Theoretical study on the mechanism of water oxidation catalyzed by a mononuclear copper complex: important roles of a redox non-innocent ligand and HPO4 2- anion.

The water oxidation reaction is the bottleneck problem of the artificial photosynthetic system. In this work, the mechanism of water oxidation catalyzed by a mononuclear copper complex in alkaline conditions was studied by density functional calculations. Firstly, a water molecule coordinating with the copper center of the complex (Cuii, 1) generates Cuii-H2O (2). 2 undergoes two proton-coupled electron transfer processes to produce intermediate (4). The oxidation process occurs mainly on the ligand moiety, and 4 (˙L-Cuii-O˙) can be described as a Cuii center interacting with a ligand radical antiferromagnetically and an oxyl radical ferromagnetically. 4 is the active species that can trigger O-O bond formation via the water nucleophilic attack mechanism. This process occurs in a step-wise manner. The attacking water transfers one of the protons to the HPO4 2- coupled with an electron transfer to the ligand radical, which generates a transient OH˙ interacting with the oxyl radical and H2PO4 -. Then the O-O bond is formed through the direct coupling of the oxo radical and the OH radical. The triplet di-oxygen could be released after two oxidation processes. According to the Gibbs free energy diagram, the O-O bond formation was suggested to be the rate-limiting step with a calculated total barrier of 19.5 kcal mol-1. More importantly, the copper complex catalyzing water oxidation with the help of a redox non-innocent ligand and HPO4 2- was emphasized.

Genome-Wide Characterization and Expression Analysis of the HD-ZIP Gene Family in Response to Salt Stress in Pepper.

HD-ZIP is a unique type of transcription factor in plants, which are closely linked to the regulation of plant growth and development, the response to abiotic stress, and disease resistance. However, there is little known about the HD-ZIP gene family of pepper. In this study, 40 HD-ZIP family members were analyzed in the pepper genome. The analysis indicated that the introns number of Ca-HD-ZIP varied from 1 to 17; the number of amino acids was between 119 and 841; the theoretical isoelectric point was between 4.54 and 9.85; the molecular weight was between 14.04 and 92.56; most of them were unstable proteins. The phylogenetic tree divided CaHD-ZIP into 4 subfamilies; 40 CaHD-ZIP genes were located on different chromosomes, and all of them contained the motif 1; two pairs of CaHD-ZIP parallel genes of six paralogism genes were fragment duplications which occurred in 58.28~88.24 million years ago. There were multiple pressure-related action elements upstream of the start codon of the HD-Z-IP family. Protein interaction network proved to be coexpression phenomenon between ATML1 (CaH-DZ22, CaHDZ32) and At4g048909 (CaHDZ12, CaHDZ31), and three regions of them were highly homology. The expression level of CaHD-ZIP gene was different with tissues and developmental stages, which suggested that CaHD-ZIP may be involved in biological functions during pepper progress. In addition, Pepper HD-ZIP I and II genes played a major role in salt stress. CaHDZ03, CaHDZ 10, CaHDZ17, CaHDZ25, CaHDZ34, and CaHDZ35 were significantly induced in response to salt stress. Notably, the expression of CaHDZ07, CaHDZ17, CaHDZ26, and CaHDZ30, homologs of Arabidopsis AtHB12 and AtHB7 genes, was significantly upregulated by salt stresses. CaHDZ03 possesses two closely linked ABA action elements, and its expression level increased significantly at 4 h under salt stress. qRT-P-CR and transcription analysis showed that the expression of CaHDZ03 and CaHDZ10 was upregulated under short-term salt stress, but CaHDZ10 was downregulated with long-term salt stress, which provided a theoretical basis for research the function of Ca-HDZIP in response to abiotic stress.

Microscopic insight into precipitation and adsorption of As(V) species by Fe-based materials in aqueous phase.

The mechanism of As(V) removal from the drinking water and industrial effluents by iron materials remains unclear at the molecular level. In this work, the association of Fe-based materials with As(V) species was explored using density functional theory and ab initio calculations. Solvent separated ion pair structures of [FeH2AsO4]2+aq species may be dominant in an acidic solution of FeAs complex. The association trend of H2AsO4- species by Fe3+aq is found to be quite weak in the aqueous solution, which may be attributed to the strong hydration of Fe3+aq and [FeH2AsO4]2+ species. However, the association of H2AsO4- species by colloidal clusters is quite strong, due to the weakened hydration of Fe(III) in colloidal structures. The hydrophobicity of Fe-based materials may be one of the key factors for their As(V) removal efficiency in an aqueous phase. When the number of OH- coordinated with Fe(III) increases, the association trend of As(V) by colloidal ferric hydroxides weakens accordingly. This study provides insights into understanding the coprecipitation and adsorption mechanisms of arsenate removal and revealing the high efficiency of arsenate removal by colloidal ferric hydroxides or iron salts under moderate pH conditions.

Insights into water-mediated ion clustering in aqueous CaSO4 solutions: pre-nucleation cluster characteristics studied by ab initio calculations and molecular dynamics simulations.

The molecular structure of growth units building crystals is a fundamental issue in the crystallization processes from aqueous solutions. In this work, a systematic investigation of pre-nucleation clusters and their hydration characteristics in aqueous CaSO4 solutions was performed using ab initio calculations and molecular dynamics (MD) simulations. The results of ab initio calculations and MD simulations indicate that the dominant species in aqueous CaSO4 solutions are monodentate ion-associated structures. Compared with charged ion clusters, neutral clusters are more likely to be present in an aqueous CaSO4 solution. Neutral (CaSO4)m clusters are probably the growth units involved in the pre-nucleation or crystallization processes. Meanwhile, hydration behavior around ion associated species in aqueous CaSO4 solutions plays an important role in related phase/polymorphism selections. Upon ion clustering, the residence of some water molecules around Ca2+ in ion-associated species is weakened while that of some bridging waters is enhanced due to dual interaction by Ca2+ and SO42-. Some phase/polymorphism selections can be achieved in aqueous CaSO4 solutions by controlling the hydration around pre-nucleation clusters. Moreover, the association trend between calcium and sulfate is found to be relatively strong, which hints at the low solubility of calcium sulfate in water.