We report a comprehensive theoretical study on the decarbonylation of acetaldehyde by Fe+ and Cr+. Various intermediates, transition states, and products involved in the decarbonylation reactions are fully optimized at the B3LYP/6-311+G(2df,2pd) level of theory. The potential energy surfaces (PESs) corresponding to [M,O,C2,H4]+(M=Cr and Fe) are examined in detail using B3LYP and CCSD(T) methods, respectively. The validity of these theoretical methods is calibrated with respect to the available thermochemical data. Calculations suggest that the Cr+ mediated decarbonylation of acetaldehyde takes place in four steps on the sextet surface: encounter complexation, C-C activation, aldehyde H-shift, and nonreactive dissociation, in good accordance with the Co+ mediated decarbonylation of acetaldehyde [Zhao, Zhang, Guo, Wu, Lu, Chem. Phys. Lett. 2005, 414, 28], while for the Fe+/acetaldehyde system decarbonylation can occur on both the quartet and the sextet PESs. The quartet pathway, which experiences spin-orbit coupling between the two surfaces, is energetically more favorable; whereas along the sextet decarbonylation coordinate several high-energy barriers are revealed. The theoretical results are compared with the experimental product kinetic energy and angular distributions of decarbonylation of acetaldehyde by Fe+ and Cr+ measured using a crossed-beam technique [Sonnenfroh, Farrar, J. Am. Chem. Soc. 1986, 108, 3521].
Conventional volumetric modulated arc therapy (C-VMAT) for breast cancer after radical mastectomy had its limitation that resulted in larger volumes of normal tissue receiving low doses. We explored whether there was a way to deal with this disadvantage and determined the potential benefit of flattening filter-free (FFF) beams.Twenty patients with breast cancer after radical mastectomy were subjected to 3D conformal radiotherapy (3DCRT) and VMAT treatment planning. For VMAT plans, 3 different designs were employed with RapidArc form: conventional-VMAT plan (C-VMAT), modified-VMAT plan (M-VMAT), and modified-VMAT plan using FFF beams (M-VMAT-F). Plan quality and efficiency were assessed for all plans.For each technique in homogeneity, there were no statistically significant differences. VMAT plans showed superiority compared with 3DCRT in conformity. C-VMAT plans were obviously not only superior to 3DCRT in the medium to high-dose regions (about 15–50 Gy) but also resulted in larger volumes in low-dose regions (about 0–10 Gy). M-VMAT plans were similar to M-VMAT-F. Both of them might significantly reduce the regions of low dose compared with C-VMAT (V5lung: ∼ 11.5%; V5heart: ∼ 23.8%, P < 0.05), even less than 3DCRT in heart irradiation (V2.5heart, 9.4%, P < 0.05). For liver, contralateral breast, and lung irradiation, M-VMAT-F plans were slightly superior to M-VMAT with a reduction of ∼0.08, 0.2, and 0.24 Gy in the respective mean doses (P < 0.05).C-VMAT plans showed superiority compared with 3DCRT, while also resulted in larger volumes of normal tissue receiving low doses. M-VMAT and M-VMAT-F plans might not only reduce the region in the medium to high doses but also have lower volumes in low-dose regions. M-VMAT-F plans were slightly superior compared with M-VMAT due to further contralateral organs sparing.
Land use pattern is an effective reflection of anthropic activities, which are primarily responsible for water quality deterioration. A detailed understanding of relationship between water quality and land use is critical for effective land use management to improve water quality. Linear mixed effects and multiple regression models were applied to water quality data collected from 2003 to 2010 from 36 stations in the Huai River basin together with topography and climate data, to characterize the land use impacts on water quality and their spatial scale and seasonal dependence. The results indicated that the influence of land use categories on specific water quality parameter was multiple and varied with spatial scales and seasons. Land use exhibited strongest association with dissolved oxygen (DO) and ammonia nitrogen (NH-N) concentrations at entire watershed scale and with total phosphorus (TP) and fluoride concentrations at finer scales. However, the spatial scale, at which land use exerted strongest influence on instream chemical oxygen demand (COD) and biochemical oxygen demand (BOD) levels, varied with seasons. In addition, land use composition was responsible for the seasonal pattern observed in contaminant concentrations. COD, NH-N, and fluoride generally peaked during dry seasons in highly urbanized regions and during rainy seasons in less urbanized regions. High proportion of agricultural and rural areas was associated with high nutrient contamination risk during spring. The results highlight the spatial scale and seasonal dependence of land use impacts on water quality and can provide scientific basis for scale-specific land management and seasonal contamination control.
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