Swansonnash9777

There is a main channel and an alternative one for the photoisomerization process of both trans isomers. CItwist-I and CItwist-II act as S1/S0 decay funnels in the main isomerization channels of 1E and 1E' isomers, respectively, and the photochemical processes of 1E and 1E' lead to different cis isomers.An accurate global potential energy surface (PES) for the HBr2 system has been constructed using the fundamental invariant neural network fitting method based upon 11 698 ab initio energies at the UCCSD(T)/CBS level of theory, with the spin-orbit coupling of the 2P3/2 orbit of the Br atom properly included. The time-dependent wave packet calculations have been performed to study the H + Br2 → HBr + Br reaction on the new PES. The total reaction probabilities for total angular momentum J = 0 for the ground initial state show no threshold due to the submerged barrier height (-0.351 kcal/mol) of the PES. The total integral cross sections (ICS) for reactant Br2 in ro-vibrational states (v0 = 0, j0 = 0, 10, 20, 30; v0 = 1-5, j0 = 0) were calculated for collision energy of up to 0.5 eV. It is found that the initial rotational excitation has a negligible effect on the ICS, and the initial vibrational excitation depresses the reactivity to some extent. The thermal rate constants for the title reaction in the temperature range of 100-1000 K were calculated from the Boltzmann averaging of the v0 = 0-5 rate constants, which overestimated the experimental results to some extent.We present several new major features added to the Monte Carlo (MC) simulation code Brick-CFCMC for phase- and reaction equilibria calculations (https//gitlab.com/ETh_TU_Delft/Brick-CFCMC). The first one is thermodynamic integration for the computation of excess chemical potentials (μex). For this purpose, we implemented the computation of the ensemble average of the derivative of the potential energy with respect to the scaling factor for intermolecular interactions (⟨∂U∂λ⟩). Efficient bookkeeping is implemented so that the quantity ∂U∂λ is updated after every MC trial move with negligible computational cost. We demonstrate the accuracy and reliability of the calculation of μex for sodium chloride in water. Second, we implemented hybrid MC/MD translation and rotation trial moves to increase the efficiency of sampling of the configuration space. In these trial moves, short Molecular Dynamics (MD) trajectories are performed to collectively displace or rotate all molecules in the system. These trajectories are accepted or rejected based on the total energy drift. The efficiency of these trial moves can be tuned by changing the time step and the trajectory length. The new trial moves are demonstrated using MC simulations of a viscous fluid (deep eutectic solvent).Prunella vulgaris is a widely used edible Chinese medicinal plant. In the present study, two new abietane-type diterpenoids, abietoquinones A (1) and B (2), were isolated from this plant by an immunosuppressive bioassay-guided isolation procedure. Their structures were elucidated unambiguously by NMR spectroscopic analysis, single-crystal X-ray crystallography, and electronic circular dichroism calculations. Compounds 1 and 2 bear a cyclohex-2-ene-1,4-dione moiety, which is uncommon among abietane diterpenes. Also, abietoquinone A (1) suppressed murine splenocyte proliferation and decreased the production of proinflammatory cytokines induced by concanavalin A (Con A) in vitro. In Con A-challenged mice, preinjection with 1 significantly ameliorated liver injury. Additionally, abietoquinone A (1) exhibited inhibitory activities against the proliferation of murine splenocytes and human T cells induced by anti-CD3/anti-CD28 monoclonal antibodies (mAbs).Iron complexes that model the structural and functional properties of the active iron site in rabbit lipoxygenase are described. The ligand sphere of the mononuclear pseudo-octahedral cis-(carboxylato)(hydroxo)iron(III) complex, which is completed by a tetraazamacrocyclic ligand, reproduces the first coordination shell of the active site in the enzyme. In addition, two corresponding iron(II) complexes are presented that differ in the coordination of a water molecule. In their structural and electronic properties, both the (hydroxo)iron(III) and the (aqua)iron(II) complex reflect well the only two essential states found in the enzymatic mechanism of peroxidation of polyunsaturated fatty acids. Furthermore, the ferric complex is shown to undergo hydrogen atom abstraction reactions with O-H and C-H bonds of suitable substrates, and the bond dissociation free energy of the coordinated water ligand of the ferrous complex is determined to be 72.4 kcal·mol-1. Theoretical investigations of the reactivity support a concerted proton-coupled electron transfer mechanism in close analogy to the initial step in the enzymatic mechanism. The propensity of the (hydroxo)iron(III) complex to undergo H atom abstraction reactions is the basis for its catalytic function in the aerobic peroxidation of 2,4,6-tri(tert-butyl)phenol and its role as a radical initiator in the reaction of dihydroanthracene with oxygen.One of the challenges in organic light-emitting diodes research is finding ways to increase device efficiency by making use of the triplet excitons that are inevitably generated in the process of electroluminescence. One way to do so is by thermally activated delayed fluorescence (TADF), a process in which triplet excitons undergo upconversion to singlet states, allowing them to relax radiatively. The discovery of this phenomenon has ensued a quest for new materials that are able to effectively take advantage of this mechanism. From a theoretical standpoint, this requires the capacity to estimate the rates of the various processes involved in the photophysics of candidate molecules, such as intersystem crossing, reverse intersystem crossing, fluorescence, and phosphorescence. Here, we present a method that is able to, within a single framework, compute all of these rates and predict the photophysics of new molecules. We apply the method to two TADF molecules and show that results compare favorably with other theoretical approaches and experimental results. Finally, we use a kinetic model to show how the calculated rates act in concert to produce different photophysical behavior.One-electron reductants (OER) photoproduced by chromophoric dissolved organic matter (CDOM) have been shown to be likely precursors for the formation of superoxide and subsequently hydrogen peroxide. An improved method that employs a nitroxide radical probe (3AP) has been developed and utilized to determine the photoproduction rates of OER from a diverse set of CDOM samples. 3AP reacts with OER to produce the hydroxylamine, which is then derivatized with fluorescamine and quantified spectrofluorometrically. Although less sensitive than traditional methods for measuring RO2•-, measuring RH provides a simpler and faster method of estimating RO2•- and is amenable to continuous measurement via flow injection analysis. Production rates of OER (RH), superoxide (RO2•-), and hydrogen peroxide (RH2O2) have a similar wavelength dependence, indicating a common origin. If all the OER react with molecular oxygen to produce superoxide, then the simplest mechanism predicts that RH/RH2O2 and RO2•-/RH2O2 should be equal to 2. However, our measurements reveal RH/RH2O2 values as high as 16 (5.7-16), consistent with prior results, and RO2•-/RH2O2 values as high as 8 (5.4-8.2). These results indicate that a substantial fraction of superoxide (65-88%) is not undergoing dismutation. A reasonable oxidative sink for superoxide is reaction with photoproduced phenoxy radicals within CDOM.The rate of formation of dichloride anions (Cl2•-) in dilute aqueous solutions of HCl (2-100 mmol·kg-1) was measured by the technique of pulse radiolysis over the temperature range of 288-373 K. The obtained Arrhenius dependence shows a concentration averaged activation energy of 7.3 ± 1.8 kJ·mol-1, being half of that expected from the mechanism assuming the •OHCl- intermediate and supporting the ionic equilibrium-based mechanism, i.e., the formation of Cl2•- in the reaction of •OH with a hydronium-chloride (Cl-·H3O+) contact ion pair. Assuming diffusion-controlled encounter of the hydronium and chloride ions and including the effect of the ionic atmosphere, we showed that the reciprocal of τ, the lifetime of (Cl-·H3O+), follows an Arrhenius dependence with an activation energy of 23 ± 4 kJ·mol-1, independent of the acid concentration. This result indicates that the contact pair is stabilized by hydrogen bonding interaction of the solvent molecules. We also found that at a fixed temperature, τ is noticeably increased in less-concentrated solutions (mHCl less then 0.01 m). Since this concentration effect is particularly pronounced at near ambient temperatures, the increasing pair lifetime may result from the solvent cage effect enhanced by the presence of large supramolecular structures (patches) formed by continuously connected four-bonded water molecules.Coarse-grained (CG) models of biomolecules have been widely used in protein/ribonucleic acid (RNA) three-dimensional structure prediction, docking, drug design, and molecular simulations due to their superiority in computational efficiency. NX-5948 cell line Most of these applications strongly depend on the reasonable estimation of solvation free energy, which requires the accurate calculation of solvent accessible surface area (SASA). Although algorithms for SASA calculations with all-atom protein and RNA structures have been well-established, accurately estimating the SASA based on CG structures is extremely challenging. In this work, we developed a deep learning-based SASA estimator (DeepCGSA), which can provide almost perfect SASA estimation based on CG structures of protein and RNA molecules. Extensive testing analysis showed that for three types of widely used CG protein models, including the Cα-based, Cα-Cβ, and Martini models, the correlation coefficients between the predicted values and the reference values can be as high as 0.95-0.99, which perform dramatically better than available methods. In addition, the new method can be used for CG RNA structures and unfolded protein structures with much improved accuracy. We anticipate that DeepCGSA will be highly useful in the protein/RNA structure prediction, drug design, and other applications, in which accurate estimations of SASA for CG biomolecular structures are critically important.Triboelectrification is a phenomenon that generates electric potential upon contact. Here, we report a viral particle capable of generating triboelectric potential. M13 bacteriophage is exploited to fabricate precisely defined chemical and physical structures. By genetically engineering the charged structures, we observe that more negatively charged phages can generate higher triboelectric potentials and can diffuse the electric charges faster than less negatively charged phages can. The computational results show that the glutamate-engineered phages lower the LUMO energy level so that they can easily accept electrons from other materials upon contact. A phage-based triboelectric nanogenerator is fabricated and it could produce ∼76 V and ∼5.1 μA, enough to power 30 light-emitting diodes upon a mechanical force application. Our biotechnological approach will be useful to understand the electrical behavior of biomaterials, harvest mechanical energy, and provide a novel modality to detect desired viruses in the future.