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The mechanical stretching behavior of the poly(styrene-b-ethylene-co-butylene-b-styrene) (SEBS) triblock copolymer (87 wt% polyethylene-co-butylene (PEB), 13 wt% polystyrene (PS)) was investigated under three different stretching modes and through in situ small-angle X-ray scattering (SAXS) analysis. The strain energy density function was investigated based on the stress and stretching ratio (λ) relationship under uniaxial, planar extension, and equi-biaxial stretching modes. As a result, the cross-effect of strain represented by the second invariants of the deformation tensor (I2) was identified, and only the Ogden model found to fit the data. In the cyclic stretching tests, SEBS exhibited smaller hysteresis during cyclic equi-biaxial stretching compared to uniaxial stretching. In other words, the Mullins effect was found to be more obvious for uniaxial stretching than equi-biaxial stretching. The λ and the stretching ratio obtained from the crystal planes by SAXS (λSAXS) were compared to investigate the relationship between the change in the microdomain structure and the macroscopic mechanical properties. Thus, affine deformation was found to occur in the smaller λ region for both uniaxial and equi-biaxial stretching and deviation from affine deformation occurred for uniaxial stretching in the larger λ region. This is because the entangled loops of PEB chains serve as cross-linking points when the films are stretched under equi-biaxial stretching. The mechanical stretching behavior of poly(styrene-b-ethylene-co-butylene-b-styrene) (SEBS) was investigated under three different stretching modes and through in situ SAXS analysis. SEBS exhibited smaller hysteresis during cyclic equi-biaxial stretching than that of uniaxial stretching. SAXS measurement revealed that affine deformation occurred in the smaller stretching ratio (λ) region for both uniaxial and equi-biaxial stretching modes and deviation from affine deformation occurred for uniaxial stretching mode at the larger λ region. This is because entangled loops of poly(ethylene-co-butylene) chains serves as cross-linking points when films are stretched under equi-biaxial stretching mode.

The specific deformation behavior of crystalline polymer films, namely unoriented crystallized isotactic polypropylene (it PP) films, was investigated under a multiaxial stress field.

It is desirable to establish a method for evaluating mechanical properties, such as modulus and strength, of micrometer and sub-micrometer thick polymer films. Bulge tests, where bulge deformation is imposed on films by the pressure of an inert gas, are suitable for satisfying this demand. However, very few studies on polymer films exist in the literature. In this study, bulge testing equipment for in situ synchrotron radiation wide-angle X-ray diffraction (WAXD) measurements is designed and used to study the relationship between the molecular aggregation structure and the mechanical properties of a crystalline nylon 12 (Ny12) film during bulge testing. Isothermally crystallized and quenched Ny12 films exhibited stress-strain curves similar to those obtained by conventional uniaxial elongation. In situ WAXD measurements during bulge testing revealed that the lattice extension of the crystallites is clearly dependent on crystallinity. Concretely, crystallites in the isothermally crystallized film show higher elastic properties than those in the quenched one. The results of the molecular aggregation structure, including the crystal structure and the amorphous chain surrounding the crystallites, of the films during bulge deformation firstly obtained in this study must be useful for designing toughened polymer films.

We have investigated the mechanism of the superior mechanical robustness of coated thin films of the catechol derivative urushiol. We synthesized hydrogenated urushiol (h-urushiol) by hydrogenating the double bonds in the long alkyl side chain of urushiol, and the physical properties of thin films of mixtures of urushiol and h-urushiol were evaluated. Atomic force microscopy observations revealed that these coated thin films have a homogeneous surface with no phase separation, regardless of the h-urushiol content, arising from the similarity of the chemical structures. The films showed good adhesive properties because the adhesion originates from the catechol structure. In contrast, curing time depended strongly upon the h-urushiol content. The curing of the h-urushiol thin film took 12 h, whereas the urushiol thin film was cured within 10 min. Moreover, the strain-induced elastic buckling instability for mechanical measurements test and the bulge test confirmed that the increase in the h-urushiol content decreased the mechanical strength. Because the double bonds in the urushiol side chain contribute to forming the highly cross-linked structure, the lack of double bonds in h-urushiol resulted in the slow curing and low mechanical strength. Interestingly, the mechanical robustness started to increase over 80 mol % h-urushiol. The saturated long alkyl side chain of h-urushiol faced the surface, and the regular structure of the uniform side chain may improve the mechanical properties of the coated film. Our results will help to develop biomimetic catechol-based coatings.

Obstructive sleep apnea syndrome (OSAS) is often associated with metabolic disorders such as obesity and type 2 diabetes and may contribute to cardiovascular events. A novel class of antidiabetic drugs, the sodium glucose cotransporter 2 inhibitors (SGLT2i) reduce body weight (BW), although there is limited data on their impact on OSAS. We therefore evaluated the effect of SGLT2i on OSAS in patients with type 2 diabetes. The presented study was a retrospective design in 18 patients with type 2 diabetes with OSAS (4 males, age range 39-81 yr) administrated a SGLT2i. HbA1c, BW, body mass index (BMI), blood pressure (BP) and apnea hypopnea index (AHI) were evaluated before and after SGLT2i administration. The relationships between the reduction in AHI and the other variables were examined using Pearson correlation analysis. We have got result that SGLT2i reduced AHI from 31.9 ± 18.0 to 18.8 ± 11.5 events per hr (p = 0.003). HbA1c, BW and BMI decreased significantly, whereas BP did not. The Pearson correlation analysis showed a significant relationship between the reduction in AHI and pre-administration of AHI. In conclusion, SGLT2i reduced not only HbA1c, BW and BMI but also AHI significantly and therefore has potential as an effective treatment of OSAS.

We implemented a 3-3-1 algorithm in order to provide safe and simple self-titration in patients who newly initiated BOT as well as who were already on BOT and evaluated its utility in clinical setting. A total of 46 patients, 21 patients in the newly-initiated group and 25 patients in the existing BOT group performed dose adjustment using 3-3-1 algorithm. HbA1c was significantly improved 4 weeks after the initiation from 8.5% ± 1.2% at baseline to 7.3% ± 0.7% at the final evaluation (p 0.01, vs. Baseline). The average daily insulin units increased throughout the study period from 10.1 ± 6.7 at baseline to 14.6 ± 8.9 units at the final evaluation. Weight didn’t significantly change throughout the study (p = 0.12). The incidents of hypoglycemia were 0.8/month during the insulin dose self-adjustment period and 0.4/month during the follow-up period. The 3-3-1 algorithm using insulin glargine provided a safe and simple dose adjustment and demonstrated its utility in patients who were newly introduced to insulin treatment as well as who were already on BOT.

We have demonstrated that the liquid/solid interfacial structure of liquid marbles is determined by the surface–interface interaction between the encapsulating particles and liquid droplet. X-ray c...

Background Angiopoietin-like protein 8 (ANGPTL8) is considered to be metabolically multifunctional. One notable function still to be elucidated definitively is a betatrophic role in protecting and preserving pancreatic beta-cell function. There is, however, a paucity of data regarding the role of ANGPTL8 in the etiology of type 2 diabetes (T2D), but some findings of human research have suggested the potential for significant involvement. Objective To examine the frequency of T2D and impaired glucose tolerance (IGT) in Japanese subjects with the ANGPTL8 R59W variant. Methods ANGPTL8 R59W (Rs2278426, c.194C > T) was determined by polymerase chain reaction–restriction fragment length polymorphism using the restriction enzyme FokI in 797 consecutive Japanese individuals. Subjects with triglyceride levels greater than or equal to 150 mg/dL were considered to be hypertriglyceridemic. Results Genotype frequencies of ANGPTL8 R59W were as follows: wild-type RR (C/C) 53.5%, RW (C/T) 36.6%, and WW (T/T) 9.9%. T2D and IGT were significantly prevalent in WW and RW subjects relative to RR among all 797 subjects ( P = .0138) and also in hypertriglyceridemic subjects ( P = .0015). In multiple logistic regression models for the existence of T2D and IGT in hypertriglyceridemic subjects, the odds ratio for heterozygote RW and homozygote WW genotypes to wild-type RR was 2.406 ( P = .0017) after controlling the risk factors of age, gender, and body mass index as covariates. Conclusions The frequency of ANGPTL8 R59W is significantly higher in Japanese subjects than in other ethnic groups. The rates of T2D and IGT were greater in subjects with the R59W variant. These findings indicate that ANGPTL8 is a participant in diabetes and a potential therapeutic target for T2D prevention, especially in East Asians.

We have demonstrated surface functionalization through the decal-like transfer of thermally cross-linked urushiol thin films onto various substrates. Tensile adhesive strength measurements showed that the film adheres strongly to the surface of various substrates including chemically inert materials, such as polyolefins and thermosetting resins, because of the properties of urushiol. Furthermore, the highly cross-linked structure of urushiol made the films mechanically robust. These two properties allowed the fabrication of practicable thin films for indirect surface modification. Actually, the robust thin film served as a scaffold for an Au thin film, which was then bound to various substrates. Surface-texturing of nanodecal was also demonstrated as an application aspects.

The scratch test was conducted for polycarbonate (PC) and poly(methyl methacrylate) (PMMA) with a load-progressive mode. Changes in the molecular aggregation structure of PC and PMMA induced by the scratch test were investigated based on polarized optical microscopic observation and small-angle X-ray scattering (SAXS) measurement. The scratching coefficient of friction (SCOF), the ratio of tangential load to normal load, of PC was much larger than that of PMMA. The width and depth of the damage on the scratch path was increased monotonically with the increase in the normal load. Hardness obtained by nanoindentation and microindentation tests were similar to those with SCOF, indicating that compression resistance mainly governs the scratch properties. The polarized optical microscopic images revealed that molecules were oriented from the edge to the center of the scratch path at a certain acute angle for both PC and PMMA. SAXS measurement revealed that microfibrils were formed along the direction of stress for PC.

Toward the establishment and realization of medical applications accompanied with a phase change such as a drug delivery system, a formulation of the effect of mass transfer (i.e., mass flux) at the bubble-liquid interface on a ultrasound propagation process has been desired. Since a large amplitude ultrasound is utilized in such an application, the consideration of both the mass flux and the wave nonlinearity is essential. Although Fuster and Montel [J. Fluid Mech.(2015)] investigated linear wave propagation, nonlinear analysis has not been performed. In this paper, we theoretically clarify the effect of mass flux at the bubble-liquid interface on weakly nonlinear (i.e., finite but small amplitude) propagation of pressure waves in bubbly liquids. The effect of total evaporation or condensation as a mass flux across the bubble interface is taken into account as a simple classical model. Although various types of dissipation are installed, the effect of viscosity of gas inside the bubble is neglected. The set of basic equations for bubbly flows is composed of the conservation laws of mass, momentum, and energy, equation of motion for radial oscillations of bubble wall, equations of state, and so on. From the method of multiple scales, some nonlinear wave equations (e.g., KdV-Burgers equation) are derived. We then discuss the effects of mass flux on the propagation processes of nonlinear waves.

The advantages of bulge testing as a method of mechanical property analysis for polymer films was described. Deformation and rupture mechanisms of glassy polymer films during bulge testing were investigated by in situ molecular aggregation structure analyses. Heat-pressed polycarbonate (PC, weight-average molecular weight (Mw) = 38k) and poly(methyl methacrylate) (PMMA, Mw = 70k and 1.2 M (PMMA-70k and PMMA-1.2 M)) films were employed as transparent glassy polymers. Evaluations of molecular aggregation structures during bulge testing were conducted by polarized high-speed camera observation and wide-angle X-ray diffraction (WAXD) measurements. PC and PMMA-1.2 M films showed a yield point in their stress-strain curves, indicating ductility, while PMMA-70k film showed brittleness. WAXD measurements revealed that the distances between the main chains slightly increased with increasing strain. With increasing film strain above the yield point, a craze-like morphology with thinning of the film was seen for the PC film, likely due to the flexible PC molecules. Although it is difficult for PMMA molecules to orient along applied stress, a transition to the thinner state with the formation of wrinkled structures occurred for the PMMA-1.2 M film above the yield point. The transition to the thinner state, which corresponds to a discontinuous decrement of the cross-section area by deformation, might be categorized as two-dimensional crazing and/or shear deformation. PMMA-70k did not show such behavior because of the small number of entanglements. The use of a small amount of films in terms of thickness and size and the capability of observation of the entire film were given as advantages of the bulge test.

Japanese lacquer, known as urushi, is a traditional natural resin used for numerous applications, including tableware, art and furniture. The main component of urushi is urushiol, which is a catechol derivative with a long unsaturated hydrocarbon side chain. Utilizing the characteristics of urushiol as a thermoset, we have demonstrated the surface texturing of an urushi thin film with a thermal imprinting technique. Thermal imprinting was conducted at 100 °C for 10 min by pressing a patterned mold onto the film, and an indented surface that replicated the surface of the mold was obtained. The static water contact angle was changed from 70±0.5° to 112±3° after the fabrication of pillared patterns on the surface. Moreover, the imprinted line and space patterns caused strong anisotropic wetting depending on the direction. Our results demonstrate that the texturing of urushi thin films is a useful technique for controlling the wettability of natural thermoset urushi thin films. Surface texturing of catechol derivative urushiol was achieved using a thermal imprinting technique. An indented surface was obtained by thermal curing at 100 °C for 10 min while pressing an urushi film with a patterned mold. The indented surface enhanced the static water contact angle in comparison with the flat urushi film.

We have demonstrated the fabrication of fluorine-free liquid marbles from halloysite nanotube. Halloysite is a naturally occurring inorganic nanotube that has a high aspect ratio, and the surface was modified with octadecyltrimethoxysilane. The surface-modified halloysite formed pincushion agglomerates on the surface of the liquid droplets, which create superhydrophobic surface similar to that of the plant gall surface prepared by aphids. As a result, the liquid marbles showed high mechanical strength upon impact without the use of low surface energy fluoroalkyl or fluorine-modified materials. Our results suggest a new strategy for designing novel materials for liquid marbles inspired by nature.

Urushi (oriental lacquer) is made from the sap of Rhus vernicifera and consists mainly of the catechol derivative urushiol. Thermal curing of urushiol, unlike other catechol derivatives, is possible because of the unsaturated double bonds in the long hydrocarbon side chain. We described here a simple, efficient method to produce a thermally cross-linked urushi thin film using iron(II) acetate as the additive. The cured thin films showed robust, flexible feature as confirmed by strain-induced elastic buckling instability for mechanical measurements (SIEBIMM) and bulging experiments. In contrast, a thin film of poly(dopamine) that is a typical catechol derivative without long hydrocarbon side chain showed brittleness. The long hydrocarbon side chain of urushiol plays an important role for both thermal processability and superior mechanical properties of the material. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3688–3692

Concealing of surface topology of substrates by decal-like attachment of nanomembrane is demonstrated. The nanomembrane attachment provides a flat surface on various substrates, including porous substrates, and the surface property such as wettability was changed to that of the nanomembrane. The monitoring of drying process revealed that a nanomembrane with certain thickness tolerates their flexural deflection during the procedure. Moreover, the supporting position of nanomembranes as well as the physical properties of nanomembranes strongly affected the degree of deflection. The decal-like attachment of nanomembranes shown here is potentially a powerful method for creating a new functional surface that is independent of the topological and chemical properties of the original substrate.

Chemical interaction between polyphenols and thiols was investigated under radical oxidation conditions using a model cysteinyl thiol derivative, N-benzoylcysteine methyl ester. The radical oxidation was carried out with a stoichiometric amount of 2,2-diphenyl-1-picrylhydrazyl (DPPH), and the decreases in the amounts of polyphenols and the thiol were measured by HPLC analysis. Cross-coupling products between various polyphenols and the thiol were examined by LC-MS in reactions that showed decreases in both the polyphenols and the thiol. The LC-MS results indicated that three phenolic acid esters (methyl caffeate, methyl dihydrocaffeate, and methyl protocatechuate) and six flavonoids (kaempferol, myricetin, luteolin, morin, taxifolin, and catechin) gave corresponding thiol adducts, whereas three polyphenols (methyl ferulate, methyl sinapate, and quercetin) gave only dimers or simple oxidation products without thiol substituents. Thiol adducts of the structurally related compounds methyl caffeate and methyl dihydrocaffeate were isolated, and their chemical structures were determined by NMR analysis. The mechanism for the thiol addition was discussed on the basis of the structures of the products.

The antioxidation mechanism of rosmarinic acid was investigated. An AIBN-induced oxidation reaction of linoleate in the presence of rosmarinic acid produced one main product. The DPPH reaction of rosmarinic acid also gave two products, one of which corresponded to the product of the lipid system. Direct isolation of the products failed because of their instability. To the DPPH reaction, the addition of 1-dodecanethiol afforded three isolable adducts. Their structures revealed that the reaction produced quinone derivatives on either the caffeoyl or 2-oxyphenylpropanoyl moieties. However, the lipid oxidation afforded one quinone, which could convert to a thiol adduct. The HPLC of the reaction clarified that the antioxidation product of rosmarinic acid was the unstable quinone on the 2-oxyphenylpropanoyl moiety. This quinone formation was the first stage of the antioxidation of rosmarinic acid in the lipid system. The odourless 1-dodecanethiol is a useful reagent to identify the unstable quinone from polyphenol oxidation.

Antioxidants themselves are oxidized to prevent oxidation of other molecules. One may ask if the oxidized antioxidants are safe for humans. However, there is very little information on the toxicity of oxidized antioxidants. We previously identified cytotoxic compounds in the products from oxidation of sesamol, a potent antioxidant in sesame oil. In this study using a flow cytometer with fluorescent probes, we revealed cytotoxic characteristics of two isomeric dimers (dimer A and B) in rat thymocytes. Increase in cell lethality by dimer A was more profound than those by sesamol and dimer B. The incubation of cells with dimer A increased the populations of shrunken cells and the cells with phosphatidylserine exposed on outer surface of cell membranes. Since these phenomena are parameters for early stage of apoptosis, the results indicate that dimer A may promote the process of apoptosis. However, the population of the cells containing hypodiploid DNA, a parameter for late stage of apoptosis, was decreased by the incubation with dimer A. It was not the case for dimer B. Results indicate that dimer A may inhibit the degradation of DNA during apoptosis. Taken together, it is likely that dimer A exerts both proapoptotic action and inhibitory action on late stage of apoptosis in rat thymocytes.

Precise control of surfaces and interfaces is essential for the fabrication of various functional materials. Although various methods have been applied to the functionalization of surfaces, these methods are specialized for the fabrication of specific surfaces for specific purpose. In this context, a versatile, yet efficient tool for the surface manipulation is strongly desired. Here, we demonstrate a simple method of functionalizing various surfaces through a decal-like transfer of a giant nanomembrane. Control of wettability was chosen as an example, and a hydrophobic nanomembrane was transferred to various other substrates, including Si, polymer film, and metal. A drastic change in contact angle clearly indicated that the wettability of the processed material was identical to that of the surface-functionalized nanomembrane. In contrast, other physical properties such as the mechanical properties of the processed material remain unchanged. The decal-like transfer of nanomembrane will become a powerful means for the fabrication of unique functional surfaces.

We have demonstrated the growth of polymer brushes from a surface-textured thin urushiol film. Thermal imprinting was done on an initiator-immobilized thin urushiol film, and surface-initiated atom...

The iron-ion catalyzed oxidation of the ethanol solution of rosmarinic acid, a potent antioxidant polyphenol of Lamiaceae (Labiatae) plants, afforded a highly tyrosinase-inhibitory active product. The structure of the active product in the oxidation product mixture was determined using extensive NMR spectroscopy to have a novel oxygen-containing seven-membered ring system. The formation mechanism of the unique ring structure from the catechol part of the rosmarinic acid was proposed.

Biohydrogen is expected as one of the alternative energy to fossil fuel. In this study, halotolerant photosynthetic hydrogen producing bacteria (ht-PHB) were isolated from a sediment of tideland, and hydrogen gas (H2) production by isolated ht-PHB from mixed short-chain fatty acids (SFAs) using a long-wavelength light emitting diode (LW-LED) was investigated. The isolated ht-PHB grow on a culture containing three kinds of SFAs (lactic acid, acetic acid, butyric acid) and produced H2 with their complete consumption at NaCl concentration in the 0–3% range in the light of tungsten lamp. The isolated ht-PHB was phylogenetically identified as Rhodobacter sp. KUPB1. The KUPB1 showed well growth and H2 production even under LW-LED light irradiation, indicating that LW-LED is quite useful as an energy-saving light source for photosynthetic H2 production.

The chain-breaking antioxidation reaction mechanism of a phenolic lignan in a lipid oxidation system was investigated. The 2,2′-azobis(isobutyronitrile) (AIBN)-induced radical oxidation reaction in a large amount of ethyl linoleate in the presence of secoisolariciresinol, one of the potent antioxidative lignans widely distributed in edible plants, produced two types of peroxides as radical termination products, as well as a cyclic derivative. The isolation and structure determination of the peroxides revealed that they have a peroxide linkage with ethyl linoleate or isobutyronitrile at the 1-position of the benzene ring of secoisolariciresinol. The cyclic derivative was also identified as lariciresinol by spectroscopic analysis. Based on the chemical structures of these products, a reaction pathway for the antioxidation reaction of secoisolariciresinol in oxidising lipid media was proposed.

Many effects of sesamol, an antioxidative constituent of sesame oil, have been reported for human health benefits due to its antioxidative action. However, we recently isolated two cytotoxic products, trimer and tetramer of sesamol, from oxidation of sesamol by an assay-guided purification. In this study, we have revealed some cytotoxic characteristics of these products in rat thymocytes and human leukemia K562 cells. Incubation of cells with trimer or tetramer at 10-30 microM for 24h significantly increased cell lethality and population of rat thymocytes containing hypodiploid DNA, suggesting cell death with DNA fragmentation, while it was not the case for 30 microM sesamol. The cytotoxic action of tetramer was more potent than that of trimer in rat thymocytes when their concentrations were 10-30 microM. The incubation of cells with 10 microM tetramer for 24h increased the population of cells with exposed phosphatidylserine, the activity of caspases, and the nick of DNA. These results indicate tetramer-induced apoptosis. In K562 cells, the incubation with tetramer at 10 microM for 72 h significantly inhibited the growth without affecting the lethality. However, tetramer at 30 microM significantly increased cell lethality. It is likely that tetramer exerts more cytotoxic action on normal non-proliferative cells (rat thymocytes) rather than proliferative cancer cells (human leukemia K562 cells). It may be necessary to consider the condition for preservation of sesamol and the safety of products from in vivo oxidation of sesamol for human health.

Potent inhibitory activity of the leaves of Myrica rubra against both chemical and enzymatic (tyrosinase and lipoxygenase) oxidation was found in our project to develop utility of unused and rarely used plant resources in the local area. A constituent analysis of the most active ethyl acetate-soluble part of a methanol extract of the leaves clarified the structures of eight major compounds. The tyrosinase and lipoxygenase inhibitory activities and DPPH radical scavenging activity of the isolated compounds were measured as indicators of the inhibitory capacity against the enzymatic and chemical oxidation of food. The obtained data indicate that the chemical and enzymatic (lipoxygenase and tyrosinase) antioxidant activities of the leaves mainly depended on the galloyl flavonoid derivatives.

The iron-ion catalyzed oxidation of ethanol solution of sesamol, a potent antioxidant of sesame, afforded two significant cytotoxic products to normal mammalian cells. The structures were determined using extensive NMR spectroscopy as a new sesamol trimer and tetramer.

The chemopreventive and chemotherapeutic actions of polyphenols and related phenolics have received considerable attention since these compounds induce apoptosis in several types of cancer cells in vitro. A plausible criterion for the use of such compounds is that they should not exert any toxic effect on normal cells. However, information about the toxicity of polyphenols and related phenolics to normal cells is limited. In this study, the effects of polyphenols and related phenolics on rat thymocytes were examined by flow cytometric analysis with appropriate fluorescent probes. The compounds examined in this study were caffeic acid, rosmarinic acid, chlorogenic acid, (+)-catechin, 6-gingerol, sesamol, resveratrol, and eugenol. Of these, resveratrol was the most cytotoxic on rat thymocytes incubated for 24 hrs with 100 microM of this compound. Resveratrol at a concentration of 10 microM or more (up to 100 microM) led to a significant dose-dependent increase in the population of dead cells, shrunken living cells, annexin V-positive cells and cells with hypodiploidal DNA. In the presence of benzyloxycarbonyl-Val-Ala-Asp (OMe) fluoromethylketone (Z-VAD-FMK), a pan-inhibitor of caspases, the resveratrol-induced increase in the population of cells with hypodiploidal DNA was partially inhibited. Overall, it is suggested that resveratrol at a concentration of 10 microM or more induces apoptosis in normal cells as well as cancer cells (previously reported elsewhere). Thus, at concentrations that are suitable for chemopreventive and chemotherapeutic actions, resveratrol may exert a cytotoxic effect on normal cells.

In this study, a novel acryl fiber biomass carrier (ABC) was applied for anammoxresearch in an up-flow column reactor. This material could retain anammox microorganismefficiently and the average weight of attached sludge in the bottom part of the reactor wascalculated to be 0.14 g-TSS/cm3 ABC. High removal efficiencies of ammonium, nitrite andTN were obtained at a high volumetric loading rate of 2.0 kg-TN/m3/d. Furthermore,anammox activity did not decrease significantly with decreasing temperature, e.g., whenthe temperature decreased from 33.0℃ to 26.2℃, nitrite removal efficiencies decreasedonly about 5% (from 94% to 89%). Scanning electronic microphotographs revealed thatthe microorganisms were in a compacted state when attached on the support material.Based on the analysis of 16S rDNA, two close matches of anammox bacteria, KSU-1 andKOLL2a, were detected. This material showed potential for treatment of wastewater withlow concentrations of nitrogen using a short hydraulic retention time.

We have demonstrated the spray-assisted coating of the catechol derivative, urushiol. Spraying a mixture of urushiol and iron(II) acetate formed a uniform coating about 10 nm thick, as confirmed by AFM observations. XPS measurements revealed that various substrates, including polyolefins and thermosetting resins, were successfully coated with urushiol. The coating showed good solvent tolerance and coating adhesion after baking at 100 °C for 10 min or after aerobic oxidation for several days. Interestingly, quartz crystal microbalance (QCM) measurements and strain-induced elastic buckling instability for mechanical measurements (SIEBIMM) revealed that density and Young's modulus of the spray-assisted nanocoatings were higher than those of spray-coated samples. Moreover, the coating was uninvolved in physical properties except surface properties, as demonstrated by several experiments. Because urushiol is a promising biobased material, our unique spray-assisted coating technique could provide a general approach for material-independent surface modification techniques that are environmentally sustainable.

The effect of conditioning for a variety of inoculums on fermentative hydrogen production was investigated. In addition, the effects of pH condition on hydrogen fermentation and bacterial community were investigated. The effect of conditioning on hydrogen production was different depending on the inoculum types. An appreciable hydrogen production was shown with anaerobic digested sludge and lake sediment without conditioning, however, no hydrogen was produced when refuse compost and kiwi grove soil were used as inoculums without conditioning. The highest hydrogen production was obtained with heat-conditioned anaerobic digested sludge, almost the same production was also obtained with unconditioned digested sludge. The pH condition considerably affected hydrogen fermentation, hydrogen gas was efficiently produced with unconditioned anaerobic sludge when the pH was controlled at 6.0 throughout the culture period and not when only the initial pH was adjusted to 6.0 and 7.0. Hydrogen production decreased when the culture pH was only adjusted at the beginning of each batch in continuous batch culture, and additionally, bacterial community varied with the change in hydrogen production. It was suggested that Clostridium and Coprothermobacter species played important role in hydrogen fermentation, and Lactobacillus species had an adverse effect on hydrogen production.

Denitrification activity behavior and bacterial community structure in a poly-β-hydroxybutyrate (PHB) embedded soil-column reactor were investigated. The influent containing nitrate (NO3-N) was applied in a downward flow. The NO3-N concentration rapidly decreased only in the middle part of the column where PHB was embedded, which indicated that the denitrification activity in the reactor was related to PHB. Influent NO3-N was effectively removed in the reactor following 60 days of continuous operation. The total number of bacteria in the lower and middle parts of the column decreased after 30 days, and then increased again after 60 days; however, the number in the upper part continuously decreased with time. The number of PHB utilizing denitrifiers increased in both the middle and lower parts with time, contributing to denitrification activity in the reactor. From the result of PCR and denaturing gradient gel electrophoresis (PCR-DGGE), the presence of two denitrifing and a few other bacteria were determined, and which suggested of Ralstonia related species played an important role in the denitrification capability of the reactor.

The Hippo pathway has the unique capacity to sense tissue architecture and the external forces that shape it, and dysregulation of this pathway leads to tumorigenesis. The study of mice bearing systemic or tissue-specific mutations of Hippo elements has driven huge progress in understanding this pathway’s role in normal physiology and disease. Here, we summarize how disruption of Hippo signaling relates to cancer, and we highlight the importance of this pathway as a new drug target for malignant tumors.

慢性脳血管障害患者の在宅生活に重要な要素となる安全性について行動評価形式で評価することによって，動作の安全性にかかわる要素と安全性が及ぼす影響を明らかにすることを目的とした。入院中の34例（平均年齢65.2±12.7歳）を対象に，車椅子駆動，移乗動作，歩行，トイレ動作の4動作における機能性と自己管理能力の評価を行い，理学療法士のみた安全性と比較するとともに実際の退院先との関連を調査した。さらに患者自身が感じている主観的安全性との比較，半側無視の有無による違いについても検討した。その結果，安全性は機能性よりも自己管理能力との関連が大きく，理学療法士のみた安全性が高い患者で実際に自宅退院が多くなっていた。また，PTによる安全性の評価と主観的安全性とは必ずしも相関せず，半側無視がある症例では自己の安全性を高く認識している傾向があった。以上のことから，理学療法評価においては機能性とともに自己管理能力を含んだ安全性の視点から評価を行うことの重要性が示唆された。

We have demonstrated a universal approach to growing polymer brushes from various substrates. Urushiol was mixed with initiator-containing catechol, and it was spin-coated or cast on various substrates. Because urushiol is strongly adhered to various substrates, the thin film can serve as a general scaffold for grafting polymer brushes from various substrates. Note that the film was formed even onto the surface of polyolefins and thermosetting resins that are known as chemically inert materials to functionalize the surface. Moreover, the initiator-immobilized scaffold showed mechanical robustness and chemical inertness because of the flexible long unsaturated hydrocarbon side chain of urushiol. After the grafting of polyelectrolyte PMTAC polymer brushes, the material obtained exhibited hydrophilicity, typical of PMTAC. The concept shown here could provide a general approach for grafting practical polymer brushes from various substrates.

Curcumin is a yellow pigment found in the spice turmeric and a main functional constituent of the rhizomes of Curcuma longa. The multi-functionality of curcumin has recently attracted much attention in various fields, including food, medicinal, and clinical industries. Three major curcuminoids, curcumin, demethoxycurcumin, and bis-demethoxycurcumin, are distributed in not only Curcuma, but also the Zingiber species; however, distribution of other curcuminoids is very limited in nature. The radical scavenging ability of curcumin, which is the basis of medicinal functionality, is its most important property. Herein, the structures of several rare curcuminoids that have been identified during the past four decades are summarized. Mechanistic studies of the radical trapping stage of curcumin are also comprehensively reviewed, and the studies on antioxidant effects derived from this radical trapping ability of curcuminoids are discussed. Various chemical reactions of curcumin, such as photo-oxidation, enzymatic oxidation, etc. are also summarized. In particular, antioxidation of curcumin in lipid media is introduced as a reaction unique to curcumin.

The functionality of spring mountain herbs, which were collected in the Kajigamori mountain area of Shikoku area in Japan, was investigated in the course of our studies for utilizing local plant resources. The radical scavenging activity of the extracts from seventeen herbs was measured. Among these herbs, two extracts from Polystichym ovato-paleaceum (Japanese name: Tsuyanashiinode) and Sambucus racemosa subsp. sieboldiana (Japanese name: Niwatoko) showed potent DPPH radical scavenging activity. The material evidence for the potent activity of the extracts was studied by a combination of our developed method for detecting antiradical compounds, LC-MS/MS, and enzymatic hydrolysis.

An efficient synthetic method for stereoselective construction of asymmetric quaternary carbon stereocenters, bearing nitrogen in the form of Boc-protected allyl amines, has been developed. This methodology is employed in the synthesis of marine alkaloids, manzacidin A and C.

Polyphenols have recently attracted much attention as potent antioxidants and related bioactive substances. These potent antioxidative polyphenols are very oxidizable due to their chemical properties, and their oxidation products must accumulate in the oxidizing foods when they are contained as the active ingredients. In this investigation, 30 polyphenols and related phenolics were oxidized with oxygen in the presence of a catalytic amount of Fe ions. Piceatannol, catechin, epicatechin, hydroxytyrosol, carnosol, and carnosic acid were oxidized very quickly. Sinapic acid, caffeic acid, chlorogenic acid, rosmarinic acid, gallic acid, propyl gallate, α-tocopherol, quercetin, and nordihydroguaiaretic acid were moderately oxidized. Protocatechuic acid, syringic acid, taxifolin, resveratrol, gentisic acid, secoisolariciresinol, and ellagic acid were oxidized for 19-20 days; however, their oxidation was very slow and did not complete. The other phenolics were not oxidized. The obtained oxidation products were next subjected to a lipoxygenase inhibition assay and the results compared to those of the corresponding phenols. Very interestingly, the oxidation product from resveratrol showed a high inhibitory activity, whereas resveratrol itself had no activity and its oxidation efficiency was low. To clarify the inhibition principle of the oxidation product, an LC-MS analysis was carried out on the oxidation product. The analytical results showed that they are the oligomeric and degraded compounds of resveratrol. Among them, the structures of three dimeric compounds were successfully identified, and their activity data clarified that the closed ring dimers were potent lipoxygenase inhibitors, whereas the opened ring dimer was not. It should be noted that resveratrol had almost no lipoxygenase inhibitory activity, contrary to some researchers' findings.

The antioxidative activity of secocyclolignanes was compared with that of the corresponding dibenzyl lignans for the first time. The radical scavenging activity of the secocyclolignanes was weaker than that of the corresponding dibenzyl lignans, the butane diol type showing the highest activity. The butane type of secocyclolignane exhibited the highest antioxidant activity of the unsaturated fatty acid.

Oxidation of rosmarinic acid (I) affords the highly tyrosinase inhibitory active product (II) (yield given in g).

Phytophenols of edible plants have recently attracted much attention as potent antioxidants and related bioactive substances. These antioxidative phytophenols are very oxidizable due to their chemical properties, and their oxidation products must accumulate in the oxidizing foods when they are contained as active ingredients. In this investigation, several phytophenols, which are well known as potent antioxidants in food science, were oxidized by oxygen in the presence of a catalytic amount of Ferric ion. Caffeic acid, catechin, chlorogenic acid, rosmarinic acid, and sesamol were quickly oxidized, whereas eugenol, resveratrol, rutin, and quercetin were not under the stated conditions. The oxidation product mixtures of the quickly oxidized phytophenols were next subjected to a cytotoxic assay using normal cells. Among the products, the oxidation product from sesamol showed a remarkably high cytotoxic activity. To clarify the cytotoxic principle of the oxidation products, an assay-guided fractionation and subsequent isolation of the oxidation compound of sesamol was carried out. Structure analysis of the isolated compounds revealed that they are new dimeric compounds (2-5) of sesamol. The cytotoxic activity of the dimers was evaluated from the population of dead cells by a flow cytometric analysis of rat thymocytes in the presence of 100 μM of each compound. Compound 2 showed the most potent cytotoxic activity among them. Compound 2 has a typical conjugated carbonyl moiety and the moiety possibly contributes to its high toxicity from a structure-activity point of view.

Anaerobic ammonium oxidation (anammox) is a novel nitrogen pathway catalyzed by anammox bacteria which are obligate anaerobic chemoautotrophs. In this study, enrichment culture of marine anammox bacteria (MAAOB) from the samples related to seawater was conducted. Simultaneous removal of ammonium and nitrite was confirmed in continuous culture inoculated with sediment of a sea-based waste disposal site within 50 days. However, no simultaneous nitrogen removal was observed in cultures inoculated with seawater-acclimated denitrifying sludge or with muddy sediment of tideland even during 200 days. Nitrogen removal rate of 0.13 kg/m3/day was achieved at nitrogen loading rate of 0.16 kg/m3/day after 320th days in the culture inoculated with the sediment of waste disposal site. The nitrogen removal ratio between ammonium nitrogen and nitrite nitrogen was 1:1.07. Denaturing gradient gel electrophoresis (DGGE) analysis indicated that an abundance of the bacteria close to MAAOB and coexistence of ammonium oxidizing bacteria and denitrifying bacteria in the culture.

The present study investigates the enrichment of anaerobic ammonium oxidation (anammox) bacteria in the marine environment using sediment samples obtained from a sea-based waste disposal site and discusses the construction of marine anammox bioreactor. Enrichment of bacteria related to Candidatus Scalindua wagneri along with simultaneous removal of nitrite and ammonium ions was observed in the continuous bioreactor culture under a total nitrogen loading rate of 0.4 kg-N m − 3 day − 1 .