Effect of Surface Treatment on the Selective Photocatalytic Oxidation of Benzyl Alcohol into Benzaldehyde by O2 on TiO2 Under Visible Light

The photocatalytic oxidation of benzyl alcohol into benzaldehyde proceeded with high conversion and selectivity on a TiO₂ photocatalyst by O₂ under visible light irradiation. Surface complex formed by the interaction of benzyl alcohol with the Ti sites and/or surface OH groups of TiO₂ play an important role in the absorption of visible light and unique selective photocatalytic reaction.     

Development of In Vitro and In Vivo Evaluation Systems for Vitamin D Derivatives and Their Application to Drug Discovery

We have developed an in vitro system to easily examine the affinity for vitamin D receptor (VDR) and CYP24A1-mediated metabolism as two methods of assessing vitamin D derivatives. Vitamin D derivatives with high VDR affinity and resistance to CYP24A1-mediated metabolism could be good therapeutic agents. This system can effectively select vitamin D derivatives with these useful properties. We have also developed an in vivo system including a Cyp27b1-gene-deficient rat (a type I rickets model), a Vdr-gene-deficient rat (a type II rickets model), and a rat with a mutant Vdr (R270L) (another type II rickets model) using a genome editing method. For Cyp27b1-gene-deficient and Vdr mutant (R270L) rats, amelioration of rickets symptoms can be used as an index of the efficacy of vitamin D derivatives. Vdr-gene-deficient rats can be used to assess the activities of vitamin D derivatives specialized for actions not mediated by VDR. One of our original vitamin D derivatives, which displays high affinity VDR binding and resistance to CYP24A1-dependent metabolism, has shown good therapeutic effects in Vdr (R270L) rats, although further analysis is needed.     

Electrochemically Assisted Photocatalysis of Hybrid WO3/TiO2 Films: Effect of the WO3 Structures on Charge Separation Behavior

In this study, the photocatalysis of hybrid WO₃/TiO₂ films with different loadings of WO₃ were investigated with and without potential bias. It was clearly indicated that hybrid WO₃/TiO₂ films show less photo-reactivity under only UV-irradiation, while more effective photocatalysis under potential bias than either TiO₂ or WO₃ by themselves, their photocatalytic performance depending on the loadings of WO₃. In particular, a hybrid WO₃/TiO₂ film involving an amorphous-like WO₃ phase plays a significant role in an enhancement of the electrochemically assisted photocatalysis.     

Stabilization of flavylium dye by incorporation into the pore of protonated zeolites

Flavylium dye, a model compound of natural anthocyanin, has a defect that its color stability is very poor. We have complexed the flavylium dye with protonated zeolites and succeeded to enhance both the thermal and chemical stability of the dye. The aqueous dispersion of the flavylium/zeolite complex maintains its color even at 353 K or at pH 9, under which conditions the aqueous solution of the flavylium loses its color immediately. The stability is enhanced when the dye is incorporated into the pore of the zeolites, and a large stabilization effect is obtained by a tight adsorption with a narrow pore, as long as the dye is incorporated into the pore. Because of its enhanced color stability, the flavylium dye incorporated in the zeolite pore can be a candidate for an environmentally friendly coloring material.     

Nanoparticle formation in H2O/N2 and H2O/Ar mixtures under irradiation by 20 MeV protons and positive corona discharge

To investigate the contribution of ions to gas nucleation, we have performed experiments on the formation of water droplets in H₂O/N₂ and H₂O/Ar gas mixtures by irradiation with a 20 MeV proton beam and by positive corona discharge. The size of the formed nanoparticles was measured using a differential mobility analyzer equipped with a Faraday cup electrometer. Using the proton beam, droplets around 10 nm in diameter were observed for both positively and negatively charged particles, but none were found when the corona discharge was used. This implies the importance of the presence of both positive and negative ions for the formation of nanosize droplets, which attract each other by Coulomb interactions, enhancing the collision frequency and leading to the formation of the 10 nm droplets.     

Surface and pore structure of alumina derived from xerogel/aerogel

The alkyl derivatives of boehmite were prepared by solvothermal reaction of aluminum isopropoxide in n-alcohols (ethanol, 1-butanol, 1-hexanol, 1-octanol and 1-dodecanol) and the products were recovered as aerogel/xerogel by the removal of the solvent at the end of reaction. Aerogel or xerogel can be obtained simply by using only a reaction vessel (autoclave) and the obtained products were composed of plate-like particles having a well-developed boehmite structure. The alumina powders obtained by calcination of these products had relatively large pore-volumes ranging from 1.35 to 2.56 cm³/g. Transformation into α-Al₂O₃ was retarded even after calcination at 1200 °C. The effect of n-alcohols used in the solvothermal reaction on the phase, morphology and pore-texture of the alumina samples are discussed.     

Proton-conducting electrolyte membranes based on hyperbranched polymer with a sulfonic acid group for high-temperature fuel cells

The hyperbranched polymers (HBP-SA-Acs) with both a sulfonic acid group as a functional group and an acryloyl group as a cross-linker at terminals in different ratios of sulfonic acid group/acryloyl group (SO₃H/Ac) were successfully synthesized as a new thermally stable proton-conducting electrolyte. The cross-linked hyperbranched polymer electrolyte membranes (CL-HBP-SAs) were prepared by thermal polymerizations of the HBP-SA-Acs using benzoyl peroxide, and their ionic conductivities under dry condition and thermal properties were investigated. The ionic conductivities of the CL-HBP-SAs were found to be in the range of 2.2 × 10⁻⁴ to 3.3 × 10⁻⁶ S/cm, depending upon the SO₃H unit contents, at 150 °C under dry condition, and showed the Vogel-Tamman-Fulcher (VTF) type temperature dependence, indicating that proton transfer is cooperated by local polymer chain motion. All CL-HBP-SAs were thermally stable up to 260 °C, and they had suitable thermal stability as electrolyte membranes for the high-temperature fuel cells under dry condition. Fuel cell measurement using a single membrane electrode assembly cell with a cross-linked electrolyte membrane was successfully performed under non-humidified condition. It was demonstrated that applying the concept of dry polymer system to proton conduction is one possible approach toward high-temperature fuel cells.     

Tyrosine-based poly(m-phenyleneethynylene-p-phenyleneethynylene)s. Helix folding and responsiveness to a base

The Sonogashira-Hagihara polymerization of 3′,5′-diiodo-N-α-tert-butoxycarbonyl-l-tyrosine methyl ester (1) and 3′,5′-diiodo-N-α-tert-butoxycarbonyl-O-methyl-l-tyrosine methyl ester (2) with para-diethynylbenzene (3) was carried out to obtain optically active poly(m-phenyleneethynylene-p-phenyleneethynylene)s [poly(1) and poly(2)] with M_n’s ranging from 9900 to 15,000 in 80-87% yields. Poly(1) exhibited intense CD signals in DMSO and THF, but did not in CH₂Cl₂, indicating that it took a predominantly one-handed helical conformation in the former two solvents. On the other hand, there was no evidence for poly(2) to take a helical structure in these solvents. Poly(1) turned the CD sign at 390 nm from plus to minus in DMSO/H₂O = 9/1 (v/v) by the addition of NaOH. Alkaline hydrolysis of ester moieties of poly(1) and poly(2) gave the corresponding polymers having carboxy groups [poly(1a) and poly(2a)]. Poly(1a) and poly(2a) increased the CD intensity by the addition of NaOH.     

Multifaceted Mechanisms of Action of Metformin Which Have Been Unraveled One after Another in the Long History

While there are various kinds of drugs for type 2 diabetes mellitus at present, in this review article, we focus on metformin which is an insulin sensitizer and is often used as a first-choice drug worldwide. Metformin mainly activates adenosine monophosphate-activated protein kinase (AMPK) in the liver which leads to suppression of fatty acid synthesis and gluconeogenesis. Metformin activates AMPK in skeletal muscle as well, which increases translocation of glucose transporter 4 to the cell membrane and thereby increases glucose uptake. Further, metformin suppresses glucagon signaling in the liver by suppressing adenylate cyclase which leads to suppression of gluconeogenesis. In addition, metformin reduces autophagy failure observed in pancreatic β-cells under diabetic conditions. Furthermore, it is known that metformin alters the gut microbiome and facilitates the transport of glucose from the circulation into excrement. It is also known that metformin reduces food intake and lowers body weight by increasing circulating levels of the peptide hormone growth/differentiation factor 15 (GDF15). Furthermore, much attention has been drawn to the fact that the frequency of various cancers is lower in subjects taking metformin. Metformin suppresses the mechanistic target of rapamycin (mTOR) by activating AMPK in pre-neoplastic cells, which leads to suppression of cell growth and an increase in apoptosis in pre-neoplastic cells. It has been shown recently that metformin consumption potentially influences the mortality in patients with type 2 diabetes mellitus and coronavirus infectious disease (COVID-19). Taken together, metformin is an old drug, but multifaceted mechanisms of action of metformin have been unraveled one after another in its long history.