Carpentercortez8350

2 V at a current density of 15 mA g-1. The parent Na0.7MnO2 is compared with alkali metal (K, Rb, and Cs)-modified Na x MnO2 in terms of surface morphology using scanning transmission electron microscopy coupled with energy-dispersive X-ray spectroscopy, scanning electron microscopy, 23Na solid-state nuclear magnetic resonance, and X-ray photoelectron spectroscopy and in terms of electrochemical performance and structural electrochemical evolution using in situ or operando synchrotron X-ray diffraction.Computational simulation of nonadiabatic molecular dynamics is an indispensable tool for understanding complex photoinduced processes such as internal conversion, energy transfer, charge separation, and spatial localization of excitons, to name a few. We report an implementation of the fewest-switches surface-hopping algorithm in the NWChem computational chemistry program. The surface-hopping method is combined with linear-response time-dependent density functional theory calculations of adiabatic excited-state potential energy surfaces. To treat quantum transitions between arbitrary electronic Born-Oppenheimer states, we have implemented both numerical and analytical differentiation schemes for derivative nonadiabatic couplings. A numerical approach for the time-derivative nonadiabatic couplings together with an analytical method for calculating nonadiabatic coupling vectors is an efficient combination for surface-hopping approaches. Additionally, electronic decoherence schemes and a state reassigned unavoided crossings algorithm are implemented to improve the accuracy of the simulated dynamics and to handle trivial unavoided crossings. We apply our code to study the ultrafast decay of photoexcited benzene, including a detailed analysis of the potential energy surface, population decay timescales, and vibrational coordinates coupled to the excitation dynamics. We also study the photoinduced dynamics in trans-distyrylbenzene. This study provides a baseline for future implementations of higher-level frameworks for simulating nonadiabatic molecular dynamics in NWChem.Stereoselective syntheses of new pyranopyrans that are related to the natural product diplopyrone, which is a phytotoxin implicated in cork oak decline, have been achieved from carbohydrate starting materials in two approaches that are based on C-glycosides as key intermediates. A C-alkynyl glycoside prepared by Ferrier rearrangement was used as the precursor to a new pyranopyran alkyne that showed potent antibacterial activity against the common bacterial pathogen Edwardsiella ictaluri that causes enteric septicemia in catfish. The C-alkynyl glycoside also showed herbicidal activity. New bioassay data for the pyranopyran nitrile (4aR,6S,8aR)-6-cyano-6,8a-dihydropyrano-[3,2-b]pyran-2(4aH)-one, the most potent of the pyranopyrans synthesized to date, were obtained in greenhouse studies that revealed additional herbicidal activity. Other new analogues that were synthesized included desmethylpyranopyrans that were prepared by Isobe C-alkynylation-rearrangement/reduction and RCM-based pyranopyran construction. The antibiotic and phytotoxic activities of the new pyranopyrans synthesized in this study highlight the importance of substituents on the nonlactone ring and demonstrate the potential of such compounds as antibiotics and herbicides.In this work, we describe a Catellani-type C-H glycosylation to provide rapid access to various highly decorated α-C-(hetero)aryl glycosides in a modular and stereoselective manner (>90 examples). Olaparib mw The termination step is flexible, which is demonstrated by ipso-Heck reaction, hydrogenation, Suzuki coupling, and Sonogashira coupling. Application of this methodology has been showcased by preparing glycoside-pharmacophore conjugates and a dapagliflozin analogue. Notably, the technology developed herein represents an unprecedented example of Catellani-type alkylation involving an SN1 pathway.Chemists have had a long-standing interest in reactive intermediates such as carbenes, carbon radicals, carbanions, and carbocations. Carbocations are an interesting part of this group because of their tendency to undergo rearrangement, sometimes forming bridged ions, as well as their ability in many cases of spreading out the positive charge over several atoms. We have re-examined some of these cases using high-level compound procedures, W1BD and G4, as well as by considering the charge distributions making use of the Hirshfeld method that has been shown to uniquely correlate with several types of experimental data.Sharpless et al. have described, while performing the molybdenum-catalyzed epoxidation reaction of olefins using alkyl hydroperoxides, that the molybdenum-oxo moiety is an active catalytic species. Thus, continuous efforts have been made to synthesize molybdenum-oxo complexes of different ligand environments. While plenty of such works on molybdenum porphyrins are reported in the literature, related molybdenum corroles are very less reported. The synthesis and characterization of two new oxo-molybdenum(V)-corrolato complexes are described herein. Both the complexes have been fully characterized by several spectroscopic techniques in conjunction with single-crystal X-ray diffraction analysis. The efficacy of the oxo-molybdenum(V)-corrolato complexes for the catalytic epoxidation reaction of olefins with the help of hydroperoxides has also been explored. The catalytic application of oxo-molybdenum(V)-corrolato complexes in the epoxidation reaction has not been reported earlier. A mechanism has been proposed to explain the experimental findings.Three-dimensional (3D) molecular descriptors, including physicochemical and shape properties, for protein-protein interaction (PPI) interface inhibitors have become a topic of discussion. However, the relationships between such properties and binding free energy have not been adequately investigated. In this study, we focused on identifying key 3D molecular descriptors related to the binding free energy and/or the ligand efficiency (LE) of PPI interface inhibitors. A positive correlation was found between the binding free energy and the diameter (D) of cylindrical 3D molecules, in addition to a correlation between LE and D/heavy atom count (HAC). In addition, we showed a correlation between LE and D/HAC for macrocyclic compounds, suggesting that the present findings could be applied during assessments of the potential of macrocyclic PPI interface inhibitors in drug discovery processes.