Lipase-Catalyzed Esterification of Triterpene Alcohols and Phytosterols with Oleic Acid

Oleic acid esters of phytosterols (PSs) and triterpene alcohols (TAs), derived from rice bran, were synthesized using lipases under mild conditions. Some lipases, especially from Candida rugosa, type VII, showed very high substrate specificity towards both PSs and TAs, when a mixture of PS and TA (PS/TA mixture) was used as the substrate source. The maximum yield of PS esters was ca. 80 % in each case; however, the maximum yield of TA esters was much lower when the reaction was continued for 7 days. Due to the difficulty in purifying the esters obtained when the PS/TA mixture was used as source of substrate, free PSs and TAs were separated from the PS/TA mixture by silica-gel and reverse-phase chromatography prior to esterification. The pure PSs or TAs were esterified with oleic acid to obtain the corresponding esters with high purity. Differential scanning calorimetric analysis of the resulting esters revealed that their melting points ranged from 7.0 to 42 °C. These values were at least 100 °C lower than those of the free PSs and TAs.     

Preparation of polydiacetylene single crystals based on physical vapor growth technique

We have succeeded in obtaining 10-mm-size polydiacetylene (PDA) single crystals using the physical vapor growth technique followed by the irradiation of ultraviolet (UV) rays, for the first time. The variety of growth conditions, such as growth temperature, growth time, carrier gases, and flow rate of gases are examined. Especially, the growth temperature and growth time have clear effects on the quality of crystals. Morphologies and sizes with relation to the various growth conditions are also observed. They show only one type of plateletlike shape with a pair of large parallelopiped planes, regardless of variety of growth conditions. The crystal thickness was estimated as about 500 nm by the observation of atomic force microscopy. The solubility of diacetylene (DA) and PDA to some organic solvents, and the X-ray diffraction data indicate that the obtained crystals are single crystals.     

Long-term D-Allose Administration Favorably Alters the Intestinal Environment in Aged Male Mice

D-Allose, a C3 epimer of D-glucose, has potential to improve human health as a functional food. However, its effect on the intestinal environment remains unknown. Aged humans progressively express changes in the gut, some of which deleteriously affect gastrointestinal health. In this study, we profiled the intestinal microbiome in aged mice and analyzed organic acids produced by bacteria in cecum contents after long-term ingestion of D-allose. D-Allose did not significantly change organic acid concentration. However, long-term ingestion did significantly increase the relative abundance of Actinobacteria and reduce the relative abundance of Proteobacteria. These results suggest that oral D-allose improves the proportion of favorable intestinal flora in aged mice. D-Allose significantly decreased the relative abundance of Lachnospiraceae bacteria, but increased the relative abundance of Bacteroides acidifaciens and Akkermansia muciniphila. Thus, D-allose might serve as a nutraceutical capable of improving the balance of gut microbiome during aging.     

Development of amperometric immunosensor using boron-doped diamond with poly(o-aminobenzoic acid)

An alternative method of a protein immunosensor has been developed at boron-doped diamond (BDD) electrode material. In order to construct the base of the immunosensor, o-aminobenzoic acid (o-ABA) was electropolymerized at an electrode by cyclic voltammetry. The poly-o-ABA-modified BDD was characterized by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The XPS result found that carboxyl groups were formed at the electrode surface. The carboxyl groups were then used to covalently attach protein probes. The amperometric sensing of mouse IgG (MIgG) was selected as the model at the poly-o-ABA-modified BDD to compare to the poly-o-ABA-modified glassy carbon (GC) at the same condition. An antimouse IgG from goat (GaMIgG) was covalently immobilized at a poly-o-ABA-modified BDD electrode which used a sandwich-type alkaline phosphatase (ALP) catalyzing amperometric immunoassay with 2-phospho-L-ascorbic acid (AAP) as substrate. The ALP enzyme conjugated at the immunosensor can generate AAP to the electroactive species of ascorbic acid (AA), which can be determined by amperometric detection. The signal was found to be proportional with the quantity of MIgG. The limits of detection (LODs) of 0.30 (3 SD) and 3.50 ng mL(-1) (3 SD) for MIgG at BDD and GC electrodes were obtained. It also was found that the dynamic range of 3 orders of magnitude (1-1000 ng mL(-1)) was obtained at BDD, whereas at GC, the dynamic range was more narrow (10-500 ng mL(-1)). The method was applied to a real mouse serum sample that contains MIgG.     

Metformin Protects against NMDA-Induced Retinal Injury through the MEK/ERK Signaling Pathway in Rats

Metformin, an anti-hyperglycemic drug of the biguanide class, exerts positive effects in several non-diabetes-related diseases. In this study, we aimed to examine the protective effects of metformin against N-methyl-D-aspartic acid (NMDA)-induced excitotoxic retinal damage in rats and determine the mechanisms of its protective effects. Male Sprague–Dawley rats (7 to 9 weeks old) were used in this study. Following intravitreal injection of NMDA (200 nmol/eye), the number of neuronal cells in the ganglion cell layer and parvalbumin-positive amacrine cells decreased, whereas the number of CD45-positive leukocytes and Iba1-positive microglia increased. Metformin attenuated these NMDA-induced responses. The neuroprotective effect of metformin was abolished by compound C, an inhibitor of AMP-activated protein kinase (AMPK). The AMPK activator, AICAR, exerted a neuroprotective effect in NMDA-induced retinal injury. The MEK1/2 inhibitor, U0126, reduced the neuroprotective effect of metformin. These results suggest that metformin protects against NMDA-induced retinal neurotoxicity through activation of the AMPK and MEK/extracellular signal-regulated kinase (ERK) signaling pathways. This neuroprotective effect could be partially attributable to the inhibitory effects on inflammatory responses.     

Double Charge Polarity Switching in Sb-Doped SnSe with Switchable Substitution Sites

Tin mono-selenide (SnSe) is one of the most promising thermoelectric materials; however, it experiences difficulty in controlling the carrier polarity, which is inevitable for realizing p-n homojunction devices. Herein, double switching of charge polarity in (Sn_1−xSb_x)Se by varying x is reported; pure SnSe shows p-type conduction, whereas the polarity of (Sn_1−xSb_x)Se switches to n-type conduction for 0.005 < x < 0.05, and then re-switches to p-type conduction for x > 0.05. The major Sb substitution site switches from the Se (Sb_Se) to Sn site (Sb_Sn) with increasing x. Sb_Sn (Sb³⁺ at Sn²⁺) works as a donor, but Sb_Se (Sb³⁻ at Se²⁻) does not produce a hole because of the Sb–Sb dimer formation. The mechanism of double polarity switching is explained by native p-type conduction in pure SnSe due to Sn-vacancy formation, whereas (Sn_1−xSb_x)Se exhibits n-type behavior due to conduction through the Sb_Se impurity band formed above the valence band maximum, and finally re-switches to weak p-type, where the Fermi level approaches the midgap level between the Sb_Se band and conduction band minimum. Clarification of the Sb doping mechanism will provide a crucial guide for developing more sophisticated doping routes for SnSe and high-performance energy-related devices.     

Single-crystal solidification of new Co–Al–W-base alloys

Solidification processing of new high-temperature Co–Al–W-base single-crystals has been investigated. Single-crystal bars with compositions of Co–9.4Al–10.7W, Co–8.8Al–9.8W–2Ta and Co–7.8Al–7.8W–1.5Ta–4.5Cr (at%) were successfully grown with a conventional Bridgman process. Helical grain selectors resulted in [001] dendritic growth with primary dendrite arm spacings in the range of 278–364 μm. Segregation of constituent elements in the dendritic structure was very limited, compared to Ni-base single-crystals. Concentration profiles obtained by electron microprobe and analyzed via the Scheil equation indicate distribution coefficients for Co, Al, W and Cr that are close to 1. The distribution coefficient of Ta was approximately 0.6, indicating preferential segregation to the liquid during solidification. These observations collectively suggest that convective instabilities and freckle formation are unlikely to occur during solidification of single-crystals of this new class of high strength Co–Al–W-base alloys.     

The Influence of Rh Addition on the Catalytic Activity of Cubic Pt Nanocrystals Supported on Alumina for NO/CH4 Reaction

The effect of the Rh addition to the well defined cubic (≈70%) Pt nanocrystals of around 13 nm supported on alumina was investigated for NO/CH₄ reaction. The impact of size and shape of Pt nanoparticles on the catalytic activity were also analyzed by comparing the results with a conventionally prepared catalyst.     

Self‐Activated Vanadate Compounds Toward Realization of Rare‐Earth‐Free Full‐Color Phosphors

Rare‐earth‐free phosphors based on vanadate compounds were investigated, where the vanadates included chloride vanadates (M^II₂VO₄Cl), pyrovanadates (M^II₂V₂O₇), orthovanadates (M^II₃(VO₄)₂) with divalent cations M^II of Mg, Sr, Ba, and Zn, and oxofluorovanadates (A^IVOF₄) with an alkali metal A^I. A chloride pyrolysis method and a liquid phase precipitation method were proposed for preparing the chloride vanadates and pyro‐ and orthovanadates, respectively. These vanadate compounds showed self‐activated photoluminescence (PL) based on the VO₄ clusters against the ultraviolet (UV) light irradiation. The colors of PL covered almost the whole visible‐light region from blue to yellow as Sr₂VO₄Cl (deep blue), Ca₂VO₄Cl (sky blue), Ba₂V₂O₇ (green), Sr₂V₂O₇ (yellowish green), Zn₃(VO₄)₂ (yellow), and Mg₃(VO₄)₂ (yellow). A correlation was suggested from these compounds between the luminescent colors and the structural feature as the longer V–O distances in the VO₄ tetrahedra in the crystal structures led to the longer wavelength in PL. This seemed to be also applicable for the oxofluorovanadates A^IVOF₄ (A^I = K and Cs) which contain the VOF₄ polyhedra with one O^2? ion and four F^‐ ions as the ligands, as they exhibited the reddish PL.     

Fabrication of fine micro protrusions on fluoropolymer surface using ion beam irradiation

Tissue reconstruction is the aim of regeneration medicine and tissue engineering. One of the techniques is cell sheet engineering, which requires creating a contiguous cell sheet and harvesting it safely. To create a favorable substrate for cultivation, we attempted to fabricate the microstructure at polytetrafluoroethylene (PTFE) surfaces using ion beam irradiation. PTFE is a typical fluoropolymer and it possesses chemical and bioinertness. When the surface is irradiated with an ion beam, it is covered with a large number of microprotrusions, which have an aspect ratio of about 100. We previously reported that fibroblast cells grow and spread between the tops of the protrusions. In this study, we fabricated fine protrusions at both the PTFE and the poly(tetrafluoroethylene-co-hexafluoropropylene) (FEP) surfaces. The composition of FEP and PTFE is similar but FEP melts at a lower temperature than PTFE does. These samples were irradiated under controlled temperature and rubbing preparation. Their surface morphology and chemical bonding were observed. When the PTFE surface was irradiated at 350 °C, the protrusions were formed at the lower fluence, with an improved uniformity of shape. This was because the morphological change and evaporation of the thin parts were enhanced during high-temperature irradiation. In the FEP sample, very fine protrusions formed at much lower fluence by irradiation at room temperature. On the surface, the cells spread closely, like a monolayer. Further, the FEP samples were still optically transparent after the irradiation. They have an advantage in that we can observe the living cells attaching to the surface in their natural state without them being killed, fixed, and stained in an optical microscope. We found that the irradiated FEP surface is suitable for making a cell sheet.