Study on the decisive factor for metal-insulator transitions in a LaVO3 Mott-Hubbard insulator.

The decisive physical parameters on electrical conduction in a LaVO3 Mott-Hubbard system are systematically investigated by analyzing pure, Ca-, and Sr-doped samples. The Rietveld refinement of the X-ray diffraction data indicates that a drastic change occurs along the c-axis to reduce the octahedral tilt thereby relaxing the distortion for the doped compounds, in contrast to an insignificant change in the in-plane distortion. From electrical, optical, and photoemission measurements, both Ca and Sr-doping in LaVO3 induce insulator to metal transitions under a similar hole carrier concentration as suppressing the Mott-gap excitation. Fitting results on temperature-dependent resistivity based on various conduction models indicate that the most localized conduction behavior takes place for the highly distorted pure LaVO3, while disordered Fermi liquid behavior starts to appear for moderately distorted Ca-doped LaVO3. The least distorted Sr-doped LaVO3 exhibits fully delocalized conduction governed by a non-Fermi-liquid-like behavior in the whole temperature range. Our analysis indicates that the difference in the transport mechanism arises from the differing degree of hybridization of the V 3d and O 2p states in the pure and doped systems, strongly associated with the structural distortion.

Earth Abundant Oxidation Catalysts for Removal of Contaminants of Emerging Concern from Wastewater: Homogeneous Catalytic Screening of Monomeric Complexes.

Twenty novel Mn, Fe, and Cu complexes of ethylene cross-bridged tetraazamacrocycles with potentially copolymerizable allyl and benzyl pendant arms were synthesized and characterized. Multiple X-ray crystal structures demonstrate the cis-folded pseudo-octahedral geometry forced by the rigidifying ethylene cross-bridge and show that two cis coordination cites are available for interaction with substrate and oxidant. The Cu complexes were used to determine kinetic stability under harsh acidic and high-temperature conditions, which revealed that the cyclam-based ligands provide superior stabilization with half-lives of many minutes or even hours in 5 M HCl at 50-90 °C. Cyclic voltammetry studies of the Fe and Mn complexes reveal reversible redox processes indicating stabilization of Fe2+/Fe3+ and Mn2+/Mn3+/Mn4+ oxidation states, indicating the likelihood of catalytic oxidation for these complexes. Finally, dye-bleaching experiments with methylene blue, methyl orange, and rhodamine B demonstrate efficient catalytic decolorization and allow selection of the most successful monomeric catalysts for copolymerization to produce future heterogeneous water purification materials.

The compartment-specific manipulation of the NAD+/NADH ratio affects the metabolome and the function of glioblastoma.

Glioblastoma multiforme (GBM) is the most aggressive type of cancer in the brain and has an inferior prognosis because of the lack of suitable medicine, largely due to its tremendous invasion. GBM has selfish metabolic pathways to promote migration, invasion, and proliferation compared to normal cells. Among various metabolic pathways, NAD (nicotinamide adenine dinucleotide) is essential in generating ATP and is used as a resource for cancer cells. LbNOX (Lactobacillus brevis NADH oxidase) is an enzyme that can directly manipulate the NAD+/NADH ratio. In this study, we found that an increased NAD+/NADH ratio by LbNOX or mitoLbNOX reduced intracellular glutamate and calcium responses and reduced invasion capacity in GBM. However, the invasion was not affected in GBM by rotenone, an ETC (Electron Transport Chain) complex I inhibitor, or nicotinamide riboside, a NAD+ precursor, suggesting that the crucial factor is the NAD+/NADH ratio rather than the absolute quantity of ATP or NAD+ for the invasion of GBM. To develop a more accurate and effective GBM treatment, our findings highlight the importance of developing a new medicine that targets the regulation of the NAD+/NADH ratio, given the current lack of effective treatment options for this brain cancer.

Promotion of Processability in a p-Type Thin-Film Transistor Using a Se-Te Alloying Channel Layer.

p-type thin-film transistors (pTFTs) have proven to be a significant impediment to advancing electronics beyond traditional Si-based technology. A recent study suggests that a thin and highly crystalline Te layer shows promise as a channel for high-performance pTFTs. However, achieving this still requires specific conditions, such as a cryogenic growth temperature and an extremely thin channel thickness on the order of a few nanometers. These conditions critically limit the practical feasibility of the fabrication process. Here, we report a high-performance pTFT incorporating a 60-nm-thick highly crystalline Se-Te alloyed channel layer, produced using pulsed laser ablation at room temperature. The Se0.5Te0.5 alloy system enhances crystalline temperature and widens the band gap compared to a pure Te channel. Consequently, this approach results in a field-effect mobility of 3 cm2/V·s, with an on/off current ratio of 3 × 105, a subthreshold slope of 2.1 V/decade, and a turn-on voltage of 6.5 V, achieved through conventional annealing at 250 °C. To demonstrate its applicability in complementary circuit applications, we integrate a complementary-type inverter using a p-type Se0.5Te0.5 TFT and an n-type Al-doped InZnSnO, demonstrating a high voltage gain of 12 and a low static power consumption of 17 nW. This suggests that the Se-Te alloyed channel approach paves the way to a more straightforward and cost-effective process for Te-based pTFT devices and their applications.

Reducing Peptidoglycan Crosslinking by Chemical Modulator Reverts ß-lactam Resistance in Methicillin-Resistant Staphylococcus aureus.

Small molecule can be utilized to restore the effectiveness of existing major classes of antibiotics against antibiotic-resistant bacteria. In this study, it is demonstrated that celastrol, a natural compound, can modify the bacterial cell wall and subsequently render bacteria more suceptible to ß-lactam antibiotics. It is shown that celastrol leads to incomplete cell wall crosslinking by modulating levels of c-di-AMP, a secondary messenger, in methicillin-resistant Staphylococcus aureus (MRSA). This mechanism enables celastrol to act as a potentiator, effectively rendering MRSA susceptible to a range of penicillins and cephalosporins. Restoration of in vivo susceptibility of MRSA to methicillin is also demonstrated using a sepsis animal model by co-administering methicillin along with celastrol at a much lower amount than that of methicillin. The results suggest a novel approach for developing potentiators for major classes of antibiotics by exploring molecules that re-program metabolic pathways to reverse ß-lactam-resistant strains to susceptible strains.

A transparent p-type semiconductor designed via a polarizability-enhanced strongly correlated insulator oxide matrix.

Electron-transporting transparent conducting oxides (TCOs) are a commercial reality, however, hole-transporting counterparts are far more challenging because of limited material design. Here, we propose a strategy for enhancing the hole conductivity without deteriorating the band gap (Eg) and workfunction (Φ) by Cu incorporation in a strongly correlated NiWO4 insulator. The optimal Cu-doped NiWO4 (Cu0.185Ni0.815WO4) exhibits a resistivity reduction of ∼109 times versus NiWO4 as well as band-like charge transport with the hole mobility approaching 7 cm2 V-1 s-1 at 200 K, a deep Φ of 5.77 eV, and Eg of 2.8 eV. Experimental and theoretical data reveal that the strength of the electron correlation in NiWO4 is unaffected by Cu incorporation, while the promoted polarizability weakens electron-phonon coupling, promoting the formation of large polarons. Quantum dot light-emitting and oxide p/n junction devices incorporating Cu0.185Ni0.815WO4 exhibit remarkable performances, demonstrating that our approach can be deployed to discover new p-type TCOs.

Acceleration of NO2 gas sensitivity in two-dimensional SnSe2 by Br doping.

The authors report a Br doping effect on the NO2 gas sensing properties of a two-dimensional (2D) SnSe2 semiconductor. Single crystalline 2D SnSe2 samples with different Br contents are grown by a simple melt-solidification method. By analyzing the structural, vibrational as well as electrical properties, it can be confirmed that the Br impurity substitutes on the Se-site in SnSe2 serving as an efficient electron donor. When we measure the change of resistance under a 20 ppm NO2 gas flow condition at room temperature, both responsivity and response time are drastically improved by Br doping from 1.02% and 23 s to 3.38% and 15 s, respectively. From these results, it can be concluded that Br doping plays a key role for encouraging the charge transfer efficiency from the SnSe2 surface to the NO2 molecule by elaborating Fermi level in 2D SnSe2.

Chemical screen uncovers novel structural classes of inhibitors of the papain-like protease of coronaviruses.

The papain-like protease (PLpro) of coronaviruses is an attractive antiviral target to inhibit both viral replication and interference of the host immune response. We have identified and characterized three novel classes of small molecules, thiophene, cyanofuran, and triazoloquinazoline, as PLpro inhibitors. Thiophene inhibited the PLpro of two major coronaviruses, Middle East respiratory syndrome coronavirus (MERS-CoV) and severe acute respiratory syndrome coronavirus (SARS-CoV) including SARS-CoV-2, while cyanofuran and triazoloquinazoline more selectively inhibited MERS-CoV PLpro. Unlike GRL0617, a known PLpro inhibitor, all three compounds contain no naphthyl group but like GRL0617 were predicted to fit on the cleft near the BL2 loop. Docking studies further revealed that the location and direction of the binding determined their specificity to different coronaviruses. Together, our work demonstrates that the BL2 loop and nearby regions are outstanding druggable targets, and our three inhibitors can be applicable to the development of therapeutics for coronavirus infection.

Potential Antimicrobial Activity of Galloyl-Flavonoid Glycosides From Woodfordia uniflora Against Methicillin-Resistant Staphylococcus aureus.

Antibiotic-resistant infections are a growing problem; to combat multi-drug resistant bacterial infections, antibiotics with novel mechanisms of action are needed. Identification of potent bioactive natural products is an attractive avenue for developing novel therapeutic strategies against bacterial infections. As part of our ongoing research to explore bioactive natural products from diverse resources, we investigated the antimicrobial compounds from Woodfordia uniflora, a flowering shrub unique to the Dhofar region of Oman. The plant has been used as a remedy for skin infections in Oman. However, to date, no study has examined the antimicrobial compounds in W. uniflora. Phytochemical analysis of the methanolic extract of W. uniflora leaves in combination with LC/MS-based analysis allowed us to isolate and identify four flavonoid-type analogs (1-4), procyanidin B3-3-O-gallate (1), rhamnetin 3-O-(6″-galloyl)-ß-D-glucopyranoside (2), rhamnetin 3-O-α-L-rhamnopyranoside (3), and quercetin 3-O-(6″-galloyl)-ß-D-glucopyranoside (4). The isolates have a novel mechanism of action; the compounds inhibit biofilm formation in methicillin-resistant Staphylococcus aureus (MRSA) and synergize with methicillin. Our metabolite analysis revealed that this synergizing activity by compounds was achieved by remodeling metabolism including central carbon metabolism and glutamine biosynthesis that resulted in abnormal cell formation and reduction in biofilm formation of MRSA. Taken together, these findings provide experimental evidence that rhamnetin 3-O-(6″-galloyl)-ß-D-glucopyranoside (2) and quercetin 3-O-(6″-galloyl)-ß-D-glucopyranoside (4) can be considered as potential therapeutic agents for the treatment of methicillin-resistant S. aureus-associated diseases.

First-Principles Study of Anisotropic Oxygen Diffusion in PrBaCo2O5.5.

We address the anisotropic oxygen diffusion in PrBaCo2O5.5 using first-principles calculations based on the density functional theory. First, the experimentally observed magnetic properties such as ferromagnetic, ferrimagnetic, and paramagnetic phases are examined through systematic consideration of cobalt spin ordering and oxygen vacancy position. Then, the diffusion mechanism of an oxygen atom, assumed to be externally supplied, is explored by evaluating the oxygen migration barriers with the formation of one-dimensional oxygen-vacancy channel.

The complete chloroplast genome sequence with a novel 24-bp deletion of a Korean solid green-type cucumber variety (Cucumis sativus var. sativus).

Cucumber (Cucumis sativus var. sativus) is one of the economically important vegetable crops. In this study, we characterized the complete chloroplast genome sequence of inbred line ID YHB bred from Korean solid green-type cucumber variety, through de novo assembly using next-generation sequencing. The chloroplast genome is 155,501 bp long and has typical quadripartite structures and gene contents as found in reported cucumber chloroplast genomes. Interestingly, sequence comparison revealed a novel 24-bp deletion present only in the chloroplast genome of the inbred line. Phylogenetic analysis confirmed that the inbred line was closely grouped with cucumber cultivars.

The complete chloroplast genome sequence of Rhus chinensis Mill (Anacardiaceae).

In this study, complete chloroplast genome sequences of Rhus chinensis was characterized by de novo assembly using whole genome sequence data. The chloroplast genome of R. chinensis were 149,011bp long, which was comprised of a large single copy region of 96,882 bp, a small single copy region of 18,647bp, and a pair of inverted repeats of 16,741 bp. The genome contained 77 protein-coding genes, four rRNA genes and 30 tRNA genes. Phylogenetic tree revealed that R. chinensis was closely grouped with Spondias species, S. tuberosa and S. bahiensis, belonging to the Anacardiaceae family.