Role of polyvinylpyrrolidone in the polyol synthesis of platinum nanoparticles.

In this work, platinum (Pt) nanoparticles (NPs) were prepared via the reduction of Pt salts in an ethylene glycol induced polyol process with an altered polyvinylpyrrolidone (PVP)/Pt molar ratio. With the systematic elucidation of the hydrodynamic size in a liquid; the solid-state size and morphology, crystal structure, surface chemical state and thermal decomposition behavior of the synthesized Pt NPs; as well as the reducing dynamic of Pt cations, the role of PVP in the polyol synthesis of Pt NPs is clarified for the first time. It was found that the amount of PVP does not affect the reducing dynamic of Pt cations, but the chemical state of PVP capped on Pt NPs and the resultant particle size significantly depend on the initial PVP/Pt molar ratio in the precursor solution. Dense-packed PVP via the chemisorption of carbonyl oxygen on the surface of Pt NPs occurs in the case of a higher PVP/Pt ratio, suppressing particle growth and resulting in smaller Pt NPs. On the contrary, the chemical structure of PVP is tuned by the cleavage of the N-C bond and results in the chemisorption of the N atom on the surface of Pt NPs, which promotes the production of larger Pt NPs when a lower PVP/Pt ratio is applied.

Glazes induced degradation of tea catechins.

In present work, the degradation behavior of tea catechins on various commercial glazes was elucidated for the first time. Four kinds of Japanese typical commercial glaze powders (Oribe /Namako/Irabo /Toumei) based on Fe/Mg /Cu /Ti oxides were utilized and deposited on ceramic tiles. Tea solution extracted from green tea leaves at 80 °C and then utilized for the examination of degradation behavior with glazes to meet a nearly identical condition in human daily tea drinking with ceramicwares. It was found that the degradation of tea catechins significantly dependent on the chemical structure of glazes, that is: Fe/Cu/Mg oxides contained glazes can promote the degradation of epigallocatechin, epicatechin, epigallocatechin gallate and epicatechin gallate, while Ti oxide contained glaze stimulated the degradation of epigallocatechin gallate selectively. Coloring pigments were produced in degraded tea solutions, whose color shows glaze dependent property. We presume that these color pigments can be assigned as oxytheotannin, especially theaflavin and its oxides as well as thearubigins, that produced through the polymerization of intermediate free radical catechin and/or the ortho-quinone generated by catalytic effect of glaze oxides worked as Lewis's acids. The specific function of glazes on degradation of catechins discovered here not only provides principal information for design and development of functional materials but also bring new impacts on daily tea drinking and long-term human health-related issues.

Noble-metal-free hydroxyapatite activated by facile mechanochemical treatment towards highly-efficient catalytic oxidation of volatile organic compound.

Controlling of volatile organic compound (VOC) emitted from industrial processes as most abundant and harmful air pollutant, has become one of the most important global environmental issues due to the rapid urbanization and industrialization. As an alternative and new type catalyst instead of conventional noble-metal nanoparticles widely utilized in oxidative decomposition of VOC, here we report the superior catalytic performance with 100% CO2/CO conversion on hydroxyapatite (HAp, Ca10(PO4)6(OH)2) with structurally well-controlled active surface tailored via facile one-step mechanochemical treatment in ambient air. With detailed characterizations of particle morphology, crystallinity and chemical structure with respects to surface defect/oxygen vacancy formation, acidity/basicity and VOC affinity on HAps activated through different mechanical stresses when altered ball size is utilized in planetary ball-milling assisted mechanochemical process, it was found that the predominant defect/oxygen vacancy generation in PO43- site and enhanced basic site population established by selective mechanochemical activation of c-plane, facilitates the favorable catalytic oxidation route towards highly-efficient CO2/CO conversion of VOC. Regards to the cost-effectiveness and non-toxic nature of HAp, incorporated with the sustainable mechanochemical surface structure tuning process, the results presented in this work opens new strategy in development of novel noble-metal-free catalyst for VOC elimination and environmental cleaning techniques.

Structural-Controlled Synthesis of Highly Efficient Visible Light TiO2 Photocatalyst via One-Step Single-Mode Microwave Assisted Reaction.

TiO2 with different chemical structures are successfully synthesized via a one-step single-mode magnetic microwave (SMMW) assisted process, during where Ti selectively oxidizes in magnetic field under Ar-O2 mixed atmosphere. The chemical state and band structure of the as-prepared TiO2 are well-controlled by changing the volume fraction of O2 (φO2) during SMMW synthesis. Ti3+ self-doped TiO2 (TiO2-x, 0 < x < 2) is synthesized under lower φO2, while TiO2 with specific core/shell structure (TiO2+y core/TiO2-x-TiO2+z shell) is observed under higher φO2. The as-synthesized TiO2 with controlled structures show sufficient light absorption in visible region and quite narrow bandgap (2.05 eV∼), whose value can be also tuned by φO2 during SMMW synthesis. In addition, the synthesized TiO2 exhibits highly efficient photocatalytic performance towards the degradation of Rhodamine B under UV and visible light irradiation. The formation mechanism for different structural TiO2 can be attributed to the specific rapid heating and cooling dynamics induced by SMMW irradiation.

A novel and facile synthesis of visible photoluminescence Si nanocrystals by room temperature mechanochemical disproportionation of SiO.

Visible photoluminescence Si nanocrystals (Si NCs) are synthesized via a novel and facile room temperature mechanochemical disproportionation of SiO.

Synthesis of 1,5-Anhydro-d-fructose derivatives and evaluation of their inflammasome inhibitors.

Synthesis of several 1,5-Anhydro-d-fructose (1,5-AF) derivatives to evaluate inhibitory activities of the inflammasome was carried out. Recently, 1,5-AF reported to suppress the inflammasome, although with only low activity. We focused on the hydration of 2-keto form of 1,5-AF and speculated that this hydration was the cause of low activity. Therefore, we synthesized some 1,5-AF derivatives that would not be able to form the dimer conformation and can be expected to have high activity against inflammasome, and then evaluated their inhibitory activities with respect to the NLRP3 inflammasome by using mouse bone marrow-derived macrophages and human THP-1 cells. As a result, some synthesized 2-keto form compounds had much higher inhibitory activities with respect to the NLRP3 inflammasome than did 1,5-AF.

Solid-state reduction of silica nanoparticles via oxygen abstraction from SiO4 units by polyolefins under mechanical stressing.

Metal oxides with an oxidation number lower than the highest often exhibit attractive functional properties. However, conventional chemical or thermal reduction of the stable oxides is often laborious and cannot be stopped at an appropriate level of reduction. Therefore, we here try to explore non-conventional reduction processes in a solid-state without external heating. Unique features of reduction processes of SiO2 toward suboxides, SiO x (1 ≤ x < 2), were made possible by milling fumed silica nanoparticles with polyolefins (POL), i.e., polypropylene (PP) or polyethylene (PE) and a fluorine-containing one, polyvinylidene difluoride (PVDF). We mainly examined the electronic and coordination states of Si by Si2p XPS spectra and 29Si MAS NMR, respectively. They significantly differ from a similar commercial product obtained via a thermal route. Judging from the chemical shift of 29Si MAS NMR as a criterion of the degree of reduction of SiO2, the function of POL as a reductant is in the order PP ≈ PE > PVDF. Since the present solid-state reaction is free from the formation of unstable gaseous SiO as an intermediate, the products are free from the Si component in a Q0 state close to that of metallic Si. From these results we conclude that the present silicon suboxides obtained by co-milling silica with POL are closer to those defined as a random bonding model of SiO, than a random mixture model, the former being unachievable by a thermal process. The main mechanism of the present solid-state reduction is the oxygen abstraction from the SiO4 units by the polarized POL, with its simultaneous oxidative decomposition up to the state of carbon. The reaction process is simple and scalable so that it may offer a new affordable fabrication method of silicon suboxides.

Preparation and biological activities of anti-HER2 monoclonal antibodies with fully core-fucosylated homogeneous bi-antennary complex-type glycans.

Recently, the absence of a core-fucose residue in the N-glycan has been implicated to be important for enhancing antibody-dependent cellular cytotoxicity (ADCC) activity of immunoglobulin G monoclonal antibodies (mAbs). Here, we first prepared anti-HER2 mAbs having two core-fucosylated N-glycan chains with the single G2F, G1aF, G1bF, or G0F structure, together with those having two N-glycan chains with a single non-core-fucosylated corresponding structure for comparison, and determined their biological activities. Dissociation constants of mAbs with core-fucosylated N-glycans bound to recombinant Fcγ-receptor type IIIa variant were 10 times higher than those with the non-core-fucosylated N-glycans, regardless of core glycan structures. mAbs with the core-fucosylated N-glycans had markedly reduced ADCC activities, while those with the non-core-fucosylated N-glycans had high activities. These results indicate that the presence of a core-fucose residue in the N-glycan suppresses the binding to the Fc-receptor and the induction of ADCC of anti-HER2 mAbs.

Influence of Surface Morphology and Conductivity on Photocatalytic Performance of Solution-Processed Zinc Oxide Film.

Solution-processed ZnO films with various structures have been fabricated and the influence of surface morphology and conductivity on photocatalytic performance, including improvement of conductivity, hydrogen production, and photodegradation of rhodamine B, has been investigated. Surface morphology was controlled by solution conditions, and as-fabricated films had rod, dense, and flower-like structures. Improved conductivity was revealed by the photocatalytic activity of ZnO, the influence of surface morphology on the photodegradation of rhodamine B, and the relationship with conductivity and hydrogen production.

Glycoengineered Monoclonal Antibodies with Homogeneous Glycan (M3, G0, G2, and A2) Using a Chemoenzymatic Approach Have Different Affinities for FcγRIIIa and Variable Antibody-Dependent Cellular Cytotoxicity Activities.

Many therapeutic antibodies have been developed, and IgG antibodies have been extensively generated in various cell expression systems. IgG antibodies contain N-glycans at the constant region of the heavy chain (Fc domain), and their N-glycosylation patterns differ during various processes or among cell expression systems. The Fc N-glycan can modulate the effector functions of IgG antibodies, such as antibody-dependent cellular cytotoxicity (ADCC) and complement dependent cytotoxicity (CDC). To control Fc N-glycans, we performed a rearrangement of Fc N-glycans from a heterogeneous N-glycosylation pattern to homogeneous N-glycans using chemoenzymatic approaches with two types of endo-ß-N-acetyl glucosaminidases (ENG'ases), one that works as a hydrolase to cleave all heterogeneous N-glycans, another that is used as a glycosynthase to generate homogeneous N-glycans. As starting materials, we used an anti-Her2 antibody produced in transgenic silkworm cocoon, which consists of non-fucosylated pauci-mannose type (Man2-3GlcNAc2), high-mannose type (Man4-9GlcNAc2), and complex type (Man3GlcNAc3-4) N-glycans. As a result of the cleavage of several ENG'ases (endoS, endoM, endoD, endoH, and endoLL), the heterogeneous glycans on antibodies were fully transformed into homogeneous-GlcNAc by a combination of endoS, endoD, and endoLL. Next, the desired N-glycans (M3; Man3GlcNAc1, G0; GlcNAc2Man3GlcNAc1, G2; Gal2GlcNAc2Man3GlcNAc1, A2; NeuAc2Gal2GlcNAc2Man3GlcNAc1) were transferred from the corresponding oxazolines to the GlcNAc residue on the intact anti-Her2 antibody with an ENG'ase mutant (endoS-D233Q), and the glycoengineered anti-Her2 antibody was obtained. The binding assay of anti-Her2 antibody with homogenous N-glycans with FcγRIIIa-V158 showed that the glycoform influenced the affinity for FcγRIIIa-V158. In addition, the ADCC assay for the glycoengineered anti-Her2 antibody (mAb-M3, mAb-G0, mAb-G2, and mAb-A2) was performed using SKBR-3 and BT-474 as target cells, and revealed that the glycoform influenced ADCC activity.

Enhanced expression of the ß4-N-acetylgalactosaminyltransferase 4 gene impairs tumor growth of human breast cancer cells.

Two ß4-N-acetylgalactosaminyltransferases (ß4GalNAcTs), ß4GalNAcT3 and ß4GalNAcT4, have been shown to be involved in the synthesis of the GalNAcß1 â†’ 4GlcNAc (LacdiNAc) group expressed on the outer branches of N- and/or O-glycans, and only ß4GalNAcT4 is expressed in human mammary gland. We found that the expression level of the LacdiNAc group decreases as human breast cancers progress. To investigate biological significances of this disaccharide in human breast cancers, we transfected the FLAG-tagged ß4GalNAcT4 cDNA into MDA-MB-231 cells, and obtained several clones showing enhanced expression of the gene. Clones 1 and 2 showed 15 and 9 times more transcript than mock-transfected cells. The FLAG-ß4GalNAcT4 protein and its product, the LacdiNAc group, were detected in clone 1 and 2 cells. No change was observed in their growth rates while significant decreases in colony forming and invasive abilities were observed for clone 1 and 2 cells. When clone 1 cells were transplanted subcutaneously into nude mice, no tumors were formed while tumors were formed with mock-transfected cells. These results indicate that the expression of the LacdiNAc group is quite important for the suppression of malignancies of the MDA-MB-231 cells.

Expression of LacdiNAc groups on N-glycans among human tumors is complex.

Aberrant glycosylation of proteins and lipids is one of the characteristic features of malignantly transformed cells. The GalNAc ß 1 → 4GlcNAc (LacdiNAc or LDN) group at the nonreducing termini of both N- and O-glycans is not generally found in mammalian cells. We previously showed that the expression level of the LacdiNAc group in N-glycans decreases dramatically during the progression of human breast cancer. In contrast, the enhanced expression of the LacdiNAc group has been shown to be associated with the progression of human prostate, ovarian, and pancreatic cancers. Therefore, the expression of the disaccharide group appears to be dependent on types of tumors. The mechanism of formation of the LacdiNAc group in human tumors and cancer cells has been studied, and two ß 4-N-acetylgalacto-saminyltransferases ( ß 4GalNAcTs), ß 4GalNAcT3 and ß 4GalNAcT4, have been shown to be involved in the biosynthesis of this disaccharide group in a tissue-dependent manner. Transfection of the ß 4GalNAcT3 gene brought about significant changes in the malignant phenotypes of human neuroblastoma, indicating that this disaccharide group is important for suppressing the tumor growth.

FE-SEM observation of swelled seaweed using hydrophilic ionic liquid; 1-butyl-3-methylimidazolium tetrafluoroborate.

The method to observe the exact morphology of swelled seaweed as an example of biological material by field emission scanning electron microscopy (FE-SEM) with the aid of hydrophilic ionic liquid (IL); 1-butyl-3-methylimidazolium tetrafluoroborate is reported. Seaweed was first swelled in 3.5% NaCl solution and then treated with the IL and water mixture in 1:7 weight ratios and centrifuged to remove the excess IL solution. Thus treated seaweed maintained its morphology even at high magnification and did not show drying in the FE-SEM chamber. This observation technique might be useful for various kinds of biological materials to be observed under FE-SEM.

Immobilization of fluorous oligosaccharide recognized by influenza virus on polytetrafluoroethylene filter.

The lactoside with PEG-fluorous tag was introduced to BHK-21(C-13) cells to generate a GM3-type oligosaccharide (Siaα2-3Galß1-4Glc). The GM3-type oligosaccharide obtained was easily immobilized by spotting onto commercially available polytetrafluoroethylene (PTFE) filter through non-covalent fluorous affinity and simply assessed by dot blot method using the interaction of carbohydrate- with proteins which recognize sialic acid such as virus membrane proteins.

[The effects of dutasteride on voiding and storage symptoms in men with benign prostatic hyperplasia].

We investigated the effects of dutasteride on voiding and storage symptoms by a post-hoc analysis from two randomized, placebo-controlled, parallel-group studies (Japanese phase II study and phase III study) which assessed the efficacy and safety of dutasteride in Japanese men with benign prostatic hyperplasia (BPH). Men aged 50 years and older, with a prostate volume of 30 cc or greater, an International Prostate Symptom Score (IPSS) of 8 or higher and maximal urinary flow rate of 15 ml/sec or lower were randomized to placebo or dutasteride groups. The number of subjects for the placebo and dutasteride groups was respectively 72 and 72 in the phase II study, and 185 and 193 in the phase III study. Questions 1, 3, 5 and 6 of IPSS were related to voiding symptoms, and Questions 2, 4 and 7 were related to storage symptoms. Changes between pre- and post-treatments were evaluated. In the phase II study, dutasteride significantly improved voiding symptoms and numerically improved storage symptoms compared with the placebo at week 24. In the phase III study, dutasteride significantly improved voiding and storage symptoms compared with the placebo after 52 weeks. These consistent results suggest that dutasteride is effective for both voiding and storage symptoms in Japanese men with BPH.

Serum protein adsorption and platelet adhesion on pluronic-adsorbed polysulfone membranes.

We examined plasma protein adsorption and platelet adhesion to polysulfone (PSf) flat membranes coated with Pluronic with varying polyethylene oxide (PEO) block length. Adsorption of albumin, globulin and fibrinogen to Pluronic-coated PSf membranes was independent of plasma dilution when concentrations of human blood plasma above 20% were applied. Increasing coating concentrations of aqueous Pluronic solution resulted in decreased protein adsorption by the PSf membranes. Pluronic F68, which was more hydrophilic than Pluronic L62 or L64 and had 80% of PEO content, was the most effective at suppressing the adsorption of plasma proteins and platelet adhesion to PSf membranes. We developed a mixed protein solution containing human albumin, gamma-globulin and fibrinogen to attempt to mimic the competitive and cooperative binding effects found in plasma. Fibrinogen adsorption from plasma could be recapitulated by the mixed protein solution. The number of platelets adhering to the PSf membranes decreased as the coating concentration of Pluronic solution was increased, and platelet adhesion decreased in parallel with fibrinogen adsorption. These results suggest that the bioinert property of PEO segments in the Pluronic, which is ascribed to their high flexibility in aqueous media, suppresses the adsorption of plasma proteins and platelets to the Pluronic-coated PSf membranes.