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61.
Maki Sachiko Eiji Nishibori Shinobu Aoyagi Makoto Sakata Masaki Takata Mio Kondo Masaki Murata Ryota Sakamoto Hiroshi Nishihara 《Acta Crystallographica. Section C, Structural Chemistry》2013,69(7):696-703
The title compound, [Fe2(C5H5)2(C40H22O2)] or 1,4‐(FcPh)2Aq [where FcPh is 2‐(4‐ferrocenylphenyl)ethynyl and Aq is anthraquinone], was synthesized in an attempt to obtain a new solvent‐incorporating porous material with a large void space. Thermodynamic data for 1,4‐(FcPh)2Aq show a phase transition at approximately 430 K. The crystal structure of solvent‐free 1,4‐(FcPh)2Aq was determined at temperatures of 90, 300 and 500 K using synchrotron powder diffraction data. A direct‐space method using a genetic algorithm was employed for structure solution. Charge densities calculated from observed structure factors by the maximum entropy method were employed for model improvement. The final models were obtained through multistage Rietveld refinements. In both phases, the structures of which differ only subtly, the planar Aq fragments are stacked alternately in opposite orientations, forming a one‐dimensional column. The FcPh arms lie between the stacks and fill the remaining space, leaving no voids. C—H...π interactions between the Ph and Fc fragments mediate crystal packing and stabilization. 相似文献
62.
RAFT synthesis of an amphiphilic block copolymer bearing chlorin rings in the hydrophobic segment and its application in photodynamic therapy
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Makoto Obata Shuto Tanaka Hiroshi Mizukoshi Eika Ishihara Masaki Takahashi Shiho Hirohara 《Journal of polymer science. Part A, Polymer chemistry》2017,55(20):3395-3403
RAFT polymerization of styrene (St) in the presence of 5,10,15,20‐tetrakis(pentafluorophenyl)porphyrin (TFPP) was conducted using 4‐cyano‐4‐(thiobenzoyl)thiopentanoic acid as a chain‐transfer agent and azobisisobutyronitrile as an initiator at 60 °C. The resulting polymer exhibited a chlorin‐like UV‐vis spectrum, which indicated that the polymer possessed a reduced TFPP structure. Furthermore, an SEC trace recorded using UV‐vis detector (λ = 410 nm), which selectively detected the TFPP‐incorporated polymer, shifted toward higher molecular mass as the polymerization progressed. This evidence indicated that TFPP acted as a vinylene‐type monomer, such as maleimide, to form a copolymer, namely, poly(St‐co‐TFPP). The mole fraction of TFPP units was estimated to be 0.74 × 10?3, which was close to that in the feed (1 × 10?3). Chain extension of poly(St‐co‐TFPP) with polyethylene glycol monomethyl ether acrylate (PEGA) was performed to afford the amphiphilic block copolymer poly(St‐co‐TFPP)‐b‐poly(PEGA). The degrees of polymerization of St and PEGA were determined to be 64 and 75, respectively. Poly(St‐co‐TFPP)‐b‐poly(PEGA) formed micelles following dialysis. The median diameter of the micelles in solution was determined to be 16 nm by DLS. The photocytotoxicity of the micelle solution was evaluated in a human glioblastoma cell line (U251) and an N‐methyl‐N'‐nitro‐N‐nitrosoguanidine‐induced mutant of a rat murine RGM‐1 gastric carcinoma mucosal cell line (RGK‐1). © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 3395–3403 相似文献
63.
Takumi Kobayashi Masahide Goto Masaki Minami Fumio Sanda 《Journal of polymer science. Part A, Polymer chemistry》2019,57(24):2581-2589
A novel polymer, poly( 1 ) containing benzoxazine and phenyleneethynylene moieties in the main chain with number‐average molecular weights ranging from 1400 to 9800 was obtained quantitatively by the Sonogashira–Hagihara coupling polymerization of the corresponding iodophenyl‐ and ethynylphenyl‐substituted monomer 1 . Poly( 1 ) was heated at 200 °C under N2 for 2 h to obtain the cured polymer, poly( 1 )′ via the ring‐opening polymerization of the benzoxazine moieties. The structures of the polymer before and after curing were confirmed by 1H‐NMR, IR, and UV–vis absorption and reflectance spectroscopies. Poly( 1 )′ was thermally more stable than monomer 1 and poly( 1 ). A specimen was prepared from a mixture of poly( 1 ) and phenol‐diaminodiphenylmethane type benzoxazine 2 by heating at 200 °C for 2 h under N2. The poly( 1 )/ 2 resin was thermally stable than bisphenol‐A type benzoxazine resin 3 . Poly( 1 ) exhibited XRD peaks corresponding to the d‐spacings of 1.26–0.98 and 0.40 nm, assignable to the repeating monomer unit and alignment of polymer molecules, respectively. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2581–2589 相似文献
64.
Nobutaka Yoshimura Dr. Atsushi Kobayashi Dr. Masaki Yoshida Prof. Masako Kato 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(70):16939-16946
To investigate the effect of the surface structure of dye-sensitized photocatalyst nanoparticles, we prepared three types of RuII-photosensitizer (PS)-double-layered Pt-cocatalyst-loaded TiO2 nanoparticles with different surface structures, Zr- RuCP6 -Zr- RuP6 @N wt %Pt-TiO2, RuCP6 -Zr- RuP6 @N wt %Pt-TiO2, and RuCP2 -Zr- RuP6 @N wt %Pt-TiO2 (N=0.2, 1, and 5), and evaluated their photocatalytic H2 evolution activity in the presence of redox-reversible iodide as the electron donor. Although the driving force of the electron injection from I− to the photo-oxidized RuIII PS is comparable, the activity increased in the following order: RuCP2 -Zr- RuP6 @1 wt %Pt-TiO2 < RuCP6 -Zr- RuP6 @1 wt %Pt-TiO2 < Zr- RuCP6 -Zr- RuP6 @1 wt %Pt-TiO2. The apparent quantum yield of Zr- RuCP6 -Zr- RuP6 @1 wt %Pt-TiO2 in the first hour reached 1 %. Zeta-potential measurements suggest that the surface Zr4+-phosphate groups attracted I− anions to the nanoparticle–solution interface. Our results indicate that the surface modification of dye-sensitized photocatalysts is a promising approach to enhance photocatalytic activity with various redox mediators. 相似文献
65.
Daisuke Saito Dr. Tomasz Galica Prof. Dr. Eiji Nishibori Dr. Masaki Yoshida Dr. Atsushi Kobayashi Prof. Dr. Masako Kato 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(32):e202200703
The vapochromic single-crystal-to-single-crystal (SCSC) transformation of a highly luminescent PtII complex bearing an N-heterocyclic carbene [Pt(CN)2(tBu-impy)] (tBu-impyH+=1-tert-butyl-3-(2-pyridyl)-1H-imidazolium) is reported. The trihydrate form of the complex, which exhibits blue 3MMLCT emission owing to weak Pt⋅⋅⋅Pt interactions, changed its luminescence color from blue to yellowish-green upon the desorption of water molecules while keeping the high emission quantum yield of more than 0.45. Variable-temperature and continuous in-situ tracking of single-crystal X-ray diffraction measurements revealed that the SCSC transformation proceeds reversibly by the release and reabsorption of water molecules, thereby changing the stacked structure slightly. As a result, the dynamics of vapor-induced SCSC transformation were elucidated: that the anhydrous form returned to the original trihydrate form in a two-step process under a water vapor atmosphere. In addition, the PtII complex exhibited a similar SCSC response accompanied by a luminescence color change in the presence of methanol vapor, while being inactive toward ethanol vapor. 相似文献
66.
Synthesis of thermally stable aromatic poly(spiroorthocarbonate)s having a Cardo or bent structure
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Masaki Moritsugu Ryota Seto Kozo Matsumoto Takeshi Endo 《Journal of polymer science. Part A, Polymer chemistry》2016,54(10):1409-1416
Novel poly(spiroorthocarbonate)s [poly(SOC)]s having a Cardo or bent structure were synthesized by polycondensation of several bis‐catechols having fluorene (BCFL), spirobisindane (BCSPI), or spirobischromane (BCSPC) in the structure with 2,2,6,6‐tetrachlorobenzo[1,2‐d:4,5‐d’]bis[1,3]dioxole (4ClBD). Synthesis of poly(SOC)s was confirmed by NMR and IR spectrometry. The poly(SOC)s obtained from BCFL or BCSPC were soluble in common organic solvents. The glass transition temperature of the poly(SOC)s was not detected by differential scanning calorimetry (DSC) in the range of 50–300 °C. The 10 wt % decomposition temperature of the poly(SOC)s was found to be above 400 °C. These results indicated the high thermal stability of the poly(SOC)s. Soluble poly(SOC)s could be possessed to form a film on a glass plate by the spin coat method. The obtained polymer films were 0.2 μm in thickness with 95% light transmission in the optical wavelength range. These results suggested that the Cardo or bent structure may block the packing of the main‐chain of the structure, which improves the solubility of the polymers, increases transparency, and enhances the thermal stability of SOCs. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1409‐1416 相似文献
67.
68.
T. Nakajima-KambeN.G. Edwinoliver H. MaedaK. Thirunavukarasu M.K. GowthamanK. Masaki S. MahalingamN.R. Kamini 《Polymer Degradation and Stability》2012,97(2):139-144
A lipase from Aspergillus niger MTCC 2594 was purified 53.8-fold to homogeneity by hydrophobic interaction chromatography using octyl sepharose and the enzyme showed two protein bands with apparent molecular mass of 35 and 37 kDa respectively. The lipase exhibited maximum activity at pH 7.0 and 37 °C and was stable between pH 4.0 and 10.0 and temperatures up to 50 °C. The values of Km and Vmax were 3.83 mM and 32.21 μmol/min/mg respectively, using olive oil as substrate. Lipase encoding gene, lipA, coded for 297 amino acid residues with conserved pentapeptide sequence, G-H-S-L-G, was cloned and expressed in Pichia pastoris. Although lipA showed high homology with the known Aspergillus lipases, it exhibited differences in putative lid domain. Both native and recombinant lipases have potential for degradation of poly(lactic acid) and poly(ε-caprolactone), and the present study will serve as a baseline of initial studies for its exploitation in polymer degradation. 相似文献
69.
70.
Mitsuji Yamashita Lakonda Nagaprasada Rao Valluru Krishna Reddy Motoki Maeda Tatsuo Oshikawa Masaki Takahashi 《Phosphorus, sulfur, and silicon and the related elements》2013,188(6-7):1661-1665
Novel pentofuranose analogs of phospha sugar derivatives were synthesized starting from 1-phenyl-2-phospholene 1-oxide ( 1 ). First, the allylic oxidation of 1-phenyl-2-phospholene 1-oxide ( 1 ) with CrO 3 in Ac 2 O-AcOH or 3-hydroxy-1-phenyl-2-phospholene ( 2 ) with MnO 2 afforded 1-phenyl-4-oxo-2-phospholene 1-oxide ( 3 ). The C-5 alkylation of 3 in the presence of NaH by using benzyl bromide or methyl iodide as electrophiles afforded the target title compounds. 相似文献