Mccullochalexander7098

The EnCurv method for maintaining membrane curvature in molecular dynamics simulations is introduced. The method allows maintaining any desired curvature in a sector of lipid membrane bent in a single plane without adding any unphysical interactions into the system and without restrictions on lateral and transversal lipid diffusion and distribution. The current implementation is limited to the membranes curved in a single plane but generalization to arbitrary curvature and membrane topology is possible. The method is simple, easy to implement, and scales linearly with the system size. EnCurv is agnostic to the force field, simulation parameters, and membrane composition. The proof of principle implementation (https//github.com/yesint/EnCurv) is compatible with the majority of modern simulation packages and shows consistent results on the model systems.Substituted arylethylamines represent a key structural motif in natural, pharmaceutical, and agrochemical compounds. Access to such scaffolds has been the subject of long-standing synthetic interest. Herein, we report the synthesis of such scaffolds via a palladium-catalyzed C(sp3)-C(sp3) coupling between (chloromethyl)aryls and air-/moisture-stable N,N-dialkylaminomethyltrifluoroborate salts. Rapid hit identification was achieved using microscale high-throughput experimentation and was followed by millimolar-scale reaction parameter optimization. A range of structurally and electronically varied arylethylamine products were obtained in moderate to excellent yields (27-96%, >60 examples). The reaction mechanism is proposed to proceed via formation of a trialkylbenzylammonium species prior to oxidative addition.In this work, we demonstrate that the nonsuperconducting single-layer FeTe can become superconducting when its structure is properly tuned by epitaxially growing it on Bi2Te3 thin films. The properties of the single-layer FeTe deviate strongly from its bulk counterpart, as evidenced by the emergence of a large superconductivity gap (3.3 meV) and an apparent 8 × 2 superlattice (SL). Our first-principles calculations indicate that the 8 × 2 SL and the emergence of the novel superconducting phase are essentially the result of the structural change in FeTe due to the presence of the underlying Bi2Te3 layer. The structural change in FeTe likely suppresses the antiferromagnetic order in the FeTe and leads to superconductivity. Our work clearly demonstrates that moiré pattern engineering in a heterostructure is a reachable dimension for investigating novel materials and material properties.Detailed kinetic and mechanistic studies have been carried out on the reaction between aquacobalamin/hydroxocobalamin (CblOH2+/CblOH) and nitroxyl (HNO) generated by Piloty's acid (PA, N-hydroxybenzenesulfonamide) over a wide pH range (3.5-13). The resulting data showed that in a basic solution HNO can react with hydroxocobalamin to form nitrosylcobalamin despite the inert nature of CblOH. It was shown that at low PA concentrations the rate-determining step is the decomposition of PhSO2NHO- to release HNO, whereas the reaction between CblOH and HNO becomes the rate-determining step at high PA concentrations. Data from kinetic studies on the reaction of CblOH with an excess of HNO enabled us to experimentally determine the pKa(HNO) value from initial rate data as a function of pH, giving pKa(HNO) = 11.47 ± 0.04. An especially interesting observation was made in the neutral pH range, where PA is stable and does not produce HNO. Under such conditions, rapid formation of CblNO was observed in the studied system. The obtained data suggest that CblOH2+ reacts directly with PA to form a Piloty's acid-bound cobalamin intermediate, which deprotonates rapidly at neutral pH followed by rate-determining S-N bond cleavage to give CblNO and release PhSO2-.Layered titanium carbide (Ti3C2T x ) MXene is a promising electrode material for use in next-generation electrochemical capacitors. However, the atomic-level information needed to correlate the distribution of intercalated cations with surface redox reactions, has not been investigated in detail. Herein we report on sodium preintercalated MXene with high sodium content (up to 2Na per Ti3C2T x formula) using a solution of Na-biphenyl radical anion complex (E0 ≈ -2.6 SHE). Multiple sodiation sites and formation of a two-dimensional sodium domain structure at interfaces/surfaces is identified through combined computational simulations with neutron pair distribution function analysis. The induced layer charges and the redox process characterized by the density-functional tight-binding method on a local scale are found to greatly depend on the location of sodium ions. Electrochemical testing of the pre-sodiated MXene as an electrode material in a sodium-ion capacitor shows excellent reversibility and promising performance, indicating the feasibility of chemical preintercalation as an approach to prepare MXene electrodes for ion capacitors.The development of first-principles-quality machine learning potentials (MLP) has seen tremendous progress, now enabling computer simulations of complex systems for which sufficiently accurate interatomic potentials have not been available. These advances and the increasing use of MLPs for more and more diverse systems gave rise to new questions regarding their applicability and limitations, which has constantly driven new developments. The resulting MLPs can be classified into several generations depending on the types of systems they are able to describe. First-generation MLPs, as introduced 25 years ago, have been applicable to low-dimensional systems such as small molecules. MLPs became a practical tool for complex systems in chemistry and materials science with the introduction of high-dimensional neural network potentials (HDNNP) in 2007, which represented the first MLP of the second generation. Second-generation MLPs are based on the concept of locality and express the total energy as a sum of environmn of organic and biomolecules, redox reactions, and defects and doping in materials. In all of these situations, small local modifications can change the system globally, resulting in different equilibrium structures, charge distributions, and reactivity. NSC 74859 price These phenomena cannot be captured by second- and third-generation MLPs. Consequently, the inclusion of nonlocal phenomena has been identified as a next key step in the development of a new fourth generation of MLPs. While a first fourth-generation MLP, the charge equilibration neural network technique (CENT), was introduced in 2015, only very recently have a range of new general-purpose methods applicable to a broad range of physical scenarios emerged. In this Account, we show how fourth-generation HDNNPs can be obtained by combining the concepts of CENT and second-generation HDNNPs. These new MLPs allow for a highly accurate description of systems where nonlocal charge transfer is important.