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71.
Cooke MW Hanan GS Loiseau F Campagna S Watanabe M Tanaka Y 《Journal of the American Chemical Society》2007,129(34):10479-10488
Ru(II) polypyridine species have been assembled about dirhodium(II, II) tetracarboxylate cores. The complexes prepared have general formulas [{(terpy)Ru(La)}n{Rh2(CH3COO)4-n(CH3CN)2}]2n+ (a-type compounds: terpy = 2,2':6',2' '-terpyridine; La = 4'-(p-carboxyphenyl)-2,2':6',2' '-terpyridine; n = 1, 1a; n = 2, cis-2a and trans-2a-cis and trans refer to the arrangement of the Ru(II) species around the dirhodium core; n = 3, 3a), [{(Lb)Ru(La)}n{Rh2(CH3COO)4-n(CH3CN)2}]2n+ (b-type compounds: Lb = 6-phenyl-2,4-di(2-pyridyl)-s-triazine; n = 1, 1b; n = 2, an inseparable mixture of cis-2b and trans-2b; n = 3, 3b; n = 4, 4b), and [{(terpy)Ru(Lc)}{Rh2(CH3COO)3(CH3CN)2}]2+ (1c; Lc = 6-(p-carboxyphenyl)-2,4-di(2-pyridyl)-s-triazine). As model species, also the mononuclear [(terpy)Ru(La)]2+ (5a), [(La)Ru(Lb)]2+ (5b), and [(terpy)Ru(Lc)]2+ (5c) have been prepared. All of the complexes have been characterized by several techniques, including NMR and mass spectra, and the stability of the various species is discussed. The absorption spectra of all of the compounds are dominated by the Ru(II) polypyridine moieties, showing intense ligand-centered (LC) bands in the UV region and intense metal-to-ligand charge-transfer (MLCT) bands in the visible. The compounds exhibit several metal-centered oxidation and ligand-centered reduction processes, which have been assigned to specific subunits. Both absorption and redox data indicate a supramolecular nature of the assembled systems. Efficient energy transfer from the MLCT triplet state of the Ru-based components to the lowest-energy excited state of the dirhodium core takes place for the a-type compounds at 298 K in acetonitrile solution, whereas such a process is inefficient for the b-type and c-type species, which exhibit the typical MLCT emission. At 77 K in butyronitrile matrix, Ru-to-Rh2 energy transfer is partly efficient for both the a-type and the b-type compounds and is inefficient for 1c. The reasons for such behavior are discussed by taking into account arguments concerning the driving force and reorganization energy of the complexes. 相似文献
72.
To prepare sulfur-containing natural polymers effectively, several plant oils and 3,3'-thiodipropionic acid (TDP) have been used as carbon sources for the biosynthesis of copolymer poly[(3-hydroxybutyrate)-co-(3-mercaptopropionate)] [poly(3HB-co-3MP)] by a wild-type bacterium Cupriviadus necator H16. By using the plant oils, copolymer accumulation and incorporation of 3MP units are greater than those of cases using sugars. The 3MP fraction is controllable over a range of 1-39 mol-% by adjusting the cultivation conditions. Microbial degradability of the copolymers has been examined in an activated sludge supernatant. The biodegradation proceeded by two mechanisms: surface erosion and auto-catalytic hydrolysis, depending on the 3MP unit fraction, and show preferential degradation of 3HB unit sequences. 相似文献
73.
Base-free catalytic alpha-alkylation of active methylene compounds with primary alcohols was successfully achieved using an [IrCl(cod)](2) complex in the presence of PPh(3) to afford the corresponding saturated alpha-alkylated products in good yields. 相似文献
74.
Taniguchi Y Ikehara T Kamo N Watanabe Y Yamasaki H Toyoshima Y 《Photochemistry and photobiology》2007,83(2):311-316
The photoreceptor phoborhodopsin (ppR; also called sensory rhodopsin II) forms a complex with its cognate the Halobacterial transducer II (pHtrII) in the membrane, through which changes in the environmental light conditions are transmitted to the cytoplasm in Natronomonas pharaonis to evoke negative phototaxis. We have applied a fluorescence resonance energy transfer (FRET)-based method for investigation of the light-induced conformational changes of the ppR/pHtrII complex. Several far-red dyes were examined as possible fluorescence donors or acceptors because of the absence of the spectral overlap of these dyes with all the photointermediates of ppR. The flash-induced changes of distances between the donor and an acceptor linked to cysteine residues which were genetically introduced at given positions in pHtrII(1-159) and ppR were determined from FRET efficiency changes. The dye-labeled complex was studied as solubilized in 0.1% n-dodecyl-beta-D-maltoside (DDM). The FRET-derived changes in distances from V78 and A79 in pHtrII to V185 in ppR were consistent with the crystal structure data (Moukhametzianov, R. et al. [2006] Nature, 440, 115-119). The distance from D102 in pHtrII linker region to V185 in ppR increased by 0.33 angstroms upon the flash excitation. These changes arose within 70 ms (the dead time of instrument) and decayed with a rate of 1.1 +/- 0.2 s. Thus, sub-angstrom-scale distance changes in the ppR/pHtrII complex were detected with this FRET-based method using far-red fluorescent dyes; this method should be a valuable tool to investigate conformation changes in the transducer, in particular its dynamics. 相似文献
75.
A triruthenium cluster, (mu3,eta2,eta3,eta5-acenaphthylene)Ru3(CO)7 (1) catalyzes the reaction of secondary amides with hydrosilanes, yielding a mixture of secondary amines, tertiary amines, and silyl enamines. Production of secondary amines with complete selectivity is achieved by the use of higher concentration of the catalyst (3 mol %) and the use of bifunctional hydrosilanes such as 1,1,3,3-tetramethyldisiloxane. Acidic workup of the reaction mixture affords the corresponding ammonium salts, which can be treated with a base, providing a facile method for isolation of secondary amines with high purity. In contrast, tertiary amines are formed with high selectivity by using lower concentration of the catalyst (1 mol %) and polymeric hydrosiloxanes (PMHS) as reducing agent. Reduction with PMHS encapsulates the ruthenium catalyst and organic byproducts to the insoluble silicone resin. The two reaction manifolds are applicable to various secondary amides and are practical in that the procedures provide the desired secondary or tertiary amine as a single product. The product contaminated with only minimal amounts of ruthenium and silicon residues. On the basis of the products and observed side products as well as NMR studies a mechanistic scenario for the reaction is also described. 相似文献
76.
A practical catalytic method to convert alkanes into the corresponding oxygen‐containing compounds with O2 under mild conditions using N‐hydroxyphthalimide (NHPI) in the presence or absence of a transition metal was developed. Thus, cyclohexane was successfully converted into adipic acid in good conversion and selectivity by a combined catalytic system consisting of NHPI and Mn(acac)2. Lower alkane such as isobutane was converted into t‐butyl alcohol (83%) under 10 atm of air by NHPI‐Co(OAc)2 system. Alkylbenzene such as toluene was oxidized to benzoic acid in high yield (81%) under normal temperature and pressure of dioxygen in the presence of a catalytic amount of NHPI and Co(OAc)2. ESR measurements showed that phthalimide‐N‐oxyl generated from NHPI under dioxygen atmosphere is a key species in this oxidation and functions as a radical catalyst. 相似文献
77.
78.
Yuki?KanazawaEmail authorView authors OrcID profile Tetsuya?Yamada Aki?Kido Koji?Fujimoto Kyoko?Takakura Hiroaki?Hayashi Yasutaka?Fushimi Satoshi?Kozawa Koji?Koizumi Makiko?Okuni Naomi?Ueda Kaori?Togashi 《Applied magnetic resonance》2017,48(2):125-134
To visualize the condition of impregnation of polyethylene glycol (PEG) in waterlogged wood, we demonstrated magnetic transfer (MT) magnetic resonance imaging (MRI) through a series of process of PEG impregnation. Three different samples were examined; reference wood, 10 cm cut wood, and 5 cm cut wood. During this study, the upper section sample was kept immersed in water, for the middle and lower sections the concentration of PEG solution was changed at 20 wt% intervals from 20 to 100 wt%. The impregnated periods of each PEG solution concentration were 14 days. Then, MR imaging were performed with/without MT pulse. The MTR value for both 10 cm- and 5 cm-samples were shown to decrease at 20 wt% PEG at peak concentration. When the sample volume was large, e.g., 10 cm-sample, the MTR value decreased to 100 wt% PEG concentration. In contrast, when a sample volume was small, e.g., 5 cm-sample, MTR value decreased to 60 wt% PEG concentration. In conclusion, MTR analysis makes it possible to nondestructively visualize and evaluate the inner condition concerning the PEG impregnation method for waterlogged wood. 相似文献
79.
Hidetaka Noritomi Kenji Kagitani Yasutaka Muratsubaki Satoru Kato 《Colloid and polymer science》2009,287(7):795-799
Palladium (Pd) nanoparticles were prepared in the reverse micellar system containing sucrose fatty acid esters with various
esterification degrees. The TEM showed that Pd nanoparticles were of spherical and relatively uniform. The size of Pd nanoparticles
strongly depended upon the composition of sucrose fatty acid esters. The resultant Pd colloid could be preserved for at least
2 months without precipitation. 相似文献
80.
Yasutaka Yatsumonji Takuya Nishimura Akira Tsubouchi Dr. Keiichi Noguchi Prof. Takeshi Takeda Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(11):2680-2686
A route with less congestion : A practical method for the highly diastereoselective preparation of anti tertiary homoallylic alcohols has been developed. The reaction of allyltitanocenes, generated by the reductive titanation of various allylic substrates with a titanocene(II) species, with a variety of ketones produced the anti tertiary homoallylic alcohols in good diastereoselectivity, even when using sterically less congested ketones (see scheme; Cp: cyclopentadienyl; Piv: pivaloyl).