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Gravesen Frank posted an update 6 months ago
The adsorption properties and formation mechanism of ammonium carbamate for CO2 capture in N,N’-dimethylethylenediamine (mmen) grafted M2(dobpdc) (dobpdc4- = 4,4′-dioxidobiphenyl-3,3′-dicarboxylate; M = Mg, Sc-Zn, except Ni) have been studied via density functional theory (DFT) calculations. We see that the mmen molecule is joined to the metal site via a M-N bond and has hydrogen bonding with neighboring mmen molecules. The binding energies of mmen range from 135.4 to 184.0 kJ/mol. CO2 is captured via insertion into the M-N bond of mmen-M2(dobpdc), forming ammonium carbamate. The CO2 binding energies (35.2 to 92.2 kJ/mol) vary with different metal centers. Toyocamycin chemical structure Furthermore, the Bader charge analysis shows that the CO2 molecules acquire 0.42 to 0.47 |e|. This charge is mainly contributed by the mmen, and a small additional amount is from the metal atom bonded with the CO2. The preferred reaction pathway is a two-step reaction. In the first step, the hydrogen bonded complex B changes into an N-coordinated intermediate D with high barriers (0.69 to 1.58 eV). The next step involves the translation and rotation of the chain in the intermediate D, resulting in the formation of the final O-coordinated product I with barriers of 0.22 to 0.61 eV. The higher barriers of CO2 reaction with mmen-M2(dobpdc) relative to attack the primary amine might be due to the larger steric hindrance of mmen. We hope this work will contribute to an improved understanding and development of future amine-grafted materials for efficient CO2 capture.The conversion of light alkanes to olefins is crucial to the chemical industry. The quest for improved catalytic performance for this conversion is motivated by current drawbacks including expensive noble metal catalysts, poor conversion, low selectivity, and fast decay of efficiency. The in situ visualization of complex catalysis at the atomic level is therefore a major advance in the rational framework upon building the future catalysts. Herein, the catalytic C-H bond activations of ethylbenzene on TiO2(110)-(1 × 1) were explored with high-resolution scanning tunneling microscopy and first-principles calculations. We report that the first C-H bond scission is a two-step process that can be triggered by either heat or ultraviolet light at 80 K, with near 100% selectivity of β-CH bond cleavage. This work provides fundamental understanding of C-H bonds cleavage of ethylbenzene on metal oxides, and it may promote the design of new catalysts for selective styrene production under mild conditions.Reversible chemistries have been extensively explored to construct highly crystalline covalent organic frameworks (COFs) via defect correction. However, the mechanisms of defect correction that can explain the formation of products as single crystals, polycrystal/crystallites, or amorphous solids remain unknown. Herein, we employed molecular dynamics simulations combined with a polymerization model to investigate the growth kinetics of two-dimensional COFs. By virtue of the Arrhenius two-state model describing reversible reactions, we figured out the conditions in terms of active energy and binding energy for different products. Specifically, the ultraslow growth of COFs under high reversibility of reactions corresponding to low binding energies resulted in a single crystal by inhibiting the emergence of nuclei as well as correcting defects through continually dropping small defective fragments off at crystal boundaries. High bonding energies responsible for the high nucleation rate and rapid growth that incorporated defects in crystals and caused the division of crystals through defect correcting processes led to small crystallites or polycrystals. The insights into the mechanisms help us to understand and further control the growth kinetics by exploiting reversible conditions to synthesize COFs of higher quality.Strong coupling to the electronic or vibronic transitions of an organic semiconductor has been extensively studied in microcavity structures in which a molecular film is placed between two closely spaced mirrors. Recent experiments suggest that such strong coupling can be used to modify chemical reactions; however, the geometry of conventional microcavity structures makes such studies difficult as they limit the ability of molecules to interact with their local environment. Here, we show that optical strong coupling to a molecular film can be achieved even when such molecules are located on the surface of a dielectric slab. We then show that such molecules on the surface of the slab can undergo facile interactions with molecules in their surrounding environment, and evidence a reversible protonation/deprotonation reaction by exposing a surface-bound porphyrin to an acidic or basic vapor. Although our proof-of-principle measurements do not evidence any change in reaction rates, we believe our structures represent a promising system in which to explore polariton-driven chemical phenomena.We report a DNA-compatible photoredox decarboxylative coupling of α-amino acids with carbonyl compounds to access DNA-encoded sp3-rich 1,2-amino alcohols. The reaction proceeds efficiently for a wide range of DNA-conjugated aldehydes and ketones and provides the desired 1,2-amino alcohols with conversions generally >50%. Additional utility of the developed protocol is demonstrated by one-pot cyclization of DNA-conjugated 1,2-amino alcohols into oxazolidiones and morpholinones. Lastly, qPCR and sequencing data analysis indicates no significant DNA damage upon photoredox decarboxylative coupling.RAS proteins work as GDP-GTP binary switches and regulate cytoplasmic signaling networks that are able to control several cellular processes, playing an essential role in signal transduction pathways involved in cell growth, differentiation, and survival, so that overacting RAS signaling can lead to cancer. One of the hardest challenges to face is the design of mutation-selective therapeutic strategies. In this work, a G12D-mutated farnesylated GTP-bound Kirsten RAt sarcoma (KRAS) protein has been simulated at the interface of a DOPC/DOPS/cholesterol model anionic cell membrane. A specific long-lasting salt bridge connection between farnesyl and the hypervariable region of the protein has been identified as the main mechanism responsible for the binding of oncogenic farnesylated KRAS-4B to the cell membrane. Free-energy landscapes allowed us to characterize local and global minima of KRAS-4B binding to the cell membrane, revealing the main pathways between anchored and released states.
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