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101.
A cyclotron resonance experiment on polarons in pure AgBr has been extended to the microwave field of 3 kV cm?1 by using a pulsed magnetron at 35 GHz at lattice temperatures of 4.2 and 17 K in magnetic fields up to 58 kOe. It was established that the ground state polaron mass is m1p(0)=(0.287±0.003)me. From microwave field dependences of the peak position and the width of resonance lines, it was established that the electron polaron follows the streaming motion repetitively emitting LO-phonons in the microwave field region above 80 V cm?1. Further, it was also suggested that, when streaming, the polaron has an enhanced effective mass of (0.353±0.006)me rather than the ground state mass m1p(0).  相似文献   
102.
Cycloanthranilylproline (1) and its derivatives (2--4) were isolated from field-collected fruit-bodies of a myxomycete Fuligo candida and their structures were elucidated by spectral data. Compound 4, which was contained in the water-soluble fraction of the extract of this myxomycete, was unstable and quite susceptible to decarboxylation to yield compound 2, which was a major constituent of the EtOAc-soluble fraction of this extract.  相似文献   
103.
Catechol dioxygenase model oxygenations have been performed for the first time in water by using water-soluble nonheme iron(III) complexes, enabling the oxygenation of protocatechuic acid and other catechols.  相似文献   
104.
To analyze a curing process of epoxy resin in terms of molecular motion, we adapted a pulsed NMR method. Three kinds of (1)H spin-spin relaxation times (T(2L) (long), T(2S) (short) and T(2M) (intermediate)) were estimated from observed solid echo train signals as the curing process proceeded. A short T(2S) value below 20 micros suggests the existence of a motion-restricted chain, that is, cured elements of resin, and its fraction, P(S), sigmoidally increased with the curing time. On the other hand, the fraction of T(2L), P(L), decreased with the reaction time reciprocally against P(S), suggesting the disappearance of highly mobile molecules raised from pre-cured resin. The spin-lattice relaxation time, T(1), was also measured to check another aspect of molecular motion in the process. T(1) of the mixed epoxy resin and curing agent gradually increased just after mixing both of them. This corresponds to an increment of a less-mobile fraction, of which the correction time is more than 10(-6) s, and also means that the occurrence of a network structure whose mobility is strongly restricted by chemically bonded bridges between the epoxy resin and curing agent. The time courses of these parameters coincided with those of IR peaks pertinent to the curing reaction. Therefore, pulsed NMR is a useful tool to monitor the hardening process of epoxy resin in real time non-distractively in terms of the molecular motion of protons.  相似文献   
105.
    
Polymerization of methacrylic esters such as benzyl methacrylate using as initiator an-equimolar mixture of methylaluminium 5,10,15,20-tetraphenylporphine [(TPP)AlMe] and 2,7,12,17-tetramethyl-3,8,13,18-tetramethylporphine [(EtioP)AlMe] proceeded from both initiators, affording a unimodal polymer of narrow molecular weight distribution, although the reactivities of (TPP)AlMe and (EtioP)AlMe are very different from each other. 1H NMR studies on a mixture of two different (porphinato)aluminium enolates, the growing species, and a mixture of a (porphinato)aluminium enolate and an alcoholate, in the absence and presence of methyl methacrylate (MMA or MMA-d8), indicated an acyclic transition state polymerization mechanism by the participation of two aluminium porphyrin molecules, where the growing species always exchange their enolate ligands whenever it grows.  相似文献   
106.
    
Both the regioselectivity and the reaction rate for the β-cyclodextrin (β-CyD)-induced P–O(3′) cleavage of adenosine 2′, 3′-cyclic phosphate (A > p) to adenosine 2′-phosphate are greatly promoted by KF. The promoting activity of KF is much larger than that of KCl. KF amplifies the difference in the chemical circumstance between the P–O(2′) and the P–O(3′) bonds of A > p, induced by β-CyD on complex formation with A > p. The higher activity of KF is ascribed to absence of complex formation of F ion with β-CyD, which results in deeper penetration of A > p into the cavity of β-CyD.  相似文献   
107.
Introduction of electron-withdrawing groups on co-ligands effectively raises the spin crossover temperature of catecholatoiron(III) complexes and induces a significant amount of the low spin species in solution even at around room temperature.  相似文献   
108.
A zinc complex of (3-pyridyl)porphyrin with an alkynyl sidearm (1) preferentially formed a cyclic tetramer in toluene, which showed supramolecular thermochromism at ambient temperatures of 0-100 degrees C. Because of an appropriate extension of pi-electronic conjugation of the porphyrin chromophore, the thermal-induced self-assembling dynamics of 1 can be detected as a vivid color change from red to yellow to green. In sharp contrast, 2 without any alkynyl group, on heating, developed only a small color change from orange to pink, while 3 bearing two alkynyl groups stayed green and did not display any thermochromism.  相似文献   
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