Development of Novel Decarboxylation-Urea Method toward Interlayer-Anion-Controlled Layered Double Hydroxides.

Layered double hydroxides (LDHs) are representative of a 2D anionic clay. Simple and homogeneous synthesis of interlayer-anion-controlled LDH is essential for studies and industrial production. In this study, we report the one-pot synthesis of an LDH that is selective for interlayer anions, which was labeled as "decarboxylation-urea method". We obtained LDHs intercalated with NO3-, Cl-, and SO42- by removing CO2 in this method. The ionic conductivities of the prepared LDHs were investigated for their applicability to electrolytes, and it was found that Zn-Al LDH intercalated with NO3- showed the highest ionic conductivity (18 mS cm-1). Therefore, the LDH intercalated with NO3- synthesized using the decarboxylation-urea method is promising as an alkaline solid electrolyte.

Molecular Insight into the Ionic Conduction of Quaternary Ammonium and Phosphonium Cation-Based Ionic Liquids Using Dielectric and Spectroscopy Analyses.

We analyzed the primary properties of ionic liquids (ILs) comprising quaternary phosphonium cations and bis(trifluoromethylsulfonyl) amide anions and compared them with those of corresponding quaternary-ammonium-cation-based ILs. Broadband dielectric spectroscopy was used to confirm the coupling between the translational and orientational motions of ions, and our results demonstrated that the high ionic conductivity of the phosphonium-based ILs was attributed to their fast rotational dynamics. The differences between ILs with different cations were further evaluated using vibrational (Raman and terahertz) spectroscopy. The Raman spectroscopy data revealed that the cation structure affected the conformation and flexibility (conformational change) of the anion. Furthermore, terahertz spectroscopy allowed us to evaluate the relationship between ion transport and intermolecular interactions between the cation and anion of ILs.

Association of alcohol intake and female gender with high expression of TMPRSS2 in tongue as potential risk for SARS-CoV-2 infection.

COVID-19 is pandemic since 2020 and further information is necessary on the risk factors associated with the infection of SARS-CoV-2. As an entry mechanism, SARS-CoV-2 uses angiotensin-converting enzyme 2 (ACE2) as receptor and transmembrane serine protease 2 (TMPRSS2) to activate fusion with host plasma membrane. Because dysgeusia is an early symptom of COVID-19, we here studied the expression of ACE2 and TMPRSS2 in the tongue and the associated tissues of mice and humans with immunohistochemistry and immunoblot analysis. ACE2 expression was low in the human tongue but was observed in the squamous epithelium, perineurium, arterial wall, salivary glands as well as taste buds. In contrast, mice showed high expression. In sharp contrast, TMPRSS2 expression was high in all the cells mentioned above in humans but relatively low in mice except for salivary glands. We then performed semi-quantitation of immunohistochemistry data of human ACE2 and TMPRSS2 and analyzed for age, sex, alcohol intake, and smoking habit with logistic regression analysis. We found that alcohol intake and female gender were the significant risk factors for increasing TMPRSS2 expression. In conclusion, TMPRSS2 is an important factor to be considered regarding SARS-CoV-2 entry and amplification in the oral cavity, which is promoted through drinking habit.

Impact of sp2 carbon material species on Pt nanoparticle-based electrocatalysts produced by one-pot pyrolysis methods with ionic liquids.

Pt-nanoparticle-supported graphene nanoplatelets (Pt/GNPs) and multiwalled carbon nanotube composite (Pt/MWCNTs) electrocatalysts for the oxygen reduction reaction (ORR) can be prepared using a one-pot method through the pyrolytic decomposition of the platinum precursor, platinum(ii) bis(acetylacetonate) (Pt(acac)2) in 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ([C4mim][Tf2N]) or N,N,N-trimethyl-N-propylammonium bis(trifluoromethanesulfonyl)amide ([N1,1,1,3][Tf2N]) ionic liquids (ILs) with the target sp2 carbon support. In this one-pot pyrolysis method, which does not require any reagents to reduce Pt metal precursors or stabilize Pt nanoparticles, Pt nanoparticles are readily immobilized onto the sp2 surface by a thin IL layer formed at the interface, which can work as a binder. We used three types of sp2 carbon materials with different geometric shapes (graphene nanoplatelets with <3 (GNPs-3) and 18-24 layers (GNPs-20) and multiwalled carbon nanotubes (MWCNTs)) to investigate Pt nanoparticle formation and anchoring. All the electrocatalysts, especially Pt/MWCNTs, showed higher durability than the commercial catalyst owing to the combined effect of the IL binder and sp2 carbon materials. Our findings strongly suggest that the original carbon surface properties are also an important factor for creating high-performance ORR electrocatalysts.

Efficient Separation of Photoexcited Charge at Interface between Pure CeO2 and Y3+-Doped CeO2 with Heterogonous Doping Structure for Photocatalytic Overall Water Splitting.

Enhancement of photoexcited charge separation in semiconductor photocatalysts is one of the important subjects to improve the efficiency of energy conversion for photocatalytic overall water splitting into H2 and O2. In this study, we report an efficient separation of photoexcited charge at the interface between non-doped pure CeO2 and Y3+-doped CeO2 phases on particle surfaces with heterogeneous doping structure. Neither non-doped pure CeO2 and homogeneously Y3+-doped CeO2 gave activities for photocatalytic H2 and O2 production under ultraviolet light irradiation, meaning that both single phases showed little activity. On the other hand, Y3+-heterogeneously doped CeO2 of which the surface was composed of non-doped pure CeO2, and Y3+-doped CeO2 phases exhibited remarkable photocatalytic activities, indicating that the interfacial heterostructure between non-doped pure CeO2 and Y3+-doped CeO2 phases plays an important role for the activation process. The role of the interface between two different phases for activated expression was investigated by selective photo-reduction and oxidation deposition techniques of metal ion, resulting that the interface between two phases become an efficient separation site of photoexcited charge. Electronic band structures of both phases were investigated by the spectroscopic method, and then a mechanism of charge separation is discussed.

Draxin-mediated Regulation of Granule Cell Progenitor Differentiation in the Postnatal Hippocampal Dentate Gyrus.

The hippocampus is characterized by the presence of life-long neurogenesis. To elucidate the molecular mechanism regulating hippocampal neurogenesis, we studied the functions of the chemorepellent Draxin in neuronal proliferation and differentiation in the postnatal dentate gyrus. The present in vivo cell labeling and fate tracking analyses revealed enhanced differentiation of hippocampal neural stem and progenitor cells (hNSPCs) in the subgranular zone (SGZ) of Draxin-deficient mice. We observed a reduction in the number of BrdU-pulse labeled or Ki-67 immunopositive SGZ cells in the mutant mice. However, Draxin deficiency did not affect cell cycle duration of SGZ cells. In situ hybridization analysis indicated that the receptor component of the canonical Wnt pathway, Lrp6, is expressed in SGZ cells, including Nestin and Sox2 double-positive hNSPCs. Taken together with the previous finding that Draxin interacts physically with Lrp6, we postulate that Draxin plays a pivotal role in the regulation of Wnt-driven hNSPC differentiation to modulate the rate of neuronal differentiation in the progenitor population.

The chemorepellent draxin is involved in hippocampal mossy fiber projection.

Lamina-specific afferent innervation of the mammalian hippocampus is critical for its function. We investigated the relevance of the chemorepellent draxin to the laminar projections of three principal hippocampal afferents: mossy fibers, entorhinal, and associational/commissural fibers. We observed that draxin deficiency led to abnormal projection of mossy fibers but not other afferents. Immunohistochemical analysis indicated that draxin is expressed in the dentate gyrus and cornu ammonis (CA) 3 at postnatal day 0, when dentate granule cells begin to extend mossy fibers towards CA3. Furthermore, a neurite growth assay using dissociated cells of the neonatal dentate gyrus revealed that draxin inhibited the growth of calbindin-D28k-expressing mossy fibers in vitro. Taken together, we conclude that draxin is a key molecule in the regulation of mossy fiber projections.

Draxin regulates hippocampal neurogenesis in the postnatal dentate gyrus by inhibiting DCC-induced apoptosis.

Hippocampal neurogenesis in the dentate gyrus (DG) is controlled by diffusible molecules that modulate neurogenic processes, including cell proliferation, differentiation and survival. To elucidate the mechanisms underlying hippocampal neurogenesis, we investigated the function of draxin, originally identified as a neural chemorepellent, in the regulation of neuronal survival in the DG. Draxin was expressed in Tbr2 (+) late progenitors and NeuroD1 (+) neuroblasts in the dentate granule cell lineage, whereas expression of its receptor DCC (deleted in colorectal cancer) was mainly detectable in neuroblasts. Our phenotypic analysis revealed that draxin deficiency led to enhanced apoptosis of DCC-expressing neuroblasts in the neurogenic areas. Furthermore, in vitro assays using a hippocampal neural stem/progenitor cell (HNSPC) line indicated that draxin inhibited apoptosis in differentiating HNSPCs, which express DCC. Taken together, we postulate that draxin plays a pivotal role in postnatal DG neurogenesis as a dependence receptor ligand for DCC to maintain and promote survival of neuroblasts.

Speciation of radioactive soil particles in the Fukushima contaminated area by IP autoradiography and microanalyses.

Radioactive soil particles several tens of micrometers in size were collected from litter soil in the radiation contaminated area by the Fukushima nuclear plant accident and characterized using electron and X-ray microanalyses. The radioactive particles were discriminated by autoradiography using imaging plates (IP) on which microgrids were formed by laser ablation in order to find the particles under microscopy. Fifty radioactive particles were identified and classified into three types from their morphology and chemical composition, namely: (1) aggregates of clay minerals, (2) organic matter containing clay mineral particulates, and (3) weathered biotite originating from local granite. With respect to the second type, dissolution of the organic matter did not reduce the radiation, suggesting that the radionuclides were also fixed by the clay minerals. The weathered biotite grains have a plate-like shape with well-developed cleavages inside the grains, and kaolin group minerals and goethite filling the cleavage spaces. The reduction of the radiation intensity was measured before and after the trimming of the plate edges using a focused ion beam (FIB), to examine whether radioactive cesium primarily sorbed at frayed edges. The radiation was attenuated in proportion to the volume decrease by the edge trimming, implying that radioactive cesium was sorbed uniformly in the porous weathered biotite.

Uptake of cesium and strontium ions by artificially altered phlogopite.

Potassium (K(+)) phlogopite was transformed to a vermiculite-like mineral through a topotactic reaction under acidic conditions (pH 2) followed by hydrothermal treatment with Na(+), Mg(2+), Ca(2+), and Al(3+) cations. The resulting Na(+)-, Mg(2+)-, Ca(2+)-, and Al(3+)-altered phlogopites (Phl) denoted as Na-Phl, Mg-Phl, Ca-Phl, and Al-Phl, respectively. Na-Phl, Mg-Phl, and Ca-Phl all exhibited the same high adsorption capacity as natural vermiculite and the absorption of Cs(+) and Sr(2+) ions on these materials followed the Langmuir model. High-angle annular dark-field scanning transmission electron microscopy showed that Cs(+) ions in the Mg-Phl layers were intercalated deep within the crystal structure, along specific interlayer regions. These adsorbed anhydrous Cs(+) ions were firmly fixed at the centers of hexagonal rings positioned simultaneously in the upper and lower tetrahedral silicate sheets, whereas Sr(2+) ions adsorb into the interlayer in the hydrous state. Al-Phl formed a hydroxyl-interlayered vermiculite and demonstrated significant selectivity for Cs(+) at very low concentrations of the isotope. Consequently, the artificially altered phlogopites prepared in this study showed controllable and versatile adsorption capabilities making them significantly more suitable than natural vermiculite for Cs and Sr decontamination.

Direct observation of cesium at the interlayer region in phlogopite mica.

To investigate the sorption mechanism of cesium (Cs) into clay minerals, high-resolution (scanning) transmission electron microscopy (TEM/STEM) imaging of Cs in mica (phlogopite) has been conducted. Platy phlogopite powders were immersed in a cesium chloride (CsCl) solution to achieve Cs(+)-K(+) ion-exchange at the interlayer regions in phlogopite. To observe many phlogopite particles with the incident electron beam parallel to the mica layers, cross-sectional thin specimens were prepared from sedimented particles using a focused ion beam. High-angle annular dark-field imaging with STEM is superior to conventional high-resolution TEM (HRTEM) for visualizing Cs at interlayer sites even in thicker crystal regions and/or at lower magnification due to the intense Z-contrast of Cs. However, HRTEM is also practical for estimating the concentration of Cs at the interlayer site from the thickness dependence of the contrast at the interlayer region. Cs sorption of micas was previously thought to be localized mainly at the frayed-edge sites of mica crystals. However, the present observations indicate that Cs substitution of K occurs not around crystal edges but deep inside the crystals along specific interlayer regions.

Swelling and gel/sol formation of perchlorate-type layered double hydroxides in concentrated aqueous solutions of amino acid-related zwitterionic compounds.

ClO(4)(-)MgAl-LDH3, a MgAl (Mg/Al = 3) layered double hydroxide (LDH) containing perchlorate, swells and forms colloidal suspensions (sols) via the gel state in concentrated aqueous solutions of zwitterionic compounds related to amino acids. In total, 36 zwitterionic compounds with different molecular structures and additional functional groups were examined at various concentrations, and the sol-formation ability was judged by the transmittance (at λ = 589 nm) of the resulting suspensions. At low concentration, the obtained suspensions were turbid, with transmittances of ~0%. However, above the threshold concentration (0.3-1.0 M), osmotic swelling occurred and the transmittances of the suspensions increased sharply with increases in concentration to reach maximum values of 70-95%. The threshold concentration and maximum transmittance value depended on the structure and the location of the functional groups. The enhancement of the permittivity of water by the zwitterions and the formation of H-bond networks were assumed to be the reasons for the swelling phenomenon. Similar gel/sol formation was observed for ClO(4)(-)LDHs with Mg/Al = 2, Ni/Al = 2, 3, and Co/Al = 2 and some NO(3)(-)LDHs. Large ClO(4)(-)LDH films could be prepared by filtration of the colloidal suspensions followed by washing and drying processes.

Hybridization of sugar alcohols into brucite interlayers via a melt intercalation process.

We report the preparation of organic-brucite (BR) hybrids using harmless sugar alcohols (xylitol, XYL, and sorbitol, SOR). Since XYL and SOR are solid materials at room temperature, the hybridization was investigated by comparing two separate methods, hydrothermal treatment and melt mixing. BR-sugar alcohol hybrids were successfully prepared by a melt intercalation method at 175 °C. X-ray diffraction and Fourier transform infrared spectroscopy analyses indicated that organic molecules were intercalated into the brucite layers, overcoming the barrier of hydroxyl bonds between the BR layers. Moreover, X-ray photoelectron spectroscopy and thermal analyses showed that the intercalated materials at 175 °C resulted in the formation of covalent Mg-O-C bond linkages on the interlayer surface of BR.

Geomaterials: their application to environmental remediation.

Geomaterials are materials inspired by geological systems originating from the billion years long history of the Earth. This article reviews three important classes of geomaterials. The first one is smectites-layered silicates with a cation-exchange capacity. Smectites are useful for removing pollutants and as intercalation compounds, catalysts and polymer nanocomposites. The second class is layered double hydroxides (LDHs). They have an anion-exchange capacity and are used as catalysts, catalyst precursors, sorbents and scavengers for halogens. The third class of geomaterials is zeolites-microporous materials with a cation-exchange capacity which are used for removing harmful cations. Zeolite composites with LDHs can absorb ammonium and phosphate ions in rivers and lakes, whereas zeolite/apatite composites can immobilize the radioactive iodine. These geomaterials are essential for environmental remediation.

One-pot synthesis of organophilic layered double hydroxides (LDHs) containing aliphatic carboxylates: extended "homogeneous precipitation" method.

One-pot synthesis of aliphatic carboxylate/LDH hybrids (org-LDHs) was accomplished via the so-called "homogeneous precipitation" method developed for preparing carbonate-type layered double hydroxides (CO(3)(2-) LDHs) with ammonia-releasing reagents such as hexamethylenetetramine (HMT) and urea. An aqueous solution of an aliphatic carboxylate (C2-C18) was added to a mixed aqueous solution of metal salts and HMT and then heated at 140-160 degrees C in a pressure vessel for 1day. Two kinds of LDHs were investigated: MgAl-LDH and NiAl-LDH. We found that only aliphatic carboxylates longer than decanoate (C10) and dodecanoate (C12) were incorporated successfully in the MgAl-LDH and NiAl-LDH interlayers without any CO(3)(2-) contamination, respectively. Shorter carboxylates were not incorporated, only yielding CO(3)(2-)LDHs. Isolation of the hydrophobic org-LDH phase from the aqueous medium containing carbonate ions was assumed to be the main reason for the lack of CO(3)(2-) contamination in the org-LDHs having longer-alkyl carboxylates. This method was also used successfully for preparing MgAl-LDHs containing dodecylbenzene sulfonate(DBS), a sulfonate-type anionic surfactant.

Novel long-term immobilization method for radioactive iodine-129 using a zeolite/apatite composite sintered body.

The amount of radioactive iodine generated from nuclear power plants is expected to increase with the proliferation of nuclear energy production, and long-term immobilization methods for such radioactive elements need to be developed to make nuclear energy sustainable. The standard immobilization method of radioactive elements, vitrification, is not very effective for radioactive iodine-129 because of the low solubility of iodine in silicate melts, its very high volatility at standard vitrification process temperatures, and its instability in the alkaline environment of deep geological layers below 300 m. We have developed a novel three-phase ceramic composite produced by a sintering process. Iodine adsorbed onto Ca-type zeolite A was covered with a hydroxyapatite nanolayer through the exchange reaction of ammonium with calcium. Clusters of iodine of 30 nm within the zeolite structure were found to be thermally stable up to 1253 K because of the partial blockage of the alpha-cage apertures by ammonium ions and the partial change from a crystalline phase to an amorphous phase at 473 K. No gasification of iodine molecules was found to occur during the sintering process. The outer phase was highly crystalline hydroxyfluorapatite in which the hydroxyapatite nanolayer plays an important role for successful sintering. The elution of iodine in low-dioxygen water, similar to that found within the Earth's crust, was investigated and was found to occur only in the surface layer of the sintered body.