Authorship：Last author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：Springer Nature  

DOI： 10.1038/s42004-021-00601-3

Language：English   Publishing type：Research paper (scientific journal)   Publisher：MDPI  

DOI： 10.3390/s21238033

Authorship：Last author   Language：English   Publishing type：Research paper (scientific journal)  

DOI： 10.1039/d1ra01743h

Authorship：Lead author,　Corresponding author   Language：English   Publishing type：Research paper (scientific journal)  

DOI： 10.1016/j.eurpolymj.2021.110325

Authorship：Last author   Language：English   Publishing type：Research paper (scientific journal)  

DOI： 10.1039/c9nj06394c

Authorship：Lead author,　Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：Elsevier Ltd.  

DOI： 10.1016/j.polymer.2020.122281

Authorship：Last author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：Royal Society of Chemistry  

<p>First observation of white fluorescence using a single fluorescent urea derivative and fluoride.</p>

DOI： 10.1039/c8nj05105d

Language：English   Publishing type：Research paper (scientific journal)   Publisher：Elsevier  

The synthesis and characterization of a ‘complete set’ of positional isomers of tetrakis(perfluorophenyl)porphyrins (TFPP)-glucose conjugates (1OH, 2OH, 3OH, 4OH, and 6OH) are reported herein. The cellular uptake and photocytotoxicity of these conjugates were examined in order to investigate the influence of location of the TFPP moiety on the D-glucose molecule on the biological activity of the conjugates. An In vitro biological evaluation revealed that the certain of these isomers have a greater effect on cellular uptake and cytotoxicity than others. The TFPP-glucose conjugates 1OH, 3OH, and 4OH were found to exert exceptional photocytotoxicity in several types of cancer cells compared to 2OH and 6OH substituted isomers.

DOI： 10.1016/j.bmc.2018.02.031

Scopus

Authorship：Last author   Language：Japanese   Publishing type：(MISC) Introduction and explanation (scientific journal)  

Authorship：Lead author,　Corresponding author   Language：Japanese   Publishing type：(MISC) Introduction and explanation (scientific journal)  

Language：English   Publishing type：Research paper (scientific journal)  

Language：Japanese   Publishing type：Research paper (scientific journal)   Publisher：ポルフィリン-ALA学会  

Authorship：Lead author,　Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：Wiley  

A series of polystyrene-block-poly(polyethylene glycol monomethyl ether acrylate) (PStm-b-PPEGAn) polymers were systematically synthesized as carriers for zinc phthalocyanine (ZnPc) for photodynamic therapy via reversible addition and fragmentation chain transfer polymerization. The degree of polymerization of the styrene (m) and PEGA units (n) of the resulting block copolymers were characterized to be n = 174, 40, and 18 for m = 52
and n = 200, 84, and 31 for m = 30. All the block copolymers formed micelles in water. The critical micelle concentration (CMC) of the PStm-b-PPEGAn was determined by fluorometry using pyrene as a hydrophobic probe. The CMC value increased from 4.5 to 20 mg·L−1 with an increase in the mole fraction of PEGA units. The median diameters of the micelles increased from 19 to 31 nm for PSt52-b-PPEGAn and from 15 to 23 nm for PSt30-b-PPEGAn with increasing n value. ZnPc-loaded micelles were prepared by dialysis of the block copolymer in the presence of ZnPc followed by removal of large aggregates by filtration. The encapsulation efficiency was dramatically changed in the range of 0–68%. The light-dose-dependent cytotoxicity of the ZnPc-loaded PSt30-b-PPEGA200 was clearly established in HeLa cell lines
while no cytotoxicity was confirmed under the dark. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 560–570.

DOI： 10.1002/pola.28929

Scopus

Authorship：Lead author,　Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：Wiley  

Authorship：Lead author,　Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：Wiley  

The block glycopolymer, poly(2-(alpha-D-mannopyranosyloxy) ethyl methacrylate)-b-poly(L-lactide) (PManEMA-b-PLLA), was synthesized via a coupling approach. PLLA having an ethynyl group was successfully synthesized via ring-opening polymerization using 2-propyn-1-ol as an initiator. The ethynyl functionality of the resulting polymer was confirmed by MALDI-TOF mass spectroscopy. In contrast, PManEMA having an azide group was prepared via AGET ATRP using 2-azidopropyl 2-bromo-2-methylpropanoate as an initiator. The azide functionality of the resulting polymer was confirmed by IR spectroscopy. The Cu(I)-catalyzed 1,3-dipolar cycloaddition between PLLA and PManEMA was performed to afford PManEMA-b-PLLA. The block structure was confirmed by H-1 NMR spectroscopy and size exclusion chromatography. The aggregating properties of the block glycopolymer, PManEMA(16k)-b-PLLA(6.4k) = (M-n,M-PManEMA = 16,000, M-n,M-PLLA = 6400) was examined by H-1 NMR spectroscopy, fluorometry using pyrene, and dynamic light scattering. The block glycopolymer formed complicated aggregates at concentrations above 21 mg.L-1 in water. The D-mannose presenting property of the aggregates was also characterized by turbidimetric assay using concanavalin A. (C) 2016 Wiley Periodicals, Inc.

DOI： 10.1002/pola.28401

Web of Science

Authorship：Lead author,　Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：Elsevier  

Porphyrin derivatives for photodynamic therapy are frequently modified with hydrophilic groups to improve their water solubility; however, such hydrophilic groups not only improve the solubility but also affect the photodynamic behavior of the compound. The suitable number and pattern of the hydrophilic substituents depend on the nature of the hydrophilic groups. In this article, we explore the optimum architecture for 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin (TFPP) derivatives bearing 2-hydroxyethylthio substituents. All five derivatives, namely mono-, cis-bis-, trans-bis-, tris- and tetrakis-substituted TFPP, were successfully synthesized by the nucleophilic aromatic substitution of TFPP with 2-hydroxyethanethiol, separated, and subsequently identified using ESI-TOF mass spectrometry and H-1 and F-19 NMR spectroscopies. The hydrophilicity of the compounds increased with an increase in the number of 2-hydroxyethylthio groups. The singlet oxygen and hydroxyl radical generation efficiencies were estimated using chemical probes following photoirradiation (lambda &gt; 500 nm). trans-Bissubstituted TFPP exhibited the highest efficiency for both singlet oxygen and hydroxyl radical generation. The photocytotoxicities of the photosensitizers were evaluated in HeLa cells following photoirradiation (lambda &gt; 500 nm, 16 J cm(-2)), and increased with an increase in number of 2-hydroxyethylthio groups. In the case of 2-hydroxyethylthio-substituted TFPPs, the fully substituted TFPP was the most efficient architecture plausibly because of the result of the hydrophilicity of the compound rather than a greater efficiency in the generation of reactive oxygen species. (C) 2016 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.jphotobiol.2016.07.006

Web of Science

Authorship：Lead author,　Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-BLACKWELL  

Copolymers of 1,1,1,3,3,3-hexafluoroisopropyl methacrylate (HFIPM) and tert-butyl methacrylate (TBM) were prepared by conventional radical copolymerization as a novel binders for pressure-sensitive paints (PSP). The monomer reactivity ratios r(HFIPM) and r(TBM) were determined as 0.45 and 0.67, respectively. The glass transition temperature of the copolymers increased from 77 to 126 degrees C with increasing mole fraction of TBM units in the copolymer. The PSP were formed by combining the resulting copolymers and 5,10,15,20-tetrakis(pentafluorophenyl)porphinato platinum(II). The pressure and temperature sensitivities of the PSPs were measured at air pressures ranging from 5 to 120 kPa and at temperatures ranging from 0 to 60 degrees C. Modified Stern-Volmer plots indicated slight increases in the pressure sensitivity, but significant decrease in the temperature sensitivity as the mole fraction of HFIPM units increased in the copolymer. Applying a theoretical model to our calibration data, we inferred that luminescence quenching is primarily responsible for increasing the temperature sensitivity in the resulting copolymers. (c) 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43316.

DOI： 10.1002/APP.43316

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Language：English  

Authorship：Lead author,　Corresponding author   Language：English  

Language：English  

Language：Japanese  

Authorship：Lead author,　Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-BLACKWELL  

Three CF3-substituted methyl methacrylates (MMAs), 2,2,2-trifluoroethyl methacrylate (TFEMA), 1,1,1,3,3,3-hexafluoroisopropyl methacrylate (HFIPMA) and nonafluoro-tert-butyl methacrylate (NFTBMA), were polymerized by conventional radical polymerization to give oxygen-permeable polymers for application in pressure-sensitive paint (PSP). The radical copolymerizations of styrene with TFEMA, HFIPMA, or NFTBMA were carried out to examine the effect of CF3 groups on the polymerizability. The e values increased in the order of MMA (0.40) &lt; TFEMA (0.76) &lt; HFIPMA (1.19) &lt; NFTBMA (1.31). The homopolymers of TFEMA, HFIPMA and NFTBMA (PTFEMA, PHFIPMA, and PNFTBM, respectively) were examined as polymers for use in PSP using 5,10,15,20-tetrakis(pentafluorophenyl)porphinato platinum(II) (PtTFPP). The PSP consisting of PNFTBMA and PtTFPP exerted very high pressure sensitivity and very low temperature sensitivity. In the absence of oxygen, the temperature sensitivity decreased in the order of PTFEMA &gt; PHFIPMA &gt; PNFTBMA = PMMA, which corresponds to the order of glass transition temperatures (T-g). However, the activation energies of the overall process of the luminescence quenching by oxygen were found to be 16.8 (PMMA), 13.0 (PTFEMA), 6.8 (PHFIPMA), and 4.3 kJ mol(-1) (PNFTBMA). Therefore, the low temperature sensitivity of PNFTBMA was attributed to its high degree of substitution with CF3 groups and to its relatively high T-g value. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 963-972

DOI： 10.1002/pola.27076

Web of Science

Language：Japanese   Publishing type：Research paper (scientific journal)  

Language：Japanese   Publishing type：Research paper (scientific journal)  

Language：Japanese  

Authorship：Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：CHEMICAL SOC JAPAN  

To examine the versatility of the trans-bisglycoconjugation architecture for 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin (TFPP) derivative-based photodynamic therapy (PDT), 25 porphyrin derivatives bearing D-glucopyranose moieties were prepared, and their in vitro photocytotoxicities were examined. trans-Bisglycoconjugated TFPP derivatives exerted the best photocytotoxicity among TFPP derivatives in the same category, regardless of the central metal ion and the type of glycoconjugation. trans-Bisglycoconjugated free-base TFPP bearing beta-D-glucopyranosylthio groups (trans-H(2)2(SG1c)) was found to be the most potent photosensitizer, not only in HeLa cells (EC50 < 5 nM), but also in highly metastatic cancer cell lines such as B16-BL6 melanoma cells (EC50 < 10 nM). UV vis and dynamic light-scattering measurements suggested that trans-bisglycoconjugated TFPP derivatives formed relatively large I-aggregates in an aqueous solution. trans-Bisglycoconjugated TFPP derivatives exhibited greater uptake by HeLa cells than those with different glycoconjugation patterns, with the exception of Zn(II) complexes. trans-Bisglycoconjugated TFPP derivatives efficiently generated hydrogen peroxide and hydroxyl radical by a type I photoreaction, while no significant differences were found in the efficiency of singlet oxygen generation by a type II photoreaction. These unique characteristics of transbisglyeoconjugated TFPP derivatives support the conclusion that trans-bisglycoconjugation is a highly efficient and robust architecture for TFPP-based PDT development.

DOI： 10.1246/bcsj.20130131

Web of Science

Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE SA  

Two new trinuclear Mn complexes containing naphthalene moieties, [Mn-3(mu(3)-O)(mu-O2CCH2-1-naph)(6) (py)(3)] (1) and [Mn-3(mu(3)-O)(mu-O2CCH2-2-naph)(6)(py)(3)] (2) (naph-1-CH2CO2H = 1-naphthylacetic acid, naph-2-CH2CO2H = 2-naphthylacetic acid, py = pyridine), were synthesized. The X-ray crystallography of 1, the EXAFS analyses of 1 and 2, and the magnetic susceptibility data for these complexes showed that they are trinuclear complexes containing a [Mn-3(mu(3)-O)(mu-O2CR)(6)] core with mixed-valence Mn-3(II, III, III) centers. CVs exhibited an oxidation peak ascribed to Mn-3(III)/(MnMn2III)-Mn-II and a reduction peak ascribed to (MnMn2III)-Mn-II/(Mn2MnIII)-Mn-II in CH2Cl2. In the fluorescence spectra, the fluorescence intensities of 1 and 2 were smaller than those of the naphthylacetic acids and depended on the dielectric constant of solvent. These results suggested that there is electron transfer between the manganese centers and the naphthyl moieties. The fluorescence decays of 1 and 2 in CH3CN were also faster than the decays in the toluene solutions; this result parallels the lower intensity of the static fluorescence spectra in solvents with a higher dielectric constant. The fluorescence decay curves of 1 and 2 were fitted by two lifetimes, tau(1) and tau(2), suggesting that electron transfer occurs from the monomer (tau(1)) and the excimer (tau(2)) of the naphthyl moieties to the manganese center. Crown Copyright (C) 2013 Published by Elsevier B.V. All rights reserved.

DOI： 10.1016/j.ica.2013.07.011

Web of Science

Authorship：Lead author,　Corresponding author   Language：Japanese  

Language：Japanese   Publishing type：Research paper (scientific journal)  

Other Link： http://search.jamas.or.jp/link/ui/2014236657

Authorship：Lead author,　Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-BLACKWELL  

In this article, we offer clear evidence for the radical copolymerizability of porphyrin rings in 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO)-mediated radical copolymerizations with styrene. The radical copolymerizations of styrene with 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin (H2TFPP) was conducted using 1-phenyl-1-(2,2,6,6-tetramethyl-1-piperidinyloxy)ethane as an initiator. The refractive index (RI) traces for the size-exclusion chromatography of the resulting copolymers were unimodal with narrow molecular weight distributions. The RI traces shifted toward higher molecular weight regions as the polymerization progressed, and the number-average molecular weights were close to those calculated on the basis of the feed compositions and monomer conversions. These features were in good agreement with a TEMPO-mediated mechanism. The traces recorded by the ultraviolet-visible (UV-vis) detector (430 nm) were identical to those obtained by the RI detector, indicating a statistical copolymerization of styrene with H2TFPP. This also indicated that H2TFPP acted as a monomer and not as a terminator or a chain-transfer agent under the conditions used. A benzyl radical addition to H2TFPP was conducted as a model reaction for the copolymerization using tributyltin hydride as a chain-transfer agent, affording a reduced porphyrin, 2-benzyl-5,10,15,20-tetrakis(pentafluorophenyl)chlorin 1, via radical addition to the beta-pyrrole position. The UV-vis spectrum of 1 was fairly similar to that of poly(styrene-co-H2TFPP), indicating that H2TFPP polymerized at its beta-pyrrole position in the TEMPO-mediated radical polymerization. TEMPO-mediated radical copolymerizations of styrene with several porphyrin derivatives were also demonstrated. (c) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012

DOI： 10.1002/pola.26147

Web of Science

Authorship：Lead author,　Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCI LTD  

Radical copolymerizations of 2-(alpha-D-mannopyranosyloxy)ethyl methacrylate (ManEMA) with 2-dimethylaminoethyl methacrylate (DMAEMA) were carried out in N,N-dimethylformamide (DMF) containing 10 vol% water at 60 degrees C to yield cationic glycopolymers. The number-average molecular weights (M(n)s, standard Pullulan calibration) and polydispersities (M-w/M(n)s) of the resulting copolymers were ranged from 17,400 to 41,700 and from 1.7 to 3.2, respectively. The compositions of the resulting copolymers were very close to those in the feed. The monomer reactivity ratios r(ManEMA) and r(DMAEMA) were 0.98 and 1.22, respectively. The lectin-binding properties of poly(ManEMA-co-DMAEMA) to concanavalin A (ConA) was examined using a turbidimetric assay. The clustering rate increased with increasing mole fractions of the ManEMA units in the copolymer (F-ManEMA), even under a constant concentration of the ManEMA units (50 mu M), indicating the typical cluster glycoside effect. The DNA-condensing ability of the resulting copolymers was examined by a gel retardation assay using pEGFP-N1 plasmid (4.7 kbp). Though the ManEMA units interfered with the complexation of the copolymer with the plasmid DNA, complete retardation was observed under the condition of lower contents of ManEMA units (F-ManEMA &lt; 0.2) in pure water. These findings indicate that poly(ManEMA-co-DMAEMA) is a cationic glycopolymer exerting lectin-binding and DNA-condensing abilities. (C) 2012 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.Polymer.2012.08.031

Web of Science

Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-V C H VERLAG GMBH  

Four platinum(II) and palladium(II) complexes with sugar-conjugated bipyridine-type triazole ligands, [PtIICl2(AcGlc-pyta)] (3), [PdIICl2(AcGlc-pyta)] (4), [PtIICl2(Glc-pyta)] (5), and [PdIICl2(Glc-pyta)] (6), were prepared and characterized by mass spectrometry, elemental analysis, 1H- and 13C-NMR, IR as well as UV/VIS spectroscopy, where AcGlc-pyta and Glc-pyta denote 2-[4-(pyridin-2-yl)-1H-1,2,3-triazol-1-yl]ethyl 2,3,4,6-tetra-O-acetyl-beta-D-glucopyranoside (1) and 2-[4-(pyridin-2-yl)-1H-1,2,3-triazol-1-yl]ethyl beta-D-glucopyranoside (2), respectively. The solid-state structure of complex 6 was determined by single-crystal X-ray-diffraction analysis. These complexes exhibited in vitro cytotoxicity against human cervix tumor cells (HeLa) though weaker than that of cisplatin.

DOI： 10.1002/cbdv.201100426

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Authorship：Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

Palladium(II) complexes of glycoconjugated porphyrin and pyrrolidine-fused chlorin were prepared to examine sugar and heavy atom effects on in vitro photocytotoxicity. Cellular uptake into HeLa cells was enhanced by introducing sugar units regardless of other features, such as the central ion (free base or palladium(II) ion) and the ring structure (porphyrin or chlorin). The palladium(II) complex of glycoconjugated pyrrolicline-fused chlorin (PdPC2) exerted an excellent degree of photocytotoxicity not only on HeLa cells, but also on metastatic B16-BL6 cells, weakly metastatic B16F1 cells, and metastatic 4T1 cells. However, free-base glycoconjugated pyrrolidine-fused chlorin (PC2) also exerted similar or much higher photocytotoxicity rather than PdPC2. Therefore, the palladium(II) ion did not improve the in vitro photocytotoxicity of PC2. The enhanced singlet oxygen generation of palladium(II) complexes (i.e., the heavy atom effect) was confirmed at least in O-2-saturated D2O. In addition, the formation of hydrogen peroxide and hydroxyl radical were also detected in O-2-saturated phosphate buffered saline. However, the reactive oxygen species (ROS) generation efficiency, which is the product of the (relative) quantum yield of each ROS and the light absorbing ability, did not fit the trends of photocytotoxicity seen for the photosensitizers. In our glycoconjugated photosensitizers tested, the best indicator of the photocytotoxicity was found to be the light absorbing ability (namely, the oscillator strength in the wavelength region applied in the photocytotoxicity test). These results indicated that photochemical characteristics of glycoconjugated photosensitizers were notably susceptible to the rnicroenvironment. The biological characteristics, such as the sugar effect, were a much more reliable approach to improving the photocytotoxicity of photosensitizers.

DOI： 10.1021/bc300223j

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Language：English  

Authorship：Lead author,　Corresponding author   Language：English  

Authorship：Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-BLACKWELL  

Metal template synthesis is a useful methodology to make sophisticated macromolecular architectures because of the variety of metal ion coordination. To use metal template methodology, chelating functionalities should be introduced to macromolecules before complexation. In this article, we demonstrate the click-to-chelate approach to install chelating functionality to polystyrene (PS) and complexation with Ru(II) ions to form 3-arm and 4-arm star-branched PS Ru(II) complexes. Azide-terminated PS (PS-N-3) was readily prepared by atom transfer radical polymerization using 1-bromoethylbenzene as an initiator followed by substitution of bromine by an azide group. The Cu(I)-catalyzed 1,3-dipolar cycloaddition of PS-N-3 with 2-ethynylpyridine or 2,6-diethynylpyridine affords 2-(1H-1,2,3-triazol-4-yl)pyridine (PS-tapy) or 2,6-bis(1H-1,2,3-triazol-4-yl)pyridine (PS-bitapy) ligands bearing one or two PS chains at the first-position of the triazole rings. Ru(II) complexes of PS-tapy and PS-bitapy were prepared by conventional procedure. The number-averaged molecular weights (M(n)s) of these complexes were determined to be 6740 and 10,400, respectively, by size exclusion chromatography using PS standards. These M-n values indicated the formation of 3-arm and 4-arm star-branched PS Ru(II) complexes [Ru(PS-tapy)(3)](PF6)(2) and [Ru(PS-bitapy)(2)](PF6)(2) on the basis of the M-n values of PS-tapy (2090) and PS-bitapy (4970). The structures of these complexes were also confirmed by UV-vis spectroscopy and X-ray crystallography of the Ru(II) complexes [Ru(Bn-tapy)(3)](PF6)(2) and [Ru(Bn-bitapy)(2)](PF6)(2), which bear a benzyl group instead of a PS chain. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 746-753, 2011

DOI： 10.1002/pola.24487

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Language：English  

Authorship：Lead author,　Corresponding author   Language：English  

Language：English   Publishing type：Research paper (scientific journal)   Publisher：PERGAMON-ELSEVIER SCIENCE LTD  

In order to explore the effect of substitution patterns on the photocytotoxicity of glycoconjugated porphyrins, we synthesized and characterized a &apos;complete set&apos; of tetrakis(perfluorophenyl) porphyrins having beta-D-glucopyranosylthio groups on the phenyl ring. Among five possible derivatives, trans-substituted S-glucosylated porphyrin trans-2(OH) exerted outstanding photocytotoxicity (EC(50) value was &lt; 5 nM) in HeLa cells. The excellent photocytotoxicity of trans-2(OH) was found to be attributable to several factors, namely high optical transition probability in aqueous media, efficient type I photoreactions and enhanced cellular uptake. (C) 2010 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.bmc.2010.01.006

Web of Science

Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-V C H VERLAG GMBH  

Cisplatin analogue complexes with platinum(II) and palladium(II) starting from 3&apos;,5&apos;-diamino-3&apos;,5&apos;-dideoxy-thymidines were synthesized, both with the D-erythro- and D-threo configurations. Complexes of the general formula [MCl(2)L] were obtained and characterized. NMR spectroscopic measurements and single crystal X-ray structure analysis showed that the metal centers are coordinated to the ligands by the amino groups in 3&apos;- and 5&apos;-positions and not through the thymine moiety. All ligands and complexes showed no significant in vitro activities except thymiplatin (cis-dichloro(3&apos;,5&apos;-diamino-3&apos;,5&apos;-dideoxy-D-threo-thymidine)platinum(11)). Detailed in vitro studies on the apoptosis pathway in lymphoma (BJAB), leukemia (NALM-6), and melanoma cells (Mel-HO) as well as on transfected or resistant cell lines were carried out. Thymiplatin significantly induced an apoptotic response, which was found to be associated with the loss of mitochondrial membrane potential and with caspase activation. The activity was shown to be independent of Fas-associated protein with death domain (FADD), but dependent on Bcl-2 expression. As a consequence, for thymiplatin a mitochondrial mode of action could be assigned. Moreover, the compound showed activity in cells resistant to common drugs, such as daunorubicin and vincristin, and showed synergistic effects with doxorubicin, vincristin, cytarabin, and daunorubicin.

DOI： 10.1002/chem.201000785

Web of Science

Authorship：Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE SA  

Eight S-glycosylated 5,10,15,20-tetrakis(tetrafluorophenyl)porphyrins (1a&apos;, 1b&apos;, la and 11b (a: S-glucosylated, b: S-galactosylated)) and their 1,3-dipolar cycloadducts, i.e. chlorins 2a&apos;, 2b&apos;, 2a and 2b were prepared by nucleophilic substitution of the pentafluorophenyl groups with S-glycoside. These photosensitizers were characterized by (1)H, (13)C and (91)F NMR spectroscopies and elemental analysis. The photocytotoxicity of the S-glycosylated photosensitizers and the parent porphyrin (1) and chlorin (2) was examined in HeLa cells. Photosensitizers 1, 2, 1a&apos;, 1b&apos;, 2a, and 2b, showed no significant photocytotoxicity at the concentration of 0.5 mu M, while the deprotected photosensitizers la, 1b, 2a and 2b were photocytotoxic. The strong inhibition by sodium azide of the photocytotoxicity of these photosensitizers suggested that 102 is the main mediator. The S-glucosylated photosensitizers; la and 2a showed higher photocytotoxicity than S-galactosylated 1b and 2b, respectively. The cellular uptake of la and 2a increased up to 24 h, while that of 1b and 2b was saturated by 12 h. (c) 2009 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.jphotobiol.2009.07.007

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Language：English  

Authorship：Lead author,　Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

Introduction of a heavy atom into photosensitizers generally facilitates intersystem crossing and improves the quantum yield (Phi(Delta)) of singlet oxygen ((1)O(2)), which is a key species in photodynamic therapy (PDT). However, little information is available about the physiological importance of this heavy-atom effect. The aim of this study is to examine the heavy-atom effect in simple metallochlorins in vitro at the cellular level. 1,3-Dipolar cycloaddition of azomethine ylide to 5,10,15,20-tetrakis(pentafluorophenyl)porphyrinato palladium(II) and platinum(II) afforded metallochlorins 4b and 4c in yields of 17.1 and 12.9%, respectively. The Phi(Delta) values increased in the order of 4a (0.28) &lt; 4b (0.89) &lt; 4c (0.92) in C(6)D(6). The photocytotoxicity of 4a, 4b, and 4c was evaluated in HeLa cells at a light dose of 16 J.cm(-2) with lambda &gt; 500 nm and increased in the order of 4a &lt; 4b &lt; 4c at the concentration of 0.5 mu M. The photocytotoxicity of 4b and 4c was significantly inhibited by addition of sodium azide, but not D-mannitol, suggesting that (1)O(2) is the major species causing cell death. Our results clearly indicate that 4b and 4c act as efficient (1)O(2) generators due to the heavy-atom effect in a cellular microenvironment as well as in nonphysiological media.

DOI： 10.1021/jm8015427

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Language：English  

Authorship：Lead author,　Corresponding author   Language：English   Publishing type：Research paper (scientific journal)  

Language：English  

Language：English  

Language：English   Publishing type：Research paper (scientific journal)  

Authorship：Lead author,　Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：ROYAL SOC CHEMISTRY  

Novel chelators, i. e., 4-(2-pyridyl)- 1,2,3- triazole derivatives, were synthesized by means of Cu( I)- catalyzed 1,3- dipolar cycloaddition and used to prepare luminescent Re( I) complexes [ReCl(CO)(3)( Bn- pyta)], [ ReCl(CO)(3)(AcGlc- pyta)] and [ ReCl(CO)(3)(Glc- pyta)] (Bn- pyta = 1- benzyl- 4-( 2- pyridyl)- 1,2,3- triazole, AcGlc- pyta = 2-( 4-( 2- pyridyl)- 1,2,3- triazol- 1- yl) ethyl 2,3,4,6- tetra- O- acetyl- beta-D- glucopyranoside, Glc- pyta = 2-( 4-( 2- pyridyl)- 1,2,3- triazol- 1- yl) ethyl beta-D- glucopyranoside). X- Ray crystallography of Bn- pyta and Glc- pyta indicated an azocompound-like structure while the 1,2,4- triazole isomer has an azine character. [ ReCl( CO) 3( Bn- pyta)] crystallized in the monoclinic system with space group P2(1)/n. Bn- pyta ligand coordinates with the nitrogen atoms of the 2- pyridyl group and the 3- position of 1,2,3- triazole ring, which is a very similar coordinating fashion to that of the 2,2' - bipyridine derivative. The glucoconjugated Re( I) complexes [ ReCl( CO)(3)( AcGlc- pyta)] and [ ReCl( CO)(3)( Glc- pyta)] hardly crystallized, and were analyzed by applying extended X- ray absorption fine structure ( EXAFS) analysis. The EXAFS analyses suggested that the glucoconjugation at the 1- position of the 1,2,3- triazole makes no influence to the coordinating fashion of 4-( 2- pyridyl)- 1,2,3- triazole. [ ReCl( CO) 3( Bn- pyta)] showed a blue-shifted maximum absorption (333 nm, 3.97 x 10(3) M-1 cm(-1)) compared with [ReCl(CO)(3)(bpy)] ( 371 nm, 3.35 x 10(3) M-1 cm(-1)). These absorptions were clearly assigned to be the mixed metal- ligand-to-ligand charge transfer (MLLCT) on the basis of time-dependent density functional theory calculation. The luminescence spectrum of [ReCl(CO)(3)( Bn- pyta)] also showed this blue- shifted feature when compared with that of [ ReCl( CO) 3( bpy)]. The luminescence lifetime of [ ReCl( CO)(3)( Bn- pyta)] was determined to be 8.90 mu s in 2-methyltetrahydrofuran at 77 K, which is longer than that of [ReCl(CO)(3)( bpy)] ( 3.17 mu s). The blue- shifted electronic absorption and elongated luminescence lifetime of [ ReCl( CO)(3)( Bn- pyta)] suggested that 4-( 2- pyridyl)- 1,2,3- triazole functions as an electron-rich bidentate chelator.

DOI： 10.1039/b718538c

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Authorship：Lead author,　Corresponding author   Language：Japanese  

Authorship：Lead author,　Corresponding author   Language：English  

Authorship：Lead author,　Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE BV  

The photocytotoxicity of four glycoconjugated porphyrins, namely 5,10,15,20-tetrakis[4-(beta-D-glucopyranosyloxy)phenyl]porphyrin (p-1a), 5,10,15,20-tetrakis[4-(beta-D-galactopyranosyloxy)phenyl]porphyrin (p-1b), 5,10,15,20-tetrakis[4-(beta-D-xylopyranosyloxy)phenyl]porphyrin (p-1c) and 5,10,15,20-tetrakis[4-(beta-D-arabinopyranosyloxy)phenyl]porphyrin (p-ld), was evaluated in HeLa cells in the concentration range from 1 to 7 mu M using a light dose of 16 J center dot cm(-2) with a wavelength greater than 500 nm. The photocytotoxicity depends on the sugar moieties, and increases in the order of p-1d&lt;p-1a&lt;p-1b&lt;p-1c. The order of the photocytotoxicity is at variance with that of the cellular uptake reported previously. On the other hand, the photophysical properties of the glycoconjugated porphyrins also depends on the sugar moieties in physiological media such as phosphate buffered saline (PBS) containing 10 wt.% bovine serum albumin (BSA). In particular, the oscillator strength in the range above 500 nm increases in the order of p-1d=p-1a&lt;p-1c&lt;p-1b, which is good agreement with the order of the photocytotoxicity in HeLa cells. The interaction between the glycoconjugated porphyrins and BSA was evaluated by means of electronic absorption, fluorometric and circular dichroic (CD) titrations. Fluorometric titration showed no differences in the apparent binding constants, K, between the glycoconjugated porphyrins p-1a, p-1b, p-1c and p-1d. On the other hand, the number of binding sites, n, depends on the sugar moieties of the glycoconjugated porphyrin, and increases in the order of p-1b&lt;p-1a&lt;p-1d&lt;p-1c. CD titration was also characterized by the n value determined by fluorometric titration, suggesting the n value is a good descriptor for the interaction between glycoconjugated porphyrins and BSA. However, it was found that the n value was poorly related to the photophysical properties in physiological media and the photocytotoxicity. Even though the role of the sugar moieties on the photodynamic effect is not fully understood, the photophysical properties of the glycoconjugated porphyrins are strongly modulated by the physiological media resulting in the sugar-dependent photocytotoxicity. (C) 2007 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.bbagen.2007.03.011

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ROYAL SOC CHEMISTRY  

An optical oxygen-sensing activity of anchored porphyrin derivatives on ordered porous aluminium oxide plates was studied in relevance to development of new oxygen-sensing systems. Porphyrin derivatives, 5,10,15,20-tetrakis(4-carboxylundecane-1-oxy) porphyrin ( 1(H)), 5-[4-(11-carboxyl-undecane-1-oxy)-10,15,20-triphenyl]porphyrin ( 2(H)), 5-(4-carboxylphenyl)-10,15,20-triphenylporphyrin ( 3(H)), and their platinum complexes, 5,10,15,20-tetrakis(4-carboxylundecane-1-oxy) porphyrinato-platinum( II) ( 1(Pt)), 5-[4-(11-carboxylundecane-1-oxy)-10,15,20-triphenyl] porphyrinato-platinum( II) ( 2(Pt)), 5-(4-carboxylphenyl)-10,15,20-triphenyl]porphyrinatoplatinum( II) ( 3(Pt)), were synthesized and anchored by an equilibrium adsorption method on aluminium oxide plates, which were prepared by an anodic oxidation. The excitation spectra of the porphyrin-anchored layers showed a broadened and blue-shifted Soret band compared with the corresponding porphyrins in DMSO. The luminescence intensity decreased with increasing oxygen concentrations. The oxygen-sensing ability estimated from I-0/I-100 ( I-0 and I-100 denote the luminescence intensity in 0 and 100% oxygen) was ( 1(H)) 9.08, ( 2(H)) 6.78, ( 3(H)) 8.71, ( 1(Pt)) 81.9, ( 2(Pt)) 35.5, and ( 3(Pt)) 39.1, which are greater than those of corresponding porphyrin derivatives in DMSO under the measured conditions, and indicates the remarkable enhancement effect of platinum( II). Non-linear Stern-Volmer plots were well. fitted by the two component system to give the oxygen-sensitive constant (KSV1/%(-1)), the oxygen-insensitive constant ( K-SV2/%(-1)), and the former contribution ( f(1)): ( 1(H)) 0.232, 3.32 x 10(-2), and 0.642; ( 2(H)) 0.141, 2.05 x 10(-2), and 0.687; ( 3(H)) 0.143, 1.05 x 10(-2), and 0.882; ( 1(Pt)) 17.3, 7.04 x 10(-3), and 0.980; ( 2(Pt)) 10.2, 1.43 x 10(-2), and 0.935; ( 3(Pt)) 16.3, 8.35 x 10(-3), and 0.954. The response time for the change of the atmospheric gas from argon to oxygen was ( 1(H)) 9.4 s, ( 2(H)) 12.5 s, ( 3(H)) 9.6 s, ( 1(Pt)) 5.0 s, ( 2(Pt)) 8.9 s, and ( 3(Pt)) 4.6 s, indicating the shortening effect of platinum. The reverse effect of platinum was observed in the change from oxygen to argon: ( 1(H)) 15.5 s, ( 2(H)) 17.0 s, ( 3(H)) 20.8 s, ( 1(Pt)) 667.4 s, ( 2(Pt)) 590.1 s, and ( 3(Pt)) 580.4 s, indicating the specific interaction of oxygen to the platinum( II) center.

DOI： 10.1039/b618030b

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Language：English  

Language：English  

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-V C H VERLAG GMBH  

A library of eleven high cis-content cis-transoidal polyphenylacetylenes (PPAs) dendronized with self-assembling dendrons was prepared from a library of fifteen convergently synthesized macromonomers. Using [Rh(C CPh)(nbd)(PPh3)(2)] (nbd=2,5-norbornadiene) in the presence of 10 equiv of N,N-dimethylaminopyridine, predictive control over molecular weight and narrow molecular weight distribution are obtained. The PPA backbone serves as a helical scaffold for the self-assembling dendrons. The dendron primary structure dictates the diameter of the cylindrical PPAs in bulk, both in the self-organized hexagonal columnar (Phi(h)) lattice determined by X-ray diffraction (XRD) and in monolayers on highly ordered pyrolytic graphite (HOPG) and mica visualized by atomic force microscopy (AFM). Thermal and bulk phase characteristics of the cylindrical PPAs reinforces the generality that flexible polymer backbones adopt a helical conformation within the cylindrical macromolecules generated by polymers jacketed with self-assembling dendrons.

DOI： 10.1002/chem.200600009

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Language：English  

Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-V C H VERLAG GMBH  

DOI： 10.1002/anie.200603127

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Language：English  

Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

High cis content (81-99%) cis-transoidal polyphenylacetylene (PPA) jacketed with amphiphilic self-assembling dendrons, poly[(3,4-3,5)mG2-4EBn] with m = 8, 10,12, 14,16, and (S)-3,7-dimethyloctyl, were synthesized by Rh(C equivalent to CPh)(nbd)(PPh(3))2 (nbd = 2,5-norbornadiene)/NN-(dimethylamino)pyridine (DMAP) catalyzed polymerization of macromonomers. The resulting cylindrical PPAs self-organize into hexagonal columnar lattices with intracolumnar order (Phi(io)(h)) and without (Phi(h)). The polymers with m = 12, 14, and 16 exhibit also a hexagonal columnar crystal phase (Phi(h,k)). The reversible Phi(h,k)-to-Phi(io)(h)-to-Phi(h) phase transition in these dendronized PPAs was analyzed by a combination of differential scanning calorimetry and small and wide-angle X-ray diffraction experiments performed on powder and oriented fibers. In the Phi(h,k) and Phi(io)(h) phases, the dendronized PPAs form helical porous columns. The helical pore disappears in the Phi(h) phase. This change is accompanied by a decrease of the external column diameter that is induced by stretching of the polymer backbone along the axis of the cylinder. The helix sense of the porous PPA is selected by homochiral alkyl dendritic tails. This transition is generated by an unprecedented conversion of the PPA backbone from the cis-cisoidal conformation in the Phi(h,k) and Phi(io)(h) phases to the cis-transoidal conformation in the Phi(h) phase. Under the same conditions, the pristine cis-PPA undergoes cis-trans isomerization and irreversible intramolecular 6 pi electrocyclization of 1,3-cis,5-hexatriene sequences followed by chain cleavage. These processes are eliminated in the dendronized cis-PPA below its decomposition temperature.

DOI： 10.1021/ja055406w

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Authorship：Lead author,　Corresponding author   Language：English  

Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE INC  

Metal complexes of 3-hydroxypyridine-2-carboxylic acid (H(2)hpic), [Co(Hhpic)(2)(H2O)(2)] (1), [Fe(Hhpic)(2)(H2O)(2)] (2), [Zn(Hhpic)(2)(H2O)(2)] (3), [Mn(Hhpic)(2)(H2O)(2)] (4), and [Cu(Hhpic)(2)] (5) have been synthesized and characterized by mass spectrometry, elemental analysis, magnetic susceptibility, infrared, electronic absorption and electron paramagnetic resonance (EPR) spectroscopies. The solid-state structure of 1 has been established by X-ray crystallography. The EPR spectra of 4 and 5 displayed six and four-line hyperfine splitting patterns, respectively, due to coupling of the unpaired electron with the Mn-55 (I=5/2) nucleus and the Cu-63 (I=3/2) nucleus. In the EPR spectrum of 5, an additional five-line super-hyperfine splitting pattern was observed at 77 K, caused by additional interaction of the unpaired electron with ligand nitrogen atoms (I=1), indicating that the structure of 5 was retained in dimethyl sulfoxide solution. The insulin-mimetic activity of these complexes was evaluated by means of in vitro measurements of the inhibition of free fatty acid (FFA) release from epinephrine-treated, isolated rat adipocytes. Complex 5 was found to exhibit the most potent insulin-mimetic activity among the complexes examined in this study. (C) 2005 Elsevier Inc. All rights reserved.

DOI： 10.1016/j.jinorgbio.2005.02.026

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Authorship：Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE SA  

Eight 5,10,15,20-tetrakis[3- or 4-(beta-D-glycopyranosyloxy)phenyl]chlorins were synthesized by means of the Whitlock method with diimide reduction and purified by reversed-phase thin layer chromatography (RP-TLC). All compounds were characterized by H-1 NMR spectroscopy, electron-spray ionization time-of-flight mass spectrometry (ESI-TOF MS), and UV-Vis spectroscopy. ESI-TOF MS could detect the 2H difference in molecular weight between a glycoconjugated chlorin and its corresponding porphyrin (i.e., 5,10,15,20-tetrakis[3- or 4-(beta-D-glycopyranosyloxy)phenyl]porphyrin). The cellular uptake of the eight chlorins was evaluated in HeLa cells. All glycoconjugated chlorins showed higher cellular uptake than tetraphenylporphyrin tetrasulfonic acid (TPPS), and 5,10,15,20-tetrakis[3-(beta-D-xylopyranosyloxy)phenyl]chlorin showed 50-fold higher uptake than TPPS. The photocytotoxicity of 5,10,15,20-tetrakis[3-(beta-D-glucopyranosyloxy)phenyl]chlorin, 5,10,15,20-tetrakis[3-(beta-D-xylopyranosyloxy)phenyl]chlorin and TPPS towards HeLa cells was examined at the concentration of 2 x 10(-7) M (mol/dm(3)). These photosensitizers had no cytotoxicity in the dark, but their photocytotoxicity decreased in the order of 5,10,15,20-tetrakis[3-(beta-D-glucopyranosyloxy)phenyl]chlorin &gt; 5,10,15,20-tetrakis[3-(beta-D-xylopyranosyloxy)phenyl]chlorin &gt; TPPS. The results indicate that the photocytotoxicity is not related simply to cellular uptake. (C) 2004 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.jphotobiol.2004.09.003

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-V C H VERLAG GMBH  

Seven discrete sugar-pendant diamines were complexed to the {M(CO)(3)}(+) (Tc-99m/Re) core: 1,3-diamino-2-propyl beta-D-glucopyranoside (L-1), 1,3-diamino-2-propyl beta-D-xylopyranoside (L-2), 1,3-diamino-2-propyl alpha-D-mannopyranoside (L-3), 1,3-diamino-2-propyl alpha-D-galactopyranoside (L-4), 1,3diamino-2-propyl beta-D-galactopyranoside (L-5), 1,3-diamino-2-propyl beta-(alpha-D-glucopyranosyl-(1,4)-D-glucopyrano- side) (L-6), and bis(aminomethyl)bis[(beta-D-glucopyranosyloxy)methyl]methane (L-7). The Re complexes [Re((LL7)-L-1)(Br)(CO)(3)] were characterized by H-1 and C-13 1D/2D NMR spectroscopy which confirmed the pendant nature of the carbohydrate moieties in solution. Additional characterization was provided by IR spectroscopy, elemental analysis, and mass spectrometry. Two analogues, [Re(L-2)(CO)(3)Br] and [Re(L-3)(CO)(3)Br], were characterized in the solid state by X-ray crystallography and represent the first reported structures of Re organometallic carbohydrate compounds. Conductivity measurements in H2O established that the complexes exist as [Re(L-1-L-7)- (H2O)(CO)(3)]Br in aqueous conditions. Radiolabelling of V-L 7 with [Tc-99m(H2O)(3)(CO)(3)](+) afforded in high yield compounds of identical character to the Re analogues. The radiolabelled compounds were determined to exhibit high in vitro stability towards ligand exchange in the presence of an excess of either cysteine or histidine over a 24 h period.

DOI： 10.1002/chem.200400719

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Authorship：Lead author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：JOHN WILEY & SONS INC  

The asymmetric cyclocopolymerization of bis(4-vinylbezoate) of a chiral diol with styrene is a promising method for the preparation of optically active polystyrene derivatives because of main-chain chirality. However, the mechanism for chirality induction from the chiral diol to the main chain is still unknown. To clarify the chirality induction mechanism, we carried out the radical cyclizations of (2S,3S)-2,3-butanediyl bis(4-vinylbenzoate), (2S,4S)-2,4-pentanediyl bis(4-vinylbenzoate), and (2S,5S)-2,5-hexanediyl bis(4-vinylbenzoate) with tri-n-butyltin hydride or allyltri-n-butyltin as a chain-transfer reagent as model reactions for asymmetric cyclocopolymerization. The absolute configuration was determined with single-crystal X-ray crystallography and a circular dichroism exciton chirality method. The distribution of the stereoisomer showed (R)-configuration selectivity (21-34% diastereomeric excess) in the intramolecular cyclization and an extremely low extent (&lt;1%) of the (S,S)-cyclized product among the four stereoisomers. Therefore, chirality induction is caused by the selective inhibition of the (SS)-racemo configuration. (C) 2004 Wiley Periodicals, Inc.

DOI： 10.1002/pola.20373

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Authorship：Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER SOC PHOTOBIOLOGY  

Thirty-two glycoconjugated porphyrins were synthesized by a modification of Lindsey method in the presence of Zn(OAc)(2).2H(2)O as a template. The Zn2+ ion template strategy improved the yield about three-fold in the case of meta-substituted tetraphenylporphyrins. In addition, free-base porphyrins were obtained almost quantitatively by demetalation with 4 M HCl. Sixteen deacetylated glycoconjugated porphyrins were tested as candidate photodynamic therapy (PDT) drugs using HeLa cells. Most of the deacetylated glycoconjugated porphyrins showed higher cellular uptake than tetraphenylporphyrin tetrasulfonic acid (TPPS), and 5,10,15, 20-tetrakis[4-(beta-D-arabinopyranosyloxy)phenyl]porphyrin (p-5d) in particular showed 18.5-fold higher uptake than TPPS. The photocytotoxicity of 5,10,15,20-tetrakis[4-(beta-D-glucopyranosyloxy)phenyl]porphyrin (p-5a), p-5d and TPPS was examined with HeLa cells, using a light dose of 16 J/cm(2). These photosensitizers had no cytotoxicity in the dark, but their photocytotoxicity increased in the order of TPPS &lt; p-5a &lt; p-5d. These results suggest p-5d is a good candidate for a PDT drug.

DOI： 10.1562/2004-03-07-RA-103.1

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：PERGAMON-ELSEVIER SCIENCE LTD  

Six palladium(II) complexes as cisplatin derivatives with a sugar unit (D-glucose, D-galactose, D-mannose, D-Xylose, and maltose) have been prepared. The structural features of the complexes have been characterized by NMR spectroscopy, elemental analysis, mass spectroscopy, and X-ray crystallography. The complexes have been tested for in vivo cytotoxicity against P388 cells implanted in mice. All of Pd compounds are apparently nontoxic. A T/C value of 120% was obtained for maltose derivative at the dose of 400mg/kg, which indicates that the compound may be endowed with antitumor activity. (C) 2004 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.bmcl.2004.02.095

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：CHEMICAL SOC JAPAN  

5-(4-cyanophenyl)-10,15,20-triphenylporphyrinato platinum(II) (3) and 5-(4-methoxycarbonylphenyl)-10,15,20-triphenylporphyrinato platinum(II) (2) were isolated from a reaction of 5(4-methoxycarbonylphenyl)-10,15,20-triphenyl porphyrin (1) with K-2[PtCl4] in benzonitrile. Seemingly, 3 was generated through the functional group substitution reaction of the phenyl group of tetraphenylporphyrin during platinum ion insertion into 1 and was characterized by H-1 NMR, mass spectroscopy, elemental analysis, and X-ray crystallography.

DOI： 10.1246/cl.2004.450

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Authorship：Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE INC  

Two chargeless VO(IV) complexes with 3-hydroxypyridine-2-carboxylic acid (H(2)hpic), [VO(Hhpic-O,O)(Hhpic-O,N)(H2O)(.)3H(2)O (1) and the cyclic tetramer [(VO)4(mu-(hpic-O,O,N))(4)(H2O)(4)](.)8H(2)O (2), have been synthesized and characterized by elemental analysis, mass, infrared, electronic absorption, electron spin resonance (ESR) spectroscopies, and X-ray crystallography. Their coordination structures are similar to each other (and 1 is readily transformed into 2), but are quite different from that of bis(pyridine-2-carboxylato)oxovanadium(IV). The magnetic susceptibility of 2 indicates the presence of a weak ferromagnetic intramolecular interaction between the V atoms at low temperature, in addition to a weak antiferromagnetic intermolecular interaction. The ESR signal of 2 was broad, while I showed an eight-line hyperfine splitting pattern due to coupling of the impaired electron with the V-51 nucleus (I = 7/2). The ESR spectrum and cyclic voltammogram of 2 clearly show that the cyclic tetramer remains intact in solution. The insulinomimetic activity of 1 and 2 was evaluated by means of in vitro measurements of the inhibition of free fatty acid release from epinephrine-treated isolated rat adipocytes. While I exerted higher insulinomimetic activity than VOSO4, the activity of 2 was significantly lower than that of VOSO4. Hence 2 appears to retain its cyclic structure during the in vitro test. These results indicate that the rational ligand design for VO complexes might be a promising approach to obtain superior insulinomimetic activity. (C) 2003 Elsevier Inc. All rights reserved.

DOI： 10.1016/j.jinorgbio.2003.09.005

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Authorship：Lead author,　Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：ROYAL SOC CHEMISTRY  

The novel (mu-alkoxo) bis(mu-carboxylato) diruthenium complex K[Ru-2(dhpta)(mu-O2C-p-ZnTPP)(2)] 3 was prepared by simple ligand substitution reaction. Strong antiferromagnetic interaction between two Ru-III ions of 3 was observed with a coupling constant of - 425 similar to - 404 cm(-1). The cyclic voltammogram of 3 can be explained in terms of superposition of those of ZnTPP-p-CO2H and K[Ru-2(dhpta)(mu-O2CPh)(2)] 2, indicating no significant electrochemical interaction. The large conproportionation constant estimated from the reduction potentials for (RuRuIII)-Ru-III and (RuRuIII)-Ru-II indicates great stability of the mixed- valence state. The mixed- valence species [(RuRuIII)-Ru-II(dhpta)(mu-O2C-p-ZnTPP) (2)](2-) 4 was prepared by controlled potential electrolysis. The electronic absorption spectrum of 4 was quite similar to that of [(RuRuIII)-Ru-II(dhpta)(mu-O2CCH3)(2)](2-) which is a typical Class II complex. The fluorescence from the S-2 state of the ZnTPP unit of 3 was significantly (78%) quenched. The electron transfer from the ZnTPP unit to RuIII ions in 3 is a plausible mechanism, even though energy transfer could not be ruled out completely. The free energy change for electron transfer, DeltaG(CS), was estimated to be ca. - 1.1 eV, which is similar to typical values for the reorganization energy lambda in polar solvents. Hence, the electron transfer scheme is situated almost at the top of the Marcus parabola, enabling ultrafast electron transfer.

DOI： 10.1039/b406410k

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Authorship：Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：SOC PORPHYRINS & PHTHALOCYANINES  

Photodynamic therapy (PDT) is one of the most effective treatments for cancer. We synthesized and characterized a series of 16 glycoconjugated porphyrins using a modification of the Lindsey method in the presence of Zn(OAc)center dot 2H(2)O as a template. The Zn 21 ion template strategy improved the yield about 3-fold in the case of meta-substituted tetraphenylporphyrins, and free-base porphyrins were obtaind almost quantitatively by demetalation with 4 M HCl. The hydrophobicity parameter (Log P) of these porphyrins was evaluated by reversed phase high-performance liquid chromatography (RP-HPLC). The Log P values ranged from +4.8 to +7.8, so that most of the compounds are amphiphilic. The effect of the glycopyranosyl unit on the hydrophobicity of these compounds is discussed on the basis of the Log P value. Copyright (c) 2004 Society of Porphyrins P Phthalocyanines.

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Sugar-pendant [60] fullerene derivatives have been prepared from carbohydrate-linked azides la-e. Both monosugar (4a-e) and bissugar derivatives (5a-e) produce singlet oxygen ((1)O(2)) under laser irradiation (355 nm) proved by the direct observation of (1)O(2) emission at 1270 nm. Monosugar derivatives exhibit photocytotoxicity varying by the attached sugar molecule. (C) 2003 Elsevier Ltd. All rights reserved.

DOI： 10.1016/S0960-894X(03)00595-X

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Authorship：Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE BV  

The ligand substitution reaction of K[Ru-2(dhpta)(mu-O2CCH3)(2)] (H(5)dhpta=1,3-diamino-2-hydroxypropanetetraacetic acid) with zinc 5-(4-carboxylphenyl)-10,15,20-triphenylporphyrin (ZnTPP-p-COOH) afforded a diruthenium complex having porphyrin moieties, K[Ru-2(dhpta)(mu-O2C-p-ZnTPP)(2)]. This product was characterized by UV-Vis and H-1 NMR spectroscopy, and EXAFS analysis. (C) 2003 Elsevier Science B.V. All rights reserved.

DOI： 10.1016/S1387-7003(03)00005-4

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-BLACKWELL  

The synthesis of 2-ethynyl-9-substituted carbazole and 3-ethynyl-9-substituted carbazole monomers containing first-generation chiral and achiral dendritic (i.e., minidendritic) substituents, 2-ethynyl-9-[3,4,5-tris(dodecan-1-yloxy)benzyl]carbazole (2ECz), 3-ethynyl-9-[3,4,5-tris(dodecan-1-yloxy)benzyllcarbazole (3ECz), 2-ethynyl-913,4,5-tris[(S)-2-methylbutan-1-yloxylbenzyl)carbazole (2ECz*), and 3-ethyny1-9-{3,4,5-tris[(S)-2-methylbutan-1-yloxylbenzyl)carbazole (3ECz*), is presented. All monomers were polymerized and copolymerized by stereospecific polymerization to produce cis-transoidal soluble stereoisomers, A structural analysis of poly(2ECz), poly(2ECz*), poly(3ECz), poly(3ECz*), poly(2ECz*-co-2ECz), and poly(3ECz*-co-3ECz) by a combination of techniques, including (1)H NAIR, ultraviolet-visible, and circular dichroism spectroscopy, thermal optical polarized microscopy, and X-ray diffraction experiments, demonstrated that these polymers had a helical conformation that produced cylindrical macromolecules exhibiting chiral and achiral nematic phases. Individual chains of these cylindrical macromolecules were visualized by atomic force microscopy. (C) 2002 Wiley Periodicals, Inc.

DOI： 10.1002/pola.10458

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：CHEMICAL SOC JAPAN  

Reaction of vanadyl sulfate with 3-hydroxypyridine-2-carboxylic acid (H(2)hpic) affords two chargeless complexes, [VO(Hhpic-O,O)(Hhpic-O,N)(H2O)].3H(2)O (1) and unprecedented cyclic tetranuclear complex [(VO)(4)(mu-(hpic-O,O',N))(H2O)(4)].8H(2)O (2), which were characterized by X-ray crystallographic analysis. The unique structural transformation between complexes 1 and 2 was found.

DOI： 10.1246/cl.2002.916

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-V C H VERLAG GMBH  

A systematic study of the asymmetric cyclocopolymerization of bis(4-vinylbenzoate)s, derived from chiral diols, with styrene has been made from the viewpoint of synthesizing the main-chain chiral polymer. On the basis of using over 30 chiral diols as templates, we summarize the relationship between the structure of the chiral template and the chiroptical properties of the template-free polymer. For simple chiral diols, the chirality induction efficiency increased in the order 1,2-diol&lt;1,4-diol&lt;1,3-diol. Chiral diols with two chiral centers exhibited higher chirality induction efficiency than those having one chiral center only. The chirality induction efficiency for cyclic 1,2-diols increased with the ring size in the orders 5-&lt;6-&lt;7-&lt;8-membered rings, and that for acyclic 1,2-diols increased with the bulkiness of the substituent of the chiral center. In addition, a chirality induction mechanism has been proposed on the basis of model radical cyclization experiments and computational studies. Chirality induction could be caused by the inhibition of the formation of one racemo unit among the four stereoisomers due to the strong dependence of the stereoselectivity in intermolecular additions on the absolute configuration of the cyclized radical. The mechanism was examined using the Lewis-acid and monomer-concentration effects.

DOI： 10.1002/1521-3927(20020401)23:7<395::AID-MARC395>3.0.CO;2-K

Web of Science

Language：English   Publishing type：Research paper (scientific journal)   Publisher：CHEMICAL SOC JAPAN  

meso-Tetraphenylporphyrin having hexa-maltosyl and decyl chain was synthesized via dipyrromethane coupling. Its singlet oxygen producing ability and phototoxicity against the HeLa cell were estimated.

DOI： 10.1246/cl.2002.388

Web of Science

Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCI LTD  

The cyclocopolymerization of (2S,3S)-2,3-butanediyl bis(4-vinylbenzoate) (1) with styrene was carried out in dry toluene at 40 degreesC in the presence of triethylaluminum (Et3Al), diethylaluminum chloride (Et2AlCl), and ethylaluminum dichloride (EtAlCl2), which played the role of Lewis acid capable of coordinating on carboxyl groups. After removal of the (2S,3S)-2,3-butanediyl units, the template-free polymer 3 exhibited an optical activity due to its main chain chirality. The specific rotations ([alpha](435), c 1.0, CHCl3) of polymers 3 prepared with alkylaluminum compound varied from -11.2 to -21.7 degrees, which was higher than those prepared without: alkylaluminum compound (-9.0 degrees). The specific rotation of polymer 3 increased with an increase in the acidity of the alkylaluminum compounds (i.e. Et3Al &lt; Et2AlCl &lt; EtAlCl2) and/or with an increase in the molar ratio of alkylaluminum compound to monomer 1. (C) 2001 Elsevier Science Ltd. All rights reserved.

DOI： 10.1016/S0032-3861(00)00876-4

Web of Science

Language：Japanese  

Language：English   Publishing type：Research paper (scientific journal)  

DOI： 10.1021/ma000853b

Language：Japanese   Publishing type：(MISC) Introduction and explanation (commerce magazine)   Publisher：ジャスコレポ-ト社  

CiNii Books

Language：English   Publishing type：Research paper (scientific journal)   Publisher：SOC POLYMER SCIENCE JAPAN  

The molecular design and synthesis of asymmetric bifunctional monomers, 3-(S)-acryloyloxy-1-(S)-methyl-butyl methyl fumarate (1a) and 3-(R)-acryloyloxy-1-(R)-methyl-butyl methyl fumarate (1b), have been carried out in terms of a novel method of producing optically active polymers based on cyclopolymerization. The polymerization of 1 proceeded via the cyclopolymerization mechanism to yield the cyclopolymer 2 with the extent cyclization of 0,87-0.96 when the monomer concentration ([M]) in the feed was 0.3 mol L-1 or less. The number-average molecular weight (M-n) decreased with a decrease in the [M] from 8300 to 3300 for polymer 2a and from 4200 to 2400 for polymer 2b. The rotation ([alpha](435)(23), c 1.0, CHCl3) of the resulting polymers changed from + 19.3degrees to + 33.4degrees for 2a and from -26.2degrees to -34.9degrees for 2b. In order to confirm the chirality induction, the chiral pentanediyl moiety was removed from polymer 2 by saponification, and the hydrolyzed polymer was treated with diazomethane to give poly(methyl acrylate-co-dimethyl fumarate) (3). The M-n was 2200-2600 for 3a and 2300-5700 for 3b, and the template-free polymers showed an optical activity with a specific rotation that ranged from -1.4degrees to -9.3degrees for 3a and from +7.5degrees to +8.8degrees for 3b. The CD spectra of 3a showed a positive Cotton effect whereas 3b showed a negative Cotton effect which is the mirror image of 3a. The optical activity of polymer 3 should be attributed to the threo-erythro sequence of the methyl acrylate and dimethyl fumarate units.

DOI： 10.1295/polymj.33.946

Web of Science

Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

Two diastereomeric chiral cycloalkanediols such as (1S,2R)-2-hydroxymethyl-1-cyclohexanol (a) and (1S,2S)-2-hydroxymethyl-1-cyclohexanol (bi, which were conformational restriction models for (S)-1,3-butanediol (c), were used as chiral templates tu investigate the conformational effect uf the 1,3-diol skeleton of the template moiety in the cyclocopolymerization of bis(4-vinylbenzoate)s (1) with styrene. The specific rotation for the resulting template-free polymer 3a was almost twice that for 3b. In comparison with chiral template c, the efficiency of the chirality induction increases in the order of b &lt; c &lt; a. These characteristics of chiral templates were discussed in terms of the conformational distribution of the monomer 1a-c.

DOI： 10.1021/ma000097+

Web of Science

Language：Japanese   Publishing type：Research paper (scientific journal)  

DOI： 10.5059/yukigoseikyokaishi.58.306

Language：English  

Language：English   Publishing type：Research paper (scientific journal)   Publisher：SOC POLYMER SCIENCE JAPAN  

The radical cyclocopolymerizations of(R)-1-phenyl-1,2-ethanediyl, (R,R)-1,2-diphenyl-1,2-ethanediyl, and (R,R)-1,2-di(1-naphthyl)- 1,2-ethanediyl bis(4-vinylbenzoate)s (1d, 1e, and 1f) with styrene yielded copolymer 2 with new chirality in the main chain. The chirality induction was based on the configurational arrangement. Optically active poly(methyl 4-vinylbenzoate-co-styrene) (3) was obtained by the removal of the chiral template in copolymer 2, followed by the treatment with diazomethane. The template having (R)- and (S)-configuration transmitted its chirality to the main chain in the intramolecular cyclization of divinyl monomers to form the enantiomeric (S,S)- and (R,R)-racemo units, respectively. Repulsive steric interactions of the substituents restricted rotation around single bonds in the 1,2-diol templates to improve the selectivity between two raceme units.

DOI： 10.1295/polymj.31.1037

Web of Science

Authorship：Lead author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：GORDON BREACH SCI PUBL LTD  

Methyl, ethyl, and isopropyl 2,3-bis-O-(4-vinylbenzoyl)-L-tartrates (1a, 1b, and 1c, respectively) were cyclocopolymerized with styrene, and the resulting copolymers 2a-c were hydrolyzed, followed by methyl esterification using diazomethane to yield the poly [(methyl 4-vinylbenzoate)-co-styrene]s (3a-c). Although 1a-c had the chiral twist of the 4-vinylbenzoyl groups, 3a-c showed extremely low optical activities with specific rotations of -2.9 degrees for 3a, -1.1 degrees for 3b, and -0.8 degrees for 3c. As is distinct from the general cases, this is the first exceptional case, in which the template-free copolymers 3a-c exhibited the specific rotations of the same sign as those of monomers 1a-c. On the other hand, the cyclocopolymerization of (2S,3S)-1,4-dimethoxy-2,3-butanediyl bis(4-vinylbenzoate) (that is, the decarbonyl analog of 1a) (1d) with styrene produced copolymer 3d, which exhibited optical activity with a specific rotation of -21.9 degrees. The specific rotation had the opposite sign to that for monomer 1d. Thus, the carbonyl groups in the L-tartrate template clearly reduced the chirality induction. The influence of the carbonyl groups on the chirality induction was discussed by analyzing the conformation of these monomers based on the exciton chirality method.

Web of Science

Authorship：Lead author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

Optically active poly(methyl 4-vinylbenzoate-co-styrene)s (3a-c) were synthesized through the cyclocopolymerizations of (2S,3S)-2,3-butanediyl, (2S,4S)-2,4-pentanediyl, and (2S,5S)-2,5-hexanediyl bis(4-vinylbenzoate)s (1a, 1b, and 1c, respectively) with styrene. The extent of chirality induction increased in the order of 1a congruent to 1c &lt; 1b, and the cyclized units predominately possessed an (R,R)-configuration. The MM2 calculation derived the conformer distributions in which monomers 1a and 1b predominately had a counterclockwise gauche form ("g(-)") and a combination of trans form and clockwise gauche form ("tg(+)"), respectively. Monomer 1c had a nide distribution into "tg(+)g(+)", "g(+)tg(+)", and "ttt" forms because of flexibility. The semiemprical molecular orbital calculations were performed for the model reaction of the radical cyclization. The calculated population difference between (R,R)- and (S,S)-configurations indicated that the template in 1b was more effective for the chirality induction than that in 1a, similar to the experimental results.

DOI： 10.1021/ma971907t

Web of Science

Language：Japanese  

Authorship：Lead author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

Radical cyclocopolymerization of the dimethacrylate 1 (M(1)), which was derived from 1,2:5,6-di-O-isopropylidene-D-mannitol, with styrene (M(2)) induced new chirality in the polymer chain. The removal of the chiral template in the copolymer 2 followed by treatment with diazomethane gave optically active poly(methyl methacrylate-co-styrene) (4). Polymer 4 had more active chirality upon increasing the M(1) unit, thus indicating that the new chirality should be induced by the M(1) diad unit rather than the isolated M(1) unit. Characteristics of monomer 1 include the considerably higher fraction of tactic triad rr in poly(methyl methacrylate) (PMMA) derived from the homopolymerization and the larger probability of forming the raceme diad of the M(1) unit during the intermolecular reaction of the copolymerization. In polymer 4, the origin of chirality was assigned to the chiral tetrad sequences of the MMA unit which were induced by participation of the raceme configuration.

DOI： 10.1021/ma961286o

Web of Science

Language：English   Publishing type：Research paper (scientific journal)  

Language：English   Publishing type：Research paper (scientific journal)  

DOI： 10.1002/actp.1997.010481101

Language：Japanese   Publishing type：Research paper (scientific journal)   Publisher：The Society of Polymer Science, Japan  

The cyclopolymerization capable of forming monomeric units without planes of symmetry provides one useful means for asymmetric polymerization. Three succharides: L-threitol, α-D-glucose, and D-mannitol, were used as a template for asymmetric induction in radical cyclocopolymerization. The bis (p-vinylbenzoate) monomers (1a-c) (M₁) derived from the templates were copolymerized with styrene (M₂). The resulting copolymers (2a-c) were canverted into poly [(methyl 4-vinylbenzoate) -co-styrene] s (3a-c). The polymers were optically active; a sourse of chirality was the isolated M₁ unit. The exciton chirality method was employed for determining the absolute configuration of the cyclic units. The template having R, R-configuration transmitted its chirality to the main chain in the intramolecular cyclization of the monomer to form an enantiomeric S, S-racemo cyclic unit. The template having S, S-configuration gave the R, R-racemo cyclic unit. The acyclic template, (2S, 4S) -2, 4-pentanediol, was more effective than the cyclic templates such as the D-mannitol and L-threitol. The (2S, 4S) -2, 4-pentanediyl template approximately doubled in effect for the asymmetric induction by comparison with the (S) -1, 3-butanediyl one. The difference in the circular dichroism (CD) spectrum between the monomers from these templates was estimated by calculating the most stable rotational conformation and its energy level. The source of the optical activity in the cyclocopolymerizations was estimated by means of molecular mechanics and semiempirical molecular orbital calculation. The copolymerization of bis (methacryloyloxy) monomer (4a) (M₁) from L-threitol with styrene (M₂) induced the new chirality due to the isolated M₁ unit in the main chain as well. In contrast to the case of the L-threitol template, the copolymerization of bis (methacryloyloxy) monomer (4b) from D-mannitol indicated that the new chirality should be induced by the M₁ diad unit rather than the isolated unit.

DOI： 10.1295/koron.54.684

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