Synthesis,crystal structure,and electronic structure of Li2PbSiS4: a quaternary thiosilicate with a compressed chalcopyrite‐like structure

The new quaternary thiosilicate, Li₂PbSiS₄ (dilithium lead silicon tetrasulfide), was prepared in an evacuated fused‐silica tube via high‐temperature, solid‐state synthesis at 800 °C, followed by slow cooling. The crystal structure was solved and refined using single‐crystal X‐ray diffraction data. By strict definition, the title compound crystallizes in the stannite structure type; however, this type of structure can also be described as a compressed chalcopyrite‐like structure. The Li⁺ cation lies on a crystallographic fourfold rotoinversion axis, while the Pb²⁺ and Si⁴⁺ cations reside at the intersection of the fourfold rotoinversion axis with a twofold axis and a mirror plane. The Li⁺ and Si⁴⁺ cations in this structure are tetrahedrally coordinated, while the larger Pb²⁺ cation adopts a distorted eight‐coordinate dodecahedral coordination. These units join together via corner‐ and edge‐sharing to create a dense, three‐dimensional structure. Powder X‐ray diffraction indicates that the title compound is the major phase of the reaction product. Electronic structure calculations, performed using the full potential linearized augmented plane wave method within density functional theory (DFT), indicate that Li₂PbSiS₄ is a semiconductor with an indirect bandgap of 2.22 eV, which compares well with the measured optical bandgap of 2.51 eV. The noncentrosymmetric crystal structure and relatively wide bandgap designate this compound to be of interest for IR nonlinear optics.     

Prediction of African Swine Fever Virus Inhibitors by Molecular Docking-Driven Machine Learning Models

African swine fever virus (ASFV) causes a highly contagious and severe hemorrhagic viral disease with high mortality in domestic pigs of all ages. Although the virus is harmless to humans, the ongoing ASFV epidemic could have severe economic consequences for global food security. Recent studies have found a few antiviral agents that can inhibit ASFV infections. However, currently, there are no vaccines or antiviral drugs. Hence, there is an urgent need to identify new drugs to treat ASFV. Based on the structural information data on the targets of ASFV, we used molecular docking and machine learning models to identify novel antiviral agents. We confirmed that compounds with high affinity present in the region of interest belonged to subsets in the chemical space using principal component analysis and k-means clustering in molecular docking studies of FDA-approved drugs. These methods predicted pentagastrin as a potential antiviral drug against ASFVs. Finally, it was also observed that the compound had an inhibitory effect on AsfvPolX activity. Results from the present study suggest that molecular docking and machine learning models can play an important role in identifying potential antiviral drugs against ASFVs.     

Characterization of Functional Groups in Estuarine Dissolved Organic Matter by DNP-enhanced 15N and 13C Solid-State NMR

Estuaries are key ecosystems with unique biodiversity and are of high economic importance. Along the estuaries, variations in environmental parameters, such as salinity and light penetration, can modify the characteristics of dissolved organic matter (DOM). Nevertheless, there is still limited information about the atomic-level transformations of DOM in this ecosystem. Solid-state NMR spectroscopy provides unique insights into the nature of functional groups in DOM. A major limitation of this technique is its lack of sensivity, which results in experimental time of tens of hours for the acquisition of ¹³C NMR spectra and generally precludes the observation of ¹⁵N nuclei for DOM. We show here how the sensitivity of solid-state NMR experiments on DOM of Seine estuary can be enhanced using dynamic nuclear polarization (DNP) under magic-angle spinning. This technique allows the acquisition of ¹³C NMR spectra of these samples in few minutes, instead of hours for conventional solid-state NMR. Both conventional and DNP-enhanced ¹³C NMR spectra indicate that the ¹³C local environments in DOM are not strongly modified along the Seine estuary. Furthermore, the sensitivity gain provided by the DNP allows the detection of ¹⁵N NMR signal of DOM, in spite of the low nitrogen content. These spectra reveal that the majority of nitrogen is in the amide form in these DOM samples and show an increased disorder around these amide groups near the mouth of the Seine.     

Interphotoreceptor Retinoid‐Binding Protein Protects Retinoids from Photodegradation

Retinol degrades rapidly in light into a variety of photoproducts. It is remarkable that visual cycle retinoids can evade photodegradation as they are exchanged between the photoreceptors, retinal pigment epithelium and Müller glia. Within the interphotoreceptor matrix, all‐trans retinol, 11‐cis retinol and retinal are bound by interphotoreceptor retinoid‐binding protein (IRBP). Apart from its role in retinoid trafficking and targeting, could IRBP have a photoprotective function? HPLC was used to evaluate the ability of IRBP to protect all‐trans and 11‐cis retinols from photodegradation when exposed to incandescent light (0 to 8842 μW cm^?2); time periods of 0–60 min, and bIRBP: retinol molar ratios of 1:1 to 1:5. bIRBP afforded a significant prevention of both all‐trans and 11‐cis retinol to rapid photodegradation. The effect was significant over the entire light intensity range tested, and extended to the bIRBP: retinol ratio 1:5. In view of the continual exposure of the retina to light, and the high oxidative stress in the outer retina, our results suggest IRBP may have an important protective role in the visual cycle by reducing photodegradation of all‐trans and 11‐cis retinols. This role of IRBP is particularly relevant in the high flux conditions of the cone visual cycle.     

Interfacial Engineering of CdO–CdSe 3D Microarchitectures with in situ Photopolymerized PEDOT for an Enhanced Photovoltaic Performance

In the present work, porous 3D CdO‐microstructured electrode obtained by pyrolysis of 3D CdCO₃ microstructures is self‐sensitized with CdSe using an ion exchange reaction. After sensitization, an interfacial treatment of the CdO–CdSe interface is performed by depositing a thin film of PEDOT using a photoinduce polymerization route. The microstructured electrode before and after interfacial treatment is characterized using field‐emission scanning microscope, energy dispersive X‐ray analyzer, contact angle measurement, UV–Visible absorption spectrophotometer and X‐ray photoelectron spectrometer. After constructing a liquid junction solar cell with a Pt counter electrode, the photovoltaic performance and interfacial charge transfer kinetics across the CdO–CdSe interface before and after PEDOT treatment are investigated. The results exhibit an improved interfacial charge‐transfer resistance after the PEDOT treatment, which leads to enhance the short‐circuit current by 15.81% and the power conversion efficiency by 19.82%.     

Origins of the Intermediate Spectral Form in M100 Mutants of Photoactive Yellow Protein

Numerous single‐site mutants of photoactive yellow protein (PYP) from Halorhodospira halophila and as well as PYP homologs from other species exhibit a shoulder on the short wavelength side of the absorbance maximum in their dark‐adapted states. The structural basis for the occurrence of this shoulder, called the “intermediate spectral form,” has only been investigated in detail for the Y42F mutation. Here we explore the structural basis for occurrence of the intermediate spectral form in a M121E derivative of a circularly permuted H. halophila PYP (M121E‐cPYP). The M121 site in M121E‐cPYP corresponds to the M100 site in wild‐type H. halophila PYP. High‐resolution NMR measurements with a salt‐tolerant cryoprobe enabled identification of those residues directly affected by increasing concentrations of ammonium chloride, a salt that greatly enhances the fraction of the intermediate spectra form. Residues in the surface loop containing the M121E (M100E) mutation were found to be affected by ammonium chloride as well as a discrete set of residues that link this surface loop to the buried hydroxyl group of the chromophore via a hydrogen bond network. Localized changes in the conformational dynamics of a surface loop can thereby produce structural rearrangements near the buried hydroxyl group chromophore while leaving the large majority of residues in the protein unaffected.     

Yttrium Complexes of Arsine,Arsenide, and Arsinidene Ligands

Deprotonation of the yttrium–arsine complex [Cp′₃Y{As(H)₂Mes}] ( 1 ) (Cp′=η⁵‐C₅H₄Me, Mes=mesityl) by nBuLi produces the μ‐arsenide complex [{Cp′₂Y[μ‐As(H)Mes]}₃] ( 2 ). Deprotonation of the As H bonds in 2 by nBuLi produces [Li(thf)₄]₂[{Cp′₂Y(μ₃‐AsMes)}₃Li], [Li(thf)₄]₂[ 3 ], in which the dianion 3 contains the first example of an arsinidene ligand in rare‐earth metal chemistry. The molecular structures of the arsine, arsenide, and arsinidene complexes are described, and the yttrium–arsenic bonding is analyzed by density functional theory.