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Hydrogen boride nanosheets (HB sheets) are facilely synthesized via ion-exchange treatment on magnesium diboride (MgB 2 ) in an acetonitrile solution. Optical absorption and fluorescence spectra of HB sheets indicate that their bandgap energy is 2.8 eV. According to first-principles calculations, optical absorption seen at 2.8 eV is assigned to the electron transition between the σ-bonding states of B and H orbitals. In addition, density functional theory (DFT) calculations suggest the other allowed transition from the σ-bonding state of B and H orbitals to the antibonding state with the gap of 3.8 eV. Significant gaseous H 2 release is found to occur only under photoirradiation, which causes the electron transition from the σ-bonding state to the antibonding state even under mild ambient conditions. The amount of H 2 released from the irradiated HB sheets is estimated to be 8 wt%, indicating that the sheets have a high H 2 -storage capacity compared with previously reported metal H 2 -storage materials. The development of lightweight and safe hydrogen carrier materials is desirable for hydrogen energy storage and release. Here, authors prepare hydrogen boride nanosheets and observe hydrogen gas production induced by light irradiation.

Corynebacterium glutamicum, a gram-positive and facultative anaerobic bacterium, is widely used for the industrial production of amino acids, such as l-glutamate and l-lysine. C. glutamicum grows and produces amino acids under aerobic conditions. When restricted under anaerobic conditions, it produces organic acids, such as l-lactate and succinate, through metabolic shift. With the increasing threat of global warming, these organic acids have drawn considerable attention as bio-based plastic monomers. In addition to the organic acids, the anaerobic bioprocess is also used to produce other value-added compounds, including isobutanol, ethanol, 3-methyl-1-butanol, 2,3-butanediol, l-alanine, and l-valine. Therefore, C. glutamicum is now a versatile cell factory for producing a wide variety of useful chemicals under both aerobic and anaerobic conditions. The growth and metabolism of the bacterium depend on the oxygen levels, which modulate the rearrangement of the carbon flux by reprogramming gene expression patterns and intracellular redox states. Anaerobic cell growth and l-lysine production as well as aerobic succinate production have been demonstrated by engineering the metabolic pathways or supplying a terminal electron acceptor instead of oxygen. In this review, we discuss the physiological and metabolic changes in C. glutamicum associated with its application as a cell factory under different oxygen states. Physiological switching in bacteria is initiated with the sensing of oxygen availability. While such a sensor has not been identified in C. glutamicum yet, the molecular mechanism for oxygen sensing in related bacteria is also discussed.Key Points• C. glutamicum produces a wide variety of useful compounds under anaerobic conditions.• C. glutamicum is a versatile cell factory under both aerobic and anaerobic conditions.• Metabolic fate can be overcome by engineering metabolic pathways.

Manganese oxides have been extensively investigated as model systems for the oxygen-evolving complex of photosystem II. However, most bioinspired catalysts are inefficient at neutral pH and functional similarity to the oxygen-evolving complex has been rarely achieved with manganese. Here we report the regulation of proton-coupled electron transfer involved in water oxidation by manganese oxides. Pyridine and its derivatives, which have p K a values intermediate to the water ligand bound to manganese(II) and manganese(III), are used as proton-coupled electron transfer induction reagents. The induction of concerted proton-coupled electron transfer is demonstrated by the detection of deuterium kinetic isotope effects and compliance of the reactions with the libido rule. Although proton-coupled electron transfer regulation is essential for the facial redox change of manganese in photosystem II, most manganese oxides impair these regulatory mechanisms. Thus, the present findings may provide a new design rationale for functional analogues of the oxygen-evolving complex for efficient water splitting at neutral pH. Manganese oxides are extensively investigated as analogues of nature's oxygen-evolving complex, but they rarely function at neutral pH. Here, the authors investigate the induction and regulation of the proton-coupled electron-transfer mechanism involved in water oxidation by manganese oxides.

Sample return missions have provided the basis for understanding the thermochemical evolution of the Moon. Mare basalt sources are likely to have originated from partial melting of lunar magma ocean cumulates after solidification from an initially molten state. Some of the Apollo mare basalts show evidence for the presence in their source of a late-stage radiogenic heat-producing incompatible element-rich layer, known for its enrichment in potassium, rare-earth elements, and phosphorus (KREEP). Here we show the most depleted lunar meteorite, Asuka-881757, and associated mare basalts, represent ancient (~3.9 Ga) partial melts of KREEP-free Fe-rich mantle. Petrological modeling demonstrates that these basalts were generated at lower temperatures and shallower depths than typical Apollo mare basalts. Calculated mantle potential temperatures of these rocks suggest a relatively cooler mantle source and lower surface heat flow than those associated with later-erupted mare basalts, suggesting a fundamental shift in melting regime in the Moon from ~3.9 to ~3.3 Ga. Ancient (~3.9 Ga) KREEP-free basalts were sourced from a relatively cool and shallow pyroxene-rich mantle distinct from later-erupted (<3.8 Ga) KREEP-bearing basalts, indicating a fundamental change in melting regimes in the Moon.

Photocatalysts are promising materials for solid-state antiviral coatings to protect against the spread of pandemic coronavirus disease (COVID-19). This paper reports that copper oxide nanoclusters grafted with titanium dioxide (Cu x O/TiO 2 ) inactivated the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) virus, including its Delta variant, even under dark condition, and further inactivated it under illumination with a white fluorescent bulb. To investigate its inactivation mechanism, the denaturation of spike proteins of SARS-CoV-2 was examined by sodium dodecyl sulphate–polyacrylamide gel electrophoresis (SDS-PAGE) and enzyme-linked immunosorbent assay (ELISA). In addition to spike proteins, fragmentation of ribonucleic acids in SARS-CoV-2 was investigated by real-time reverse transcription quantitative polymerase chain reaction (RT-qPCR). As a result, both spike proteins and RNAs in the SARS-CoV-2 virus were damaged by the Cu x O/TiO 2 photocatalyst even under dark condition and were further damaged under white fluorescent bulb illumination. Based on the present antiviral mechanism, the Cu x O/TiO 2 photocatalyst will be effective in inactivating other potential mutant strains of SARS-CoV-2. The Cu x O/TiO 2 photocatalyst can thus be used to reduce the infectious risk of COVID-19 in an indoor environment, where light illumination is turned on during the day and off during the night.

Most of previous photocatalysts contain metal species, thus exploring a metal-free photocatalyst is still challenging. A metal-free photocatalyst has an advantage for the development of economical and non-toxic artificial photosynthesis system and/or environmental purification applications. In this study, rhombohedral boron monosulfide (r-BS) was synthesized by a high-pressure solid-state reaction, and its photocatalytic properties were investigated. r-BS absorbed visible light, and its photocurrent action spectrum also exhibited visible light responsivity. The r-BS evolved hydrogen (H 2 ) from water under ultraviolet (UV) as well as under visible light irradiation, and its internal quantum efficiency reached 1.8% under UV light irradiation. In addition to the H 2 evolution reaction, the r-BS photocatalyst drove carbon dioxide (CO 2 ) reduction and dye oxidation reactions under UV irradiation. Although bare r-BS was not so stable under strong light irradiation in water, cocatalyst modification improved its stability. These results indicate that r-BS is a new class of non-metal photocatalyst applicable for H 2 production, CO 2 reduction, and environmental purification reactions.

Keratocystic odontogenic tumor (KCOT) arises as part of Gorlin syndrome (GS) or as a sporadic lesion. Gene mutations and loss of heterozygosity (LOH) of the hedgehog receptor PTCH1 plays an essential role in the pathogenesis of KCOT. However, some KCOT cases lack evidence for gene alteration of PTCH1, suggesting that other genes in the hedgehog pathway may be affected. PTCH2 and SUFU participate in the occurrence of GS-associated tumors, but their roles in KCOT development are unknown. To elucidate the roles of these genes, we enrolled 36 KCOT patients in a study to sequence their entire coding regions of PTCH1, PTCH2 and SUFU. LOH and immunohistochemical expression of these genes, as well as the downstream targets of hedgehog signaling, were examined using surgically-excised KCOT tissues. PTCH1 mutations, including four novel ones, were found in 9 hereditary KCOT patients, but not in sporadic KCOT patients. A pathogenic mutation of PTCH2 or SUFU was not found in any patients. LOH at PTCH1 and SUFU loci correlated with the presence of epithelial budding. KCOT harboring a germline mutation (Type 1) showed nuclear localization of GLI2 and frequent histological findings such as budding and epithelial islands, as well as the highest recurrence rate. KCOT with LOH but without a germline mutation (Type 2) less frequently showed these histological features, and the recurrence rate was lower. KCOT with neither germline mutation nor LOH (Type 3) consisted of two subgroups, Type 3A and 3B, which were characterized by nuclear and cytoplasmic GLI2 localization, respectively. Type 3B rarely exhibited budding and recurrence, behaving as the most amicable entity. The expression patterns of CCND1 and BCL2 tended to correlate with these subgroups. Our data indicates a significant role of PTCH1 and SUFU in the pathogenesis of KCOT, and the genotype-oriented subgroups constitute entities with different potential aggressiveness.

Calcifying cystic odontogenic tumors (CCOTs) are benign cystic tumors that form abnormally keratinized ghost cells. Mutations in CTNNB1, which encodes beta-catenin, have been implicated in the development of these tumors, but a causal relationship has not been definitively established. Thus, mutational hot spots in 50 cancer genes were examined by targeted next-generation sequencing in 11 samples of CCOT. Mutations in CTNNB1, but not in other genes, were observed in 10 of 11 cases. These mutations constitutively activate beta-catenin signaling by abolishing the phosphorylation sites Asp32, Ser33, or Ser37, and are similar to those reported in pilomatrixoma and adamantinomatous craniopharyngioma. In contrast, BRAF or NRAS mutations were observed in 12 and two control samples of ameloblastoma, respectively. In HEK293 cells, overexpression of mutated CTNNB1 also upregulated hair keratin, a marker of ghost cells. Furthermore, ghost cells were present in two cases of ameloblastoma with BRAF and CTNNB1 mutations, indicating that ghost cells form due to mutations in CTNNB1. The data suggest that mutations in CTNNB1 are the major driver mutations of CCOT, and that CCOT is the genetic analog of pilomatrixoma and adamantinomatous craniopharyngioma in odontogenic tissue.

Silica polymorphs occur under various pressures and temperature conditions, and their characteristics can be used to better understand the complex metamorphic history of planetary materials. Here, we conducted isothermal heating experiments of silica polymorphs in basaltic eucrites to assess their formation and stability. We revealed that each silica polymorph exhibits different metamorphic responses: (1) Quartz recrystallizes into cristobalite when heated at ≥ 1040 °C. (2) Monoclinic (MC) tridymite recrystallizes into no other polymorphs when heated at ≤ 1070 °C. (3) Silica glass recrystallizes into quartz when heated at 900–1010 °C, and recrystallize into cristobalite when heated at ≥ 1040 °C. These results suggest that MC tridymite in eucrites does not recrystallize into other polymorphs during the reheating events, nor does it recrystallize from other silica phases below the solidus temperature of eucrite (~ 1060 °C). Additionally, we found that pseudo-orthorhombic (PO) tridymite crystallizes from quenched melts in the samples heated at ≥ 1070 °C. Previously, cristobalite has been considered as the initial silica phase, which crystallizes from eucritic magma. Our findings suggest that the first crystallizing silica minerals may not always be cristobalite. These require a reconsideration of the formation process of silica minerals in eucrites.