Ebbesenhein8811

EPR spectroscopy resolves the dissimilar Sb hyperfine tensors of 4, reflecting the inequivalent spin distribution, setting 4 uniquely apart from all previously characterized dipnictene radical anions.We revisit the important issues of polymorphism, structure, and nucleation of cholesterol·H2O using first-principles calculations based on dispersion-augmented density functional theory. For the lesser known monoclinic polymorph, we obtain a fully extended H-bonded network in a structure akin to that of hexagonal ice. We show that the energy of the monoclinic and triclinic polymorphs is similar, strongly suggesting that kinetic and environmental effects play a significant role in determining polymorph nucleation. Furthermore, we find evidence in support of various O-H···O bonding motifs in both polymorphs that may result in hydroxyl disorder. We have been able to explain, via computation, why a single cholesterol bilayer in hydrated membranes always crystallizes in the monoclinic polymorph. We rationalize what we believe is a single-crystal to single-crystal transformation of the monoclinic form on increased interlayer growth beyond that of a single cholesterol bilayer, interleaved by a water bilayer. We show that the ice-like structure is also relevant to the related cholestanol·2H2O and stigmasterol·H2O crystals. The structure of stigmasterol hydrate both as a trilayer film at the air-water interface and as a macroscopic crystal further assists us in understanding the polymorphic and thermal behavior of cholesterol·H2O. Finally, we posit a possible role for one of the sterol esters in the crystallization of cholesterol·H2O in pathological environments, based on a composite of a crystalline bilayer of cholesteryl palmitate bound epitaxially as a nucleating agent to the monoclinic cholesterol·H2O form.Plasmon-induced photocatalysis is a topic of rapidly increasing interest, due to its potential for substantially lowering reaction barriers and temperatures and for increasing the selectivity of chemical reactions. Of particular interest for plasmonic photocatalysis are antenna-reactor nanoparticles and nanostructures, which combine the strong light-coupling of plasmonic nanostructures with reactors that enhance chemical specificity. Here, we introduce Al@TiO2 core-shell nanoparticles, combining earth-abundant Al nanocrystalline cores with TiO2 layers of tunable thickness. We show that these nanoparticles are active photocatalysts for the hot electron-mediated H2 dissociation reaction as well as for hot hole-mediated methanol dehydration. The wavelength dependence of the reaction rates suggests that the photocatalytic mechanism is plasmonic hot carrier generation with subsequent transfer of the hot carriers into the TiO2 layer. The Al@TiO2 antenna-reactor provides an earth-abundant solution for the future design of visible-light-driven plasmonic photocatalysts.Peptides are prime drug candidates due to their high specificity of action but are disadvantaged by low proteolytic stability. Here, we focus on the development of stabilized analogues of EPI-X4, an endogenous peptide antagonist of CXCR4. We synthesized macromolecular peptide conjugates and performed side-by-side comparison with their albumin-binding counterparts and considered monovalent conjugates, divalent telechelic conjugates, and Y-shaped peptide dimers. All constructs were tested for competition with the CXCR4 antibody-receptor engagement, inhibition of receptor activation, and inhibition of the CXCR4-tropic human immunodeficiency virus infection. We found that the Y-shaped conjugates were more potent than the parent peptide and at the same time more stable in human plasma, with a favorable outlook for translational studies.Illicium verum Hook.f. (Chinese star anise), a known Chinese traditional spice, is commonly applied in Chinese cuisine and cooking in Southeast Asia. As a kind of medicinal and edible resource, the fruit of I. verum has attracted great attention for its chemical constituents and physiological activities. In this work, the phytochemical study of the fruits of I. verum led to the isolation and identification of 20 compounds, including 6 new lignans and phenylpropanoids (1-6) and 14 known ones (7-20). Their structures were characterized by extensive analysis of spectroscopic data (IR, UV, high-resolution electrospray ionization mass spectrometry (HR-ESI-MS), one-dimensional (1D) and two-dimensional (1D) NMR), electronic circular dichroism (ECD) calculation, and by comparison with literature data. Meanwhile, all compounds (1-20) were evaluated for their antiviral and antioxidant activities. Especially, compound 7 [(-)-bornyl p-coumarate] showed strong antiviral activities against influenza virus A/Puerto Rico/8/34 H1N1 (PR8) with an IC50 value of 1.74 ± 0.47 μM, which is much better than those of Tamiflu (IC50 = 10.01 ± 0.92 μM) and ribavirin (IC50 = 10.76 ± 1.60 μM). The antiviral activity against PR8 of compound 7 was reported for the first time, which was sufficiently confirmed by cell counting kit 8 (CCK-8), cytopathic effect (CPE) reduction, and immunofluorescence assays. In this study, the discovery of antiviral and antioxidant components from the fruits of I. verum could benefit the further development and utilization of this plant.The accurate and reliable prediction of protein-ligand binding affinities can play a central role in the drug discovery process as well as in personalized medicine. Of considerable importance during lead optimization are the alchemical free energy methods that furnish an estimation of relative binding free energies (RBFE) of similar molecules. Recent advances in these methods have increased their speed, accuracy, and precision. This is evident from the increasing number of retrospective as well as prospective studies employing them. However, such methods still have limited applicability in real-world scenarios due to a number of important yet unresolved issues. Here, we report the findings from a large data set comprising over 500 ligand transformations spanning over 300 ligands binding to a diverse set of 14 different protein targets which furnish statistically robust results on the accuracy, precision, and reproducibility of RBFE calculations. We use ensemble-based methods which are the only way to provide reliable uncertainty quantification given that the underlying molecular dynamics is chaotic. These are implemented using TIES (Thermodynamic Integration with Enhanced Sampling). Results achieve chemical accuracy in all cases. Ensemble simulations also furnish information on the statistical distributions of the free energy calculations which exhibit non-normal behavior. We find that the "enhanced sampling" method known as replica exchange with solute tempering degrades RBFE predictions. We also report definitively on numerous associated alchemical factors including the choice of ligand charge method, flexibility in ligand structure, and the size of the alchemical region including the number of atoms involved in transforming one ligand into another. Our findings provide a key set of recommendations that should be adopted for the reliable application of RBFE methods.This report presents nanoparticles composed of a liquid gallium core with a reduced graphene oxide (RGO) shell (Ga@RGO) of tunable thickness. The particles are produced by a simple, one-pot nanoprobe sonication method. The high near-infrared absorption of RGO results in a photothermal energy conversion of light to heat of 42.4%. This efficient photothermal conversion, combined with the large intrinsic thermal expansion coefficient of liquid gallium, allows the particles to be used for photoacoustic imaging, that is, conversion of light into vibrations that are useful for imaging. The Ga@RGO results in fivefold and twofold enhancement in photoacoustic signals compared with bare gallium nanoparticles and gold nanorods (a commonly used photoacoustic contrast agent), respectively. A theoretical model further reveals the intrinsic factors that affect the photothermal and photoacoustic performance of Ga@RGO. These core-shell Ga@RGO nanoparticles not only can serve as photoacoustic imaging contrast agents but also pave a new way to rationally design liquid metal-based nanomaterials with specific multi-functionality for biomedical applications.Hydrogels have attracted considerable interest in developing flexible bioelectronics such as wearable devices, brain-machine interface products, and health-monitoring sensors. However, these bioelectronics are always challenged by microbial contamination, which frequently reduces their service life and durability due to a lack of antibacterial property. Herein, we report a class of inherently antibacterial conductive hydrogels (ACGs) as bioelectronics for motion and temperature detection. The ACGs were composed of poly(N-isopropylacrylamide) (pNIPAM) and silver nanowires (AgNWs) via a two-step polymerization strategy, which increased the crosslink density for enhanced mechanical properties. The introduction of AgNWs improved the conductivity of ACGs and endowed them with excellent antibacterial activity against both Gram-positive and -negative bacteria. Meanwhile, pNIPAM existed in ACGs and exhibited a thermal responsive behavior, thereby inducing sharp changes in their conductivity around body temperature, which was successfully employed to assemble a temperature alarm. Moreover, ACG-based sensors exhibited excellent sensitivity (within a small strain of 5%) and the capability of capturing various motion signals (finger bending, elbow bending, and even throat vibrating). Selleckchem TC-S 7009 Benefiting from the superiority of ACG-based sensors, we further demonstrated a wearable wireless system for the remote control of a vehicle, which is expected to help disabled people in the future.The Co-O covalency in perovskite oxide cobaltites such as La1-xSrxCoO3 is believed to impact the electrocatalytic activity during electrochemical water splitting at the anode where the oxygen evolution reaction (OER) takes place. Additionally, space charge layers through band bending at the interface to the electrolyte may affect the electron transfer into the electrode, complicating the analysis and identification of true OER activity descriptors. Here, we separate the influence of covalency and band bending in hybrid epitaxial bilayer structures of highly OER-active La0.6Sr0.4CoO3 and undoped and less-active LaCoO3. Ultrathin LaCoO3 capping layers of 2-8 unit cells on La0.6Sr0.4CoO3 show intermediate OER activity between La0.6Sr0.4CoO3 and LaCoO3 evidently caused by the increased surface Co-O covalency compared to single LaCoO3 as detected by X-ray photoelectron spectroscopy. A Mott-Schottkyanalysis revealed low flat band potentials for different LaCoO3 capping layer thicknesses, indicating that no limiting extended space charge layer exists under OER conditions as all catalyst bilayer films exhibited hole accumulation at the surface. The combined X-ray photoelectron spectroscopy and Mott-Schottky analysis thus enables us to differentiate between the influence of the covalency and intrinsic space charge layers, which are indistinguishable in a single physical or electrochemical characterization. Our results emphasize the prominent role of transition metal oxygen covalency in perovskite electrocatalysts and introduce a bilayer approach to fine-tune the surface electronic structure.