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For 2-propenol, hydrogen bonding in the multilayer correlates with observation of the C[double bond, length as m-dash]C stretch at 1646 cm-1, which is invisible for the monolayer. This suggests that for monolayer coverages, 2-propenol bonds with the C[double bond, length as m-dash]C bond parallel to the surface. Similarly, the C[double bond, length as m-dash]O stretch of propanal is very weak for low coverages but becomes the largest peak for the multilayer, indicating a change in orientation with coverage.C-C cross coupling reactions have been widely used for developing synthesis protocols for pharmaceuticals and agricultural products in the past few decades. Of all the reported C-C cross coupling reactions, the Suzuki-Miyaura reaction is preferred because of its mild reaction conditions, the commercial availability of associated reagents and the ease of removal of boron containing by-products. Recently, Corma and co-workers [Leyva-Perez et al., Angew. Chem., 2013, 125, 11768] reported water-stabilized three- and four-atom Pd clusters as highly active catalytic species for C-C coupling reactions. The present work focuses on developing detailed mechanistic insights into the Suzuki-Miyaura reaction with Pd3 and Pd4 clusters utilizing density functional theory calculations. The role of the base in the reaction was analysed in this study, which was found to lower the activation barriers of transmetalation over both Pd3 and Pd4. Free energy landscapes for Suzuki-Miyaura coupling of bromobenzene and phenylboronic acid over Pd3 and Pd4 clusters were developed. The highest free energy barriers of 34.7 and 30.4 kcal mol-1 were observed for the oxidative addition over Pd3 and Pd4, respectively, indicating the oxidative addition as the rate limiting step. Detailed energetics conclusively proved the active nature of small-atom Pd clusters for catalyzing the Suzuki-Miyaura reaction.Metal organic framework (MOF)-encapsulated metal clusters have shown superior catalytic activity due to geometric and electronic properties of metal clusters, which are largely determined by adsorption sites and sizes and morphologies of encapsulated metal clusters. In the present work, anchoring sites, the stability, and the agglomeration probability of Ptn (n = 1-23) clusters over an MOF-808 framework structure were studied using density functional theory calculations and ab initio molecular dynamics simulation. It has been found that Ptn (n = 1-7) clusters bind more strongly at the Zr6 metal node sites than at the interface and linker sites. Upon adsorption, significant amounts of electrons (+0.92 to +1.96 |e|) are transferred from Ptn clusters to the MOF framework. The agglomeration of single Pt1 atoms at the Zr6 metal node to form a Ptn cluster is unlikely, while the agglomeration at the interface or the linker is energetically feasible. Compared with the single Zr6 node, the bonding of Ptn clusters with two Zr6 metal nodes is weaker, with less electron (+0.12 to +0.89 |e|) transfer. Finally, our calculations show that CO adsorption at the single Pt atom is stabilized at the interface site, preventing its further agglomeration with Ptn clusters between the two Zr6 metal nodes.The reaction OH + HO2 → H2O + O2 is a prototype of radical-radical reactions. It plays an important role in interstellar/atmospheric chemistry and combustion, and considerable attention has thus been dedicated to its kinetics. In our previous work, we reported an accurate full-dimensional potential energy surface for the title reaction on the ground triplet electronic state. The quasi-classical trajectory (QCT) approach was employed to investigate its kinetics. Although the QCT rate coefficients were in good agreement with some experimental and theoretical results, QCT cannot account for the quantum mechanical effects, such as zero-point vibrational energy, recrossing, and tunneling, which may significantly affect the rate coefficients, particularly at low temperatures. In this work, the reduced-dimensional quantum dynamics and ring polymer molecular dynamics calculations were carried out to examine these effects and their impact on rate coefficients over the temperature range of 300-1300 K.Lack of quality data and difficulty generating these data hinder quantitative understanding of reaction kinetics. Specifically, conventional methods to generate transition state structures are deficient in speed, accuracy, or scope. We describe a novel method to generate three-dimensional transition state structures for isomerization reactions using reactant and product geometries. selleck kinase inhibitor Our approach relies on a graph neural network to predict the transition state distance matrix and a least squares optimization to reconstruct the coordinates based on which entries of the distance matrix the model perceives to be important. We feed the structures generated by our algorithm through a rigorous quantum mechanics workflow to ensure the predicted transition state corresponds to the ground truth reactant and product. In both generating viable geometries and predicting accurate transition states, our method achieves excellent results. We envision workflows like this, which combine neural networks and quantum chemistry calculations, will become the preferred methods for computing chemical reactions.Gene therapy is a promising strategy for treating ischemic disease by solving the dual dilemma of ischemia and inflammation. However, its development remains limited by inefficient gene transfection. Hence, we propose a "dual genes + all-adaptive carrier" idea. We have innovatively co-delivered eNOS gene and the ZNF580 gene encoding its transcription factor to enhance the efficiency of eNOS expression. The overexpressed ZNF580 protein significantly promotes angiogenesis via regulating the transcription of multiple genes. This implies a potential synergistic effect of eNOS and ZNF580 genes in anti-ischemic therapy. Additionally, we have designed an all-adaptive gene carrier with cascaded bio-responsive functions based on the characteristic bio-signals of the ischemic site (including extracellular excessive matrix metalloproteinase-2, the endo/lysosomal pH gradient and high cytoplasmic glutathione level). This carrier can sequentially overcome transfection bottlenecks and achieve high transfection. Excitingly, this cascaded bio-responsive delivery strategy remarkably enhanced blood perfusion, accelerated angiogenesis and alleviated inflammation in critical limb ischemia (CLI) mice, which was attributed to the combined effects of pro-angiogenic ZNF580 expression and synergistically produced eNOS expression.