The massive emission of CO₂ has caused a series of environmental problems, including global warming, which exacerbates natural disasters and human health. Cu-based catalysts have shown great activity in the reduction of CO₂, but the mechanism of CO₂ activation remains ambiguous. In this work, we performed density functional theory (DFT) calculations to investigate the hydrogenation of CO₂ on Cu(211)-Rh, Cu(211)-Ni, Cu(211)-Co, and Cu(211)-Ru surfaces. The doping of Rh, Ni, Co, and Ru was found to enhance CO₂ hydrogenation to produce COOH. For CO₂ hydrogenation to produce HCOO, Ru plays a positive role in promoting CO dissociation, while Rh, Ni, and Co increase the barriers. These results indicate that Ru is the most effective additive for CO₂ reduction in Cu-based catalysts. In addition, the doping of Rh, Ni, Co, and Ru alters the electronic properties of Cu, and the activity of Cu-based catalysts was subsequently affected according to differential charge analysis. The analysis of Bader charge shows good predictions for CO₂ reduction over Cu-based catalysts. This study provides some fundamental aids for the rational design of efficient and stable CO₂-reducing agents to mitigate CO₂ emission.

Ionic liquids (ILs) have shown great catalytic effects in the conversion of fructose to 5-hydroxymethylfurfural (HMF) but the dehydration mechanism remains ambiguous. In this work, density functional theory (DFT) calculations have been carried out for the mechanism of the dehydration of fructose to HMF, catalyzed by functionalized ILs. ILs with different kinds of functionalized imidazolium-based cations and SO₃ group-based anions have been used to investigate the catalytic effects of different anions and cations on the dehydration of fructose. The whole reaction process of fructose to HMF includes three dehydration steps. The overall rate-determining step is the second dehydration, and the functionalized cations showed good proton transfer ability to catalyze the reaction in the dehydration steps. The proton shuttling ability of cations is better than that of anions. The anions can form strong H-bonds with the fructose and cations and provide a polar environment to stabilize intermediates and transition states. The high catalytic activity is attributed to the synergetic catalysis of cations and anions to complete the dehydration of fructose. The dehydration reaction mechanism from fructose to HMF catalyzed by [BmimHSO₃][HSO₄]-functionalized ILs has been proposed by DFT calculations. This study emphasizes the catalytic performance of functionalized ILs replaced by different substituent groups and the dehydration mechanism of fructose to HMF.

Calmodulin (CaM) is a multifunctional protein commonly found in various eukaryotic cells that can bind Ca2+, making it highly valuable for research in agriculture, medicine, the environment, and other fields. Protein functionality is intricately linked to its structure. To understand how varying temperatures affect the structural integrity of CaM protein at the molecular level, the effect of temperature on the structural stability of CaM-peptide complex was investigated based on the molecular dynamics (MD) simulation. Some analyses including the root mean square deviation (RMSD) values, interaction energies, the decomposition of total energy of the system, the binding mechanism for Ca2+, and the secondary structure of CaM-peptide at different temperatures have been made in this work. The RMSD increased from 0.5277 nm (298 K) to 0.6949 nm (400 K), indicating a loss of structural stability. As temperature increases, the interaction energies between CaM-peptide and Ca2+ exhibit a decline, and the number of oxygen atoms in the 4 Å range around the CaM-peptide ion tends to decrease, with the average value of the number of oxygen atoms in the 4 Å range of CaM-peptide decreasing from 7.48039 (298 K) to 6.36614 (400 K) with Coulombic interactions playing a pivotal role in stabilizing Ca2+. This decline in hydrogen bonding is directly linked to a decrease in protein stability at higher temperatures, highlighting the thermal sensitivity of the protein’s structural framework. The stable secondary structures, including the α-helix, are disrupted as temperatures increase, leading to the gradual unwinding of the α-helix and a loss of structural integrity. This work explores the molecular-level structural stability of CaM, enhancing our understanding of CaM protein and its potential applications.

The Fischer–Helferich glycosidation reaction is generally the initial step in the conversion of glucose to levulinate in alcohol media. However, the relevant molecular mechanism catalyzed by Al-based catalysts is still not well understood. In this work, the reaction mechanism of the glycosidation from glucose to methyl glycosides catalyzed by Al³⁺ coordinated with methanol/methoxyl was investigated through density functional theory (DFT) calculations. The whole reaction process includes ring-opening, addition, and ring-closure events. The addition of methanol to the ring-opening structure of glucose makes the electronegativity of C1 site stronger to proceed with the following ring-closure reaction. Among the 28 kinds of ways of ring-closure reaction, the most preferred way is to close the loop through the six-membered ring (O5–C1) to generate methyl glucoside (MDGP). The rate-determining step is the ring-closure and the Al³⁺ shows a great catalytic effect which is mainly reflected in coordinating with the solvents to transfer protons. The results would be helpful to understanding the Fischer–Helferich glycosidation mechanism catalyzed by Al-based catalysts and comprehend the conversion of glucose to high value-added chemicals.

The light-modulated isomerization and aggregation behavior of ionic liquids (ILs) in aqueous solutions holds fundamental and technological significance. Although several azobenzene-based photoresponsive ILs have been synthesized, there is still a lack of understanding regarding the aggregation mechanism, regularity of the alkyl chain length, and the position of the azobenzene (cis- and trans-) in these photoresponsive ILs. To elucidate the structure-property relationship of photoresponsive ILs, four types of azobenzene groups photosensitive ILs ([AzoC_nDMEA]Br, n = 2,4,6,10) in both trans- and cis- configurations were investigated by density functional theory (DFT) calculations. We investigated the geometric properties of cations, H-bonds interactions of ionic pairs, microstructures of clusters, and the interactions between ILs and water molecules. It was found that the molecular volume of cis- is smaller than that of trans- cation structures. Despite multiple H-bonds between the anions and the ammonium group of cations, longer alkyl chains weaken anion-cation interactions. The interaction energies of trans- n[AzoC₂DMEA]Br (1 ≤ n ≤ 4) clusters are stronger than those of cis-. Moreover, the interaction energy between trans-structures of photoresponsive ILs and water molecules is smaller than that of cis- structures based on the DFT calculations. The interaction energies per water molecule in the ILs-water clusters tend to saturation as the number of water molecules increases. The electrostatic interaction plays a crucial role in the stabilization of ILs and water systems. The structure-property relationship of photoresponsive ILs including the regularity of the alkyl chain length and the azobenzene position as well as the microscopic interaction mechanism of ILs and ILs-water clusters had been studied from theoretical calculation perspective. This work can contribute to an in-depth understanding of the microcosmic interactions of azobenzene-based photoresponsive ILs and aid in designing them in a "task-specific" way.