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排序方式: 共有281条查询结果,搜索用时 15 毫秒
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Jörn Müller Helmuth Menig Gottfried Huttner Albin Frank 《Journal of organometallic chemistry》1980,185(2):251-263
The complexes [Ir(COD)(η5-C7H9)] and [Ir(COD)(η5-C8H11)] are obtained by the isoprophyl Grignard synthesis of [Ir(COD)Cl]2 (COD = η4-1,5-cyclooctadiene) in the presence of cycloheptatriene, and cyclooctatriene, respectively. The later reaction yields [IrH(COD)(δ4-1,3,6-C8H10)] as a by-product which, in contrast to other [IrH(η4-cyclodiene)2] complexes, does not show H-addition-elimination equilibria. Reduction of [Ir(1,3-C7H10)2Cl] with C2H5OH/Na2CO3 yields [Ir(η4-1,3-C7H10)](η5-C7H9)] which was characterized by X-ray analysis. [Ir(COD)Cl]2 reacts with Na2C8H8, and after hydrolysis unstable [Ir(COD)(η5-C8H9)] is formed which by protonation with HPF6 is converted into the [Ir(COD)(η6-1,3,5-C8H10)]+ cation. All these compounds are fluxional in solution. 相似文献
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A novel capsule composed of an azo dye, Congo red (CR), and different polymers, including poly(styrenesulfonate, sodium salt) (PSS), poly(allylamine hydrochloride) (PAH), and poly(diallyldimethylammonium chloride) (PDDA), have been successfully fabricated by the layer-by-layer self-assembly technique. The stepwise linear deposition process was monitored by means of UV-visible absorption measurements. The formation of hollow capsules was verified by confocal laser scanning microscopy (CLSM) and scanning force microscopy (SFM). The resulting hollow PSS/PAH/CR/PDDA capsules displayed a sensitive response to visible light. Optical changes of the hollow capsules prior to and after the photoreaction were investigated in detail by means of UV-visible spectroscopy, CLSM, and SFM. It was found that the photochemical reaction of the assembled hollow capsules depends strongly on the matrix. Qualitative results on the permeability of the hollow capsule walls with CR as one component indicate that the permeability of the walls can be easily photo-controlled at varying irradiation time intervals without addition of external chemicals. 相似文献
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Alfred Trautwein Yutaka Maeda Frank E. Harris Helmuth Formanek 《Theoretical chemistry accounts》1974,36(1):67-76
Experimental Mössbauer spectra of the Fe57-enriched CO complex of sperm whale myoglobin (MbCO) at T= 4.2 K with and without applied magnetic field (H⊥γ) were measured to derive the sign of the electric field gradient (EFG), the quadrupole splitting ΔE Q, and the isomer shift δ of the heme iron. We find a positive EFG, δE Q = 0.363 mm/sec, and δ + 0.266 mm/sec. Molecular orbital calculations were carried out to obtain theoretical estimates of EFG and ΔE Q for several steric arrangements of the CO ligand relative to the heme group. Our results are most consistent with the conclusion that the iron is situated in the heme plane, and that a bent geometry with a Fe-C-O angle of about 135 ° is more favorable than a more symmetric structure with a linear Fe-C-O geometry. 相似文献
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The complexes [(1,3-C6H8)2IrR] and [(1,3-C7H10)2IrR] (R = CH3, C6H5) are obtained by reaction of the corresponding chloro compounds with RLi. Interaction of [Ir(COD)Cl]2 (COD = 1,5-cyclooctadiene) with CH3Li in the presence of 1,3-cyclohexadiene or isoprene yields [(COD)(1,3-C6H8IrCH3] and [(COD)(C5H8IrCH3], respectively. The products of the reaction of chlorodicyclodieneiridium with n-C4H9Li depend on the ring size of the cyclodiene ligands; with 1,3-cyclohexadiene [(1,3-C6H8)2IrH] is formed while with 1,3-cycloheptadiene [(1,3-C7H10)(C7H9)Ir] is obtained together with [(1,3-C7H10)3Ir2(μ-H)2]. Chemical and spectroscopic properties of the new compounds are discussed. 相似文献
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Petrov JG Andreeva TD Kurth DG Möhwald H 《The journal of physical chemistry. B》2005,109(29):14102-14111
The dipole potential, affecting the structure, functions, and interactions of biomembranes, lipid bilayers, and Langmuir monolayers, is positive toward the hydrocarbon moieties. We show that uncharged Langmuir monolayers of docosyl trifluoroethyl ether (DFEE) exhibit large negative dipole potentials, while the nonfluorinated docosyl ethyl ether (DEE) forms films with positive dipole potentials. Comparison of the Delta V values for these ethers with those of the previously studied(37-39) monolayers of trifluoroethyl ester (TFEB) and ethyl ester of behenic acid (EB) shows that the reversal of the sign of Delta V causes the same change Delta(Delta V) = -706 +/- 16 mV due to fluorination of heads. The Delta V values of both TFEB and EB films differ by -122 +/- 16 mV from those of DFEE and DEE monolayers, respectively, with the same density. Such quantitative coincidence points to a common mechanism of reversal of the sign of the dipole potential for the ether and ester films despite the different structure of their heads. The mechanical properties and phase behaviors of these monolayers show that both fluorinated heads are less hydrated, suggesting that the change of the sign of Delta V could, at least partially, be related to different hydration water structure. The same negative contribution of the carbonyl bond in both TFEB and EB films contrasts with the generally accepted positive contribution of the C(delta+)=O(delta-) bond in condensed Langmuir monolayers of fatty acids, their alcohol esters, glycerides, and phospholipids but concurs with the theoretical analysis of Delta V of stearic acid monolayers. Both results question the literature values of the molecular dipole moments of these substances calculated via summation of bonds and atomic group contributions. Mixed monolayers of DFEE and DEE show smooth monotonic variation of Delta V from +450 to -235 mV, indicating a way for adjustment of the sign and magnitude of the dipole potential at the membrane-water boundary and regulation of such membrane behaviors as binding and translocation rate of hydrophobic ions and ion-carriers, adsorption and penetration of amphiphilic peptides, polarization of hydration water, and short-range repulsion. The interaction of the hydrophobic ions tetraphenylboron TPhB- and tetraphenylphosphonium TPhP+ with DFEE and DEE monolayers qualitatively follows the theory of binding of such ions to lipid bilayers, but the shifts Delta(Delta V) from the values obtained on water are much smaller than those for DPPC monolayers. This difference seems to be due to the solid (polycrystalline) character of the DFEE and DEE films that hampers the penetration of TPhB- and TPhP+ in the monolayers and reduces the attractive interaction with the hydrophobic moiety. This conclusion orients the future synthesis of amphiphiles with fluorinated heads to those which could form liquid-expanded Langmuir monolayers. 相似文献
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