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241.
Yoshihito Kayaki Dr. Masafumi Yamamoto Takao Ikariya Prof. Dr. 《Angewandte Chemie (International ed. in English)》2009,48(23):4194-4197
Getting a fix : N‐heterocyclic carbenes (NHCs) and NHC–CO2 adducts serve as potent organocatalysts for carbonate synthesis by the addition of a CO2 unit to propargylic alcohols or epoxides under mild and solvent‐free reaction conditions (see scheme). The enhanced Lewis basicity of imidazol‐2‐ylidenes bearing electron‐donating alkyl groups on the nitrogen atoms leads to utilizing CO2 as a nucleophilic fragment in the chemical fixation processes.
242.
We propose a statistical dynamical theory for the violation of the hydrodynamic Stokes-Einstein (SE) diffusion law for a spherical nanoparticle in entangled and unentangled polymer melts based on a combination of mode coupling, Brownian motion, and polymer physics ideas. The non-hydrodynamic friction coefficient is related to microscopic equilibrium structure and the length-scale-dependent polymer melt collective density fluctuation relaxation time. When local packing correlations are neglected, analytic scaling laws (with numerical prefactors) in various regimes are derived for the non-hydrodynamic diffusivity as a function of particle size, polymer radius-of-gyration, tube diameter, degree of entanglement, melt density, and temperature. Entanglement effects are the origin of large SE violations (orders of magnitude mobility enhancement) which smoothly increase as the ratio of particle radius to tube diameter decreases. Various crossover conditions for the recovery of the SE law are derived, which are qualitatively distinct for unentangled and entangled melts. The dynamical influence of packing correlations due to both repulsive and interfacial attractive forces is investigated. A central finding is that melt packing fraction, temperature, and interfacial attraction strength all influence the SE violation in qualitatively different directions depending on whether the polymers are entangled or not. Entangled systems exhibit seemingly anomalous trends as a function of these variables as a consequence of the non-diffusive nature of collective density fluctuation relaxation and the different response of polymer-particle structural correlations to adsorption on the mesoscopic entanglement length scale. The theory is in surprisingly good agreement with recent melt experiments, and new parametric studies are suggested. 相似文献
243.
Hirota K Hasegawa T Nakajima T Makino K Terada H 《Colloids and surfaces. B, Biointerfaces》2011,87(2):293-298
In this work we obtain the thermodynamic properties of mixed (1-stearoyl-2-oleoyl-sn-glycero-3-phosphocholine) PC and (1-stearoyl-2-oleoyl-sn-glycero-3-phospho-l-serine (sodium salt)) PS monolayers. Measurements of compressibility (isotherms, bulk modulus, and excess area per molecule) and surface potential show that the properties of monolayers at the air–water interface depend on the concentration of ions (Na+ and K+) and the proportion of PS in the mixture. The dependence on PS arises because the molecule is originally bound to a Na+ counterion; by increasing the concentration of ions the entropy changes, creating a favorable system for the bound counterions of PS to join the bulk, leaving a negatively charged molecule. This change leads to an increase in electrostatic repulsions which is reflected by the increase in area per molecule versus surface pressure and a higher surface potential. The results lead to the conclusion that this mixture of phospholipids follows a non ideal behavior and can help to understand the thermodynamic behavior of membranes made of binary mixtures of a zwitterionic and an anionic phospholipid with a bound counterion. 相似文献
244.
Nagao S Hirai Y Suzuki A Yamamoto Y 《Journal of the American Chemical Society》2005,127(12):4146-4147
A 19F NMR study on the acid-alkaline transition in sperm whale myoglobin reconstituted with a perfluoromethyl heme, 13,17-bis(2-carboxylatoethyl)-3,8-diethyl-2,12,18-trimethyl-7-trifluoromethylporphyrinatoiron(III), demonstrated that the thermodynamics of the transition is predominantly controlled by the stability of acidic form. 相似文献
245.
Yuya Ikeuchi Dr. Hiroshi Takatsu Dr. Cédric Tassel Yoshihiro Goto Taito Murakami Prof. Hiroshi Kageyama 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(21):5864-5867
A high-pressure reaction yielded the fully occupied tetragonal tungsten bronze K3W5O15 (K0.6WO3). The terminal phase shows an unusual transport property featuring slightly negative temperature-dependence in resistivity (dρ/dT<0) and a large Wilson ratio of RW=3.2. Such anomalous metallic behavior possibly arises from the low-dimensional electronic structure with a van Hove singularity at the Fermi level and/or from enhanced magnetic fluctuations by geometrical frustration of the tungsten sublattice. The asymmetric nature of the tetragonal tungsten bronze KxWO3-K0.6−yBayWO3 phase diagram implies that superconductivity for x≤0.45 originates from the lattice instability because of potassium deficiency. A cubic perovskite KWO3 phase was also identified as a line phase—in marked contrast to NaxWO3 and LixWO3 with varying quantities of x (<1). This study presents a versatile method by which the solubility limit of tungsten bronze oxides can be extended. 相似文献
246.
Measurements of rate constants and substituent effects for three important elementary steps of proton-transfer reactions of phenylnitromethane were reported. The Hammett ρ values for the deprotonation of ArCH(2)NO(2) with OH(-), protonation of ArCH═NO(2)(-) with H(2)O, and protonation of ArCH═NO(2)(-) with HCl were determined in aqueous MeOH at 25 °C. Comparison of these experimentally observed ρ values with those calculated at B3LYP/6-31G* revealed that aci-nitro species (ArCH═NO(2)H), which is formed on the O-protonation of ArCH═NO(2)(-), does not lie on the main route of the proton-transfer reaction. Analysis of the Br?nsted plot implies that the proton-transfer reaction of most XC(6)H(4)CH(2)NO(2) exhibits nitroalkane anomaly, but not for p-NO(2)C(6)H(4)CH(2)NO(2), and that the transition state charge imbalance is an origin of anomaly. 相似文献
247.
We found that La(2)Sb with a layered structure composed of alternate stacking of La square nets and LaSb layers exhibits bulk superconductivity with a critical temperature of 5.3 K. This suggests that the presence of the square net with strong La-La metal bonding is essential for the emergence of superconductivity. 相似文献
248.
Recently, there has been a progressive development of insulated π-conjugated metallopolymers with accumulated features of π-conjugated bridging units, transition metal complexes, and encapsulating moieties, as higher-order functionalized materials. A number of insulated conjugated metallopolymers have been successfully synthesized and their fascinating properties have been reported. In addition to the conventional features derived from π-conjugation and transition metals, their insulated structures can compensate for solubility, a disadvantage in conventional metallopolymers, and enhance their functionalities, such as sensing, luminescence, and conduction. In this review, we summarize the synthetic methodologies, structural characteristics, and functionalities of one-dimensional insulated π-conjugated metallopolymers, while focusing on the effect of transition metals and insulation on their properties. 相似文献
249.
Shotaro Hayashi Minami Sakamoto Fumitaka Ishiwari Takanori Fukushima Shin-ichi Yamamoto Toshio Koizumi 《Tetrahedron》2019,75(8):1079-1084
Here we report the facile derivatization of a cyano-substituted stilbene into higher π-extended analogues. The cyano-substituted stilbene, which serves as a synthetic scaffold, has a bromo group and a formyl group on its 4- and 4′-position of the phenylene rings and thus readily undergoes selective transformation into other functional groups using various simple organic reactions. The resultant π-conjugated molecules that contain a cyano-substituted stilbene skeleton exhibit fluorescence in solution and in the solid state. 相似文献
250.
Dr. Ko Sato Dr. Hiroshi Tanaka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(36):9422-9428
Lignans are a group of polyphenolic phytochemicals that possess a large spectrum of chemical structures and biological activities. Here the syntheses of lignans – anwulignan, burseran, dehydroxycubebin, ruburisandrin B, and sesamin – are achieved based on a borate-mediated one-pot sequential Suzuki-Miyaura coupling of cis- and trans-fused bicyclic boranes, which were prepared by diastereoselective cyclic hydroboration of exo-cyclic diene with cyclopentyl- and thexylboranes, respectively. A one-pot sequential Suzuki-Miyaura coupling of each cyclic borate with various aryl bromides initiated by activation of the cyclic borane with the carbon nucleophile provided 2,3-dibenzylbutane derivatives with different aromatic substituents. Finally, the syntheses of naturally occurring lignans were accomplished in several steps from the products of Suzuki-Miyaura coupling. 相似文献