Synthesis of Honeycomb-Structured Beryllium Oxide via Graphene Liquid Cells

Using high-resolution transmission electron microscopy and electron energy-loss spectroscopy, we show that beryllium oxide crystallizes in the planar hexagonal structure in a graphene liquid cell by a wet-chemistry approach. These liquid cells can feature van-der-Waals pressures up to 1 GPa, producing a miniaturized high-pressure container for the crystallization in solution. The thickness of as-received crystals is beyond the thermodynamic ultra-thin limit above which the wurtzite phase is energetically more favorable according to the theoretical prediction. The crystallization of the planar phase is ascribed to the near-free-standing condition afforded by the graphene surface. Our calculations show that the energy barrier of the phase transition is responsible for the observed thickness beyond the previously predicted limit. These findings open a new door for exploring aqueous-solution approaches of more metal-oxide semiconductors with exotic phase structures and properties in graphene-encapsulated confined cells.     

External electric field effect on electronic properties and charge transfer in CoI2/NiI2 spinterface

Electronic structure and spin-related properties of CoI₂/NiI₂ heterostructure were studied by means of density functional theory. It was shown that the electronic structure at the Fermi level can be characterized by a band gap. The effect of the external electric field on charge transfer and electronic properties of the CoI₂/NiI₂ interface was investigated, and it was found that band gap width depends on the strength of the applied electric field, switching its nature from semiconducting to a half-metallic one. An easy control of the electronic properties and promising spin-polarized nature of the CoI₂/NiI₂ spinterface allows the heterostructure to be used in spin-related applications.     

Synthesis,characterization, and biological screening of metal complexes of novel sulfonamide derivatives: Experimental and theoretical analysis of sulfonamide crystal

This study reports the synthesis of sulfonamide-derived Schiff bases as ligands L ¹ and L ² as well as their transition metal complexes [VO(IV), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II)]. The Schiff bases (4-{E-[(2-hydroxy-3-methoxyphenyl)methylidene]amino}benzene-1-sulfonamide ( L ¹ ) and 4-{[(2-hydroxy-3-methoxyphenyl)methylidene]amino}-N-(5-methyl-1,2-oxazol-3-yl)benzene-1-sulfonamide ( L ² ) were synthesized by the condensation reaction of 4-aminobenzene-1-sulfonamide and 4-amino-N-(3-methyl-2,3-dihydro-1,2-oxazol-5-yl)benzene-1-sulfonamide with 2-hydroxy-3-methoxybenzaldehyde in an equimolar ratio. Sulfonamide core ligands behaved as bidentate ligands and coordinated with transition metals via nitrogen of azomethine and the oxygen of the hydroxyl group. Ligand L ¹ was recovered in its crystalline form and was analyzed by single-crystal X-ray diffraction technique which held monoclinic crystal system with space group (P2₁/c). The structures of the ligands L ¹ and L ² and their transition metal complexes were established by their physical (melting point, color, yields, solubility, magnetic susceptibility, and conductance measurements), spectral (UV–visible [UV–Vis], Fourier transform infrared spectroscopy, ¹H NMR, ¹³C NMR, and mass analysis), and analytical (CHN analysis) techniques. Furthermore, computational analysis (vibrational bands, frontier molecular orbitals (FMOs), and natural bonding orbitals [NBOs]) were performed for ligands through density functional theory utilizing B3LYP/6-311+G(d,p) level and UV–Vis analysis was carried out by time-dependent density functional theory. Theoretical spectroscopic data were in line with the experimental spectroscopic data. NBO analysis confirmed the extraordinary stability of the ligands in their conjugative interactions. Global reactivity parameters computed from the FMO energies indicated the ligands were bioactive by nature. These procedures ensured the charge transfer phenomenon for the ligands and reasonable relevance was established with experimental results. The synthesized compounds were screened for antimicrobial activities against bacterial (Streptococcus aureus, Bacillus subtilis, Eshcheria coli, and Klebsiella pneomoniae) species and fungal (Aspergillus niger and Aspergillus flavous) strains. A further assay was designed for screening of their antioxidant activities (2,2-diphenyl-1-picrylhydrazine radical scavenging activity, total phenolic contents, and total iron reducing power) and enzyme inhibition properties (amylase, protease, acetylcholinesterase, and butyrylcholinesterase). The substantial results of these activities proved the ligands and their transition metal complexes to be bioactive in their nature.     

Enhanced Dual Fuel Cell Electrocatalysis with Trimetallic PtPdCo Mesoporous Nanoparticles

The facile preparation of platinum‐based catalysts with designed compositions and structures is of great importance for fuel cells. In this work, a one‐pot method is developed to synthesize monodispersed trimetallic PtPdCo mesoporous nanoparticles (PtPdCo MNs) with uniform morphology and size. The proposed synthetic method does not require any hard template or organic solvent, which greatly simplifies the preparation procedure. PtPdCo MNs, with a highly porous structure, exhibit enhanced electrocatalytic activities and excellent stabilities for both the formic acid oxidation reaction and the oxygen reduction reaction, relative to bimetallic PtPd MNs and commercial Pt/C catalyst. The proposed synthetic method is highly valuable for the design of mesoporous multimetallic catalysts for fuel cells.     

Semiclassical transition state theory/master equation kinetics of HO + CO: Performance evaluation

Previously, master equation (ME) simulations using semiclassical transition state theory (SCTST) and high-accuracy extrapolated ab initio thermochemistry (HEAT) predicted rate constants in excellent agreement with published experimental data over a wide range of pressure and temperatures ≳250 K, but the agreement was not as good at lower temperatures. Possible reasons for this reduced performance are investigated by (a) critically evaluating the published experimental data and by investigating; (b) three distinct ME treatments of angular momentum, including one that is exact at the zero- and infinite-pressure limits; (c) a hindered-rotor model for HOCO that implicitly includes the cis- and trans-conformers; (d) possible empirical adjustments of the thermochemistry; (e) possible empirical adjustments to an imaginary frequency controlling tunneling; (f) including or neglecting the prereaction complex PRC1; and (g) its possible bimolecular reactions. Improvements include better approximations to factors in SCTST and using the Hill and van Vleck treatment of angular momentum coupling. Evaluation of literature data does not reveal any specific shortcomings, but the stated uncertainties may be underestimated. All ME treatments give excellent fits to experimental data at T ≥ 250 K, but the discrepancy at T < 250 K persists. Note that each ME model requires individual empirical energy transfer parameters. Thermochemical adjustments were unable to match the experimental H/D kinetic isotope effects. Adjusting an imaginary frequency can achieve good fits, but the adjustments are unacceptably large. Whether PRC1 and its possible bimolecular reactions are included had little effect. We conclude that none of the adjustments is an improvement over the unadjusted theory. Note that only one set of experimental data exists in the regime of the discrepancy with theory, and data for DO + CO are scanty.     

Simultispin: A versatile graphical user interface for the simulation of solid-state continuous wave EPR spectra

Solid-state continuous wave (cw) electronic paramagnetic resonance (EPR) spectroscopy is particularly suitable for metal complex analysis. Extracting magnetic parameters by simulation is often necessary to describe the electronic structure of the studied molecular compounds that can have various electronic spin states and characterized by different parameters like g-values, hyperfine coupling or zero field splitting values. Easyspin toolbox on MATLAB is a powerful tool, but for the user, it requires spending time with coding and could discourage nonexperts. Facing this context, we have developed a graphical user interface called Simultispin, dedicated to solid-state cw-EPR spectra simulation. Some examples of experimental spectra of metal complexes (mixture of low spin and high spin Fe^III complexes, dynamic disorder of a Cu^II complex, photogeneration of a Mn^III complex), highlighting specific solid-state functions, are described and analyzed based on simulations performed with Simultispin. We hope that its ergonomy and the ease to set up a complete set of parameters to get reliable simulations could help a large EPR community to improve the efficiency of their interpretations.     

Architectural control of polystyrene physical properties using branched anionic polymerization initiated at ambient temperature

Ambient temperature-initiated anionic polymerization has generated branched polystyrenes of varying molecular weights and architectures by inclusion of a distyryl branching comonomer into a conventional sec-Butylithium-initiated polymerization of styrene. Primary chain length control within the branched polymers, and restriction of the branching points to varying segments of the primary chains, led to variations of glass transition temperature with no direct correlation to the branched polymer molecular weight but a strong relationship to the length of individual chains comprising the branched macromolecules.     

Photoinitiated polymerization of methacrylates comprising phenyl moieties

Investigation of photopolymerization kinetics of 4-(4-methacryloyloxyphenyl)-butan-2-one (1) in comparison with 2-phenoxyethyl methacrylate (2) and phenyl methacrylate (3) using a UV-LED emitting at 395 nm shows significantly faster polymerization of 1 compared to both 2 and 3 at 40°C. Vitrification affects photopolymerization kinetics of all methacrylates under investigation. Interestingly, quantitative final conversion is observed during photoinitiated polymerization of 1 and 2 whereas 3 shows limited conversion at about 80%. Furthermore, higher degree of polymerization is obtained by photoinitiated polymerization of 1 compared to 2 and 3. This shows that the 3-oxobutyl substituent at the phenyl ring of 1 significantly affects both polymerization kinetics and final conversion of the photoinitiated polymerization. Moreover, an additional higher molecular weight fraction is observed in case of polymerization of 1 at 85°C that is above the glass transition temperature of the polymer formed during photoinitiated polymerization. As a thermal polymerization at 85°C in the absence of light results in a high molecular weight polymer as well, an additional thermal process may be discussed as reason for the higher molecular weight polymer fraction in case of the photopolymer made at 85°C.     

Zn–Co Sulfide Microflowers Anchored on Three-Dimensional Graphene: A High-Capacitance and Long-Cycle-Life Electrode for Asymmetric Supercapacitors

Zinc–cobalt double-metal sulfides (ZCS) as Faradic electrode materials with high energy density have great potential for supercapacitors, but their poor transfer efficiency for electrons and ions hinders their electrochemical response. Herein, ZnCo₂(CO₃)_1.5(OH)₃@ZCS microflower hybrid arrays consisting of thin nanolayer petals were anchored on three-dimensional graphene (ZnCo₂(CO₃)_1.5(OH)₃@ZCS/3DG) by a simple hydrothermal method and additional ion-exchange process. A ZnCo₂(CO₃)_1.5(OH)₃@ZCS/3DG electrode delivered high capacitance (2228 F g⁻¹ at 1 A g⁻¹) and long cycling life (85.7 % retention after 17 000 cycles), which are ascribed to the multicomponent structural design. The 3DG conductive substrate improves the electron-transfer dynamics of the electrode material. Meanwhile, the microflowers consisting of thin nanolayer petals could not only provide many active sites for ions to improve the capacitance, but also alleviate the volume expansion to ensure the structural stability. Furthermore, an all-solid-state asymmetric supercapacitor based on a ZnCo₂(CO₃)_1.5(OH)₃@ZCS/3DG electrode achieved a high energy density of 27 W h kg⁻¹ at 528.3 W kg⁻¹ and exhibits exceptional cyclic stability for 23 000 cycles. Its ability to light a blue LED for 9 min verified the feasibility of its application for energy storage devices.     

Coordinating Ability of Anions,Solvents, Amino Acids,and Gases towards Alkaline and Alkaline-Earth Elements,Transition Metals,and Lanthanides

After briefly reviewing the applications of the coordination ability indices proposed earlier for anions and solvents toward transition metals and lanthanides, a new analysis of crystal structures is applied now to a much larger number of coordinating species: anions (including those that are present in ionic solvents), solvents, amino acids, gases, and a sample of neutral ligands. The coordinating ability towards s-block elements is now also considered. The effect of several factors on the coordinating ability will be discussed: (a) the charge of an anion, (b) the chelating nature of anions and solvents, (c) the degree of protonation of oxo-anions, carboxylates and amino carboxylates, and (d) the substitution of hydrogen atoms by methyl groups in NH₃, ethylenediamine, benzene, ethylene, pyridine and aldehydes. Hit parades of solvents and anions most commonly used in the areas of transition metal, s-block and lanthanide chemistry are deduced from the statistics of their presence in crystal structures.