Ishihara Sangyo Research Articles

Fungicidal spectrum and biological properties of a new fungicide, pyriofenone.

Pyriofenone is a new fungicide developed by Ishihara Sangyo Kaisha, Ltd. To determine the fungicidal spectrum of pyriofenone, in vivo pot tests and in vitro mycelial growth-inhibition tests were conducted. Pyriofenone showed excellent activity against wheat and cucumber powdery mildew and moderate efficacy against rice blast in the pot tests. In the mycelial growth-inhibition tests, most fungi were not affected by pyriofenone except for Botrytis cinerea, Helminthosporium sacchari, Pseudocercosporella herpotrichoides, Pyricularia oryzae, Rosellinia necatrix, and Verticillium dahliae. The fungicidal properties of pyriofenone on powdery mildew in cucumber and wheat were evaluated precisely. Pyriofenone exhibited excellent preventive and residual activities. It had high rainfastness in the cucumber leaves against powdery mildew. Pyriofenone also showed inhibitory activity on lesion development upon application until 2 days after inoculation, and the lesion expansion and sporulation of the cucumber powdery mildew fungus were effectively controlled. Furthermore, pyriofenone showed translaminar and vapor activities.

Lithium-based transition-metal oxides for battery electrodes analyzed by x-ray photoelectron spectroscopy. X. Li4Ti5O12

X-ray photoelectron spectroscopy (XPS) and x-ray-induced Auger electron spectroscopy were used to analyze untreated Li4Ti5O12 powders obtained from Ishihara Sangyo Kaisha, Ltd. and Samsung Fine Chemicals Company, Ltd. X-ray photoelectron and x-ray-induced Auger electron spectra were obtained using incident monochromatic Al Kα radiation at 0.834 01 nm. A survey spectrum together with O 1s, Ti 2p, C 1s, Ti 3s, Li 1s, and Ti 3p are presented. The spectra indicate the principal core level photoelectron and Auger electron signals and show only minor potassium signal. Making use of the O 1s, Li 1s, and Ti 3p lines and neglecting the components related to surface contaminants, XPS quantitative analysis reveals an altered stoichiometry of the air-exposed powder surfaces from Ishihara Sangyo Kaisha, Ltd. and Samsung Fine Chemicals Company, Ltd. of Li4Ti4.7O14.1 and Li4Ti4.3O13.2, respectively.

Photocatalytic Reduction of Hexavalent Chromium with Nanosized TiO2 in Presence of Formic Acid

Nanosized titanium dioxide (TiO2) nanoparticles were used for the photocatalytic reduction of hexavalent chromium in the presence of formic acid. The photoreduction of Cr(VI) in the absence of formic acid was quite slow. When formic acid was added in the chromium solution as the hole scavenger, a rapid photocatalytic reduction of Cr(VI) was observed, owing to the consumption of hole and the acceleration of the oxidation reaction. Furthermore, three commercial TiO2 nanoparticles (AEROXIDE® P25; Ishihara Sangyo ST-01; FUJIFILM Wako Pure Chemical Corp.) were evaluated for the photoactivity of reduction of Cr(VI).

Effect of process parameters on fouling and stability of MF/UF TiO2 membranes in a photocatalytic membrane reactor

The investigations on the influence of TiO2 photocatalyst (Aeroxide® TiO2 P25) loading, feed cross-flow velocity (vF) and transmembrane pressure (TMP) on the fouling and stability of ceramic membranes in a photocatalytic membrane reactor are presented. Two ultrafiltration membranes with molecular weight cut-off of 5kDa (Filtanium 5) and 100kDa (Filtanium 100), and one microfiltration membrane (Filtanium 0.2) with maximum pore size of 0.2μm were used. Regardless of the applied vF (3–6m/s), TMP (1–3bar) and TiO2 P25 loading (0.5–1.5g/dm3) no permeate flux decline was observed when the UF membranes were used. On the opposite, an increase of the flux for 5–10% compared to pure water flux due to abrasion of the membranes separation layer by TiO2 P25 particles was found. In case of MF membrane a significant influence of vF and TMP on permeate flux was observed. Application of vF=3m/s led to a significant membrane fouling while at vF=6m/s the permeate flux exceeded pure water flux in the whole range of TMP. The fine UF Filtanium 5 membrane lost its separation properties due to abrasion by TiO2 P25 particles, whereas the performance of the ordinary UF Filtanium 100 membrane did not change during 100h of operation in the PMR. Additionally, the influence of a commercial TiO2 ST01 (Ishihara Sangyo, Japan) and laboratory made A700 (anatase) and A800 (rutile) on the permeate flux through Filtanium 100 membrane were assessed. The difference between the lowest and the highest values of the permeate fluxes measured for various TiO2 materials did not exceed 12%.

Effect of ball-milling and Fe-/Al-doping on the structural aspect and visible light photocatalytic activity of TiO2 towards Escherichia coli bacteria abatement

Escherichia coli abatement was studied in liquid phase under visible light in the presence of two commercial titania photocatalysts, and of Fe- and Al-doped titania samples prepared by high energy ball-milling. The two commercial titania photocatalysts, Aeroxide P25 (Evonik industries) exhibiting both rutile and anatase structures and MPT625 (Ishihara Sangyo Kaisha), a Fe-, Al-, P- and S-doped titania exhibiting only the rutile phase, are active suggesting that neither the structure nor the doping is the driving parameter. Although the MPT625 UV–visible spectrum is shifted towards the visible domain with respect to the P25 one, the effect on bacteria is not increased. On the other hand, the ball milled iron-doped P25 samples exhibit low activities in bacteria abatement under visible light due to charge recombinations unfavorable to catalysis as shown by photoluminescence measurements. While doping elements are in interstitial positions within the rutile structure in MPT625 sample, they are located at the surface in ball milled samples and in isolated octahedral units according to 57Fe Mössbauer spectrometry. The location of doping elements at the surface is suggested to be responsible for the sample cytotoxicity observed in the dark.

Photocatalytic Reduction of Carbon Dioxide over Shape-Controlled Titanium(IV) Oxide Nanoparticles with Co-catalyst Loading

Photocatalytic reduction of carbon dioxide (CO2) was carried out using titanium(IV) oxide (TiO2). Methanol (CH3OH) was detected as the main product, and trace amounts of formic acid, carbon monoxide, methane, and hydrogen were also detected. The prepared decahedral-shaped anatase TiO2 with larger {011} and smaller {001} exposed crystal faces showed larger CH3OH generation than that of commercial anatase TiO2 powder, ST-01 (Ishihara Sangyo Co.). Photodeposition of silver and gold nanoparticles on the decahedral-shaped anatase TiO2 induced an increase in CH3OH production because the deposited metal particles work as reductive sites for multi-electron reduction of CO2. Keywords: Photocatalysis, Reduction of carbon dioxide, Decahedral-shaped anatase Titanium(IV) oxide

Ishihara Sangyo Kaisha closes Singapore TiO2 plant

Japanese speciality chemicals company Ishihara Sangyo Kaisha, Ltd (ISK) has announced that it is to close the titanium dioxide (TiO2) production plant of its 100% subsidiary ISK Singapore Pte Ltd, and consolidate the production of TiO2 products into its existing plant in Yokkaichi, Japan. The company says the move is part of the on-going reformation of its inorganic chemicals business portfolios.

The story of a new insecticidal chemistry class: the diamides

This paper describes the story of the invention of the diamides, a novel chemical class of insecticides. It starts with the pioneering work by Nihon Nohyaku researchers, who developed a herbicide lead with weak insecticidal activity to flubendiamide, a highly potent lepidoptericide. The journey continues with Nissan's isoxazolines and the invention of the anthranilamides by DuPont, culminating in the discovery of the blockbuster chlorantraniliprole and its analogue cyantraniliprole. The next steps are Syngenta's sulfoximines and bicyclic anthranilamides, Ishihara Sangyo Kaisha's cyclopropylamides, Sumitomo's hydrazides, Bayer's pyrazoles and tetrazoles, BASF's sulfoximines and more recent contributions from Chinese agrochemical companies and academic institutions. The diamides affect calcium homeostasis by binding to ryanodine receptors and releasing calcium from the intracellular stores. Investigations at Nihon Nohyaku, DuPont and Bayer on the action of the diamides on ryanodine receptors will be briefly reported.

ChemInform Abstract: Molecular Metal Oxide Cluster‐Surface Modified Titanium(IV) Dioxide Photocatalysts.

AbstractReview: 49 refs.

Molecular Metal Oxide Cluster-Surface Modified Titanium(IV) Dioxide Photocatalysts

The surface modification of TiO2 with molecular sized metal oxide clusters has recently been shown to be a promising approach for providing TiO2 with visible-light activity and/or improved UV activity. This short review summarizes the effects of the surface modification of TiO2 with the oxides of iron and tin selected from d- and p-blocks, respectively, on the photocatalytic activity. Fe(acac)3 and [Sn(acac)2]Cl2 chemisorption on the TiO2 surface occurs by ligand-exchange and ion-exchange, respectively. Taking advantage of the strong adsorption, we formed extremely small metal oxide clusters on TiO2 by the chemisorption–calcination cycle (CCC) technique with their loading amount strictly controlled. The iron oxide surface modification of P-25 (anatase/rutile = 4 : 1, w/w, Degussa) gives rise to a high level of visible-light activity and a concomitant increase in the UV-light activity for the degradation of model organic pollutants. On the other hand, only the UV-light activity is increased by the tin oxide surface modification of ST-01 (anatase, Ishihara Sangyo). This striking difference can be rationalized on the basis of the material characterization and DFT calculations, which show that FeOx surface modification of rutile leads to visible-light activity, while SnO2-modified anatase enhances only the UV-light activity. We propose the mechanisms behind the FeOx and SnO2 surface modification, where the surface-to-bulk and bulk-to-surface interfacial electron transfer are taken into account in the former and the latter, respectively.

Human poisoning with spinosad and flonicamid insecticides

This report describes the first known case in the literature of acute exposure to a mixture of spinosad and flonicamid that resulted in a substantial clinical toxicities. An 80-year-old depressed female attempted suicide by drinking a mixture of 80-mL Conserve (Dow AgroSciences, Taipei, Taiwan) and 2-3 gram powder of flonicamid (Ishihara Sangyo Kaisha, Taipei, Taiwan). Spinosad was the main compound ingested. The clinical manifestations were mostly neurological, i.e. consciousness disturbance, shock, respiratory failure, pneumonitis and urinary retention. Endoscopic examination found grade 2a corrosive esophageal injury. After resuscitation, detoxification procedures and intensive care, the patient recovered fully without leaving any chronic sequels. An emerging question arising from this report is, why are the clinical symptoms so severe, given that both compounds were claimed safe in laboratory animals? The answer is unclear. One possible explanation is, the amount of spinosad ingested was far beyond the physiological safety dose that can be handled by human body. Other potential contributors to the clinical toxicities in this patient are the solvent compositions that were found in the Conserve insecticide formulation.

Fabrication of Ti/TiO2 and Cu/TiO2 Composite Photocatalyst by Spark Plasma Sintering and its Characteristics

Ti/TiO2 and Cu/TiO2 composite photocatalysts were fabricated by spark plasma sintering (SPS) technique. TiO2 powder (ST-01, Ishihara Sangyo Kaisha, LTD.) with an average diameter of 7 nm was used as the matrix material. Ti powder with 99.8 % purity and an average diameter of 35 μm and Cu powder with 99.9 % purity and an average diameter of 30 μm were used as the addition metals, respectively. The sintering was carried out at 973 K for 3 min with a heating rate of 100 K/min under a uniaxial pressure of 30 MPa. The microstructure and crystal form of the composite photocatalysts were examined by SEM and XRD. The photocatalytic activity of the composite photocatalysts was evaluated by measuring the decomposition rate of methylene blue (MB) solution at room temperature. The results show that TiO2 photocatalyst fabricated at 973 K had the high activity, and that anatase crystal form was kept for the composite photocatalyst with 0∼5 wt%Ti, but the composite photocatalysts with 10 wt%Ti had two crystal forms, anatase and rutile. Antase crystal form was kept for all Cu/TiO2 composite photocatalyst. High photocatalytic activity was obtained because of the composite effect. Photocatalytic activity goes up with addition amount of Ti or Cu powder and reached the maximum about 1 vol%, then goes down.

Boron-doped TiO2: Characteristics and photoactivity under visible light

Boron-doped TiO2 was prepared by the sol-gel method and by grinding TiO2 powder with a boron compounds (boric acid and boric acid triethyl ester followed by calcinations at temperature range 200 to 600°C. Three types of pristine TiO2: ST-01 (Ishihara Sangyo Ltd., Japan; 300 m2/g), P25 (Degussa, Germany, 50 m2/g), A11 (Police S.A., Poland 12 m2/g) were used in grinding procedure. The photocatalytic activity of obtained powders in visible light was estimated by measuring the decomposition rate of phenol (0.21 mmol/dm3) in an aqueous solution. The photocatalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron emission spectroscopy (XPS), UV-VIS absorption and BET surface area measurements. The best photoactivity under visible light was observed for B-TiO2 modified with 2 wt% of boron prepared by grinding ST-01 with dopant followed by calcinations at 400°C. This photocatalyst contains 16.9 at.% of carbon and 6.6 at.% of boron in surface layer and its surface area is 192 m2/g.

Nano-Scaled Particles of Titanium Dioxide Convert Benign Mouse Fibrosarcoma Cells into Aggressive Tumor Cells

Nanoparticles are prevalent in both commercial and medicinal products; however, the contribution of nanomaterials to carcinogenesis remains unclear. We therefore examined the effects of nano-sized titanium dioxide (TiO(2)) on poorly tumorigenic and nonmetastatic QR-32 fibrosarcoma cells. We found that mice that were cotransplanted subcutaneously with QR-32 cells and nano-sized TiO(2), either uncoated (TiO(2)-1, hydrophilic) or coated with stearic acid (TiO(2)-2, hydrophobic), did not form tumors. However, QR-32 cells became tumorigenic after injection into sites previously implanted with TiO(2)-1, but not TiO(2)-2, and these developing tumors acquired metastatic phenotypes. No differences were observed either histologically or in inflammatory cytokine mRNA expression between TiO(2)-1 and TiO(2)-2 treatments. However, TiO(2)-2, but not TiO(2)-1, generated high levels of reactive oxygen species (ROS) in cell-free conditions. Although both TiO(2)-1 and TiO(2)-2 resulted in intracellular ROS formation, TiO(2)-2 elicited a stronger response, resulting in cytotoxicity to the QR-32 cells. Moreover, TiO(2)-2, but not TiO(2)-1, led to the development of nuclear interstices and multinucleate cells. Cells that survived the TiO(2) toxicity acquired a tumorigenic phenotype. TiO(2)-induced ROS formation and its related cell injury were inhibited by the addition of antioxidant N-acetyl-l-cysteine. These results indicate that nano-sized TiO(2) has the potential to convert benign tumor cells into malignant ones through the generation of ROS in the target cells.

Strains in the common cutworm, Spodoptera litura (Lepidoptera: Noctuidae) with differing host ranges

The larvae of two strains of Spodoptera litura, Ishihara and Sumitomo, supplied by Ishihara Sangyo Co. Ltd. and Sumitomo Chemical Co. Ltd., respectively, were raised on an artificial diet until last larval-larval ecdysis, and their growth and survival were compared when fed on leaves from 15 different plants known as host plants of this species. The Ishihara strain grew better and a higher percentage of larvae pupated when fed on spinach, leaf mustard, tomato, Chinese kale, taro, green pepper, red pepper or eggplant, compared with the Sumitomo strain. Whereas, much lower percentage of the larvae of the Sumitomo strain pupated especially on the last four plants, indicating that these plants were not suitable diets for larvae of this strain. The presence of strains differing in their host ranges is discussed in relation to the migration of S. litura.

New water-soluble complexes of titanium with amino acids and their application for synthesis of TiO2 nanoparticles

We prepared two new water-soluble complexes of titanium with L-serine and L(-)-threonine amino acids. It was demonstrated that these compounds can be outstanding precursors for a hydrothermal synthesis of nanocrystalline TiO2. The obtained powders were composed of anatase or a mixture of anatase and brookite. Particles diameters were ~10 nm and BET surface areas were ~120 m2/g. The powder composed of anatase and brookite synthesized by hydrothermal treatment of the titanium-threonine complex aqueous solution at 200°C for 24 h exhibited higher photocatalytic activity for oxalic acid oxidation than the commercial anatase-type TiO2 photocatalyst (ST-01, Ishihara Sangyo Kaisya, average diameter: 7 nm, specific surface area: 257.5 m2/g).

SOX6 Suppresses Cyclin D1 Promoter Activity by Interacting with β-Catenin and Histone Deacetylase 1, and Its Down-regulation Induces Pancreatic β-Cell Proliferation

Sex-determining region Y-box (SOX) 6 negatively regulates glucose-stimulated insulin secretion from beta-cells and is a down-regulated transcription factor in the pancreatic islet cells of hyperinsulinemic obese mice. To determine the contribution of SOX6 to insulin resistance, we analyzed the effects of SOX6 on cell proliferation. Small interfering RNA-mediated attenuation of SOX6 expression stimulated the proliferation of insulinoma INS-1E and NIH-3T3 cells, whereas retroviral overexpression resulted in inhibition of cell growth. Quantitative real time-PCR analysis revealed that the levels of cyclin D1 transcripts were markedly decreased by SOX6 overexpression. Luciferase-reporter assay with beta-catenin showed that SOX6 suppresses cyclin D1 promoter activities. In vitro binding experiments showed that the LZ/Q domain of SOX6 physically interacts with armadillo repeats 1-4 of beta-catenin. Furthermore, chromatin immunoprecipitation assay revealed that increased SOX6 expression significantly reduced the levels of acetylated histones H3 and H4 at the cyclin D1 promoter. By using a histone deacetylase (HDAC) inhibitor and co-immunoprecipitation analysis, we showed that SOX6 suppressed cyclin D1 activities by interacting withbeta-catenin and HDAC1. The data presented suggest that SOX6 may be an important factor in obesity-related insulin resistance.

1140835246 Aberrant activation of LIF‐downstream signal caused decidualization failure in pseudopregnant mice

As the leukemia inhibitory factor (LIF) knockout mice is infertile because of implantation failure, the downstream signals of LIF, such as STAT‐3, should play crucial roles for implantation. We have focused on the function of multifunctional transcription factors in endometrium during implantation window. We investigated here the effect of STAT‐3 decoy introduction into mouse uterus in vivo on pregnancy and decidualization. STAT‐3 decoy and scramble decoy were synthesized with phosphorotioate‐modification. On day 1.5 p.c., 80 μg decoy DNA+1000HAU HVJ‐E vector (GenomONE – Neo, Ishihara Sangyo, Osaka, Japan) suspension/horn was introduced into the uterine cavity. On day 5.0 p.c., implantation rate was determined by Evans blue injection. On day 3.5 p.c., 10 μL of sesame oil was injected single horn of pseudopregnant mice and fold‐increase of uterine wet weights was compared. Uterine morphology was examined by conventional Hematoxylin‐Eosin staining. Implantation rate was suppressed more than 70% in STAT‐3 decoy treated mice. In scramble decoy treated pseudopregnant mice, the uterine wet weight of infusion side was approximately 6.5‐fold of the control side. In STAT‐3 decoy infused mice, sesame oil induced ~2‐fold increase of the uterine wet weight. Histological examination indicated that decidualization of interstitial cells was apparently suppressed in the STAT‐3 decoy treated uterus, as compared with scramble decoy treated uteri. We revealed that in vivo transfection of STAT‐3 decoy into early pregnant mice uterus effectively inhibited implantation. The activation of STAT‐3 deeply concern with decidualization, which is one of very important steps to determine uterine receptivity.

Simple and highly efficient method for transient in vivo gene transfer to mid-late pregnant mouse uterus

Up- and down-regulation of various genes in the placenta, decidua and amnion has been reported during the mid-late period of pregnancy and in pregnancy-related complications, such as preeclampsia and preterm labor. However, whether this gene regulation at the feto-maternal interface directly influences the physiology/pathophysiology of disease remains unknown. In order to study this problem, transient gene transfer into the pregnant uterus at mid-late term would be a useful tool. We injected exogenous plasmid entrapped using a commercially available Hemagglutinating Virus of Japan Envelope (HVJ-E) vector system (GenomONE Neo, Ishihara Sangyo) into the extra-amniotic space of the upper part of the pregnant mouse uterus on day 14.5 post-coitus (p.c.). Luciferase activity driven by the cytomegalovirus promoter was detectable for 3 days after transfection in the upper, middle and lower part of the uterus. β-Galactsidase activity was localized in the basal lamina of the placenta, the decidual membrane and the fetal membrane. Exogenous plasmid was not transmitted to the fetus. The course of pregnancy was not disturbed by this procedure; rupture of membranes, intrauterine fetal growth restriction and preterm birth were not observed. Thus, we demonstrated that this transient gene transfer method is highly efficient and minimally invasive, and expect that this procedure will be a useful tool to analyze the pathophysiology of pregnancy-related disorders.

Photocatalytic degradation of reactive dye RED‐3BA in aqueous TiO2 suspension under UV‐visible light

The photo‐catalytic degradation efficiency of several commercial titania powders (Degussa P‐25 and Ishihara Sangyo ST‐01) and of TiO2 supported on diatomite were investigated in the degradation of a reactive dye (RED‐3BA) under UV‐Visible light. The observed rate constant for Degussa P‐25 was found to be higher than that achieved by using Ishihara Sangyo ST‐01 (kobs = 3.3 × 10−2min−1 for Degussa P‐25 and 4 × 10−4min−1 for Ishihara Sangyo ST‐01). This could be related to the amount of basic hydroxyl groups on the surface of TiO2 particles as shown in the IR spectra. TiO2 Degussa P‐25 supported on diatomite was prepared by dip‐coating method. The photo‐catalytic activity of supported TiO2 was twice smaller than TiO2 Degussa P‐25 (kp-25 = 3.3 × 10−2min−1;kp25/diatomite = 1.6 × 10−2min−1). The higher surface areas of ST‐01 and the TiO2/diatomite could not lead to a higher degradation rate and to a higher degree of mineralization but TiO2/diatomite could be separated more promptly and more easily from the solution. The effect of pH was investigated in the range 4–9. Acidic (pH = 4) medium was found to favor the adsorption and degradation rate with P‐25 particles.