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Abstract: Nonlinear interactions between X-rays and long wavelength radiation can be used as a powerful atomic-scale probe for light-matter interactions and for properties of valence electrons. However, reported X-ray nonlinear effects were small and their observations required tremendous efforts. Here we report the observation of strong nonlinearities in parametric down-conversion (PDC) of X-rays to long wavelength radiation in gallium arsenide and lithium niobate crystals, with efficiencies about 4 orders of magnitude stronger than the efficiencies measured in any material studied before. Furthermore, we show that the efficiency in the ferroelectric phase of strontium barium niobite is two orders of magnitude stronger than in its paraelectric phase. This observation suggests that the lack of inversion symmetry is the origin for the strong observed nonlinearity. Additionally, we demonstrate the ability to use the effect for the investigation of the spectral response of non-centrosymmetric materials at wavelengths ranging from infrared to soft X-rays.

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Abstract: Theoretical formulations capable of modeling chemical interactions over 3–4 orders of magnitude of bond strength, from covalent to van der Waals (vdW) forces, are one of the primary goals in materials physics, and chemistry. Development of vdW corrections for density-functional theory has thus been a major research field for two decades. While many of these corrections are semiempirical, more theoretically rigorous ab initio functionals have been developed. The ab initio functional vdW-DF2, when coupled with the reoptimized B86 exchange function (vdW-DF2-rB86), has typically performed as well, if not better than most semiempirical formulations. Here we present a system, Co intercalation of graphene on Ir(111), for which a semiempirical correction predicts local corrugation maxima in locations at which the vdW-DF2-rB86 functional predicts global minima. Sub-angstrom precision quantitative structural measurements show better agreement with the semiempirical correction. We posit that it is balancing the weak vdW interaction with the stronger, even covalent, interactions that proves a challenge for the vdW-DF2-rB86 functional.

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Abstract: The 2‐oxoglutarate‐dependent hypoxia inducible factor prolyl hydroxylases (PHDs) are targets for treatment of a variety of diseases including anaemia. One PHD inhibitor is approved for use for the treatment of renal anaemia and others are in late stage clinical trials. The number of reported templates for PHD inhibition is limited. We report structure–activity relationship and crystallographic studies on a promising class of 4‐hydroxypyrimidine‐containing PHD inhibitors.

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Abstract: X-ray absorption fine structure analysis has been successfully used to determine the coordination environment and therefore uptake mechanism towards the uranyl cation for a selection of commercially available ion exchange resins in non-saline and saline conditions ([Cl−] = 22.7 g L−1, 0.64 M) similar to those found in sea water. The resins tested were Purolite S985, S910 and S957, Dowex M4195, Ps-EDA, Ps-DETA and Ps-PEHA, which contain polyamine, amidoxime, mixed sulfonic/phosphonic acid, bispicolylamine, ethylenediamine, diethylenetriamine and pentaethylenehexamine functional groups, respectively. Purolite S910 and S957 were both found to extract the uranyl cation through a chelation mechanism. The uranium coordination environment on uranyl loaded Purolite S910 was found to be either tetra- or hexa-coordinate in the equatorial plane, with a 2:1 ratio of amidoxime:uranium in the fit suggesting either monodentate or η2 coordination by two amidoxime groups. The uranium environment for uranyl loaded Purolite S957 was found to be tetra-coordinate in the equatorial plane, with both sulfonic and phosphonic acid groups being involved in sorption. The presence of chloride in the loading solution had no effect on the uranyl coordination environment observed on any of the resins. In contrast, Dowex M4195, Purolite S985, Ps-EDA, Ps-DETA and Ps-PEHA exhibited an anion exchange mechanism for uranyl uptake as the corresponding extended X-ray absorption fine structure (EXAFS) data best fit a [UO2(SO4)3]4− structure.

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Abstract: β-Lactamases comprise the most important known mode of resistance to β-lactam antibiotics. Boronic acids/boronate esters show promise as a new class of β-lactamase inhibitors with the potential to inhibit both the metallo- and serine-β-lactamases. We report studies employing representative β-lactamases concerning a bicyclic boronate ester with a thioether rather than the more typical β-lactam antibiotic ‘C-6/C-7’ acylamino side chain as present in the penicillin/cephalosporin antibiotics. The results, including a crystal structure of the clinically relevant VIM-2 metallo β-lactamase in complex with the inhibitor, reveal the potential of boronate inhibitors without the canonical acylamino side chain for inhibition of a broader range of serine- and metallo- β-lactamases compared to previous bicyclic boronates, including the metallo-β-lactamase L1. They imply further SAR studies will expand the already broad scope of -lactamase inhibition by bicyclic boronates.