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BACKGROUND The increase in patients suffering from type I hypersensitivity, including hay fever and food allergy, is a serious public health issue around the world. Recent studies have focused on allergy prevention by food factors with fewer side effects. The purpose of this study was to evaluate the effect of dietary glucosylceramide from pineapples (P-GlcCer) on type I hypersensitivity and elucidate mechanisms. RESULTS Oral administration of P-GlcCer inhibited ear edema in passive cutaneous anaphylaxis reaction. In a Caco-2/RBL-2H3 co-culture system, P-GlcCer inhibited β-hexosaminidase release from RBL-2H3 cells. The direct treatment of P-GlcCer on RBL-2H3 did not affect β-hexosaminidase release, but sphingoid base moiety of P-GlcCer did. These results predicted that sphingoid base, a metabolite of P-GlcCer, through the intestine inhibited type I hypersensitivity by inhibiting mast cell degranulation. In addition, the inhibitory effects of P-GlcCer on ear edema and degranulation of RBL-2H3 cells were canceled by pretreatment of leukocyte mono-immunoglobulin-like receptor 3 (LMIR3)-Fc, which can block LMIR3-mediated inhibitory signals. CONCLUSION It was demonstrated that a sphingoid base, one of the metabolites of P-GlcCer, may inhibit mast cell degranulation by binding to LMIR3. The oral administration of P-GlcCer is a novel and attractive food factor that acts directly on mast cells to suppress allergy. © 2021 The Authors. Journal of The Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

Introduction Human norovirus (HuNoV) is a leading cause of infectious gastroenteritis. Since HuNoV shows resistance to alcohol, chlorine-based sanitizers are applied to decontaminate the virus on environmental surfaces. Chlorous acid water (CA) has been recently approved as a novel chlorine-based disinfectant categorized as a Type 2 OTC medicine in Japan. In this study, we aimed to evaluate the capability of CA to inactivate HuNoV. Methods HuNoV (genogroups GII.2 and GII.4) was exposed to the test disinfectants including CA and sodium hypochlorite (NaClO), and the residual RNA copy was measured by reverse transcription quantitative PCR (RT-qPCR) after pretreatment with RNase. In addition, the log10 reduction of HuNoV RNA copy number by CA and NaClO was compared in the presence of bovine serum albumin (BSA), sheep red blood cells (SRBC), polypeptone, meat extract or amino acids to evaluate the stability of these disinfectants under organic-matter-rich conditions. Results In the absence of organic substances, CA with 200 ppm free available chlorine provided >3.0 log10 reduction in the HuNoV RNA copy number within 5 min. Even under high organic matter load (0.3% each of BSA and SRBC or 0.5% polypeptone), 200 ppm CA achieved >3.0 log10 reduction in HuNoV RNA copy number while less than 1.0 log10 reduction was observed with 1,000 ppm sodium hypochlorite (NaClO) in the presence of 0.5% polypeptone. CA reacted with only cysteine, histidine and glutathione while NaClO reacted with all of the amino acids tested. Conclusions CA is an effective disinfectant to inactivate HuNoV under organic-matter-rich conditions.

In this study, we developed an analytical method for simultaneous determination of 14 quinolones and 4 tetracyclines in livestock and fishery products using LC-MS/MS. The analytes were extracted from food samples with citrate buffer (containing EDTA)-methanol-acetonitrile (3 : 1 : 1, v/v/v) in the presence of n-hexane, and the extract was purified with an Oasis PRiME HLB cartridge column. It was suggested that this analytical method can also extract analytes from solid samples containing fat by using n-hexane. In addition, using methanol-acetonitrile (3 : 7, v/v) containing 0.1 vol% formic acid as an eluent from the cartridge column, the purification effect could be improved, while minimizing the impairment of the recovery rate. As a result of the validation using six types of food samples, trueness (accuracy) was 70.6%-113.8%, the RSD of repeatability was 9.0% or less, and the RSD of within-laboratory reproducibility was 15.5% or less. Using this approach, the standard values mentioned in the Japanese guideline were successfully met.

Accepted: 2021-08-30, 資料番号: PA2210059000

The aim of this article is to elucidate the short-circuit failure mechanism of SiC metal–oxide–semiconductor field-effect transistors that cause mechanical failure of the interlayer dielectric adjacent to the gate, to find the relationship between the short-circuit withstand capability and short-circuit failure time, and to classify failure modes by the short-circuit failure time. When the short-circuit failure time is shorter than the critical time, the stresses acting on the interlayer dielectric caused by the thermal expansion of the SiC die exceed the fracture stress limit of the oxide films. Therefore, cracks occur at the interlayer dielectric between the gate and the source. In this case, the short-circuit withstand capability can be predicted by thermal theory because the thermal expansion of the SiC die is determined by the temperature rise. However, when the short-circuit failure time is longer than the critical time, the stresses acting on the interlayer dielectric are less than the fracture stress limit of the oxide films. Thus, the failure mode changes to metallization short mode without causing interlayer dielectric cracks. Thermal stress simulations and experiments ascertain that the stress acting on the interlayer dielectric due to the thermal expansion of SiC varies with the short-circuit failure time, resulting in an altered failure mode.

In guided bone regeneration (GBR), a barrier membrane is applied to provide a space for bone regeneration to promote cell adhesion, cell proliferation, and bone regeneration by inducing cell migration to the surface of the bone-deficient site. We prepared a non-woven absorbable membrane for GBR comprised of a copolymer of L-lactic acid and glycolic acid (PLLGA) using the dry spinning method. A thin and dense membrane comprising unsintered hydroxyapatite (uHA) and poly-L-lactic acid (PLLA) was used for comparison. Osteoblast TMS-12 cells were seeded onto the membranes, and cell adhesion and proliferation rates were examined. Calcification levels were quantified by Alizarin Red S staining after cell culture in calcification induction medium. Osteoblastic gene expression was examined by RT-PCR. Cell adhesion and proliferation rates and calcification on PLLGA membranes were significantly higher than those on uHA/PLLA membranes. PLLGA membranes upregulated osteogenic gene expression compared to on uHA/PLLA membranes. Non-woven PLLGA membranes may be useful in GBR for promoting bone formation and maturation.

Introduction The objective of this study is to investigate the effect of gelatin microspheres incorporating growth factors on the therapeutic efficacy in cell transplantation. The strength of this study is to combine gelatin hydrogel microspheres incorporating basic fibroblast growth factor and platelet growth factor mixture (GM/GF) with bioabsorbable injectable hydrogels (iGel) for transplantation of adipose-derived stem cells (ASCs). Methods The rats ASCs suspended in various solutions were transplanted in masseter muscle. Rats were euthanized 2, 7, 14 days after injection for measurement of the number of ASCs retention in the muscle and morphological evaluation of muscle fibers and the inflammation of the injected tissue by histologic and immunofluorescent stain. Results Following the injection into the skeletal muscle, the GM/GF allowed the growth factors to release at the injection site over one week. When ASCs were transplanted into skeletal muscle using iGel incorporating GM/GF (iGel+GM/GF), the number of cells grafted was significantly high compared with other control groups. Moreover, for the groups to which GM/GF was added, the cells transplanted survived, and the Myo-D expression of a myoblast marker was observed at the region of cells transplanted. Conclusions The growth factors released for a long time likely enhance the proliferative and differentiative capacity of cells. The simple combination with iGel and GM/GF allowed ASCs to enhance their survival at the injected site and consequently achieve improved therapeutic efficacy in cell transplantation., Highlights • The rats adipose-derived stem cells (ASCs) suspended in various solutions were transplanted in masseter muscle. • The number of cells transplanted using this study's technology was significantly high compared with other control groups. • For the groups with growth factors, the Myo-D (myoblast marker) expression was observed at the region of cells transplanted.

Bulky epoxides are industrially produced by organic synthesis in multistep procedures, generating significant amounts of waste products in the process. Efficient catalyst in combination with a simple oxidant (H2O2 or O2) would significantly reduce the waste production. Four types of microporous titanosilicates with extra-large pores (Ti-UTL), and shortened diffusion pathways (L-TS, Ti-MCM-22, and Ti-SPP) were prepared and investigated in the epoxidation of cyclooctene with H2O2 and photocatalytic oxidation using O2. Ti-UTL is a zeolite possessing 14−12-ring channel system. l -TS-1 and Ti-MCM-22 are composed of aggregates of titanosilicate nanosheets with the thickness of ca. 2 nm and hexagonal thin platelets, respectively. Ti-SPP is composed of olive-like aggregates with approximately length of 0.88–1.12 μm and width of 0.44−0.68 μm consisting of intergrown (self-pillared) nanosheets having 13−70 nm in size. In the epoxidation with H2O2 as an oxidant, Ti-MCM-22 showed the highest catalytic activity due to the wide interlayer space, which enhanced the accessibility of cyclooctene to active titanium site. While, in the photocatalytic epoxidation in the presence of O2 instead of H2O2, Ti-UTL showed the highest activity. The incorporated germanium atoms, which is indispensable component for the construction of extra-large pores, may affect the electronic properties of active titanium species, leading to high photocatalytic activity.

BACKGROUND: Chronic kidney disease (CKD) impairs the anti-inflammatory effects of high-density lipoprotein (HDL) and increases cardiovascular mortality. Though the potential role of dietary interventions to manage HDL is well studied, the clinical trials aimed to increase HDL levels have failed to reduce cardiovascular risk, rendering HDL function to be explored as a more relevant clinical parameter. This study investigates the effects of rice endosperm protein (REP), a plant-based protein, on the anti-inflammatory properties of HDL and renal injury-driven atherosclerosis in comparison with casein, an animal protein. MATERIALS AND METHODS: Ten-week-old apolipoprotein E-deficient hyperlipidemic mice underwent uninephrectomy. The mice (n = 6 each) were pair-fed a normal casein-based diet or a REP-based diet (both with 20.0% protein content) for seven weeks. Atherosclerotic lesions were detected by en face Sudan IV staining of the aorta. RESULTS: The number and sizes of the atherosclerotic lesions were significantly lower in the REP-based diet-fed group than the casein-based diet-fed group (p = 0.038). However, the REP-based diet neither elicited an ameliorative effect on kidney function or histology nor impacted the cholesterol profiles. Furthermore, HDL from the REP-based diet-fed mice significantly suppressed the inflammatory cytokine response of human umbilical vein endothelial cells than that from the casein-based diet-fed mice (MCP-1, p = 0.010; IL-6, p = 0.011; IL-1β, p = 0.028). CONCLUSIONS: The REP-based diet has a higher potential to lessen the atherosclerotic lesions accelerated by renal mass reduction than a casein-based diet, which could be associated with the anti-inflammatory effects of HDL.

An enantioselective total synthesis of sporothriolide, a bioactive furofurandione-type fungal metabolite, has been achieved in a 21% overall yield from a commercially available β,γ-unsaturated carboxylic acid via seven steps. The key steps of this synthesis include a highly diastereoselective Michael addition of a chiral oxazolidinone derivative to a nitro olefin, the exploitation of an aromatic ring as a masked carboxylic acid functionality, and the base-promoted elimination of nitrous acid to install the α-methylene lactone unit of sporothriolide in the final step.

The development of reliable catalysts with both excellent activity and recyclability for carbon dioxide (CO2) hydrogenation is challenging. Herein, a ternary hybrid heterogeneous catalyst, involving mononuclear Ru complex, N, P-containing porous organic polymers (POPs), and mesoporous hollow carbon spheres (Ru3+-POPs@MHCS) is reported for CO2 hydrogenation to formate. Based on comprehensive structural analyses, we demonstrated that Ru3+-POPs were successfully immobilized within MHCS. The optimized Ru3+-0.5POPs@MHCS catalyst, which was obtained with about 5 wt.% Ru3+ and 0.5 mmol POPs polymers confined into 0.3 g MHCS, exhibited high catalytic activity for CO2 hydrogenation to formate (turnover number (TON) > 1,200 for 24 h under mild reaction conditions (4.0 MPa, 120 °C)) and improved durability, compared to Ru3+ catalysts without POPs polymers (Ru3+-MHCS) and unencapsulated MHCS (Ru3+-0.5POPs) catalysts. The improved catalytic performance is attributed to the high surface area and large pore volume of MHCS which favors dispersion and stabilization of Ru3+-POPs. Furthermore, the MHCS and POPs showed high CO2 adsorption ability. Ru3+-POPs encapsulated into MHCS reduces the activation energy barrier for CO2 hydrogenation to formate.

Lipid oxidation is involved in various biological phenomena (e.g., oxylipin generation and oxidative stress). Of oxidized lipid structures, the hydroperoxyl group position of lipid hydroperoxides (LOOHs) is a critical factor in determining their biological roles. Despite such interest, current methods to determine hydroperoxyl group positions possess some drawbacks such as selectivity. While we previously reported mass spectrometric methods using Na+ for the highly selective determination of hydroperoxyl group positions, nothing was known except for the fact that sodiated LOOHs (mainly linoleate) provide specific fragment ions. Thus, this study was aimed to investigate the effects of different alkali metals on the fragmentation of LOOHs, assuming its further application to analysis of other complex LOOHs. From the analysis of PC 16:0/18:2;OOH (phosphatidylcholine) and FA 18:2;OOH (fatty acid), we found that fragmentation pathways and ion intensities largely depend on the binding position and type of alkali metals (i.e., Li+, Hock fragmentation; Na+ and K+, α-cleavage (Na+ > K+); Rb+ and Cs+, no fragmentation). Furthermore, we proved that this method can be applied to determine the hydroperoxyl group position of esterified lipids (e.g., phospholipids and cholesterol esters) as well as polyunsaturated fatty acids (PUFAs) including n-3, n-6, and n-9 FA. We anticipate that the insights described in this study provide additional unique insights to conventional lipid oxidation research.

Breast cancer, the most common malignancy among women, is closely associated with mutations in the tumor suppressor gene BRCA. DSS1, a component of the TRanscription-EXport-2 (TREX-2) complex involved in transcription and mRNA nuclear export, stabilizes BRCA2 expression. DSS1 is also related to poor prognosis in patients with breast cancer owing to the induction of chemoresistance. Recently, BRCA2 was shown to be associated with the TREX-2 component PCID2, which prevents DNA:RNA hybrid R-loop formation and transcription-coupled DNA damage. This study aimed to elucidate the involvement of these TREX-2 components and BRCA2 in the chemosensitivity of breast carcinomas. Our results showed that compared with that in normal breast tissues, DSS1 expression was upregulated in human breast carcinoma, whereas PCID2 expression was comparable between normal and malignant tissues. We then compared patient survival time among groups divided by high or low expressions of DSS1, BRCA2, and PCID2. Increased DSS1 expression was significantly correlated with poor prognosis in recurrence-free survival time, whereas no differences were detected in the high and low BRCA2 and PCID2 expression groups. We performed in vitro analyses, including propidium iodide nuclear staining, single-cell gel electrophoresis, and clonogenic survival assays, using breast carcinoma cell lines. The results confirmed that DSS1 depletion significantly increased chemosensitivity, whereas overexpression conferred chemoresistance to breast cancer cell lines; however, BRCA2 expression did not affect chemosensitivity. Similar to DSS1, PCID2 expression was also inversely correlated with chemosensitivity. These results strongly suggest that DSS1 and PCID2 depletion is closely associated with increased chemosensitivity via BRCA2-independent DNA damage. Together with the finding that DSS1 is not highly expressed in normal breast tissues, these results demonstrate that DSS1 depletion confers a druggable trait and may contribute to the development of novel chemotherapeutic strategies to treat DSS1-depleted breast carcinomas independent of BRCA2 mutations.

Argentivorous molecules with mono, di, tri, tetra, and penta-oxyethylene chains in aromatic side-arms were prepared (L1-L5). Titration experiments using proton nuclear magnetic resonance and cold electrospray ionization (cold-spray ionization, CSI) mass spectrometry showed that silver ions were trapped in the cyclen moiety and the arranged oxyethylene chains of the side-arms when two equivalents of silver ions were added. The silver complexes formed by adding one equivalent of silver ion to L2-L5 bind alkali metal ions using the oxyethylene chains; alkali metal ion-induced CSI mass spectral changes of L2-L5 were measured in the absence and presence of silver ions to compare the binding properties of the ligand for Li+, Na+, and K+ ions. As a result, the intensity ratios of [L + H + M]2+/[L + H]+ in L1-L3 were almost zero or very low. L4 and L5, which have tetra(oxyethylene) and penta(oxyethylene) chains, respectively, bind a larger size of alkali metal ions. On the other hand, in the presence of silver ions, the ratio for [L + Ag + M]2+/[L + H]+ (M = Li, Na, K) in L2-L5 was increased. The highest [L + Ag + M]2+/[L + H]+ ratios for K+ were observed in L4 and L5, while selectivity for Na+ was observed in the case of L2 and L3. These results indicate that the increased binding ability and selectivity by L2-L5 are due to the arrangement of oxyethylene chains by the conformational change of the aromatic side-arms. The Ag+-induced carbon-13 nuclear magnetic resonance spectral changes suggested that the second and third oxyethylene units, close to the benzene, are involved in the coordination of the second metal ion.

This review describes the design of nanostructured plasmonic catalysts, such as nanoparticles and nanosheet morphologies, that strongly absorb visible light over a wide range of the solar spectrum due to localized surface plasmon resonance (LSPR) and application to enhanced hydrogen evolution. A new method for the synthesis of Ag nanoparticles, with color dependent on the particle size and morphology, combined microwave heating and the use of mesoporous silica materials. Further combination with Pd nanoparticles significantly enhanced the catalytic activities for hydrogen production from ammonia borane (NH3BH3) compared with the inherent Ag catalysts under both dark and visible-light irradiation conditions. We also describe the synergistic catalysis activities of plasmonic Au(core)–Pd(shell) nanoparticles supported on amine-functionalized metal-organic frameworks (MOFs) for boosting room-temperature hydrogen production from formic acid (HCOOH) under visible light irradiation. Our search for plasmonic materials based on earth abundant elements found that reduced molybdenum oxide (HxMoO3−y) nanosheet with oxygen defects and doped hydrogen displayed intense absorption in a wide range from the visible to the near-infrared region. This unique plasmonic HxMoO3−y nanosheet can enhance dehydrogenation from ammonia borane under visible light irradiation.

The synthesis of an octa-armed 24-membered cyclic octaamine (1) is reported. When 4-benzyl-1,4,7,10-tetraazacyclododecane-2,6-dione (3a) was prepared by the reaction of diethylenetriamine with diethyl N-benzyliminodiacetate (2), a dimeric macrocycle (3b) was obtained as a byproduct in a 5% yield. An octa-armed 24-membered cyclic octaamine (1), named Cosmosen, was prepared via the reductive amination and reduction of 3b. The binding constants for the 1:1 and 2:1 (Ag+/1) complexation of 1 were estimated to be ca. 7.9 and 13.9, respectively, by titration experiments using UV-vis spectrometry in methanol and chloroform (v/v, 9:1) solutions at 298 K.

The phosphorylated pathway of serine biosynthesis is initiated with 3-phosphoglycerate dehydrogenase (PGDH). The liverwort Marchantia polymorpha possesses an amino acid-sensitive MpPGDH which is inhibited by l-serine and activated by five proteinogenic amino acids, while the eudicot Arabidopsis thaliana has amino acid-sensitive AtPGDH1 and AtPGDH3 as well as amino acid-insensitive AtPGDH2. In this study, we analyzed PGDH isozymes of the representative land plants: the monocot Oryza sativa (OsPGDH1–3), basal angiosperm Amborella trichopoda (AmtriPGDH1–2), and moss Physcomitrium (Physcomitrella) patens (PpPGDH1–4). We demonstrated that OsPGDH1, AmtriPGDH1, PpPGDH1, and PpPGDH3 were amino acid-sensitive, whereas OsPGDH2, OsPGDH3, AmtriPGDH2, PpPGDH2, and PpPGDH4 were either sensitive to only some of the six effector amino acids or insensitive to all effectors. This indicates that PGDH sensitivity to effectors has been diversified among isozymes and that the land plant species examined, except for M. polymorpha, possess different isozyme types in terms of regulation. Phylogenetic analysis suggested that the different sensitivities convergently evolved in the bryophyte and angiosperm lineages. Site-directed mutagenesis of AtPGDH1 revealed that Asp538 and Asn556 residues in the ACT domain are involved in allosteric regulation by the effectors. These findings provide insight into the evolution of PGDH isozymes, highlighting the functional diversification of allosteric regulation in land plants.

Production of methanol from anthropogenic carbon dioxide (CO2) is a promising chemical process that can alleviate both the environmental burden and the dependence on fossil fuels. In catalytic CO2 hydrogenation to methanol, reduction of CO2 to intermediate species is generally considered to be a crucial step. It is of great significance to design and develop advanced heterogeneous catalysts and to engineer the surface structures to promote CO2-to-methanol conversion. We herein report an oxygen-defective molybdenum sub-oxide coupled with Pt nanoparticles (Pt/HxMoO3−y) which affords high methanol yield with a methanol formation rate of 1.53 mmol g-cat−1 h−1 in liquid-phase CO2 hydrogenation under relatively mild reaction conditions (total 4.0 MPa, 200 °C), outperforming other oxide-supported Pt catalysts in terms of both the yield and selectivity for methanol. Experiments and comprehensive analyses including in situ X-ray absorption fine structure (XAFS), in situ diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy and density functional theory (DFT) calculations reveal that both abundant surface oxygen vacancies (VO) and the redox ability of Mo species in quasi-stable HxMoO3−y confer the catalyst with enhanced adsorption and activation capability to subsequently transform CO2 to methanol. Moreover, the Pt NPs act as H2 dissociation sites to regenerate oxygen vacancies and as hydrogenation sites for the CO intermediate to finally afford methanol. Based on the experimental and computational studies, an oxygen-vacancy-mediated “reverse Mars–van Krevelen (M–vK)” mechanism is proposed. This study affords a new strategy for the design and development of an efficient heterogeneous catalyst for CO2 conversion., Oxygen-defective molybdenum sub-oxide coupled with Pt nanoparticles affords high methanol yield in liquid-phase CO2 hydrogenation via reverse Mars–van Krevelen mechanism.

Seiridiasteriscane A is an asteriscane-type sesquiterpenoid bearing a trans-fused bicyclo[6.3.0]undecane skeleton. Although its biosynthesis has been proposed to involve a semipinacol rearrangement of a putative intermediary acetate bearing a bicyclo[7.2.0]undecane ring system (presumably derived from coisolated pestalotiopsin M) followed by epimerization of the resulting cis-fused seiridiasteriscane B, such a type of semipinacol rearrangement has never been reported so far. Our model study revealed that a 1-hydroxybicyclo[7.2.0]undecan-2-yl acetate underwent a smooth and stereospecific semipinacol rearrangement with the assistance of Et2AlCl to give the corresponding bicyclo[6.3.0]undecane-9-one. In addition, the resulting cis-fused 5,8-bicyclic ketone was partially epimerized to the corresponding trans-fused ketone by prolonged adsorption onto a silica gel plate. These results may support a recently proposed biosynthetic pathway of seiridiasteriscane A.

Certain issues may be encountered when traditional composite fillers are mixed with cement and bentonite (CF-CB) and applied to cavities in the ground. These issues include the bleeding and separating of water, cement and bentonite, and the long time needed for the strength development. In a series of studies, it has been shown that the suppression of bleeding, earlier gelling and earlier development of strength can be expected by mixing a suitable amount of sodium carbonate in the CF-CB, that is, creating a CF-CBS. The mechanisms of the various properties of CF-CBS and CF-CB were investigated by physical analyses. The following points were clarified from the results of this work. Earlier development of strength and gelling are brought about by the earlier formation of ettringite accompanying the promotion of the cement hydration reaction. The suppression of bleeding can be accomplished by earlier gelling due to the bentonite taking the Na+ ionised from sodium carbonate as an interlayer cation. The increase in strength is attributed to the calcium carbonate produced by CO32− ionising from the sodium carbonate bonding with the Ca2+ dissolved from the interlayer cations of the cement or bentonite.

Reductive production of hydrogen peroxide (H2O2) from dioxygen (O2) coupled with the oxidative synthesis of value-added products using hydrophobic metal–organic frameworks (MOFs) is very important ...

Direct elemental and isotope analyses of solid samples have attracted considerable interest due to their potential role in preventing serious accidents at nuclear facilities. We previously developed an analytical method for detecting radioactive isotopes, combining diode laser absorption spectroscopy with a supersonic plasma jet. Its basic performance, that is, the detection limit as well as the translational temperature upstream and downstream of the supersonic nozzle, was investigated using stable Xe isotopes. The developed apparatus could atomize a solid sample and reduce the translational temperature for isotope identification. For direct isotope analysis, translational temperature and atomization efficiency during powder feeding are remarkably important. In the present study, a novel approach for the atomization of Sr powder samples containing isotopes with highly radiotoxic radionuclides is described. We found that the temperature of Sr atoms in the supersonic plasma jet decreased to approximately 85 K, which is comparable with the slight isotope shift of 88Sr–90Sr due to the difference in mass number. Moreover, based on the measured atomic number density and flow velocity, the atomization efficiency was found to be 10.4 ± 1.8%. The results of this study and further improvements in the efficiency can lead to the development of powerful tools for the rapid analysis of solid samples, particularly those contaminated with highly radioactive species, without the necessity for complex chemical separation.

Effects of morphology and exposed crystal planes of NiOx-decorated CeO2 (NiCeO2) nanostructured catalysts on activity during CO2 methanation were examined, using nanorod (NR), nanocube (NC), and nanooctahedron (NO) structures. The NiCeO2 nanorods (NiCeO2-NR) showed superior activity to NiCeO2-NC and NiCeO2-NO along with excellent selectivity for CH4. This material also demonstrated exceptional durability, with no significant loss of catalytic activity or structural change after use. Comprehensive physicochemical characterization as well as density functional theory calculations determined that the high performance of the NiCeO2-NR was closely related to the large quantity of surface oxygen vacancies and the high degree of reversibility associated with the Ce4+ ↔ Ce3+ redox cycle of the support. These effects originate from the enhanced reactivity of oxygen atoms on the (110) surfaces of the oxide compared with the (100) and (111) surfaces. This information is expected to assist in the rational design of practical catalysts for the activation of CO2 molecules and other important transformations.

The 2011–2016 reports from the Food and Agriculture Organization of the United Nations has stated that annual food loss and waste occurs on a massive scale in fisheries and aquaculture. This study aimed to explore advanced technologies to recycle wasted salmon as an industrial resource with high commercial value by applying enzymatic hydrolysis under HPCD. Our results showed that HPCD treatment at 50 °C and 1 MPa for 16 h effectively prevents salmon from microbial contamination. Real-time PCR analysis demonstrated that HPCD was also able to inhibit an increase in bacteria at moderate temperatures. Based on NGS analysis, there was a very low abundance of Bacillus and some histamine producers, such as Pseudomonas, Acinetobacter, Enterobacter, and Klebsiella, detected in samples treated using HPCD at 50 °C and 1 MPa for 16 h. Hydrolysate analysis showed that HPCD treatment at 1 MPa did not affect the hydrolysates from salmon. It is anticipated that the results from this study will support the application of HPCD in industrial enzymatic hydrolysis and increase the sustainability of bio-based materials.

A promotional effect of surface plasmon resonance (SPR) on direct hydrogen peroxide (H2O2) formation from H2 and O2 over a structure-controlled Pd-Au catalytic system is reported herein. Pd NPs supported on reduced graphene oxide (rGO) layer-coated Au nanorod (NR) nanocomposite catalysts were synthesized, and the structure was confirmed by multiple characterization techniques. H2O2 production is highly enhanced under visible light irradiation in the direct H2O2 formation from H2 and O2. The H2O2 decomposition test and the H2-D2 exchange reaction reveal that the SPR of Au NRs facilitates H2 activation on the Pd NP surface, leading to efficient H2O2 production. Furthermore, the rGO layer not only functions as an electron mediator in the catalytic reaction, but also contributes to the control of Pd NP sizes in the catalyst synthesis.

Luminescent silver(I) coordination polymers having a {Ag2(μ-X)2} rhombic core (X = I, Br) were prepared using pyrazine (pyz), methylpyrazine (Mepyz), and aminopyrazine (ampyz) as bridging ligands. Photophysical measurements show that the complexes were strongly luminescent in the solid state at room temperature; further, the emissive excited state of the pyz and Mepyz complexes was a triplet charge-transfer (3CT) excited state, similar to that of their copper(I) congeners, whereas that of the ampyz complex was a intraligand (3IL) excited state. The energy of the 3CT excited state of a silver halogenido complex was revealed to be ca. 5000 cm-1 higher than that of the corresponding copper complex.

OBJECTIVE Prediabetes has been suggested to increase risk for death; however, the definitions of prediabetes that can predict death remain elusive. We prospectively investigated the association of multiple definitions of prediabetes with the risk of death from all causes, cardiovascular disease (CVD), and cancer in Japanese workers. RESEARCH DESIGN AND METHODS The study included 62,785 workers who underwent a health checkup in 2010 or 2011 and were followed up for death from 2012 to March 2019. Prediabetes was defined according to fasting plasma glucose (FPG) or glycated hemoglobin (HbA1c) values or a combination of both using the American Diabetes Association (ADA) or World Health Organization (WHO)/International Expert Committee (IEC) criteria. The Cox proportional hazards regression model was used to investigate the associations. RESULTS Over a 7-year follow-up, 229 deaths were documented. Compared with normoglycemia, prediabetes defined according to ADA criteria was associated with a higher risk of all-cause mortality (hazard ratio [HR] 1.53; 95% CI 1.12–2.09) and death due to cancer (HR 2.37; 95% CI 1.45–3.89) but not with death due to CVD. The results were materially unchanged when prediabetes was defined according to ADA FPG, ADA HbA1c, WHO FPG, or combined WHO/IEC criteria. Diabetes was associated with the risk of all-cause, CVD, and cancer deaths. CONCLUSIONS In a cohort of Japanese workers, FPG- and HbA1c-defined prediabetes, according to ADA or WHO/IEC, were associated with a significantly increased risk of death from all causes and cancer but not CVD.

To determine eye drop type and usage frequency and investigate risk factors for no eye drop use in individuals with symptomatic dry eye (DE) in Japan. Crowdsourced observational study. This study was conducted using the DryEyeRhythm smartphone application between November 2016 and September 2019. Data collected included the type and frequency of eye drop use, demographics, medical history, lifestyle, and self-reported symptoms. Symptomatic DE was defined as an Ocular Surface Disease Index total score of ≥ 13. Risk factors for no eye drop use were identified using multivariate logistic regression analyses. Among 2619 individuals with symptomatic DE, 1876 did not use eye drops. The most common eye drop type was artificial tears (53.4%), followed by hyaluronic acid 0.1% (33.1%) and diquafosol sodium 3% (18.7%). Risk factors (odds ratio [95% confidence interval]) for no eye drop use were age (0.97 [0.97–0.98]), body mass index (1.04 [1.01–1.07]), brain disease (0.38 [0.15–0.98]), collagen disease (0.30 [0.13–0.68]), mental illness other than depression and schizophrenia (0.65 [0.45–0.93]), cataract surgery (0.12 [0.02–0.59]), ophthalmic surgery other than cataract and laser-assisted in situ keratomileusis (0.55 [0.34–0.88]), current (0.47 [0.38–0.57]) or past (0.58 [0.43–0.77]) contact lens use, >8 h screen exposure time (1.38 [1.05–1.81]), 9 h (1.34 [1.04–1.72]) sleep time, and water intake (0.97 [0.94–0.98]). Many participants with symptomatic DE did not use optimized eye drop treatment and identified risk factors for no eye drop use. The DryEyeRhythm application may help improve DE treatment.

Contraction of vascular smooth muscle is regulated primarily by calcium concentration and secondarily by ROCK activity within the cells. In contrast to the wealth of information regarding regulation of calcium concentration, little is known about the spatiotemporal regulation of ROCK activity in live blood vessels. Here, we report ROCK activation in subcutaneous arterioles in a transgenic mouse line that expresses a genetically encoded ROCK biosensor based on the principle of Fӧrster resonance energy transfer by two-photon excitation in vivo imaging. Rapid vasospasm was induced upon laser ablation of arterioles, concomitant with a transient increase in calcium concentration in arteriolar smooth muscles. Unlike the increase in calcium concentration, vasoconstriction and ROCK activation continued for several minutes after irradiation. Both the ROCK inhibitor, fasudil, and the ganglionic nicotinic acetylcholine receptor blocker, hexamethonium, inhibited laser-induced ROCK activation and reduced the duration of vasospasm at the segments distant from the irradiated point. These observations suggest that vasoconstriction is initially triggered by a rapid surge of cytoplasmic calcium and then maintained by sympathetic nerve-mediated ROCK activation.

Metal–organic frameworks (MOFs) are promising materials for photocatalytic hydrogen peroxide (H2O2) production from water (H2O) and dioxygen (O2). However, H2O2 production from H2O and O2 using MOFs has remained challenging due to the fast recombination of photogenerated charges in the MOF matrix. Herein, a heterojunction structure was constructed by modification of an organic semiconductor, perylenetetracarboxylic diimide (PDI), upon a titanium-based MOF (MIL-125-NH2), forming MIL-125-PDI to promote the separation of photogenerated charges between PDI and MOFs. Photo/electrochemical characterizations confirmed that the constructed heterostructure indeed promoted the separation and transfer of photogenerated charges. As a result, the as-formed MIL-125-PDI displayed a H2O2 production rate of 4800 μM g−1 h−1, which was 4.3 times that of the pristine MIL-125-NH2 under visible-light irradiation (λ > 420 nm). Furthermore, MIL-125-PDI exhibited a better durability compared with MIL-125-NH2 with noble-metal Pt nanoparticles as co-catalysts. The results of trapping experiments and electron spin resonance (ESR) spectra of active species for H2O2 production indicated that a new one-step two-electron process of O2 reduction to H2O2 occurred in MIL-125-PDI, while the original one observed in MIL-125-NH2 was a two-step one-electron process. This work used MOFs as the main active component in photocatalysts, which opens up the new application of MOFs in photocatalysis and provides an effective strategy to design MOF-based photocatalysts for artificial photosynthesis of clean liquid fuels.

Solar-to-chemical conversion processes, assisted by localised surface plasmon resonance (LSPR), are a fast-growing field of plasmonics that efficiently utilise solar energy due to their unique catalytic and optical responses. Plasmonic nanostructures can harvest abundant sunlight by concentrating the incident light energy in the nanoscale regime to drive chemical reactions on the surface of nanoparticles. The advantages of employing LSPR in catalysis include higher conversion rates and improved selectivity under mild reaction conditions. This review highlights the latest progress on harnessing plasmonic photocatalysts involving noble metal nanoparticles (Au, Ag) and doped semiconductor (WO3−x, MoO3−x) nanostructures for their application in the enhanced hydrogen evolution from ammonia borane (AB) under visible-NIR light irradiation. An overview of multi-metallic heterostructures, in combination with plasmonic nanoparticles, which are available at the current stage in plasmon chemistry has been included. The rational design, tuning of plasmonic absorption and their underlying mechanisms for enhanced catalytic activities have also been reviewed. Finally, the current challenges and future perspectives have been discussed to further improve the efficiency of plasmon-mediated heterogeneous catalysis to achieve more practical applications in the near future.

The proton signals at the 2′- and 6′-positions of the aromatic side arms of a silver(I) complex with a chiral tetra-armed cyclen ((S)-L2) are assigned by comparison with 1H NMR spectra and X-ray st...

Tetra-armed cyclen (1) bearing two 4-(4'-pyridyl)benzyl and two 3,5-difluorobenzyl groups and its Ag+ complexes were prepared and structurally characterized. The complexes formed between 1 and Ag+ undergoes a reversible structural transformation between a 2:2 dimeric complex and a 3:5 pentacyclic trefoil complex with changes in the Ag+ /1 molar ratio. It was also revealed that the 3:5 trefoil complex could encapsulate benzene and [D6 ]benzene selectively in solid-state. The benzene-included structures are stabilized by C-H⋅⋅⋅F-C interactions between the benzene molecule and the ligand molecule.

Xenin-25 has a variety of physiological functions in the gastrointestinal tract, including ion transport and motility. Xenin-25 and neurotensin show sequence homology, especially near their C-terminal regions. The sequence similarity between xenin-25 and neurotensin indicates that the effects of xenin-25 is mediated by the neurotensin receptor but some biological actions of xenin-25 are independent. We have previously reported that xenin-25 modulates intestinal ion transport and colonic smooth muscle activity. However, minimal biological domain of xenin-25 to induce ion transport was not clear. To improve the mechanistic understanding of xenin-25 and to gain additional insights into the functions of xenin-25, the present study was designed to determine the minimal biological domain of xenin-25 required for ion transport in the rat ileum using various truncated xenin fragments and analogues in an Ussing chamber system. The present results demonstrate that the minimum biological domain of xenin-25 to induce Cl-/HCO3- secretion in the ileum contains the C-terminal pentapeptide. Furthermore, Arg at position 21 is important to retain the biological activity of xenin-25 and induces Cl-/HCO3- secretion in the rat ileum.

The most widely used method for measuring bacterial production is tritium-labeled leucine (3H-Leu). Although this method provides methodological simplicity and high sensitivity, the employment of radioactive isotopes is often restricted by regulations, particularly in field settings. In this study, we developed a non-radioactive method for measuring bacterial productivity based on the protein synthesis rate, using deuterium-labeled leucine ((CD3)2CDCD2CD(NH2)COOH; D10-Leu); the proposed method was then compared and verified with the3H-Leu method. The procedures of the proposed method are (1) incorporation of D10-Leu by bacteria, (2) acid hydrolysis (HCl) to amino acids and (3) quantification of D10-Leu (m/z142.10) by liquid chromatography mass spectrometry (LC-MS/MS). In the LC-MS/MS analysis, we detected a larger amount of D9-Leu (m/z141.10) and D8-Leu (m/z140.10) than that of D10-Leu, suggesting that incorporated D10-Leu was rapidly metabolized such as in deamination and aminotransferase reactions. The incorporation rates of D10-Leu, D10-Leu + D9-Leu (D10+D9-Leu) and D10-Leu + D9-Leu + D8-Leu (D10+D9+D8-Leu) were significantly positively correlated to that of3H-Leu, confirming the validity of the proposed method. Since D7-Leu (m/z139.10) could not be detected, the amount of exogenous leucine incorporated into protein can be accurately estimated through D10+D9+D8-Leu measurement. The new compound-based quantification method using stable isotope-labeled leucine can be a powerful tool to estimate pure protein synthesis rate for measuring bacterial production.

An efficient and stereoselective syntheses of all the possible stereoisomers of coronafacic acid (CFA) has been developed. The stereochemistries of C3a and C7a were controlled in a diastereoselective Diels‐Alder type cycloaddition using a chiral auxiliary. CFA and 6‐epi‐CFA were synthesized by hydrogenation of a common intermediate. During the synthesis of 6‐epi‐CFA, we established that its cis‐fused configuration is important for the introduction of C4‐C5 double bond by dehydration. This report is the first practical synthesis of both 6‐epi‐CFA, and its enantiomer.

The localized surface plasmon resonance (LSPR) mediated enhanced chemical activity can be entitled as a promising strategy for efficient solar to chemical energy conversion. To tune the selectivity of a desired product in a chemical reaction is of paramount importance yet a great challenge. In this paper, a new strategy to effectively enhance the selectivity of the product formation under visible light irradiation is reported. A series of Ag catalysts deposited on metal oxide support materials (TiO2, ZrO2, Al2O3 and CeO2) along with their preparative techniques, optimum metal content ratio and effect of different wavelength of light is explored for the chemoselective reduction of p-nitrostyrene to p-aminostyrene under visible light irradiation. The prepared catalysts were characterized by a range of physicochemical techniques including UV–vis, transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The reduction reaction was carried out in ethanolic suspension at room temperature and pressure utilizing ammonia borane (AB) as an in-situ source of H2. The reaction results displayed 100% conversion with a maximum chemoselectivity of 81% shown by Ag/TiO2 under light irradiation conditions. The high chemoselectivity could be attributed to the preferential alignment of polar nitro group on the surface of plasmonic silver under light irradiation conditions.

Here we report the construction of an mRNA-encoded library of thioether-closed macrocyclic peptides by using an N-chloroacetyl-cyclopropane-containing exotic initiator whose structure is more constrained than the ordinary N-chloroacetyl-α-amino acid initiators. The use of such an initiator has led to a macrocycle library with significantly suppressed population of lariat-shaped species compared with the conventional libraries. We previously used a conventional library and identified a small lariat thioether-macrocycle with a tail peptide with a C-terminal free Cys whose sidechain plays an essential role in potent inhibitory activity against a parasitic model enzyme, phosphoglycerate mutase. On the other hand, the cyclopropane-containing macrocycle library has yielded a larger thioether-macrocycle lacking a free Cys residue, which exhibits potent inhibitory activity to the same enzyme with a different mode of action. This result indicates that such a cyclopropane-containing macrocycle library would allow us to access mechanistically distinct macrocycles.

In the research reported in this contribution, chromium-zirconium nitride (CrZrN) layers were deposited on (100) silicon wafer by balance magnetron sputtering using argon and nitrogen as working and reactive gas, respectively. The coating layers were categorized into three groups according to zirconium content; low-zirconium (Low-Zr), medium-zirconium (Med-Zr) and high-zirconium (High-Zr). All layers had thicknesses in the range of 1.0-1.3 μm and the Med-Zr was the thickest sample. From the X-ray diffraction (XRD) results, zirconium could partially dissolve in chromium nitride (CrN) and formed complex nitride of chromium-zirconium [(Cr,Zr)N]. This phasic group was dominant for all samples, and the average crystallite sizes decreased with increasing zirconium fraction. In addition, the High-Zr sample had an extra broadened peak among (Cr,Zr)N peaks which could not clearly be identified by XRD. This ambiguity was eliminated by X-ray photoelectron spectroscopy (XPS). It was determined to be amorphous of zirconium oxynitride (Zr2ON2). Because of the high oxygen sensitivity of zirconium, it reacted with nitrogen and residual oxygen forming Zr2ON2. This study is among the first to examine the resulting nanoscale structure of the CrN layers incorporated with a high amount of zirconium.

Despite recent developments in various therapies, heart failure remains a leading cause of morbidity and mortality worldwide. New pharmacological approaches are therefore needed to improve the outcomes of patients with heart failure. Diabetes mellitus is an important risk factor for heart failure, but until recently there had been no evidence that hypoglycemic agents prevent heart failure. Sodium-glucose cotransporter-2 (SGLT2) inhibitors have now been shown to prevent cardiovascular events, especially hospitalization for heart failure, in three large randomized clinical trials: EMPA-REG OUTCOME, the CANVAS program, and the DECLARE-TIMI58 trial. It is expected, therefore, that SGLT2 inhibitors will be useful therapeutic agents for the treatment of heart failure. The DAPA-HF trial recently demonstrated that dapagliflozin significantly reduces cardiovascular death and hospitalization for heart failure in patients with heart failure with reduced ejection fraction (HFrEF). Importantly, these benefits of dapagliflozin were similarly observed in patients with or without diabetes, suggesting the drug's efficacy is independent of glycemic reduction. The results of that study highlight the significance of SGLT2 inhibition as a novel therapeutic approach to treating HFrEF, irrespective of the presence or absence of diabetes. Findings of the DAPA-HF trial may also challenge current assumptions about the mechanisms underlying the cardioprotective action of SGLT2 inhibitors. It is anticipated that ongoing clinical trials, mainly using dapagliflozin and empagliflozin, will provide further insight into the clinical importance of these drugs for the treatment of heart failure, including heart failure with preserved ejection fraction (HFpEF), and also the mechanisms underlying those clinical benefits.

The synthesis of a tetra-armed cyclen (L) with two benzyl groups at the 1- and 7-positions and two pyridin-4-ylmethyl groups at the 4- and 10-positions as side arms and the solvent- and/or molar-ratio-dependent coordination modes in the formation of silver(I) complexes are reported. 1H NMR and cold-spray-ionization mass spectrometry studies suggest that a silver(I) complex with L gives different species depending on the molar ratio of silver ions used as the reactant. Furthermore, the conformation of cyclen in the one-dimensional (1D) coordination polymers, obtained using 2 equiv of silver(I), changes depending on the presence or absence of acetonitrile. When L was reacted with 1 and 2 equiv of silver(I) triflate in a mixed solvent system (CH2Cl2/CH3OH/CH3CN), a dimetallo[3.3]paracyclophane-like discrete cyclic dimer, [Ag2L2](OTf)2 (1), and a 1D coordination polymer, [Ag2L(OTf)2(CH3CN)]n (2), respectively, were obtained as single crystals. In the absence of acetonitrile, a zigzag 1D coordination polymer, {[Ag2L(OTf)]OTf·3CH2Cl2}n (3), was obtained when 2 equiv of silver(I) was used. Molar-ratio-dependent structural changes were not observed when L was reacted with AgBF4 or AgPF6 in the CH2Cl2/CH3OH/CH3CN mixed-solvent system. The solvent effect on the coordination modes can be explained by the coordination ability of the solvents toward the metal cation affecting the conformation of the cyclen.

Lanthanum Strontium Cobalt (LSC) perovskite-based catalysts were prepared and evaluated in the ammonia borane dehydrogenation reaction. Doping with additional non-noble metals, such as Ni or Cu greatly enhanced the catalytic performance, especially in the case of Cu. In order to evaluate the effect of the Cu loading, catalysts with various Cu contents ranging from 0.82 to 5.42 wt.% were synthesized. It was found that the Cu-doped sample with a nominal formula of La0.7Sr0.3Co0.90Cu0.10O3 containing 2.72 wt.% of Cu displayed the highest catalytic activity among investigated, which outperformed the counterpart Cu-supported catalyst (Cu/La0.7Sr0.3CoO3). La0.7Sr0.3Co0.90Cu0.10O3 showed good durability during five consecutive reaction runs, confirming the suitability of perovskite-type catalysts in stabilizing the catalytic active phase. The present catalytic system provides a cost-effective alternative to the noble-metal-based catalysts commonly used to catalyze the ammonia borane dehydrogenation reaction.

RSK2 is a serine/threonine kinase downstream signaling mediator in the RAS/ERK signaling pathway and may be a therapeutic target in mantle cell lymphoma (MCL), an almost incurable disease subtype of non‐Hodgkin lymphoma. In this study, serine‐227 (RSK2Ser227) in the N‐terminal kinase domain (NTKD) of RSK2 was found to be ubiquitously active in five MCL‐derived cell lines and in tumor tissues derived from five MCL patients. BI‐D1870, an inhibitor specific to RSK2‐NTKD, caused RSK2Ser227 dephosphorylation, and thereby, induced dose‐dependent growth inhibition via G2/M cell cycle blockade and apoptosis in four of the five cell lines, while one cell line showed only modest sensitivity. In addition, RSK2 gene knockdown caused growth inhibition in the four BI‐D1870‐sensitive cell lines. Comparative gene expression profiling of the MCL‐derived cell lines showed that inhibition of RSK2Ser227 by BI‐D1870 caused downregulation of oncogenes, such as c‐MYC and MYB; anti‐apoptosis genes, such as BCL2 and BCL2L1; genes for B cell development, including IKZF1, IKZF3, and PAX5; and genes constituting the B cell receptor signaling pathway, such as CD19, CD79B, and BLNK. These findings show that targeting of RSK2Ser227 enables concomitant blockade of pathways that are critically important in B cell tumorigenesis. In addition, we found favorable combinatory growth inhibitory effects of BI‐D1870 with inhibitors of BTK (ibrutinib), AKT (ipatasertib), and BCL2 (venetoclax) in cell characteristic‐dependent manners. These results provide a rationale for RSK2Ser227 in the NTKD as a potential therapeutic target in MCL and for future development of a novel bioavailable RSK2 NTKD‐specific inhibitor., RSK2Ser227 in the N‐terminal kinase domain (NTKD) of RSK2 was found to be ubiquitously active in mantle cell lymphoma (MCL). RSK2 concomitantly regulates series of genes involved in oncogenesis, apoptosis, B cell development, and B cell receptor signaling. RSK2Ser227 in the NTKD is a potential therapeutic target in MCL.

Catalytic formate/bicarbonate interconversion is a promising means of achieving a reversible hydrogen storage/release energy cycle because this system is easily controlled by varying only the H2 pr...