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331.
The development of a water-soluble and small molecular weight fluorescent probe, 3-(4-methoxyphenyl)-4-(methylsulfanyl)-6-(pyridin-2-yl)pyridin-2(1H)-one (3), for detecting Zn2+ based on pyridine-pyridone skeleton is reported. We observed a clear chelation enhanced fluorescence effect of 3 in the presence of Zn2+. Other fluorescent properties of 3 are discussed. 相似文献
332.
New structurally constrained BODIPY dyes having electron-donating substituents were synthesized. As the key compounds for the construction of the BODIPY dyes, 1′H-spiro-[fluorene-9,4′-indeno[1,2-b]pyrrole] (sp-FIP) derivatives with electron-donating groups, such as OMe and NMe2 at its 6′-position, were prepared using palladium-catalyzed intramolecular direct C-H arylation of a pyrrole moiety. The resulting BODIPY dyes showed bathochromic shift in absorption and fluorescence spectra in comparison to the unsubstituted analogs. Furthermore, pH-dependent reversible spectrum changes of the BODIPY dye were observed with the addition of trifluoroacetic acid (TFA) and subsequent addition of i-Pr2NEt. 相似文献
333.
Hidetsura Cho Yoshio Nishimura Yoshizumi YasuiSatoshi Kobayashi Shin-ichiro Yoshida Eunsang Kwon Masahiko Yamaguchi 《Tetrahedron》2011,67(14):2661-2669
Synthesis of novel 4-unsubstituted dihydropyrimidines (DPs) was performed. Subsequently, a variety of 4-unsubstituted 1,4(3,4)-DPs with amino moieties at position-2 were obtained in excellent yields by activation of position-2 owing to regioselective alkoxycarbonylation at position-3 of the DP skeleton. 3-Oxo-2-phenyl-2,3,5,8-tetrahydro[1,2,4]triazolo[4,3-a]pyrimidine was obtained using phenylhydrazine instead of amines. Individual tautomers of 1,4(3,4)-DP were observed in the 1H NMR spectra of one derivative depending on temperature and concentration. On the other hand, only 1,4-DP was found in the solid state by single-crystal X-ray crystallography. 相似文献
334.
Keiji Kinoshita Toru SaitoAkira Ito Takashi KawakamiYasutaka Kitagawa Shusuke YamanakaKizashi Yamaguchi Mitsutaka Okumura 《Polyhedron》2011,30(18):3249-3255
Recently, graphene sheet is one of interesting systems to realize novel electronic properties. Especially, interaction between graphene and adsorbed oxygen molecule is very important to control electronic condition. In this paper, we employed some aromatic hydrocarbons as simple systems of graphene sheet and ab initio MO calculations were carried out to investigate inter-molecular interaction. It is found that not triplet but singlet O2 molecule have potential of chemisorption onto graphene surface. From the calculated potential energy surface (PES) for distance between benzene and O2 molecules, meta-stable structure is found at about 1.5 Å with potential barrier. In the optimized structure of its meta-stable state, structural strain can be relaxed through bending of planer benzene ring. Its energy is estimated at 70.10 kcal/mol for benzene. We also estimated the strain effects for naphthalene and pyrene molecules as larger case of graphene and they were 80.85 and 72.45 kcal/mol, respectively. 相似文献
335.
Chen X Yamaguchi A Namekawa M Kamijo T Teramae N Tong A 《Analytica chimica acta》2011,696(1-2):94-100
A Schiff base (SB) immobilized hybrid mesoporous silica membrane (SB-HMM) was prepared by immobilizing a Schiff base onto the pore surface of mesoporous silica (pore size=3.1 nm) embedded in the pores of a porous anodic alumina membrane. In contrast to the non-fluorescent analogous SB molecule in homogeneous solutions, SB-HMM exhibited intense fluorescence due to emission enhancement caused by aggregation of SB groups on the pore surface. The high quantum efficiency of the surface SB groups allows SB-HMM to function as a fluorescent sensor for Cu(II) ions in an aqueous solution with good sensitivity, selectivity and reproducibility. Under the optimal conditions described, the linear ranges of fluorescence intensity for Cu(II) are 1.2-13.8(M (R(2)=0.993) and 19.4-60 (R(2)=0.992) (M. The limit of detection for Cu(II) is 0.8 μM on basis of the definition by IUPAC (C(LOD)=3.3S(b)/m). 相似文献
336.
Saito T Yasuda N Kataoka Y Nakanishi Y Kitagawa Y Kawakami T Yamanaka S Okumura M Yamaguchi K 《The journal of physical chemistry. A》2011,115(22):5625-5631
The spin-unrestricted Hartree-Fock (UHF)-based coupled cluster singles and doubles (UHF-CCSD) and Mukherjee's state-specific multireference CCSD (MkCCSD) methods are applied to four ring-opening reactions. The spin-restricted Hartree-Fock (RHF)-based CCSD (RHF-CCSD) calculations are also performed for comparison. In the case of the UHF-CCSD method, an approximate spin-projection (AP) method is applied to the broken-symmetry (BS) singlet solution to remove the spin contamination effect. For potential energy curves (PECs) of all reactions presented in this study, the results of RHF-CCSD and UHF-CCSD are substantially different from those of MkCCSD, while the results after the AP method (AP-UCCSD) reproduce the MkCCSD results well. It strongly suggests that the spin contamination effect should be removed by the AP correction even at the UHF-CCSD level to predict reliable energetics of these reactions. 相似文献
337.
Ohtaka A Yamaguchi T Teratani T Shimomura O Nomura R 《Molecules (Basel, Switzerland)》2011,16(11):9067-9076
Linear polystyrene-stabilized PdO nanoparticles (PS-PdONPs) were prepared by thermal decomposition of Pd(OAc)(2) in the presence of polystyrene. X-ray diffraction (XRD) and transmission electron microscopy (TEM) indicated the production of PdO nanoparticles. The loading of palladium was determined by inductively coupled plasma-atomic emission spectroscopy (ICP-AES). PS-PdONPs exhibited high catalytic activity for Mizoroki-Heck reactions under air in water and could be recycled without loss of activity. 相似文献
338.
Tano T Ertem MZ Yamaguchi S Kunishita A Sugimoto H Fujieda N Ogura T Cramer CJ Itoh S 《Dalton transactions (Cambridge, England : 2003)》2011,40(40):10326-10336
Copper(II) complexes 1a and 1b, supported by tridentate ligand bpa [bis(2-pyridylmethyl)amine] and tetradentate ligand tpa [tris(2-pyridylmethyl)amine], respectively, react with cumene hydroperoxide (CmOOH) in the presence of triethylamine in CH(3)CN to provide the corresponding copper(II) cumylperoxo complexes 2a and 2b, the formation of which has been confirmed by resonance Raman and ESI-MS analyses using (18)O-labeled CmOOH. UV-vis and ESR spectra as well as DFT calculations indicate that 2a has a 5-coordinate square-pyramidal structure involving CmOO(-) at an equatorial position and one solvent molecule at an axial position at low temperature (-90 °C), whereas a 4-coordinate square-planar structure that has lost the axial solvent ligand is predominant at higher temperatures (above 0 °C). Complex 2b, on the other hand, has a typical trigonal bipyramidal structure with the tripodal tetradentate tpa ligand, where the cumylperoxo ligand occupies an axial position. Both cumylperoxo copper(II) complexes 2a and 2b are fairly stable at ambient temperature, but decompose at a higher temperature (60 °C) in CH(3)CN. Detailed product analyses and DFT studies indicate that the self-decomposition involves O-O bond homolytic cleavage of the peroxo moiety; concomitant hydrogen-atom abstraction from the solvent is partially involved. In the presence of 1,4-cyclohexadiene (CHD), the cumylperoxo complexes react smoothly at 30 °C to give benzene as one product. Detailed product analyses and DFT studies indicate that reaction with CHD involves concerted O-O bond homolytic cleavage and hydrogen-atom abstraction from the substrate, with the oxygen atom directly bonded to the copper(II) ion (proximal oxygen) involved in the C-H bond activation step. 相似文献
339.
Sakamoto K Takashima Y Hamada N Ichida H Yamaguchi H Yamamoto H Harada A 《Organic letters》2011,13(4):672-675
An energy transfer process was investigated using cyclodextrin-oligothiophene rotaxanes (2T-[2]rotaxane). The excited energy of 2T-[2]rotaxane is transferred to the sexithiophene derivative which is included in the cavity of β-CD stoppers of 2T-[2]rotaxane. 相似文献
340.
This review article summarizes our recent researches for molecular design of polyoxometalates (POMs) and their related compounds
for environmentally-friendly functional group transformations. The divacant POM [γ-SiW10O34(H2O)2]4− exhibits high catalytic performance for mono-oxygenation-type reactions including epoxidation of olefins and allylic alcohols,
sulfoxidation, and hydroxylation of organosilanes with H2O2. We have successfully synthesized several POM-based molecular catalysts (metal-substituted POMs) with controlled active sites
by the introduction of metal species into the divacant POM as a “structural motif”. These molecular catalysts can efficiently
activate H2O2 (vanadium-substituted POM for epoxidation) and alkynes (copper-substituted POM for click reaction and oxidative homocoupling
of alkynes). The aluminum-substituted POM exhibits Lewis acidic catalysis for diastereoselective cyclization of (+)-citronellal
to (−)-isopulegol. In addition, we have developed POM-based “molecular heterogeneous catalysts” by the “solidification” and
“immobilization” of catalytically active POMs. 相似文献