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排序方式: 共有528条查询结果,搜索用时 15 毫秒
21.
利用激光光解装置检测了C60-地塞米松(C60-DE)的苯溶液在355 nm激光照射下产生的激发三重态, 3C60-DE*出现四个吸收峰, 分别位于700、440、350 和310 nm. 在330 nm处观察到了它的漂白吸收最大值, 这与其基态吸收最大值相对应. 3C60-DE*能够将能量转移给O2分子而淬灭. 与3C60*相比, 3C60-DE*的三重态鄄三重态(T-T)淬灭速率常数减小(3C60*为(5.03±1.31)×109 L·mol-1·s-1, 3C60-DE*为(3.53±0.87)×109 L·mol-1·s-1), 而寿命增加了(3C60*为(12.0±2.6) μs, 3C60-DE*为(18.0±3.3) μs), 这可能是C60分子上连接了地塞米松分子后减小了C60球之间碰撞的几率所致. 相似文献
22.
Cai X Sakamoto M Fujitsuka M Majima T 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(22):6471-6477
The lifetimes of benzophenone in the higher triplet excited state (BP(T(n))) and several BP derivatives in the T(n) states were measured directly to be tau(T(n))=37+/-7 ps and 20-33 ps, respectively, by using the nanosecond-picosecond (ns-ps) two-color/two-laser flash photolysis method. Based on the direct measurements of tau(T(n)) of BP(T(n)), the triplet energy transfer (TET) from BP(T(n)) to quenchers (Q), such as carbon tetrachloride (CCl4), benzene (Bz), and p-dichlorbenzene (DCB), was investigated. The fast TET from BP(T(n)) to Q can be attributed to the lifetime-dependent quenching process, according to the Ware theoretical model of the bimolecular energy transfer reaction. The contribution of the lifetime-dependent term on k(TET) was 27, 60, and 86% for CCl4, Bz, and DCB as the Q of BP(T(n)), respectively, indicating that the TET from BP(T(n)) to Q is influenced not only by tau(T(n)), but also by the size of Q. 相似文献
23.
Minoru Yamaji Ai Suzuki Fuyuki Ito Shozo Tero-Kubota Seiji Tobita Bronislaw Marciniak 《Journal of photochemistry and photobiology. A, Chemistry》2005,170(3):253-259
Photodissociation of the carbon-X (X = Br and Cl) bonds in p-bromo- and p-chloromethylbenzophenone (BMBP and CMBP) in solution were investigated by time-resolved EPR and laser flash photolysis techniques. BMBP and CMBP were found to undergo ω-bond cleavage to yield the p-benzoylbenzyl radical (BBR) at 295 K, and the quantum yields (ΦBBR) were determined. The CIDEP signal originated from BBR formed upon decomposition of CMBP was obtained while that for BMBP was absent. By using triplet sensitization of acetone, the efficiencies (BBR) of the CX bond fission in the triplet states of BMBP and CMBP were determined. The agreement between the ΦBBR and BBR values for CMBP indicates that the CCl bond dissociation occurs only in the triplet state. In contrast to CMBP, the cleavage of the CBr bond in BMBP upon direct excitation was concluded to be the event only in the excited singlet state without triplet formation, whereas the triplet state was also reactive for ω-bond dissociation. The rate of CBr bond dissociation seemed to be greater than that of intersystem crossing from the S1 to the T1 state. Schematic energy diagrams of the excited states of BMBP and CMBP were shown, and the reaction profiles were discussed from the viewpoint of the CX bond enthalpies. 相似文献
24.
Using laser flash photolysis/transient absorption technique for the study of two photon photodissociation of carbon disulfide in acetonitrile solution at 266 nm, the transient UV-Vis absorption spectrum of Rydberg state CS2 (6sσg) within 240-370 nm and subsequent dissociation product CS (α^3П) with the maximum absorption at 260 nm were directly observed. The lifetime of CS (α^3П) in the nitrogen and oxygen saturated solution is also studied in our experiment. 相似文献
25.
María L. Dell'Arciprete Carlos J. Cobos Dr. Jorge P. Furlong Dr. Daniel O. Mártire Dr. Mónica C. Gonzalez Dr. 《Chemphyschem》2007,8(17):2498-2505
The kinetics of the oxidation of pyridine, 3‐chloropyridine, 3‐cyanopyridine, 3‐methoxypyridine and 3‐methylpyridine mediated by SO4 < M ‐> radicals are studied by flash photolysis of peroxodisulphate, S2O82?, at pH 2.5 and 9. The absolute rate constants for the reactions of both, the basic and acid forms of the pyridines, are determined and discussed in terms of the Hammett correlation. The monosubstituted pyridines react about 10 times faster with sulphate radicals than their protonated forms, the pyridine ions. The organic intermediates are identified as the corresponding hydroxypyridine radical adducts and their absorption spectra compared with those estimated employing the time‐dependent density functional theory with explicit account for bulk solvent effects. A reaction mechanism which accounts for the observed intermediates and the pyridinols formed as products is proposed. 相似文献
26.
Corinna Kerst Rabah Boukherroub William J. Leigh 《Journal of photochemistry and photobiology. A, Chemistry》1997,110(3):215-246
The far-UV (193 nm) laser flash photolysis of nitrogen-saturated isooctane solutions of 1,1-dimethylsiletane allows the direct detection of 1,1-dimethylsilene as a transient species, which (at low laser intensities) decays with pseudo-first-order kinetics (τ 10 μs) and exhibits a UV absorption spectrum with λmax 255 nm. Characteristic rapid quenching is observed for the silene with methanol (kMcOH = (4.9 ± 0.2) × 109 M−1 s−1), tert-butanol (kBuOH = (1.8 ± 0.1) × 109 M−1 s−1) and oxygen (kO2 = (2.0 ± 0.5) × 108 M−1 s−1). The Arrhenius activation parameters for the reaction with methanol have been determined to be Ea = −2.6 ± 0.6 kcal mol−1 and log A = 7.7 ± 0.3. 相似文献
27.
The hydrogen donation kinetics of four 3-aryl-benzofuranones with different chemical structures toward tert-butoxyl radicals were studied using laser flash photolysis (LFP) technique. The rate constants of hydrogen reactions, which can be used to evaluate the hydrogen donating abilities of 3-aryl-benzofuranones toward radicals, were obtained. The results showed that the position of substituted methyl group has a very important effect on the hydrogen donating ability of benzofuranone toward tert-butoxyl radicals, i.e. if the methyl group is on 2′-position, the hydrogen donation of 3-aryl-benzofuranone toward tert-butoxyl radicals will be prevented and the hydrogen donating ability will be weakened. 相似文献
28.
Changyuan Lu Side Yao Wenfeng Wang Yongpeng Tong Weizhen Lin Tingwen Rong Nianyun Lin 《中国科学B辑(英文版)》1998,41(3):259-265
Fullerols of C60 and of C70 [C60(OH)n, C70(OH)m], water-soluble fullerene derivatives, unlike some other fullerene derivatives (such as C60 (C4H6O), C60 (C3H7N) and C60 [C(COOEt)2]x), do not result in excited triplet state but in ionization via monophotonic process in aqueous solutions with 248 nm laser.
The quantum yields of formation of hydrated electron (Φe
−) are determined to be 0.08 and 0.11 for fullerols of C60 and of C70 respectively at room temperature (ca. 15°C) with KI solution used as reference. By laser flash photolysis and oxidation of
sulfate radical anion SO4
−, the fullerol radical cation or neutral radical of C60 is confirmed to be existent and the transient absorption spectra of fullerol radical cation of C70 are observed for the first time.
Project supported by the National Natural Science Foundation of China 相似文献
29.
研究了客体模型FTO的闪光照相系统X光输运过程,给出了直穿照射量、散射照射量、直散比、直穿照射量能谱、散射照射量能谱、直穿X光通量能谱和散射X光通量能谱在记录平面的空间分布。结果表明:后锥是照射量散射成分的主要来源,后锥照射量占总散射量97%;后锥也是造成散射的空间分布不均匀的主要器件,这一不均匀性高达58%。照相系统的最小直散比非常小,表明锥造成的散射已经严重地淹没了直穿(轫致辐射)信号。计算中使用高空间分辨率记录法进行分点,合成图像对吸收系数的复原结果与国外报道的结果相符。 相似文献
30.
Gonzalo Astray Juan F. Gálvez Juan C. Mejuto Oscar A. Moldes Iago Montoya 《Journal of computational chemistry》2013,34(5):355-359
In this article, an artificial neural network to predict the flash point of 95 esters was implemented. Four variables were used for its development. A neural network with 4‐5‐8‐5‐1 topology was encountered to gain the best agreement of the experimental results with those predicted (square correlation coefficient (R2) and root mean square error were 0.99 and 5.46 K for the training phase and 0.96 and 13.02 K for the testing set). © 2012 Wiley Periodicals, Inc. 相似文献