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991.
The fluorescence excitation spectrum, the MPI spectrum, and the absorption spectrum of acetylene due to the à 1Au←
transition were observed in a gas and in a supersonic jet. A sudden decrease in the fluorescence quantum yield Φf was found above the V4 K2 (46339 cm−1) vibronic sublevel. The decrease is due to predissociation into C2H + H. AK and J dependence on Φf was also found. 相似文献
992.
An enzyme assay method for D(-)-3-hydroxybutyrate and acetoacetate involving acetoacetyl coenzyme A (CoA) synthetase was developed. To determine the concentration of D-3-hydroxybutyrate, it was oxidized with D-3-hydroxybutyrate dehydrogenase in the presence of nicotinamide adenine dinucleotide (NAD+) to acetoacetate, which was then converted to acetyl CoA via acetoacetyl CoA through the combined actions of acetoacetyl CoA synthetase and 3-ketothiolase in the presence of adenosine triphosphate (ATP) and CoA. To determine the concentration of acetoacetate, acetoacetyl CoA generated from acetoacetate with acetoacetyl CoA synthetase was reduced to 3-hydroxybutyryl CoA with 3-hydroxyacyl CoA dehydrogenase in the presence of NADH. The amount of D-3-hydroxybutyrate or acetoacetate was estimated from the increase or decrease in the absorbance at 340 nm, respectively. The present assay method seemed to be accurate and quick. Furthermore, as to the assaying of D-3-hydroxybutyrate, the omission of hydrazine, which is included for the standard method, may be preferable for routine assaying. 相似文献
993.
994.
Ch. He E. Hamada T. Suzuki H. Kobayashi K. Kondo V. P. Shantarovich Y. Ito 《Journal of Radioanalytical and Nuclear Chemistry》2003,255(3):431-435
A new pulsed mono-energetic slow positron beam as well as the conventional positron annihilation lifetime spectroscopy (PALS) have been applied to study the sub-surface and the bulk of epoxy polymer. Significant changes of o-Ps parameters were found at a short distance from the surface. The lifetime of o-Ps was observed to decrease with increasing the positron implantation depth, while its intensity increased. The temperature effect on o-Ps parameters at sub-surface was also investigated. The glass transition temperature for the sub-surface was lower than that for the bulk. Furthermore, the thermal expansion coefficient of the sub-surface was found smaller than that of the bulk. 相似文献
995.
Traditional Pariser-Parr-Pople and variable electronegativity calculations have been carried out on C6H5B(OR)2 and p-CH3OC6H4B(OR)2, and the results compared with calculations for C6H5BR2. It is concluded that the VE-SCF method offers a real advantage over the simple PPP method for predicting percent charge transfer and transition intensity in cases where excited states possess substantial C.T. character. The restriction that empirically chosen parameters fit the observed transition energies and intensities of both triarylboranes and ArB(OR)2 requires the choice of a boron VSIP greater than 2.0 eV in the fixed parameter procedure of the usual PPP-SCF-CI method for these molecules. Observed transitions in C6H5B(OR)2 correlate with 1
L
b, 1
L
a, 1
B
b, whereas the first absorption maximum of (C6H5)3B is assigned to C.T. (1
A
11
A
1) local C
2v
symmetry.
Zusammenfassung PPP- und VE SCF-Rechnungen wurden für C6H5B(OR)2 und p-CH3OC6H4(OR)2 durch- geführt, und die Ergebnisse wurden mit denjenigen für C6H5BR2 verglichen. Es kann der Schluß gezogen werden, daß die VE SCF-Methode einen Vorteil gegenüber der einfachen PPP-Methode bietet, um den prozentualen Charge Transfer und Übergangsintensitäten in Fällen zu bestimmen, in denen die angeregten Zustände einen wesentlichen C.T.-Charakter besitzen. Die Bedingung, daß die empirisch gewählten Parameter den beobachteten Übergangsenergien und -intensitäten von sowohl Triarylboranen als auch ArB(OR)2 angepaßt sein sollen, erfordert die Wahl eines Bor-VSIP größer als 2,0 eV im Rahmen der üblichen Parametrisierung der PPP-SCF-CI-Methode. Beobachtete Über-gänge in C6H5B(OR)2 korrelieren mit 1 L b, 1 L a, 1 B b, wogegen das erste Absorptionsmaximum des (C6H5)3B einem C.T.-Übergang (1 A 11 A 1) lokaler C2v -Symmetrie zugeordnet wird.
Résumé Des calculs traditionnels Pariser-Parr-Pople et des calculs d'électronégativité variable ont été effectués sur C6H5B(OR)2 et p-CH3OC6H4B(OR)2 avec comparison aux résultats obtenus pour C6H5BR2. La conclusion est que la méthode VE-SCF offre un réel avantage sur la méthode PPP simple en ce qui concerne la prédiction du transfert de charge et de l'intensité de transition pour les états excités possédant un net caractère de transfert de charge. La restriction selon laquelle les paramètres empiriques doivent permettre de reproduire les énergies de transition et les intensités des deux triarylboranes et de ArB(OR)2, nécessite le choix d'un potential d'ionisation de l'état de valence du bore supérieur de 2 eV à celui employé dans les méthodes ordinaires. Les transitions observées dans C6H5B(OR)2 sont reliées à 1 L b, 1 L a, 1 B b, tandis que la première absorption de (C6H5)3B est attribuée à un transfert de charge (1 A 11 A 1) de symétrie locale C2v.相似文献
996.
997.
Ji-Ben Meng Wen-Guang Wang Hong-Gen Wang Teruo Matsuura Hideko Koshima Iwao Sugimoto Yoshikatsu Ito 《Photochemistry and photobiology》1993,57(4):597-602
Abstract— Solid-state irradiation of mixed crystals prepared by meltinga 1:3 molar mixture of indole and phenanthrene followed by resolidifying the melt gave an adduct 2a in 13.5% yield. An adduct 2b was obtained by irradiation of the mixed crystals of 3-methylindole and phenanthrene. Irradiation of the same mixtures of indoles and phenanthrene in solution gave no photoproduct. Irradiation of the mixed crystals of indole and naphthalene gave a similar photoadduct 3a, which was also formed in solution. The 1:1 mixed crystals of indole and phenanthrene and of indole and naphthalene were characterized by various spectroscopic methods. Among them powder X-ray diffraction spectral analysis and differential scanning calorimetry revealed that the former mixed crystal is a simple mixture of microcrystals of indole and phenanthrene, while the latter forms a molecular compound. 相似文献
998.
999.
Abstract— By a technique which combines rapid mixing of cells and hematoporphyrin (HP) with a short duration of illumination, the photodynamic inactivation of yeast cells was investigated, particularly, in seeking for the information of the location of HP at the time of action. The fluence-survival curves obtained under the conditions where the reaction mixture was kept in the dark for Is, 60s and even 35 min before illumination were indistinguishable from each other, indicating no interaction between cells and sensitizers took place in about 30 min in such a way that the photodynamic efficiency could be modified. It is unlikely that HP acted intracellularly, since the protective effect of N?3 was observed at concentrations as low as 0.5 mM. Furthermore, the rate constant kp related to the protective effect of NJ, was estimated to be 1 × 108M?1 s?1 under the assumption that 1O2 was the active intermediate and had a lifetime of 2 μs under the present conditions. This value of kp is rather close to that of kq, the quenching rate constant of N?3 for 1O2, of which the accepted value is 2 × 108M?1s?1 in the homogeneous aqueous system. This information, together with the absence of uptake of HP by cells and a well response of survival upon illumination to the D2O fraction of the reaction mixture, provide strong bases for the argument that direct interaction of HP with yeast cells is of minor importance in the photodynamic processes, and the photodynamic action is largely mediated by an intermediate (102) generated in bulk medium. 相似文献
1000.
Dissociation pathways of tellurium clusters, Te(n)(+) (n = 25-85), were investigated by secondary ion mass spectrometry. Positively charged ions were generated from a tellurium sheet by bombardment with 10 keV xenon ion beam. Mass analyses of cluster ions were performed using a grand-scale sector mass spectrometer. In the first field-free region, Te(n)(+) (n = 25-80) had a large dissociation probability with five- and six-atom emission and Te(n)(+) (n = 50-85) had a slightly large dissociation probability with 10- and 11-atom emission. Five- and six-atom dissociation in the second field-free region could be also observed. These results were most likely due to the cluster emission processes for Te(n)(+), although sequential atom emission and cluster emission could not be distinguished by this type of experiments. 相似文献