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91.
Murahashi T Higuchi Y Katoh T Kurosawa H 《Journal of the American Chemical Society》2002,124(48):14288-14289
The linear sandwich tripalladium complexes [Pd3{Ar(CH=CH)4Ar}2[BArf]2 (Ar = Ph, p-t-Bu-C6H4, p-styryl-C6H4) undergo photoinduced isomerization involving face-inversion of the tetraene ligands. Irradiation of these complexes with visible light (>510 nm) resulted in rac (staggered sandwich) to meso (eclipsed sandwich) isomerization. The structures of rac and meso isomers are determined by X-ray crystallographic analyses. 相似文献
92.
Ogata H Mizoguchi Y Mizuno N Miki K Adachi S Yasuoka N Yagi T Yamauchi O Hirota S Higuchi Y 《Journal of the American Chemical Society》2002,124(39):11628-11635
The carbon monoxide complex of [NiFe]hydrogenase from Desulfovibrio vulgaris Miyazaki F has been characterized by X-ray crystallography and absorption and resonance Raman spectroscopy. Nine crystal structures of the [NiFe]hydrogenase in the CO-bound and CO-liberated forms were determined at 1.2-1.4 A resolution. The exogenously added CO was assigned to be bound to the Ni atom at the Ni-Fe active site. The CO was not replaced with H(2) in the dark at 100 K, but was liberated by illumination with a strong white light. The Ni-C distances and Ni-C-O angles were about 1.77 A and 160 degrees, respectively, except for one case (1.72 A and 135 degrees ), in which an additional electron density peak between the CO and Sgamma(Cys546) was recognized. Distinct changes were observed in the electron density distribution of the Ni and Sgamma(Cys546) atoms between the CO-bound and CO-liberated structures for all the crystals tested. The novel structural features found near the Ni and Sgamma(Cys546) atoms suggest that these two atoms at the Ni-Fe active site play a role during the initial H(2)-binding process. Anaerobic addition of CO to dithionite-reduced [NiFe]hydrogenase led to a new absorption band at about 470 nm ( approximately 3000 M(-1)cm(-1)). Resonance Raman spectra (excitation at 476.5 nm) of the CO complex revealed CO-isotope-sensitive bands at 375/393 and 430 cm(-1) (368 and 413 cm(-1) for (13)C(18)O). The frequencies and relative intensities of the CO-related Raman bands indicated that the exogenous CO is bound to the Ni atom with a bent Ni-C-O structure in solution, in agreement with the refined structure determined by X-ray crystallography. 相似文献
93.
M Mitsukuchi J Nakagami T Ikemoto S Higuchi Y Tarumoto H Yasui K Sota 《Chemical & pharmaceutical bulletin》1989,37(6):1534-1539
A series of 17-succinyl derivatives of four corticosteroids was prepared. They were tested for vasoconstrictive activity in humans, using 9 alpha-fluoro-11 beta, 21-dihydroxy-16 beta-methyl-17 alpha-valeryloxy-1,4-pregnadiene-3,20-dione (betamethasone 17-valerate, BV) as a standard. The activities of the 21-chloro 17-methylsuccinate compounds (6A, 6C and 6D) were greater than that of BV. A structure-activity relationship study showed that the activities of the 21-chloro 17-methylsuccinates were more potent than those of the corresponding 21-esters. 相似文献
94.
Tetsuya Shimizu Yasuka Komatsu Hidenobu Kamihata Young Hoon Lee Akira Fuyuhiro Seiichiro Iijima Shinya Hayami 《Journal of inclusion phenomena and macrocyclic chemistry》2011,71(3-4):363-369
Iron(III) spin-crossover compounds, [Fe(qnal)2]CF3SO3·MeOH (1·MeOH) and [Fe(qnal)2]CF3SO3·acetone (1·acetone) were prepared and their spin transition properties were characterized by magnetic susceptibility measurement, Mössbauer spectroscopy and single crystal analysis. Two iron(III) compounds exhibited abrupt spin transition with thermal hysteresis loop (T 1/2?? = 115 K and T 1/2?? = 104 K for 1·MeOH, and T 1/2?? = 133 K and T 1/2?? = 130 K for 1·acetone). Single crystal analysis revealed both of the structures in high-spin (HS) and low-spin (LS) states for 1·acetone. The difference of bond length between the HS and LS states for 1·acetone was ~0.10 Å, which was corresponding to that of typical iron(III) SCO compounds. Specially, it showed strong intermolecular interactions by ???C?? stacking formed between the neighbor complexes leading to 2-D sheet. Both 1·MeOH and 1·acetone exhibited LIESST effect when it was illuminated at 1000 nm. We also confirmed that the introduction of strong intermolecular interactions, such as ???C?? stacking, can play an important role in LIESST effect. 相似文献
95.
96.
Fujinami T Nishi K Matsumoto N Iijima S Halcrow MA Sunatsuki Y Kojima M 《Dalton transactions (Cambridge, England : 2003)》2011,40(45):12301-12309
Two Fe(II) complexes fac-[Fe(II)(HL(n-Pr))(3)]Cl·Y (Y = AsF(6) (1) and BF(4) (2)) were synthesized, where HL(n-Pr) is 2-methylimidazole-4-yl-methylideneamino-n-propyl. Each complex-cation has the same octahedral N(6) geometry coordinated by three bidentate ligands and assumes facial-isomerism, fac-[Fe(II)(HL(n-Pr))(3)](2+) with Δ- and Λ-enantiomorphs. Three imidazole groups per Δ- or Λ-fac-[Fe(II)(HL(n-Pr))(3)](2+) are hydrogen-bonded to three Cl(-) ions or, from the viewpoint of the Cl(-) ion, one Cl(-) ion is hydrogen-bonded to three neighbouring fac-[Fe(II)(HL(n-Pr))(3)](2+) cations. The 3?:?3 NH···Cl(-) hydrogen bonds between Δ- or Λ-fac-[Fe(II)(HL(n-Pr))(3)](2+) and Cl(-) generate two kinds of assembly structures. The directions of the 3?:?3 NH···Cl(-) hydrogen bonds and hence the resulting assembly structures are determined by the size of the anion Y, though Y is not involved into the network structure and just accommodated in the cavity. Compound 1 has a 1D ladder structure giving a larger cavity, in which the Δ- and Λ-fac-[Fe(II)(HL(n-Pr))(3)](2+) enantiomorphs are bridged by two NH···Cl(-) hydrogen bonds. Compound 2 has a 2D network structure with a net unit of a cyclic trimer of {fac-[Fe(II)(HL(n-Pr))(3)](2+)···Cl(-)}(3) giving a smaller cavity, in which Δ- or Λ-fac-[Fe(II)(HL(n-Pr))(3)](2+) species with the same chirality are linked by NH···Cl(-) hydrogen bonds to give a homochiral 2D network structure. Magnetic susceptibility and M?ssbauer spectral measurements demonstrated that compound 1 showed an abrupt one-step spin crossover with 4.0 K thermal hysteresis of T(c↓) = 125.5 K and T(c↑) = 129.5 K and compound 2 showed no spin transition and stayed in the high-spin state over the 5-300 K temperature range. 相似文献
97.
Two types of thiophene-capped [2]rotaxanes, i.e., bithienyl (2T)- and bis(3,4-ethylenedioxythiophene)-yl (BEDOT)-capped [2]rotaxanes, were synthesized. The electron-deficient cyclophane of cyclobis(paraquat-p-phenylene) (CBPQT4+) was used as a macrocycle. Association constants for inclusion complexation of 2T- and BEDOT-derivatives with CBPQT4+ were obtained by 1H NMR titration. Due to the donor-acceptor charge transfer absorption band, 2T- and BEDOT-capped [2]rotaxanes have red and green colors, respectively. On the basis of electrochemical analysis, we confirmed that only BEDOT-capped [2]rotaxane is a promising candidate for [3]rotaxane synthesis through oxidation coupling of the thiophene unit. 相似文献
98.
Dai Kato Atsumu Oda Mutsuo Tanaka Seiichiro Iijima Tomoyuki Kamata Masami Todokoro Yasuo Yoshimi Osamu Niwa 《Electroanalysis》2014,26(3):618-624
We developed an electrochemical system for detecting lipopolysaccharide (LPS) that uses an ultraflat nanocarbon film electrode modified with poly‐ε‐lysine with a high affinity to LPS. LPS was captured on the modified electrode, and then ferrocene labeled polymyxin B (FcPMB) was captured on the LPS adsorbed electrode via the LPS‐PMB affinity interaction. The adsorbed FcPMB provided an amplified response with Fe2+ ions, and the current response was dependent on the amount of captured LPS (LOD=2.0 ng/mL). This was due to the efficient accumulation of the obtained current for LPS and the very low noise made possible by the ultraflat surface. 相似文献
99.
Despite the fact that many transition-metal-catalyzed reactions of organosulfur compounds with internal alkynes are ineffective, cobalt carbonyl (Co2(CO)8) is an excellent catalyst for carbonylative cyclization of internal alkynes with carbon monoxide. When Co2(CO)8-catalyzed reactions of internal alkynes with organic thiols are conducted in acetonitrile under 4 MPa pressure of carbon monoxide, thiolative lactonization of internal alkynes successfully takes place with incorporation of two molecules of CO. This carbonylation provides a useful tool to prepare the corresponding α,β-unsaturated γ-thio-γ-lactones (butenolide derivatives) in good yields. In the cases of unsymmetrical alkynes, such as 2-octyne and 6-methyl-2-heptyne, the thiolative lactonization proceeds with moderate regioselectivity to give the butenolide derivatives on which the carbonyl group preferentially bonds to the less hindered acetylenic carbon. Mechanistic pathways about the present thiolative lactonization are also discussed. 相似文献
100.
The heterogeneous dielectric generalized Born (HDGB) methodology is an the extension of the GBMV model for the simulation of integral membrane proteins with an implicit membrane environment. Three large integral membrane proteins, the bacteriorhodopsin monomer and trimer and the BtuCD protein, were simulated with the HDGB model in order to evaluate how well thermodynamic and dynamic properties are reproduced. Effects of the truncation of electrostatic interactions were examined. For all proteins, the HDGB model was able to generate stable trajectories that remained close to the starting experimental structures, in excellent agreement with explicit membrane simulations. Dynamic properties evaluated through a comparison of B-factors are also in good agreement with experiment and explicit membrane simulations. However, overall flexibility was slightly underestimated with the HDGB model unless a very large electrostatic cutoff is employed. Results with the HDGB model are further compared with equivalent simulations in implicit aqueous solvent, demonstrating that the membrane environment leads to more realistic simulations. 相似文献