39 results on '"Sugiura K"'
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2. Tuning of Electronic Structures of Quasi-One-Dimensional Bromo-Bridged Bi(III( Complexes with Strong Electron-Correction by Doping of Co(III) Ions, [Ni[sub 1-x]Co[sub x](Chxn0[sub 2]Br]Br[sub 2].
- Author
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Yamashita, M., Yokoyama, K., Furukawa, S., Manabe, T., Ono, T., Nakata, K., Kachi-Terajima, C., Iwahori, F., Ishii, T., Miyasaka, H., Sugiura, K., Matsuzasi, H., Kishida, H., Okamoto, H., Tanaka, H., Hasegawa, Y., Marumoto, K., Ito, H., and Kuroda, S.
- Published
- 2002
- Full Text
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3. Extremely Sensitive Genetically Encoded Temperature Indicator Enabling Measurement at the Organelle Level.
- Author
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Fukushima SI, Wazawa T, Sugiura K, and Nagai T
- Subjects
- Humans, Organelles chemistry, Organelles metabolism, Green Fluorescent Proteins chemistry, Green Fluorescent Proteins genetics, Endoplasmic Reticulum metabolism, Mitochondria metabolism, Mitochondria chemistry, HeLa Cells, Bacterial Proteins, Fluorescence Resonance Energy Transfer methods, Temperature, Luminescent Proteins genetics, Luminescent Proteins chemistry, Luminescent Proteins metabolism
- Abstract
Intracellular temperature is a fundamental parameter in biochemical reactions. Genetically encoded fluorescent temperature indicators (GETIs) have been developed to visualize intracellular thermogenesis; however, the temperature sensitivity or localization capability in specific organelles should have been further improved to clearly capture when and where intracellular temperature changes at the subcellular level occur. Here, we developed a new GETI, gMELT, composed of donor and acceptor subunits, in which cyan and yellow fluorescent proteins, respectively, as a Förster resonance energy transfer (FRET) pair were fused with temperature-sensitive domains. The donor and acceptor subunits associated and dissociated in response to temperature changes, altering the FRET efficiency. Consequently, gMELT functioned as a fluorescence ratiometric indicator. Untagged gMELT was expressed in the cytoplasm, whereas versions fused with specific localization signals were targeted to the endoplasmic reticulum (ER) or mitochondria. All gMELT variations enabled more sensitive temperature measurements in cellular compartments than those in previous GETIs. The gMELTs, tagged with ER or mitochondrial targeting sequences, were used to detect thermogenesis in organelles stimulated chemically, a method previously known to induce thermogenesis. The observed temperature changes were comparable to previous reports, assuming that the fluorescence readout changes were exclusively due to temperature variations. Furthermore, we demonstrated how macromolecular crowding influences gMELT fluorescence given that this factor can subtly affect the fluorescence readout. Investigating thermogenesis with gMELT, accounting for factors such as macromolecular crowding, will enhance our understanding of intracellular thermogenesis phenomena.
- Published
- 2024
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4. Development of Polymer-Lipid Hybrid Nanoparticles for Large-Sized Plasmid DNA Transfection.
- Author
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Maeki M, Uno S, Sugiura K, Sato Y, Fujioka Y, Ishida A, Ohba Y, Harashima H, and Tokeshi M
- Subjects
- mRNA Vaccines, Transfection, DNA chemistry, Plasmids genetics, RNA, Lipids chemistry, Polymers, Nanoparticles chemistry, Polyelectrolytes, Liposomes
- Abstract
RNA and DNA delivery technologies using lipid nanoparticles (LNPs) have advanced significantly, as demonstrated by their successful application in mRNA vaccines. To date, commercially available RNA therapeutics include Onpattro, a 21 bp siRNA, and mRNA vaccines comprising 4300 nucleotides for COVID-19. However, a significant challenge remains in achieving efficient transfection, as the size of the delivered RNA and DNA increases. In contrast to RNA transfection, plasmid DNA (pDNA) transfection requires multiple steps, including cellular uptake, endosomal escape, nuclear translocation, transcription, and translation. The low transfection efficiency of large pDNA is a critical limitation in the development of artificial cells and their cellular functionalization. Here, we introduce polymer-lipid hybrid nanoparticles designed for efficient, large-sized pDNA transfection. We demonstrated that LNPs loaded with positively charged pDNA-polycation core nanoparticles exhibited a 4-fold increase in transfection efficiency for 15 kbp pDNA compared with conventional LNPs, which encapsulate a negatively charged pDNA-polycation core. Based on assessments of the size and internal structure of the polymer-lipid nanoparticles as well as hemolysis and cellular uptake analysis, we propose a strategy to enhance large-sized pDNA transfection using LNPs. This approach holds promise for accelerating the in vivo delivery of large-sized pDNA and advancing the development of artificial cells.
- Published
- 2024
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5. Isolation of Caldorazole, a Thiazole-Containing Polyketide with Selective Cytotoxicity under Glucose-Restricted Conditions.
- Author
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Ohno O, Iwasaki A, Same K, Kudo C, Aida E, Sugiura K, Sumimoto S, Teruya T, Tashiro E, Simizu S, Matsuno K, Imoto M, and Suenaga K
- Subjects
- Deoxyglucose pharmacology, Glycolysis, Humans, Thiazoles pharmacology, Glucose, Polyketides pharmacology
- Abstract
Caldorazole ( 1 ) was isolated from the marine cyanobacterium Caldora sp. collected on Ishigaki Island, Okinawa, Japan. Its structure was determined to be a new polyketide that contained two thiazole rings and an O -methylenolpyruvamide moiety. Caldorazole ( 1 ) showed strong cytotoxicity toward tumor cells that had been seeded at a high density. Cell death induced by 1 in HeLa and A431 cells was also observed only in the presence of the glycolysis blocker 2-deoxy-d-glucose (2DG). Co-treatment with 1 and 2DG remarkably decreased ATP levels in these cells. Furthermore, 1 selectively inhibited complex I in the mitochondrial respiratory chain. Thus, 1 was demonstrated to exert cytotoxicity toward human tumor cells by blocking mitochondrial respiration.
- Published
- 2022
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6. New Class of Drug Modalities: Directed Evolution of a De Novo Designed Helix-Loop-Helix Peptide to Bind VEGF for Tumor Growth Inhibition.
- Author
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Michigami M, Ramanayake Mudiyanselage TMR, Suzuki M, Ishizako H, Notsu K, Sugiura K, and Fujii I
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- Animals, Human Umbilical Vein Endothelial Cells metabolism, Humans, Mice, Peptide Library, Peptides chemistry, Peptides pharmacology, Neoplasms, Vascular Endothelial Growth Factor A metabolism
- Abstract
As a small affinity molecule to serve as an alternative to antibodies, we have developed a conformationally constrained peptide with a de novo designed helix-loop-helix (HLH) scaffold. To evaluate its potential for biomedical applications, we performed directed evolution of HLH peptides to obtain an inhibitor for vascular endothelial growth factor-A (VEGF). A phage-displayed library of HLH peptides was constructed and screened against VEGF, giving the peptide VS42 that inhibits the VEGF/VEGF receptor-2 interaction (IC
50 = 210 nM), which was further improved by in vitro affinity maturation using a yeast-displayed library. An identified HLH peptide, VS42-LR3, exhibited improved inhibitory activity (IC50 = 37 nM), high thermal stability, and excellent resistance against chemical denaturation. In biological activity tests, the HLH peptide was found to block VEGF-induced proliferation of human umbilical vein endothelial cells and suppress tumor growth in a murine xenograft model of human colorectal cancer.- Published
- 2022
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7. Characterization and Specification of a Trivalent Protein-Based Pneumococcal Vaccine Formulation Using an Adjuvant-Free Nanogel Nasal Delivery System.
- Author
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Yuki Y, Uchida Y, Sawada SI, Nakahashi-Ouchida R, Sugiura K, Mori H, Yamanoue T, Machita T, Honma A, Kurokawa S, Mukerji R, Briles DE, Akiyoshi K, and Kiyono H
- Subjects
- Administration, Intranasal, Animals, Bacterial Proteins genetics, Bacterial Proteins immunology, Bacterial Proteins pharmacokinetics, Drug Liberation, Female, Glucans chemistry, Humans, Immunogenicity, Vaccine, Mice, Models, Animal, Nasal Mucosa metabolism, Pneumococcal Infections microbiology, Pneumococcal Vaccines genetics, Pneumococcal Vaccines immunology, Pneumococcal Vaccines pharmacokinetics, Recombinant Fusion Proteins administration & dosage, Recombinant Fusion Proteins genetics, Recombinant Fusion Proteins immunology, Streptococcus pneumoniae genetics, Streptococcus pneumoniae immunology, beta-Cyclodextrins chemistry, Bacterial Proteins administration & dosage, Hygroscopic Agents chemistry, Nanogels chemistry, Pneumococcal Infections prevention & control, Pneumococcal Vaccines administration & dosage
- Abstract
We previously developed a safe and effective nasal vaccine delivery system using a self-assembled nanosized hydrogel (nanogel) made from a cationic cholesteryl pullulan. Here, we generated three pneumococcal surface protein A (PspA) fusion antigens as a universal pneumococcal nasal vaccine and then encapsulated each PspA into a nanogel and mixed the three resulting monovalent formulations into a trivalent nanogel-PspA formulation. First, to characterize the nanogel-PspA formulations, we used native polyacrylamide gel electrophoresis (PAGE) to determine the average number of PspA molecules encapsulated per nanogel molecule. Second, we adopted two methods-a densitometric method based on lithium dodecyl sulfate (LDS)-PAGE and a biologic method involving sandwich enzyme-linked immunosorbent assay (ELISA)-to determine the PspA content in the nanogel formulations. Third, treatment of nanogel-PspA formulations by adding methyl-β-cyclodextrin released each PspA in its native form, as confirmed through circular dichroism (CD) spectroscopy. However, when nanogel-PspA formulations were heat-treated at 80 °C for 16 h, CD spectroscopy showed that each PspA was released in a denatured form. Fourth, we confirmed that the nanogel-PspA formulations were internalized into nasal mucosa effectively and that each PspA was gradually released from the nanogel in epithelial cells in mice. Fifth, LDS-PAGE densitometry and ELISA both indicated that the amount of trivalent PspA was dramatically decreased in the heat-treated nanogel compared with that before heating. When mice were immunized nasally using the heat-treated formulation, the immunologic activity of each PspA was dramatically reduced compared with that of the untreated formulation; in both cases, the immunologic activity correlated well with the content of each PspA as determined by LDS-PAGE densitometry and ELISA. Finally, we confirmed that the trivalent nanogel-PspA formulation induced equivalent titers of PspA-specific serum IgG and mucosal IgA Abs in immunized mice. These results show that the specification methods we developed effectively characterized our nanogel-based trivalent PspA nasal vaccine formulation.
- Published
- 2021
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8. An Immune-Stimulatory Helix-Loop-Helix Peptide: Selective Inhibition of CTLA-4-B7 Interaction.
- Author
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Ramanayake Mudiyanselage TMR, Michigami M, Ye Z, Uyeda A, Inoue N, Sugiura K, Fujii I, and Fujiwara D
- Subjects
- Amino Acid Sequence, Dendritic Cells drug effects, Helix-Loop-Helix Motifs, Humans, Immunologic Factors chemical synthesis, Immunologic Factors genetics, Leukocytes, Mononuclear drug effects, Lymphocyte Activation drug effects, Peptide Library, Peptides chemical synthesis, Peptides genetics, Saccharomyces cerevisiae genetics, B7-1 Antigen metabolism, CTLA-4 Antigen metabolism, Immunoglobulin Fc Fragments metabolism, Immunologic Factors pharmacology, Peptides pharmacology, Protein Binding drug effects
- Abstract
Molecular-targeting peptides and mini-proteins are promising alternatives to antibodies in a wide range of applications in bioscience and medicine. We have developed a helix-loop-helix (HLH) peptide as an alternative to antibodies to inhibit specific protein interactions. Cytotoxic T lymphocyte antigen-4 (CTLA-4) downregulates immune responses of cytotoxic T-cells by interaction with B7-1, a co-stimulatory molecule expressed on antigen presenting cells (APCs). To induce immune stimulatory activity, we used directed evolution methods to generate a HLH peptide that binds to CTLA-4, inhibiting the CTLA-4-B7-1 interaction and inducing immune stimulatory activity. Yeast-displayed libraries of HLH peptides were constructed and screened against CTLA-4 and identified the binding peptide Y-2, which exhibits a moderate affinity. The affinity of Y-2 was improved by in vitro affinity maturation to afford a stronger binder, ERY2-4. Peptide ERY2-4 specifically bound to CTLA-4 with a K
D of 196.8 ± 2.3 nM, comparable to the affinity of the CTLA-4-B7-1 interaction. Furthermore, ERY2-4 inhibited the CTLA-4-B7-1 interaction with an IC50 of 1.1 ± 0.03 μM and blocked the interaction between CTLA-4 and dendritic cells (DCs) presenting B7 on their surface. Importantly, ERY2-4 showed no cross-reactivity against CD28, suggesting it does not suppress T-cell activation. Finally, in a mixed lymphocyte reaction assay with DCs and T cells, ERY2-4 enhanced an allogeneic lymphocyte response. Since CTLA-4 is a critical immune checkpoint for restricting the cancer immune response, this inhibitory HLH peptide represents a new class of drug candidates for immunotherapy.- Published
- 2020
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9. Tailoring the Surface Functionalities of Radio Frequency Magnetron-Sputtered ZnO Thin Films by Ar/NH 3 Gas Mixture Surface-Wave Plasmas.
- Author
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Ciolan MA, Motrescu I, Sugiura K, Luca D, and Nagatsu M
- Abstract
The surface functionalization of radio frequency magnetron-sputtered zinc oxide (ZnO) thin films tailored by low-pressure Ar/NH
3 mixture surface-wave plasmas (SWPs) is discussed based on the results of photoluminescence (PL), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and spectrophotometric measurements. At an Ar/NH3 gas mixture ratio of 70%/30%, both the PL intensity of the near-band-edge emission and the XRD intensity of the ZnO(002) reflection peak were enhanced by about 5.5 and 8 times, respectively, compared to the values for the as-grown sample. Furthermore, the XPS and spectrophotometric analyses using the fluorescent dye showed that the amine group functionalization over the surface of the ZnO films reached their maximum values at the same gas ratio. From the results of optical emission spectroscopic and ion mass spectrometric measurements in the Ar/NH3 mixture SWPs, it is inferred that the nitrogen-containing reactive species, such as NHx + ( x = 1-4) ions and NHy ( y = 1, 2) molecules in addition to H radicals might crucially interact with the defective ZnO surface lattices to repair the ZnO thin films from compressive to strain-free crystallized structures, enhance the PL intensity, and produce the amine group surface functionalization.- Published
- 2018
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10. Photovoltaic Properties and Long-Term Durability of Porphyrin-Sensitized Solar Cells with Silicon-Based Anchoring Groups.
- Author
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Higashino T, Nimura S, Sugiura K, Kurumisawa Y, Tsuji Y, and Imahori H
- Abstract
Anchoring groups for dye-sensitized solar cells (DSSCs) play a decisive role in high-power conversion efficiency (η) and long-term cell durability. To date, a carboxylic acid is the most widely used anchoring group for DSSCs. However, the carboxylic acid tends to dissociate from a TiO
2 surface during the cell operation as well as in the presence of water. Considering that the dye dissociation from TiO2 leads to a decrease in the cell performance, stable anchoring groups are highly desirable to achieve long-term durability of DSSCs toward their practical application. In this study, we designed and synthesized a series of porphyrin dyes with the triethoxysilyl anchoring groups, ZnPSi1 , ZnPSi2 , and ZnPSi3 , to evaluate the effects of the silicon-based anchoring group on cell durability and photovoltaic properties. The DSSCs based on ZnPSi1 , ZnPSi2 , and ZnPSi3 exhibited moderate η-values of 2.2, 4.7, and 2.3%, respectively. It is noteworthy that the η-value of the DSSC based on ZnPSi2 (4.7%) is the highest among DSSCs based on porphyrin dyes with silicon-based anchoring groups. The moderate η-values are mainly attributed to the low charge collection efficiency originating from the low surface coverage and plausible tilted geometry of the dyes on TiO2 . More importantly, we demonstrated that the DSSC based on ZnPSi2 revealed higher long-term cell durability under illumination than that based on reference porphyrin YD2 -o -C8 having a conventional carboxylic acid anchoring group., Competing Interests: The authors declare no competing financial interest.- Published
- 2017
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11. Effects of Bulky Substituents of Push-Pull Porphyrins on Photovoltaic Properties of Dye-Sensitized Solar Cells.
- Author
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Higashino T, Kawamoto K, Sugiura K, Fujimori Y, Tsuji Y, Kurotobi K, Ito S, and Imahori H
- Abstract
To evaluate the effects of substituent bulkiness around a porphyrin core on the photovoltaic properties of porphyrin-sensitized solar cells, long alkoxy groups were introduced at the meso-phenyl group (ZnPBAT-o-C8) and the anchoring group (ZnPBAT-o-C8Cn, n = 4, 8) of an asymmetrically substituted push-pull porphyrin with double electron-donating diarylamino groups and a single electron-withdrawing carboxyphenylethynyl anchoring group. The spectroscopic and electrochemical properties of ZnPBAT-o-C8 and ZnPBAT-o-C8Cn were found to be superior to those of a push-pull porphyrin reference (YD2-o-C8), demonstrating their excellent light-harvesting and redox properties for dye-sensitized solar cells. A power conversion efficiency (η) of the ZnPBAT-o-C8-sensitized solar cell (η = 9.1%) is higher than that of the YD2-o-C8-sensitized solar cell (η = 8.6%) using iodine-based electrolyte due to the enhanced light-harvesting ability of ZnPBAT-o-C8. In contrast, the solar cells based on ZnPBAT-o-C8Cn, possessing the additional alkoxy chains in the anchoring group, revealed the lower η values of 7.3% (n = 4) and 7.0% (n = 8). Although ZnPBAT-o-C8Cn exhibited higher resistance at the TiO2-dye-electrolyte interface by virtue of the extra alkoxy chains, the reduced amount of the porphyrins on TiO2 by excessive addition of coadsorbent chenodeoxycholic acid (CDCA) for mitigating the aggregation on TiO2 resulted in the low η values. Meanwhile, the ZnPBAT-o-C8-sensitized solar cell showed the lower η value of 8.1% than the YD2-o-C8-sensitized solar cell (η = 9.8%) using cobalt-based electrolyte. The smaller η value of the ZnPBAT-o-C8-sensitized solar cell may be attributed to the insufficient blocking effect of the bulky substituents of ZnPBAT-o-C8 under the cobalt-based electrolyte conditions. Overall, the alkoxy chain length and substitution position around the porphyrin core are important factors to affect the cell performance.
- Published
- 2016
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12. Catalyst-free aromatic nucleophilic substitution of meso-bromoporphyrins with azide anion: efficient synthesis and structural analyses of meso-azidoporphyrins.
- Author
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Yamashita K, Kataoka K, Asano MS, and Sugiura K
- Subjects
- Anions chemistry, Catalysis, Models, Molecular, Molecular Structure, Azides chemistry, Bromine chemistry, Porphyrins chemical synthesis
- Abstract
meso-Mono- or diazidoporphyrins were readily obtained in high yields by the catalyst-free aromatic nucleophilic reaction of the corresponding bromoporphyrins with azide anions under mild conditions. The molecular structures of the obtained azides were unambiguously determined by X-ray crystallographic analysis., (© 2011 American Chemical Society)
- Published
- 2012
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13. Manipulating double-decker molecules at the liquid-solid interface.
- Author
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Takami T, Ye T, Pathem BK, Arnold DP, Sugiura K, Bian Y, Jiang J, and Weiss PS
- Abstract
We have used a scanning tunneling microscope (STM) to manipulate heteroleptic phthalocyaninato, naphthalocyaninato, and porphyrinato double-decker (DD) molecules at the liquid-solid interface between 1-phenyloctane solvent and graphite. We employed nanografting of phthalocyanines with eight octyl chains to place these molecules into a matrix of heteroleptic DD molecules; the overlayer structure is epitaxial on graphite. We have also used nanografting to place DD molecules in matrices of single-layer phthalocyanines with octyl chains. Rectangular scans with a STM at low bias voltage resulted in the removal of the adsorbed DD molecular layer and substituted the DD molecules with bilayer-stacked phthalocyanines from phenyloctane solution. Single heteroleptic DD molecules with lutetium sandwiched between naphthalocyanine and octaethylporphyrin were decomposed with voltage pulses from the probe tip; the top octaethylporphyrin ligand was removed, and the bottom naphthalocyanine ligand remained on the surface. A domain of decomposed molecules was formed within the DD molecular domain, and the boundary of the decomposed molecular domain self-cured to become rectangular. We demonstrated a molecular "sliding block puzzle" with cascades of DD molecules on the graphite surface.
- Published
- 2010
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14. Biosynthesis of vanillin via ferulic acid in Vanilla planifolia.
- Author
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Negishi O, Sugiura K, and Negishi Y
- Subjects
- Benzaldehydes chemistry, Coumaric Acids chemistry, Propionates, Vanilla chemistry, Benzaldehydes metabolism, Biosynthetic Pathways, Coumaric Acids metabolism, Vanilla metabolism
- Abstract
(14)C-Labeled phenylalanine, 4-coumaric acid, 4-hydroxybenzaldehyde, 4-hydroxybenzyl alcohol, ferulic acid, and methionine were applied to disks of green vanilla pods 3 and 6 months after pollination (immature and mature pods), and the conversion of these compounds to vanillin or glucovanillin was investigated. In mature green vanilla pods, radioactivities of 11, 15, 29, and 24% from (14)C-labeled phenylalanine, 4-coumaric acid, ferulic acid, and methionine, respectively, were incorporated into glucovanillin within 24 h. In the incorporation processes of methionine and phenylalanine into glucovanillin, some of the (14)C labels were also trapped by the unlabeled ferulic acid. However, (14)C-labeled 4-hydroxybenzaldehyde and 4-hydroxybenzyl alcohol were not converted to glucovanillin. On the other hand, in immature green vanilla pods radioactivities of the above six compounds were not incorporated into glucovanillin. Although 4-coumaric acid, ferulic acid, 4-hydroxybenzaldehyde, and 4-hydroxybenzyl alcohol were converted to the respective glucose esters or glucosides and vanillin was converted to glucovanillin, their conversions were believed to be from the detoxication of the aglycones. These results suggest that the biosynthetic pathway for vanillin is 4-coumaric acid --> --> ferulic acid --> --> vanillin --> glucovanillin in mature vanilla pods.
- Published
- 2009
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15. First total synthesis of hinckdentine A.
- Author
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Higuchi K, Sato Y, Tsuchimochi M, Sugiura K, Hatori M, and Kawasaki T
- Subjects
- Molecular Structure, Quinazolines chemistry, Stereoisomerism, Quinazolines chemical synthesis
- Abstract
We have accomplished the first total synthesis of (+/-)-hinckdentine A (1). The key steps are m-CPBA oxidation of 2-arylindole followed by acid-mediated Mannich-type C-C bond formation of 2-hydroxyindolin-3-one, seven-membered ring closure, and regioselective tribromination.
- Published
- 2009
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16. Recent progress in oxide thermoelectric materials: p-type Ca3Co4O9 and n-type SrTiO3(-).
- Author
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Ohta H, Sugiura K, and Koumoto K
- Abstract
Thermoelectric energy conversion technology to convert waste heat into electricity has received much attention. In addition, metal oxides have recently been considered as thermoelectric power generation materials that can operate at high temperatures on the basis of their potential advantages over heavy metallic alloys in chemical and thermal robustness. We have fabricated high-quality epitaxial films composed of oxide thermoelectric materials that are suitable for clarifying the intrinsic "real" properties. This review focuses on the thermoelectric properties of two representative oxide epitaxial films, p-type Ca 3Co 4O 9 and n-type SrTiO 3, which exhibit the best thermoelectric figures of merit, ZT (= S (2)sigma Tkappa (-1), S = Seebeck coefficient, sigma = electrical conductivity, kappa = thermal conductivity, and T = absolute temperature) among oxide thermoelectric materials reported to date. In addition, we introduce the recently discovered giant S of two-dimensional electrons confined within a unit cell layer thickness ( approximately 0.4 nm) of SrTiO 3.
- Published
- 2008
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17. Two types of beta-fructofuranosidases from Aspergillus oryzae KB.
- Author
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Kurakake M, Ogawa K, Sugie M, Takemura A, Sugiura K, and Komaki T
- Subjects
- Amino Acid Sequence, Fructose metabolism, Gene Expression, Glucose metabolism, Peptide Fragments chemistry, RNA, Messenger analysis, Sucrose metabolism, Trypsin metabolism, beta-Fructofuranosidase chemistry, beta-Fructofuranosidase genetics, Aspergillus oryzae enzymology, beta-Fructofuranosidase metabolism
- Abstract
Aspergillus oryzae KB produces two types of beta-fructofuranosidases, F1 and F2. F1 produces 1-kestose, nystose, and fructosyl nystose from sucrose through its transfructosylation action. F2 hydrolyzes sucrose to glucose and fructose. N-Terminal amino acid sequences of the purified enzymes were DYNAAPPNLST for F1 and YSGDLRPQ for F2. Each enzyme encoding gene was identified in the genome of Aspergillus oryzae. Although the KB strain showed a higher production of F2 than F1 in a low sucrose liquid medium, F2 production gradually decreased, whereas F1 production increased with increasing sucrose concentration in the medium. Synthesis of F1 and F2 mRNAs analyzed on reverse-transcription polymerase chain reaction corresponded to individual enzymatic production. During liquid culture of the KB strain, F1 synthesizes fructooligosaccharides from sucrose through transfructosylation, and F2 gradually hydrolyzes it. In a highly concentrated sucrose medium, intake of sucrose into the KB strain was depressed by F1 through synthesis of transfer products, fructooligosaccharides.
- Published
- 2008
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18. Metal-insulator transition of charge-transfer salts based on unsymmetrical donor DMET and metal halide anions (DMET)4(MCl4)(TCE)2 (M = Mn, Co, Cu, Zn; TCE = 1,1,2-trichloroethane).
- Author
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Ito H, Suzuki D, Watanabe H, Tanaka H, Kuroda S, Umemiya M, Kobayashi N, Goto M, Sugiura K, Miyasaka H, Takaishi S, Kajiwara T, Yamashita M, Ohmichi E, and Osada T
- Abstract
New charge-transfer salts based on an unsymmetrical donor DMET [dimethyl(ethylenedithio)diselenadithiafulvalene] and metal halide anions (DMET)4MIICl4(TCE)2 (M = Mn, Co, Cu, Zn; TCE = 1,1,2-trichloroethane) have been synthesized and characterized by transport and magnetic measurements. The crystal structures of the DMET salts are isostructural, consisting of a quasi-one-dimensional stack of DMET and insulating layers containing metal halide anions and TCE. Semimetallic band structures are calculated by the tight-binding approximation. Metal-insulator transitions are observed at TMI = 25, 15, 5-20, and 13 K for M = Mn, Co, Cu, and Zn, respectively. The M = Cu salt exhibits anisotropic conduction at ambient pressure, being semiconducting in the intralayer current direction but metallic for the interplane current direction, down to T(MI). The metal-insulator transitions are suppressed under pressure. In the M = Co and Zn salts, large magnetoresistances with hysteresis are observed at low temperatures, on which Shubnikov-de Haas oscillations are superposed above 30 T. In the M = Cu salt, no hysteresis is observed but clear Shubnikov-de Haas oscillations are observed. The magnetoresistance is small and monotonic in the M = Mn salt. Paramagnetic susceptibilities of the spins of the magnetic ions are observed for the M = Mn, Co, and Cu salts with small negative Weiss temperatures of approximately 1 K. In the nonmagnetic M = Zn salt, Pauli-like pi-electron susceptibility that vanishes at TMI is observed. The ground state of the pi-electron system is understood as being a spin density wave state caused by imperfect nesting of the Fermi surfaces. In this pi-electron system, the magnetic ions of the M = Mn, Co, and Cu salts interact differently, exhibiting a variety of transport behaviors.
- Published
- 2007
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19. From an S(T) = 3 single-molecule magnet to diamagnetic ground state depending on the molecular packing of Mn(III)salen-type dimers decorated by N,N'-dicyano-1,4-naphthoquinonediiminate radicals.
- Author
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Kachi-Terajima C, Miyasaka H, Sugiura K, Clérac R, and Nojiri H
- Abstract
Two manganese(III) tetradentate Schiff-base dimers to which N,N'-dicyano-1,4-naphthoquinonediiminate (DCNNQI) radicals are attached have been selectively synthesized by varying the solvents used in the reactions: [Mn2(5-MeOsaltmen)2(DCNNQI)2].MeOH (1) and [Mn2(5-MeOsaltmen)(2)(DCNNQI)(2)] x 2CH2Cl2.2CH3CN (2) [5-MeOsaltmen2- = N,N'-(1,1,2,2-tetramethylethylene)bis(5-methoxysalicylideneiminate)]. These two complexes share the same molecular core, [(DCNNQI.-)-Mn(III)-(O)2-Mn(III)-(DCNNQI.-)], where -(O)2- is a biphenolate bridge in the out-of-plane dimerized [Mn(2)(5-MeOsaltmen)2]2+ moiety. However, their packing arrangements are completely different. Whereas complex 1 is found to be relatively isolated, strong intermolecular dimerization of the DCNNQI moieties (with the nearest contact being approximately 3.0 A) is observed in 2, forming a one-dimensional chain of [-Mn(III)-(O)2-Mn(III)-(DCNNQI.-)2-](infinity). The magnetic susceptibility of 1 can be modeled with an [S = 1/2, 2, 2, 1/2] four-spin system including strong antiferromagnetic Mn(III)/DCNNQI radical coupling (J(Mn/rad)/kB = -23 K) and ferromagnetic Mn(III)/Mn(III) coupling through the biphenolate bridge (J(Mn/Mn)/kB = +2.0 K). These interactions lead to an ST = 3 ground state that possesses significant uniaxial anisotropy (D(S=3)/kB = -2.1 K). Low-temperature ac and dc magnetic data of 1 reveal its single-molecule magnet behavior with quantum tunneling of the magnetization. By contrast, 2 possesses the diamagnetic ground state induced by dominating Mn(III)-Mn(III) antiferromagnetic interactions mediated by the diamagnetic DCNNQI dimers and/or pi-pi contact along the b axis.
- Published
- 2006
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20. Dynamical valence fluctuation at the charge-density-wave phase boundary in iodide-bridged Pt compound [Pt(chxn)2I]I2.
- Author
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Takaishi S, Kawakami D, Yamashita M, Sasaki M, Kajiwara T, Miyasaka H, Sugiura K, Wakabayashi Y, Sawa H, Matsuzaki H, Kishida H, Okamoto H, Watanabe H, Tanaka H, Marumoto K, Ito H, and Kuroda S
- Abstract
We synthesized a novel iodo-bridged linear chain platinum compound, having the quasi-two-dimensional charge-density-wave (CDW) ground state and the smallest band gap. In this compound, we discovered an anomalous valence state in the boundary region at which the CDW phase alternates in the crystal by means of ESR, X-ray diffuse scattering, STM, and electrical resistivity. This anomalous state can be explained by the fast fluctuation between Pt(IV)-I...Pt(II) and Pt(II)...I-Pt(IV) in the double well potential. This is the first observation of the dynamical fluctuation of the CDW phase among the quasi one-dimensional halogen-bridged complexes.
- Published
- 2006
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21. Two-dimensional networks based on Mn4 complex linked by dicyanamide anion: from single-molecule magnet to classical magnet behavior.
- Author
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Miyasaka H, Nakata K, Lecren L, Coulon C, Nakazawa Y, Fujisaki T, Sugiura K, Yamashita M, and Clérac R
- Abstract
Three two-dimensional (2D) network compounds based on Mn(III)/Mn(II) tetranuclear single-molecule magnets (SMMs) connected by dicyanamide (dcn-) linkers have been synthesized: [Mn4(hmp)4(Hpdm)2(dcn)2](ClO4)2 x 2 H2O x 2 MeCN (2), [Mn4(hmp)4Br2(OMe)2(dcn)2] x 0.5 H2O x 2 THF (3), [Mn4(hmp)6(dcn)2](ClO4)2 (4), where Hhmp and H2pdm are 2-hydroxymethylpyridine and pyridine-2,6-dimethanol, respectively. The [Mn4]/dcn- system appears very versatile, but enables its chemistry to be rationalized by a fine-tune of the synthetic conditions. The double cuboidal [Mn4] unit is preserved in the whole family of compounds, despite strong modifications of its Mn(II) coordination sphere. The chemical control of the coordination number of dcn- on the Mn(II) sites has been the key to obtain the following series of compounds: a discrete cluster, [Mn4(hmp)6(NO3)2(dcn)2] x 2 MeCN (1), 2D networks (2, 3, and 4), and the previously reported 3D compound, [Mn4(hmp)4(mu3-OH)2][Mn(II)(dcn)6] x 2 MeCN x THF. Direct current magnetic measurements show that both Mn2+-Mn3+ and Mn3+-Mn3+ intra-[Mn4] magnetic interactions are ferromagnetic leading to an S(T) = 9 ground state for the [Mn4] unit. Despite the very similar 2D lattices in 2-4, the two kinds of orientation of the [Mn4] unit (i.e., angle variations between the two easy axes) lead to different magnetic properties ranging from SMM behavior for 2 and 1 to a long-range canted antiferromagnetic order for 4. Compound 3 is more complicated as the magnetic measurements strongly suggest the presence of a canted antiferromagnetic order below 2.1 K, although the magnetization slow relaxation is simultaneously observed. Heat capacity measurements confirm the long-range magnetic order in 4, while in 3, the critical behavior is frozen by the slow relaxation of the anisotropic [Mn4] units.
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- 2006
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22. Epitaxial film growth and superconducting behavior of sodium-cobalt oxyhydrate, NaxCoO2.yH2O (x approximately 0.3, y approximately 1.3).
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Sugiura K, Ohta H, Nomura K, Yanagi H, Hirano M, Hosono H, and Koumoto K
- Abstract
We have developed a unique multistep film growth technique, combining reactive solid-phase epitaxy (R-SPE) with an intercalation process, to fabricate epitaxial films of superconducting sodium-cobalt oxyhydrate, Na(0.3)CoO2.1.3H2O. An epitaxial film of Na(0.8)CoO2 grown on an alpha-Al2O3(0001) substrate by R-SPE was subjected to oxidation and hydration treatment, leading to the formation of a Na(0.3)CoO2.1.3H2O epitaxial film. The film exhibited metallic electrical resistivity with a superconducting transition at 4 K, similar to that of bulk single crystals. The present technique is suitable and probably the only method for the epitaxial growth of superconducting Na(0.3)CoO2.1.3H2O.
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- 2006
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23. Two-dimensional crystal growth and stacking of bis(phthalocyaninato) rare earth sandwich complexes at the 1-phenyloctane/graphite interface.
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Takami T, Arnold DP, Fuchs AV, Will GD, Goh R, Waclawik ER, Bell JM, Weiss PS, Sugiura K, Liu W, and Jiang J
- Abstract
Initial stages of two-dimensional crystal growth of the double-decker sandwich complex Lu(Pc*)2 [Pc* = 2,3,9,10,16,17,23,24-octakis(octyloxy)phthalocyaninato] have been studied by scanning tunneling microscopy at the liquid/solid interface between 1-phenyloctane and highly oriented pyrolytic graphite. High-resolution images strongly suggest alignment of the double-decker molecules into monolayers with the phthalocyanine rings parallel to the surface. Domains were observed with either hexagonal or quadrate packing motifs, and the growing interface of the layer was imaged. Molecular resolution was achieved, and the face of the phthalocyanine rings appeared as somewhat diffuse circular features. The alkyl chains are proposed to be interdigitating to maintain planar side-by-side packing.
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- 2006
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24. Direct observation of the disorder of the methyl group of (R)-1,2-diaminopropane ligand in the quasi-1D bromo-bridged Ni(III) complex by STM.
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Sasaki M, Takaishi S, Miyasaka H, Sugiura K, and Yamashita M
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Scanning tunneling microscopy (STM) has been measured in quasi-one-dimensional (Quasi-ID) bromo-bridged Ni(III) complexes. In the STM image of [Ni(pn)2Br]Br2 (pn = (R)-1,2-diaminopropane), the bright spots are fluctuated zigzags. Such a result indicates that the methyl groups of the pn ligands are not arranged on the right- and left-hand alternatively along the chains, but in the domain structures or fluctuated structures. This is the first direct observation of the disorder of the methyl group of pn ligands in real space.
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- 2005
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25. Cyano-bridged Mn(III)3M(III) (M(III) = Fe, Cr) complexes: synthesis, structure, and magnetic properties.
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Miyasaka H, Takahashi H, Madanbashi T, Sugiura K, Clérac R, and Nojiri H
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Two cyano-bridged tetranuclear complexes composed of Mn(III) salen (salen = N,N'-ethylene bis(salicylideneiminate)) and hexacyanometalate(III) (M = Fe, Cr) in a stoichiometry of 3:1 have been selectively synthesized using {NH2(n-C12H25)2}3[M(III)(CN)6] (M(III) = Fe, Cr) starting materials: [{Mn(salen)(EtOH)}3{M(CN)6}] (M = Fe, 1; Cr, 2). Compounds 1 and 2 are isostructural with a T-shaped structure, in which [M(CN)6]3- assumes a meridional-tridentate building block to bind three [Mn(salen)(EtOH)]+ units. The strong frequency dependence and observation of hysteresis on the field dependence of the magnetization indicate that 1 is a single-molecule magnet.
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- 2005
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26. Single-chain magnet (NEt4)[Mn2(5-MeOsalen)2Fe(CN)6] Made of Mn(III)-Fe(III)-Mn(III) trinuclear single-molecule magnet with an S(T) = 9/2 spin ground state.
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Ferbinteanu M, Miyasaka H, Wernsdorfer W, Nakata K, Sugiura K, Yamashita M, Coulon C, and Clérac R
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The cyano-bridged trinuclear compound, (NEt(4))[Mn(2)(salmen)(2)(MeOH)(2)Fe(CN)(6)] (1) (salmen(2)(-) = rac-N,N'-(1-methylethylene)bis(salicylideneiminate)), reported previously by Miyasaka et al. (ref 19d) has been reinvestigated using combined ac and dc susceptibility measurements. The strong frequency dependence of the ac susceptibility and the slow relaxation of the magnetization show that 1 behaves as a single-molecule magnet with an S(T) = (9)/(2) spin ground state. Its relaxation time (tau) follows an Arrhenius law with tau(0) = 2.5 x 10(-)(7) s and Delta(eff)/k(B) = 14 K. Moreover, below 0.3 K, tau saturates around 470 s, indicating that quantum tunneling of the magnetization becomes the dominant process of relaxation. (NEt(4))[Mn(2) (5-MeOsalen)(2)Fe(CN)(6)] (2) (5-MeOsalen(2)(-) = N,N'-ethylenebis(5-methoxysalicylideneiminate)) is a heterometallic one-dimensional assembly made of the trinuclear [Mn(III)(SB)-NC-Fe(III)-CN-Mn(III)(SB)] (SB is a salen-type Schiff-base ligand) motif similar to 1. Compound 2 has two types of bridges, a cyano bridge (-NC-) and a biphenolate bridge (-(O)(2)-), connecting Mn(III) and Fe(III) ions and the two Mn(III) ions, respectively. Both bridges mediate ferromagnetic interactions, as shown by modeling the magnetic susceptibility above 10 K with g(av) = 2.03, J(Mn)(-)(Fe)/k(B) = +6.5 K, and J'/k(B) = +0.07 K, where J' is the exchange coupling between the trimer units. The dc magnetic measurements of a single crystal using micro-SQUID and Hall-probe magnetometers revealed a uniaxial anisotropy (D(T)/k(B) = -0.94 K) with an easy axis lying along the chain direction. Frequency dependence of the ac susceptibility and time dependence of the dc magnetization have been performed to study the slow relaxation of the magnetization. A mean relaxation time has been found, and its temperature dependence has been studied. Above 1.4 K, both magnetic susceptibility and relaxation time are in agreement with the dynamics described in the 1960s by R. J. Glauber for one-dimensional systems with ferromagnetically coupled Ising spins (tau(0) = 3.7 x 10(-)(10) s and Delta(1)/k(B) = 31 K). As expected, at lower temperatures below 1.4 K, the relaxation process is dominated by the finite-size chain effects (tau'(0) = 3 x 10(-)(8) s and Delta(2)/k(B) = 25 K). The detailed analysis of this single-chain magnet behavior and its two regimes is consistent with magnetic parameters independently estimated (J'and D(T)) and allows the determination of the average chain length of 60 nm (or 44 trimer units). This work illustrates nicely a new strategy to design single-chain magnets by coupling ferromagnetically single-molecule magnets in one dimension.
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- 2005
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27. Linear NiII-MnIII2-NiII tetramers: an oligomeric component of the MnIII2NiII single-chain magnets.
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Miyasaka H, Nezu T, Sugimoto K, Sugiura K, Yamashita M, and Clérac R
- Subjects
- Models, Chemical, Temperature, Chelating Agents chemical synthesis, Chelating Agents chemistry, Magnetics, Manganese chemistry, Nickel chemistry, Organometallic Compounds chemical synthesis, Organometallic Compounds chemistry
- Abstract
Heterometallic linear tetramers [Mn(5-R-saltmen)Ni(pao)(bpy)(2)](2)(ClO(4))(4) (5-R-saltmen(2-) = N,N'-1,1,2,2-tetramethylethylene bis(5-R-salicylideneiminate); pao(-) = pyridine-2-aldoximate; bpy = 2,2'-bipyridine, R = H, 1; Cl, 2; Br, 3; MeO, 4) have been synthesized and structurally characterized. These compounds exhibit a [Ni(II)-NO-Mn(III)-(O)(2)-Mn(III)-ON-Ni(II)] skeleton where -ON- is an oximate bridge between Mn(III) and Ni(II) ions and -(O)(2)- is a bi-phenolate bridge between Mn(III) ions. These tetramers can be seen as oligomeric units of the heterometallic Mn(III)(2)-Ni(II) chain observed in a family of single-chain magnets (Clérac, R.; Miyasaka, H.; Yamashita, M.; Coulon, C. J. Am. Chem. Soc. 2002, 124, 12837. Miyasaka, H.; Clérac, R.; Mizushima, K.; Sugiura, K.; Yamashita, M.; Wernsdorfer, W.; Coulon, C. Inorg. Chem. 2003, 42, 8203.). Magnetic measurements on these tetramers confirm the nature of the magnetic interactions reported for the Mn(III)(2)-Ni(II) chains: a strong antiferromagnetic Mn(III)/Ni(II) coupling via the oximate bridge (J(Ni-Mn) ranges from -23.7 to -26.1 K) and a weak ferromagnetic Mn(III)/Mn(III) coupling through the bi-phenolate bridge (J(Mn-Mn) ranges from +0.4 to +0.9 K). These magnetic interactions lead to tetramers with an S = 2 ground state.
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- 2004
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28. [Mn2(saltmen)2Ni(pao)2(L)2](A)2 with L=pyridine, 4-picoline, 4-tert-butylpyridine, N-methylimidazole and A=ClO4-, BF4-, PF6-, ReO4-: a family of single-chain magnets.
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Miyasaka H, Clérac R, Mizushima K, Sugiura K, Yamashita M, Wernsdorfer W, and Coulon C
- Abstract
A series of single-chain magnets, [Mn2(saltmen)2Ni(pao)2(L)2](A)2 (saltmen(2-)=N,N'-(1,1,2,2-tetramethylethylene) bis(salicylideneiminate), pao-=pyridine-2-aldoximate; A-=ClO4- with L=4-picoline; 2, 4-tert-butylpyridine; 3, N-methylimidazole; 4, and L=pyridine with A-=BF4-; 5, PF6-; 6, ReO4-; 7), was prepared by reactions between MnIII dimer units, i.e., [Mn2(saltmen)2(H2O)2](A)2 (A-=ClO4-, BF4-, PF6-) or Mn2(saltmen)2(ReO4)2, and NiII monomeric units, i.e., Ni(pao)2(L)2, in methanol/water media. The crystal structures of 4, 6, and 7 were established by single-crystal X-ray crystallography. These three compounds are isostructural with [Mn2(saltmen)2Ni(pao)2(py)2](ClO4)2 (1) (Clérac, R.; Miyasaka, H.; Yamashita, M.; Coulon, C. J. Am. Chem. Soc. 2002, 124, 12837) and crystallize in monoclinic space group C2/c. The linear arrangement of MnIII dimer units and NiII building blocks leads to an alternating chain having a repeating unit, [-(O)2-Mn-ON-Ni-NO-Mn-]. The chains are well separated with the nearest interchain intermetallic distance of 10.36 A for 4, 10.51 A for 6, and 10.30 A for 7, and there is no significant pi-pi interchain interaction between ligands. The void space between the chains is occupied by counteranions, which control the three-dimensional organization of the chains. The X-ray diffraction analysis (XRD) on a powder sample was also performed for all compounds. The XRD patterns for 1, 2, and 4-7 are very similar, emphasizing the isostructural nature of these materials although they have individually slight different interchain distances. Inversely, the XRD pattern for 3 reveals a completely different shape being indicative of the peculiar crystal packing compared to the others. Nevertheless, the one-dimensional nature of the structure is also kept in 3 as indicated by magnetic measurements. The whole family of compounds exhibits quasi-identical magnetic behavior compared to that described for 1. Above 30 K, the heterometallic chain can be described as an assembly of antiferromagnetically coupled Mn...Ni....Mn trimers (via oximate bridge, -24.2 K
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- 2003
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29. A family of diruthenium compounds with dianionic tridentate ligands of N-(2-pyridyl)-2-oxy-5-R-benzylaminate (R = H, Me, Cl, Br, NO(2)): isolation, structure determination, and electrochemistry.
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Miyasaka H, Izawa T, Sugiura K, and Yamashita M
- Abstract
The ligand substitution reaction of Ru(2)(O(2)CCH(3))(4)Cl with 5-substituted N-(2-pyridyl)-2-oxy-5-R-benzylaminate (R = H, Me, Cl, Br, NO(2)) resulted in a family of anionic diruthenium species of [Ru(2)(O(2)CCH(3))(2)(R-salpy)(2)](-) that were isolated by using Na(+)- or K(+)-18-crown-6-ether as the countercation: [A(18-crown-6)(S)(x)()][Ru(2)(O(2)CCH(3))(2)(R-salpy)(2)] (A = Na(+), K(+); S = solvent; R = H, 1; Me, 2; Cl, 3; Br, 4; NO(2), 5). All compounds were structurally characterized by X-ray crystallography. The structural features of the anionic parts are very similar among the compounds: two acetate and two R-salpy(2)(-) ligands are, respectively, located around the Ru(2) unit in a trans fashion, where the R-salpy(2)(-) ligand acts as a tridentate ligand having both bridging and chelating characters to form the M-M bridging/axial-chelating mode. Compounds 1 and 5 with K(+)-18-crown-6-ether have one-dimensional chain structures, the K(+)-18-crown-6-ether interacting with phenolate oxygens of the [Ru(2)(O(2)CCH(3))(2)(R-salpy)(2)](-) unit to form a repeating unit, [.K.O-Ru-Ru-O.], whereas 2-4 are discrete. Cyclic voltammetry and differential pulse voltammetry revealed systematic redox activities based on the dimetal center and the substituted ligand, obeying the Hammett law with the reaction constants per substituent, rho, for the redox processes being 127 mV for Ru(2)(5+)/Ru(2)(4+), 185 mV for Ru(2)(6+)/Ru(2)(5+), 92 mV for Ru(2)(7+)/Ru(2)(6+), and 179 mV for R-salpy(-)/R-salpy(2)(-). For 3, the singly oxidized and reduced species, Ru(2)(6+) and Ru(2)(4+), respectively, generated by bulk controlled-potential electrolyses were finally monitored by spectroscopy. The singly oxidized species can also be slowly generated by air oxidation.
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- 2003
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30. Novel ET-coordinated copper(I) complexes: syntheses, structures, and physical properties (ET = BEDT-TTF = Bis(ethylenedithio)tetrathiafulvalene).
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Kanehama R, Umemiya M, Iwahori F, Miyasaka H, Sugiura K, Yamashita M, Yokochi Y, Ito H, Kuroda S, Kishida H, and Okamoto H
- Abstract
New molecular charge-transfer complexes of bis(ethylenedithio)tetrathiafulvalene (ET), (ET)Cu(2)Br(4) (1), (ET)(2)Cu(6)Br(10) (2), (ET)(2)[Cu(4)Br(6)ET] (3), (ET)(2)Cu(2)Br(4) (4), (ET)(2)Cu(3)Br(7)(H(2)O) (5), and (ET)(2)Cu(6)Br(10)(H(2)O)(2) (6), have been synthesized by diffusing reaction of ET and Cu(II)Br(2). Their crystal structures and physical properties have been investigated. X-ray analyses revealed that ET molecules coordinated to the copper ions with the sulfur atoms of the ethylenedithio groups in all compounds. The Cu-S distances are found in the range 2.268(5)-2.417(8) A, being close to the typical Cu(I)-S coordination bond distances. Strong d-pi interactions between d-electrons of the copper ions and pi-electrons of the ET molecules can be expected through the Cu-S coordination bonds. ET molecules behave as trans-bidentate ligands bonding to two different copper ions in 1 and 3, as cis-bidentate ligands in 2, 5, and 6, and as monodentate ligands in 4. In the crystal structure of 3, there are two types of ET molecules in the crystal structure, where the first type is a trans-bidentate ligand and the second forms a stacking structure by itself. Compounds 1, 2, 4, and 6 show semiconducting behavior down to low temperature (sigma(RT) = 1.6 x 10(-2) S cm(-1) and E(a) = 122 meV for 1, sigma(RT) = 2.1 S cm(-1) and E(a) = 21 meV for 2, sigma(RT) = 5.4 x 10(-4) S cm(-1) and E(a) = 239 meV for 4, and sigma(RT) = 5.1 x 10(-2) S cm(-1) and E(a) = 207 meV for 6). On the other hand, in 3, a metal-like region is observed along the b-axis and c-axis, due to the contribution of stacked ET molecules, and a metal-semiconductor transition occurs at 280 and 270 K, respectively. Also, 5 exhibits metallic conductivity in the temperature ranges 240-300 and 200-300 K along the b-axis and c-axis, respectively, despite the oxidation state of ET with 2+.
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- 2003
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31. Heterometallic hexanuclear cluster with an S = 8 spin ground state: MnII[MnII(hfac)2]3[NiII(pao)3]2 (hfac- = hexafluoroacetylacetonate, pao- = pyridine-2-aldoximate).
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Miyasaka H, Nezu T, Iwahori F, Furukawa S, Sugimoto K, Clérac R, Sugiura K, and Yamashita M
- Abstract
The heterometallic Mn(II)(4)Ni(II)(2) title compound has been synthesized and characterized by X-ray crystallography. The compound consists of a Ni-Mn-Ni linear moiety, [[Ni-(mu-NO)(3)](2)-Mn], linked by oximate bridges and three Mn(II) hfac terminal units attached by oximate oxygens in a di-mu-oxo fashion, forming a novel heterometallic cluster: Mn[Mn(hfac)(2)](3)[Ni(pao)(3)](2) (1). Magnetic measurements reveal the antiferromagnetic nature of the oximate pathway between Mn(II) and Ni(II) metal ions, which imposes an unusual high-spin ground state (S = 8) for 1.
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- 2003
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32. Structure and magnetic properties of the two-dimensional ferrimagnet (NEt4)[[Mn(salen)]2Fe(CN)6]: investigation of magnetic anisotropy on a single crystal.
- Author
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Miyasaka H, Ieda H, Matsumoto N, Sugiura K, and Yamashita M
- Abstract
The title compound, (NEt(4))[[Mn(salen)](2)Fe(CN)(6)] (1), was synthesized via a 1:1 reaction of [Mn(salen)(H(2)O)]ClO(4) with (NEt(4))(3)[Fe(CN)(6)] in a methanol/ethanol medium (NEt(4)(+) = tetraethylammonium cation, salen(2)(-) = N,N'-ethylenebis(salicylidene)iminate). The two-dimensional layered structure of 1 was revealed by X-ray crystallographic analysis: 1 crystallizes in monoclinic space group P2(1)/c with cell dimensions of a = 12.3660(8) A, b = 15.311(1) A, c = 12.918(1) A, beta = 110.971(4) degrees, Z = 2 and is isostructural to the previously synthesized compound, (NEt(4))[[Mn(5-Clsalen)](2)Fe(CN)(6)] (5-Clsalen(2-) = N,N'-ethylenebis(5-chlorosalicylidene)iminate; Miyasaka, H.; Matsumoto, N.; Re, N.; Gallo, E.; Floriani, C. Inorg. Chem. 1997, 36, 670). The Mn ion is surrounded by an equatorial salen quadridentate ligand and two axial nitrogen atoms from the [Fe(CN)(6)](3-) unit, the four Fe[bond]CN groups of which coordinate to the Mn ions of [Mn(salen)](+) units, forming a two-dimensional network having [[bond]Mn[bond]NC[bond]Fe[bond]CN[bond]](4) cyclic repeating units. The network is spread over the bc-plane of the unit cell, and the layers are stacked along the a-axis. The countercation NEt(4)(+) is located between the layers. Compound 1 is a ferrimagnet with T(c) = 7.7 K and exhibits hysteresis with a remnant magnetization of 13.44 cm(3).mol(-1) (M/N mu(B) = 2.4) at zero field and a coercivity of 1000 Oe when the powder sample was measured at 1.9 K. Magnetic measurements of a direction-arranged single crystal were also carried out. The orientation of the crystallographic axes of a selected single crystal was determined by X-ray analysis, and magnetization was measured when an external field was applied in the a*, b, and c directions. The magnetization in the a* direction increased more easily than those in the b and c directions below the critical temperature. No hysteresis was observed only for the measurement in the a* direction, indicating the presence of strong structural anisotropy with potential anisotropy on Mn(III) ions.
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- 2003
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33. Tuning of spin density wave strengths in quasi-one-dimensional mixed-halogen-bridged nickel(III) complexes with strong electron correlation, [Ni(III)(chxn)(2)Cl(1-x)Br(x)](NO(3))(2).
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Manabe T, Yokoyama K, Furukawa S, Kachi-Terajima C, Nakata K, Iwahori F, Miyasaka H, Sugiura K, Yamashita M, Kishida H, and Okamoto H
- Abstract
This communication describes the syntheses of the quasi-one-dimensional mixed-halogen-bridged Ni(III) complexes with strong electron correlation [Ni(chxn)(2)Cl(1-x)Br(x)](NO(3))(2) and the tuning of the spin density wave strengths of these compounds. If the Cl 3p and Br 4p make one band in the compounds, we should observe a single peak in the electronic spectra. As a result, we should observe the single peak from 1.45 to 2.00 eV depending on the mixing ratios of Cl and Br ions. Therefore, the Cl 3p and Br 4p make one band. Then, we have succeeded in tuning the spin density wave strengths of the Ni(III) complexes with the strong electron correlation by mixing the bridging halogen ions successively.
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- 2002
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34. Tuning of electronic structures of quasi-one-dimensional bromo-bridged Ni(III) complexes with strong electron-correlation by doping of Co(III) ions, [Ni(1-x)Co(x)(Chxn)(2)Br]Br(2).
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Yamashita M, Yokoyama K, Furukawa S, Manabe T, Ono T, Nakata K, Kachi-Terajima C, Iwahori F, Ishii T, Miyasaka H, Sugiura K, Matsuzaki H, Kishida H, Okamoto H, Tanaka H, Hasegawa Y, Marumoto K, Ito H, and Kuroda S
- Abstract
We have succeeded in synthesizing the Ni(III) complexes doped by Co(III) ions, [Ni(1-x)Co(x)(chxn)(2)Br]Br(2) (x = 0, 0.043, 0.093, and 0.118) by using an electrochemical oxidation method. The single-crystal reflectance spectrum of x = 0.118 shows an intense CT band about 0.5 eV, which is lower than that of [Ni(chxn)(2)Br]Br(2) (1.3 eV). The single-crystal electrical conductivities at room temperature of these compounds increase with increase of the amounts of doping of Co(III) ions. In the ESR spectra, peak-to-peak line widths DeltaH(pp) at room temperature change about 600 G in [Ni(chxn)(2)Br]Br(2) to 200 G in x = 0.118. Such a large x dependence of DeltaH(pp) seems to be ascribed to the increasing contribution from the increasing Curie spins which have smaller line width. Therefore, we have tuned the electronic structures of quasi-one-dimensional bromo-bridged Ni(III) complexes with strong electron correlations by doping of Co(III) ions.
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- 2002
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35. Bis(phthalocyaninato)gadolinium(III) hexacyanobutadienide(1-), [GdPc2]+[C4(CN)6]-. An electron transfer salt with four paramagnetic sites.
- Author
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Rittenberg DK, Sugiura K, Sakata Y, Arif AM, and Miller JS
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- 2001
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36. Solvent dependence of the structure and magnetic ordering of ferrimagnetic manganese(III) meso-tetraphenylporphyrin tetracyanoethenide, [MnTPP]+[TCNE]*-.
- Author
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Hibbs W, Rittenberg DK, Sugiura K, Burkhart BM, Morin BG, Arif AM, Liable-Sands L, Rheingold AL, Sundaralingam M, Epstein AJ, and Miller JS
- Abstract
Tetraphenylporphinatomanganate(III) tetracyanoethenide, [MnTPP][TCNE], is the prototype of a growing family of linear chain (1-D) coordination polymers that magnetically order as ferrimagnets. [MnTPP][TCNE].xS [S = PhMe (x = 2), 1,2-C(6)H(4)Me(2) (x = 1), 1,2-C(6)H(4)Cl(2) (x = 3), 1,2,4-C(6)H(3)Cl(3) (x = 2), and 1,3-C(6)H(4)Cl(2) (x = 2)] have been prepared and structurally and magnetically characterized. All form 1-D chain structures with intrachain Mn.Mn separations ranging from 9.202 to 10.218 A. The 173 K crystal structure of [MnTPP][TCNE].2PhMe has been rerefined, revealing that the [TCNE](*)(-) is 2-fold-disordered and coordinated to Mn(III) by a pair of trans cyano nitrogen atoms to form parallel one-dimensional chains. The two orientations of [TCNE](*)(-) are related by a 180 degrees rotation about the diagonal axis joining the trans nitrogen atoms bound to Mn(III). The major form has an occupancy of 83.3(4)% with a Mn-N(TCNE) distance of 2.328(3) A and a MnNC angle of 146.8(8) degrees. The minor form, with 16.7(4)% occupancy, has a Mn-N(TCNE) distance of 2.176(15) A and a MnNC angle of 152.3(39) degrees. Lattice packing and molecular bonding imply static as opposed to dynamic disorder. The magnetic properties depend on the type and quantity of the solvent present in the structure. Desolvation via heating in n-octane (127 degrees C), n-dodecane (216 degrees C), and/or vacuum thermolysis (175 degrees C) leads to numerous different desolvated materials with differing magnetic properties. At higher temperatures the magnetic susceptibility can be fit by the Curie-Weiss expression, chi varies with (T - theta)(-1), with theta = 44, 52, 72, 55, and 77 K for the toluene, 1,2-xylene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, and 1,2,4-trichlorobenzene solvates, respectively. The T(c)'s were taken as the maximum in 10 Hz chi'(T) and are 7.8, 9.2, 11.3, 10.8, and 8.2 K for the PhMe, 1,2-xylene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, and 1,2,4-trichlorobenzene solvates, respectively. Upon desolvation the T(c)'s increase for the PhMe, 1,2-xylene, 1,2,4-trichlorobenzene solvates and decrease for the 1,2- and 1,3-dichlorobenezene solvates. The compounds show one-dimensional ferrimagnetic exchange behavior at high temperatures with intrachain exchange of J/k(b) = -63, -99, -234, -100, and -200 K for toluene, 1,2-xylene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, and 1,2,4-trichlorobenzene solvates, respectively, as determined from fits to the Seiden expression, which models isolated 1-D interactions among alternating S = 2 classical and S = (1)/(2) quantum spins. For variation in the temperature at which the peak occurs per decade of frequency, phi, (DeltaT(f)/T(f))/Delta(log omega) is 0.167, 0.168, 0.066, 0.171, and 0.024 for toluene, 1,2-xylene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, and 1,2,4-trichlorobenzene, respectively, typical of spin glass behavior. Since [TCNE](*)(-) is only disordered for the PhMe solvate and all five solvates exhibit spin glass behavior, the spin glass behavior cannot be attributed to this disorder.
- Published
- 2001
- Full Text
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37. Inverted meso-aryl porphyrins with heteroatoms; characterization of thia, selena, and oxa N-confused porphyrins.
- Author
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Pushpan SK, Srinivasan A, Anand VR, Chandrashekar TK, Subramanian A, Roy R, Sugiura K, and Sakata Y
- Abstract
Synthesis and characterization of inverted porphyrins containing S, Se, and O are reported. A simple 3 + 1 MacDonald-type condensation using modified tripyrrane containing the N-confused ring and diols afforded various N-confused porphyrins 6a-f in 19-30% yield. The single-crystal X-ray structure of 6b shows a ruffled conformation with tilt angles of 21.11 degrees and 31.23 degrees for the N-confused ring and the adjacent pyrrole ring III, respectively, revealing its severe nonplanarity. Significant changes in C alpha-C beta, C beta-C beta, and C alpha-X bond lengths are observed in 6b relative to free thiophene and pyrrole, suggesting the altered delocalization pathway in the modified N-confused porphyrins. The two molecules in the unit cell show a cyclophane-type noncovalent dimer with a face to face orientation of two N-confused pyrrole rings as a result of the presence of weak N-H...N and C-H...N intermolecular hydrogen bonds involving pyrrole-NH, the N atom of the N-confused ring, and the C atom of the pyrrole ring. A detailed 1H and 13C NMR study by 1D and 2D methods allowed assignments of all the peaks in the free base and protonated forms. NMR studies reveal the presence of three different tautomeric forms in solution for 6c in CDCl3 at low temperature. UV-visible studies reveal absorption band shifts upon heteroatom substitution, and the magnitudes of these shifts are dependent on the nature of the heteroatom. In all cases both monoprotonated and diprotonated species have been identified, and on addition of acid, the first proton goes to the outer N2 atom of the N-confused ring.
- Published
- 2001
- Full Text
- View/download PDF
38. M+(12-crown-4) supramolecular cations (M+ = Na+, K+, Rb+, and NH4+) within Ni(2-thioxo-1,3-dithiole-4,5-dithiolate)2 molecular conductor.
- Author
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Akutagawa T, Hasegawa T, Nakamura T, Takeda S, Inabe T, Sugiura K, Sakata Y, and Underhill AE
- Abstract
Monovalent cations (M+ = Na+, K+, Rb+, and NH4+) and 12-crown-4 were assembled to new supramolecular cation (SC+) structures of the M+(12-crown-4)n (n = 1 and 2), which were incorporated into the electrically conducting Ni(dmit)2 salts (dmit = 2-thioxo-1,3-dithiole-4,5-dithiolate). The Na+, K+, and Rb+ salts are isostructural with a stoichiometry of the M+(12-crown-4)2[Ni(dmit)2]4, while the NH4+ salt has a stoichiometry of NH4+(12-crown-4)[Ni(dmit)2]3(CH3CN)2. The electrical conductivities of the Na+, K+, Rb+, and NH4+ salts at room temperature are 7.87, 4.46, 0.78, and 0.14 S cm-1, respectively, with a semiconducting temperature dependence. The SC+ structures of the Na+, K+, and Rb+ salts have an ion-capturing sandwich-type cavity of M+(12-crown-4)2, in which the M+ ion is coordinated by eight oxygen atoms of the two 12-crown-4 molecules. On the other hand, the NH4+ ion is coordinated by four oxygen atoms of the 12-crown-4 molecule. Judging from the M(+)-O distances, thermal parameters of oxygen atoms, and vibration spectra, the thermal fluctuation of the Na+(12-crown-4)2 structure is larger than those of K+(12-crown-4)2 and Rb+(12-crown-4)2. The SC+ unit with the larger alkali metal cation gave a stress to the Ni(dmit)2 column, and the SC+ structure changed the pi-pi overlap mode and electrically conducting behavior.
- Published
- 2000
- Full Text
- View/download PDF
39. A NITROGEN MUSTARD DERIVATIVE OF 6-MERCAPTOPURINE.
- Author
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LEVIN G, SUGIURA K, and BROWN GB
- Subjects
- Animals, Cricetinae, Mice, Rats, Chemistry, Pharmaceutical, Mechlorethamine, Mercaptopurine, Neoplasms, Neoplasms, Experimental, Nitrogen Mustard Compounds, Pharmacology, Research
- Published
- 1964
- Full Text
- View/download PDF
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