The advances and insights gained in this work are useful for the application and development of long-range corrected hybrid functionals, while emphasizing the significance of developing effective and low-cost long-range correlation functionals.Vibrational configuration interaction calculations (VCI) have been performed to study the impact of the nature of the underlying coordinate systems, i.e., canonical vs localized normal coordinates, on accurate vibrational structure calculations for non-Abelian molecules. Once the correlation space is represented by real-valued primitive Hartree products, the assignment of vibrational states beyond the fundamentals is usually a tedious task and is further complicated by the use of non-symmetry-adapted coordinates. Our recently presented approach based on sparse grid integration of overlap integrals of the VCI wave function with the corresponding harmonic oscillator wave function has been used to determine and assign all fundamentals and vibrational overtones of allene and its deuterated isotopologue. Excellent agreement with available experimental results is observed in all cases.A new member to the A2IBIICIVX4 compound family, Cu2ZnSbS4, was synthesized successfully using ball milling and postannealing in H2S-atmosphere. For comparative purposes, Cu3SbS4 was additionally prepared using the same synthetic approach. As is common for A2IBIICIVX4 compounds, Cu2ZnSbS4 crystallizes isostructural to Cu3SbS4 in the stannite-type structure in space group I42m. Both antimony sulfides contain monovalent diamagnetic copper and are characterized by substantial covalent bonding. This is consistent with the 121Sb isomer shifts occurring for the Mössbauer spectra of Cu2ZnSbS4 (-7.71 mm s-1) and Cu3SbS4 (-7.68 mm s-1) which fall in the region of covalently bonded Sb(V) compounds. These spectroscopic results are supported by electronic structure calculations.Stimuli-responsive emulsifiers have emerged as a class of smart agents that can permit regulated stabilization and destabilization of emulsions, which is essential for food, cosmetic, pharmaceutical, and petroleum industries. Here, we report the synthesis of novel “smart” hydroxyapatite (HaP) magnetic nanoparticles and their corresponding stimuli-responsive Pickering emulsions and explore their movement under confined spaces using a microfluidic platform. Pickering emulsions prepared with our magnetic stearic acid-functionalized Fe2O3@HaP nanoparticles exhibited pronounced pH-responsive behavior. We observed that the diameter of emulsion droplets decreases with an increase in pH. Swift demulsification was achieved by lowering the pH, whereas the reformation of emulsions was achieved by increasing the pH; this emulsification-demulsification cycling was successful for at least ten cycles. We used a microfluidic platform to test the stability of the emulsions under flowing conditions and their response to a magnetic field. We observed that the emulsion stability was diminished and droplet coalescence was enhanced by the application of the magnetic field. The smart nanoparticles we developed and their HaP-based emulsions present promising materials for pharmaceutical and petroleum industries, where responsive emulsions with controlled stabilities are required.Recently, it has been reported that the enstatite chondrite (EC) meteorite may contain enough hydrogen to provide a plausible explanation for water’s initial existence on Earth. Perryite mineral is one of the key components of EC, but its detailed chemical composition and phase width remain elusive compared with other minerals found in EC. Therefore, we embark on a series of investigations of the synthesis, crystal structure, and electronic structure of the synthetic perryite mineral (Ni x Fe1-x)8(T y P1-y)3 (T = Si and Ge; 1 ≥ x, y ≥ 0). Its crystal structures were established based on single-crystal and powder X-ray diffraction techniques. It is realized that its structural and phase stabilities are highly dependent on the nature of the doping element (i.e., Fe and Si). The inclusion of Si and Fe elements can greatly alter the bonding scheme near the Fermi level (Ef), which is vital to the phase stability and accounts for the chemical composition of the natural perryite mineral (quaternary compound) in EC meteorites. Furthermore, this phase exhibits good electrocatalytic activity toward the hydrogen evolution reaction (HER). The best and the worst HER performances are for the Ni8Ge2P and Ni8Si2P samples, respectively, which suggests that the long bond length and high polarity of the covalent bond are the preferred criteria to enhance the electrocatalytic HER in this series.Magnetic carbon nanostructures are currently under scrutiny for a wide spectrum of applications. Here, we theoretically investigate armchair graphene nanoribbons patterned with asymmetric edge extensions consisting of laterally fused naphtho groups, as recently fabricated via on-surface synthesis. We show that an individual edge extension acts as a spin- 1 2 center and develops a sizable spin-polarization of the conductance around the band edges. The Heisenberg exchange coupling between a pair of edge extensions is dictated by the position of the second naphtho group in the carbon backbone, thus enabling ferromagnetic, antiferromagnetic, or nonmagnetic states. The periodic arrangement of edge extensions yields full spin-polarization at the band extrema, and the accompanying ferromagnetic ground state can be driven into nonmagnetic or antiferromagnetic phases through external stimuli. Overall, our work reveals a precise tunability of the π-magnetism in graphene nanoribbons induced by naphtho groups, thereby establishing these one-dimensional architectures as suitable platforms for logic spintronics.LnmK stereospecifically accepts (2R)-methylmalonyl-CoA, generating propionyl-S-acyl carrier protein to support polyketide biosynthesis. LnmK and its homologues are the only known enzymes that carry out a decarboxylation (DC) and acyl transfer (AT) reaction in the same active site as revealed by structure-function studies. Substrate-assisted catalysis powers LnmK, as decarboxylation of (2R)-methylmalonyl-CoA generates an enolate capable of deprotonating active site Tyr62, and the Tyr62 phenolate subsequently attacks propionyl-CoA leading to a propionyl-O-LnmK acyl-enzyme intermediate. Due to the inherent reactivity of LnmK and methylmalonyl-CoA, a substrate-bound structure could not be obtained. selleckchem To gain insight into substrate specificity, stereospecificity, and catalytic mechanism, we determined the structures of LnmK with bound substrate analogues that bear malonyl-thioester isosteres where the carboxylate is represented by a nitro or sulfonate group. The nitro-bearing malonyl-thioester isosteres bind in the nitronate form, with specific hydrogen bonds that allow modeling of the (2R)-methylmalonyl-CoA substrate and rationalization of stereospecificity.