing climate. Furthermore, under the changing climate the cumulative amount of E_c and E_g were significantly higher, while E_t was largely lower than under the current climate. Additionally, the elevated temperature and increased expansion of needle area index (L) enhanced E_c. Under the changing climate, the increasing soil water deficit (W_d) reduced the canopy stomatal conductance (g_cs), the E_t, humus yield (H, available nitrogen source) and nitrogen uptake (N_up) of the trees. During the latter phases of the simulation period, the canopy net photosynthesis (P_nc) was lower due to the reduced N_up and soil water availability. This also reduced the total stem volume production (V_s) on the site with the lower initial soil moisture content. The growth was slightly more sensitive to the change in precipitation than to the change in nitrogen content of the needles, when the elevated temperature was assumed. According to our findings, drought stress episodes may become more frequent under the changing climate. Thus, adaptive management strategies should be developed to sustain the productivity of Norway spruce in these conditions, and thus, to mitigate the adverse impacts of climate change.     

A peaked function for modeling temperature dependence of plant productivity

We suggests that temperature response of plant productivity can be modeled by the Arrhenius function modified to describe the effect of temperature on enzyme activity: G_A(T) = 2f(T)/(1 + f²(T)), where f(T) = exp(E_a/RT_opt − E_a/RT), R the universal gas constant, E_a the activation energy and T_opt is the optimal temperature. In common with other functions used for modeling the temperature response of plant productivity, the curve of function G is almost symmetrical and bell-shaped. The special convenience of G_A is that it relates the width of the “bell” to thermodynamic concepts, such as activation energy of chemical reactions converting carbon dioxide and water to carbohydrates.     

有机化学品生物富集因子定量结构-活性关系模型

依据经济合作与发展组织(OECD)关于定量结构-活性关系(QSAR)模型构建和使用导则,将780个有机化合物,以4:1的比例随机划分为训练集(624个化合物)和验证集(156个化合物),通过多元线性回归(MLR)方法构建了一个包含12个描述符的有机化合物鱼类生物富集因子(BCF)的QSAR模型。QSAR模型的调整决定系数R2ad j=0.809,去一法交叉验证系数Q2LOO=0.803,外部验证系数Q2EXT=0.732,表明模型具有较好的拟合优度、稳健性和预测能力。采用欧几里德距离方法表征模型应用域,通过威廉姆斯图分析模型离群点,并对模型进行机理解释。所构建的模型,可以用于预测应用域内有机化学品的生物富集因子。     

Removal of congo red and basic violet 1 by chir pine (Pinus roxburghii) sawdust,a saw mill waste: batch and column studies

The efficiency of chir pine sawdust (CPS) for adsorptive removal of the dyes, congo red (CR) and basic violet 1 (BV), from aqueous solution was evaluated using batch and column studies. The equilibrium was attained in 60 min for CR and 45 min for BV. The adsorption of BV obeyed the Langmuir isotherm model while the Freundlich isotherm fitted the equilibrium data of CR adsorption. The Langmuir monolayer adsorption capacities (Q_o) of CPS for BV and CR were 11.3 and 5.8 g kg^?1, respectively. The kinetic data for CR were best fitted to the Lagergren pseudo-first-order model and for BV to the pseudo-second-order model. The intra-particle diffusion was found to be the rate-controlling step for CR adsorption, while the adsorption kinetics of BV were controlled by both intra-particle and liquid-film diffusion. The thermodynamic parameters indicated that the adsorption process was spontaneous and endothermic in nature. The adsorption activation energy (E_a) for CR (124 kJ mol^?1) implied chemical adsorption while that for BV (5.4 kJ mol^?1) indicated physical adsorption. An increase in the Thomas model constant (K_Th) with increasing flow indicated that for both dyes the mass transport resistance decreased during adsorption. Thus, CPS may be an efficient low-cost adsorbent for decolorization of dye-containing wastewaters.     

Climate, canopy conductance and leaf area development controls on evapotranspiration in a boreal coniferous forest over a 10-year period: A united model assessment

The aim of this work was to test a process-based model (hydrological model combined with forest growth model) on the simulation of seasonal variability of evapotranspiration (ET) in an even-aged boreal Scots pine (Pinus sylvestris L.) stand over a 10 year period (1999-2008). The water flux components (including canopy transpiration (E_t) and evaporation from canopy (E_c) and ground surface (E_g) were estimated in order to output the long-term stand water budget considering the interaction between climate variations and stand development. For validation, half-hourly data on eddy water vapor fluxes were measured during the 10 growing seasons (May-September). The model predicted well the seasonal course of ET compared to the measured values, but slightly underestimated the water fluxes both in non-drought and drought (2000, 2003 and 2006) years. The prediction accuracy was, on average, higher in drought years. The simulated ET over the 10 years explained, on average, 58% of the daily variations and 84% of the monthly amount of ET. Water amount from E_t contributed most to the ET, with the fractions of E_t, E_c and E_g being, on average, 67, 11 and 23% over the 10-year period, respectively. Regardless of weather conditions, the daily ET was strongly dependent on air temperature (T_a) and vapor pressure deficit (D_a), but less dependent on soil moisture (W_s). On cloudy and rainy days, there was a non-linear relationship between the ET and solar radiation (R_o). During drought years, the model predicted lower daily canopy stomatal conductance (g_cs) compared with non-drought years, leading to a lower level of E_t. The modeled daily g_cs responded well to D_a and W_s. In the model simulation, the annual LAI increased by 35% between 1999 and 2008. The ratio of E_c: ET correlated strongly with LAI. Furthermore, LAI reduced the proportion of E_g as a result of the increased share of E_c and E_t and radiation interception. Although the increase of LAI affected positively E_t, the contribution of E_t in ET was not significantly correlated with LAI. To conclude, although the model predicted reasonably well the seasonal course of ET, the calculation time steps of different processes in the model should be homogenized in the future to increase the prediction accuracy.     

基于形态修正的描述符构建可电离化合物对大型溞急性毒性的QSAR模型

在环境水体中,可电离有机化合物(IOCs)可解离为分子和离子形态。研究表明,IOCs离子形态的环境行为、毒性效应等都与其分子形态存在较大差异,因而在研究IOCs环境行为、毒性效应时不应忽略离子化的影响。在构建IOCs相关预测模型时如何表征离子化的影响是当前研究的重要内容之一。探讨了采用基于形态修正的描述符构建IOCs水生毒性预测模型的可行性。具体而言,采用逐步多元线性回归(MLR)方法,构建了可预测63种取代酚、取代苯甲酸和取代苯胺等IOCs对大型溞急性毒性的定量结构-活性关系(QSAR)模型。与仅采用分子形态描述符的模型相比,使用基于形态修正描述符的模型决定系数(R2)、去一法交叉验证系数(Q2LOO)、外部验证系数(Q2EXT)等参数从0.622～0.705提高到了0.840～0.875,表明基于形态修正描述符的模型具有更好的拟合优度、稳健性和预测能力。因此,在将来的研究中,可采用基于形态修正的描述符构建IOCs水生毒性效应预测模型。     

15种取代酚对淡水发光菌Q67的毒性及定量构效分析

为了更加准确和便捷地预测各种取代酚类化合物的急性毒性,以淡水发光菌Q67(Vibrio qinghaiensis sp.-Q67)为受试生物,测定了15种典型取代酚的急性毒性;采用logD(正辛醇/水分配系数),LUMO(分子最低空轨道能)和MW(分子量)等取代酚的7种主要结构参数,利用偏最小二乘回归法建立了定量结构-活性相关(quantitative structure-activity relationships,QSAR)模型。结果表明,15种取代酚的EC_(50)在5.76×10~(-6)～1.27×10~(-3)mol·L~(-1)之间,且有很好的剂量-效应关系;QSAR模型的主成分分析显示,-logEC_(50)与logD、LUMO和MW值正相关,且logD对模型的贡献最大,即越容易与Q67菌结合的酚类化合物对其的急性毒性越大;建立的QSAR模型具有较好的预测能力(Q~2_(EXT)=0.91,RMSE=0.49)和较高的稳定性(Q~2_(CUM)=0.58),能够用于预测其他酚类化合物对Q67菌的急性毒性。     

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。     

基于TLSER和QSPR关系预测PAHs和PCBs的LDPE膜-空气分配系数

有机污染物在被动采样材料与环境介质之间的平衡分配系数(K_P),是测定环境中有机污染物浓度的重要参数,但K_P值大部分都需要经过繁琐的实验测定获取,无法逐个测定数量繁多的污染物,因此需开发一种预测K_P值的方法。为此,搜集整理了一些多环芳香烃(PAHs)和多氯联苯(PCBs)的低密度聚乙烯(LDPE)-空气分配系数(K_PA)的实测值,基于理论线性溶解能(TLSER)和定量结构性质关系(QSPR),利用逐步多元线性回归(MLR)分别构建了预测K_PA值的模型。模型的决定系数R2adj分别为0.927和0.956,交叉验证系数Q2LOO分别为0.915和0.946,外部系数Q2ext分别为0.913和0.960。结果表明,2种模型具有良好的拟合优度、稳健性和预测能力,并解释了模型的机理。所构建的2种模型均可用来预测应用域内有机污染物的LDPE膜-空气分配系数。     

A photolysis coefficient for characterizing the response of aqueous constituents to photolysis

UV photolysis and UV based advanced oxidation processes (AOPs) are gaining more and more attention for drinking water treatment. Quantum yield (ø) and molar absorption coefficient (ε) are the two critical parameters measuring the effectiveness of photolysis of a compound. The product of the two was proposed as a fundamental measure of a constituent’s amenability to transformation by photolysis. It was shown that this product, named the photolysis coefficient, k _p , can be determined using standard bench tests and captures the properties that govern a constituent’s transformation when exposed to light. The development showed the photolysis coefficient to be equally useful for microbiological, inorganic and organic constituents. Values of k _p calculated by the authors based on quantum yield and molar absorption coefficient data from the literature were summarized. Photolysis coefficients among microorganisms ranged from 8500 to more than 600000 and are far higher than for inorganic and organic compounds, which varied over a range of approximately 10 to 1000 and are much less sensitive to UV photolysis than the microorganisms.     

卤代有机化合物生物富集因子的定量结构-活性关系模型

依据经济合作与发展组织(OECD)关于定量结构-活性关系(QSAR)模型构建和使用导则,通过多元线性回归(MLR)方法建立了一个包含9个描述符的卤代有机化合物鱼类生物富集因子(BCF)的QSAR模型。QSAR模型的调整决定系数R²_adj = 0.877,去一法交叉验证系数Q²_LOO= 0.873,外部验证系数Q²_EXT= 0.757,表明模型具有较好的拟合优度、稳健性和预测能力。采用欧几里德距离方法表征了模型应用域,并对模型进行了机理解释。所构建的模型,可以用于预测应用域内卤代化合物的BCF。     

Phototransformation of oxamyl in aqueous solution

The photolysis of the N methyl carbamate pesticide oxamyl (Z isomer) has been studied in aqueous solution. Continuous irradiation at mainly λ = 254 and λ > 290 nm has been performed to characterise the pesticide photochemical behaviour in water at pH = 6.0. Upon monochromatic irradiation, the phototransformation quantum yield was evaluated to be roughly constant, with a value of 0.54 ± 0.08. Upon polychromatic irradiation, a photochemical efficiency has been estimated to be 0.5 ± 0.1 by using phenol as a reference compound. Two main degradation products were identified: the isomer (E) of oxamyl and the nitrile derivative (N,N-dimethyl-2-nitrilo-acetamide). The photolysis of the oximino derivative, an hydrolysis product of oxamyl, was also studied. Upon irradiation at 254 nm, the quantum yield of phototransformation was found to be 0.28. A unique photoproduct was detected: it corresponds to the (E) isomer of the oximino derivative. For prolonged irradiations, a photostationary state was reached between the oximino and its (E) isomer. From kinetics data, the removal of oxamyl and of the oximino derivative during a UV disinfection step used in drinking water production was calculated to be 45 and 13%, respectively.     

有机化学品不同温度下(过冷)液体蒸气压预测模型的建立与评价

(过冷)液体蒸气压(PL)是评价化学品在环境中分配、迁移和归趋行为的重要参数。PL具有较强的温度依附性。发展一种能够精确预测不同环境温度下化学品PL的方法,有助于填补化学品生态风险评估的大量数据缺失。本研究收集整理了661种有机化合物在不同温度下(200~830 K)共计10 478个log PL值。在此基础上,采用偏最小二乘(PLS)回归和支持向量机(SVM)方法,构建了PL的线性和非线性预测模型。结果表明:2种模型均具有良好的拟合度、稳健性及预测能力,SVM模型的预测性能略高于PLS模型(PLS:R2adj.tra=0.912,RMSEtra=0.477,Q2ext=0.910;SVM:R2adj.tra=0.997,RMSEtra=0.092,Q2ext=0.967)。机理分析表明,温度是影响PL的主要因素,温度越高,蒸气压越大;其次,X1sol也影响PL大小,X1sol用来描述分子间的色散作用,分子间色散力越小,蒸气压越大;此外,化合物的氢键个数、极性和分子构型等因素也影响PL大小。采用Wiliams plot方法表征了PLS模型应用域。所建立的模型可用来预测烷烃、烯烃、醇、酮、羧酸、苯、酚、联苯、卤代芳香烃、含N化合物及含S化合物在不同温度下的PL数据。     

Complexation of iron by salicylic acid and its effect on atrazine photodegradation in aqueous solution

The photodegradation of atrazine and the photochemical formation of Fe(II) and H₂O₂ in aqueous solutions containing salicylic acid and Fe(III) were studied under simulated sunlight irradiation. Atrazine photolysis followed first-order reaction kinetics, and the rate constant (k) corresponding to the solution of Fe(III)-salicylic acid complex (Fe(III)-SA) was only 0.0153 h^?1, roughly one eighth of the k observed in the Fe(III) alone solution (0.115 h^?1). Compared with Fe(III) solution, the presence of salicylic acid significantly enhanced the formation of Fe(II) but greatly decreased H₂O₂ generation, and their subsequent product, hydroxyl radical (˙OH), was much less, accounting for the low rate of atrazine photodegradation in Fe(III)-SA solution. The interaction of Fe(III) with salicylic acid was analyzed using Fourier-transform infrared (FTIR) spectroscopy and UV-visible absorption, indicating that Fe(III)-salicylic acid complex could be formed by ligand exchange between the hydrogen ions in salicylic acid and Fe(III) ions.