Crystal structure and density functional theory studies of toxic quinone metabolites of polychlorinated biphenyls

Lower chlorinated polychlorinated biphenyls (PCBs) are readily metabolized via hydroxylated metabolites to reactive PCB quinones. Although these PCB metabolites elicit biochemical changes by mechanisms involving cellular target molecules, such as the aryl hydrocarbon receptor, and toxicity by interacting with enzymes like topoisomerases, only few PCB quinones have been synthesized and their conformational properties investigated. Similar to the parent compounds, knowledge of the three-dimensional structure of PCB quinones may therefore be important to assess their fate and risk. To address this gap in our knowledge, the gas phase molecular structure of a series of PCB quinones was predicted using HF/3-21G, B3LYP/6-31G?? and UB3LYP/6-311G?? calculations and compared to the respective solid state structure. All three methods overestimated the Cl-C bond length, but otherwise provided a reasonable approximation of the solid state bond angles and bond lengths. Overall, the UB3LYP/6-311G?? level of theory yielded the best approximation of the molecular structure of PCB quinones in the solid state. Chlorine addition at the ortho position of both rings was found to increase the dihedral angle of the resulting quinone compound, which may have important implications for their interaction with cellular targets and, thus, their toxicity.     

Design of control strategies for nutrient removal in a biological wastewater treatment process

Wastewater treatment plants (WWTP) are highly non-linear operations concerned with huge disturbances in flow rate and concentration of pollutants with uncertainties in the composition of influent wastewater. In this work, the activated sludge process model with seven reactor configuration in the ASM3bioP framework is used to achieve simultaneous removal of nitrogen and phosphorus. A total of 8 control approaches are designed and implemented in the advanced simulation framework for assessment of the performance. The performance of the WWTP (effluent quality index and global plant performance) and the operational costs are also evaluated to compare the control approaches. Additionally, this paper reports a comparison among proportional integral (PI) control, fuzzy logic control, and model-based predictive control (MPC) configurations framework. The simulation outcomes indicated that all three control approaches were able to enhance the performance of WWTP when compared with open loop operation.