28 resultados para photochemical reaction mechanisms

em Chinese Academy of Sciences Institutional Repositories Grid Portal


Relevância:

100.00% 100.00%

Publicador:

Resumo:

Within the framework of a dinuclear system model, a new master equation is constructed and solved, which includes the relative distance of nuclei as a new dynamical variable in addition to the mass asymmetry variable so that the nucleon transfer, which leads to fusion and the evolution of the relative distance, which leads to quasifission (QF) are treated simultaneously in a consistent way. The QF mass yields and evaporation residual cross sections to produce superheavy nuclei are systematically investigated under this framework. The results fit the experimental data well. It is shown that the Kramers formula gives results of QF, which agree with those by our diffusion treatment, only if the QF barrier is high enough. Otherwise some large discrepancies occur.

Relevância:

90.00% 90.00%

Publicador:

Resumo:

The sensitized fluorescence intensity of terbium ion can be notably enhanced when the Tb3+-fleroxacin complex is exposed to 365 nm light. By the measurements of fluorescence spectra, phosphorescence spectra, fluorescence quantum yield and fluorescence lifetime of the system, it is proved that irradiation makes the complex undergo a photochemical reaction and produces a new terbium complex which is more favorable to intramolecular energy transfer. The mechanism of the photochemical fluorescence enhancement was discussed.

Relevância:

90.00% 90.00%

Publicador:

Resumo:

A simple double logarithmic method in potential-controlled thin-layer spectroelectrochemistry for an irreversible electrochemical process has been studied by numerical analysis and examined by experimental examples. This simple algorithm has a novel function offering some important information about the mechanism of a complex electrochemical process directly from a limited amount of potential-spectrum data, and can be used to distinguish different reaction mechanisms such as E, EC, EE, as well as to determine the electron-transfer coefficient, a, and the kinetically modified E-0'. Combination of the double logarithmic method with nonlinear regression provides a powerful tool to examine the proposed mechanism and also to estimate other thermodynamic and kinetic parameters. (C) 1999 The Electrochemical Society. S0013-4651(98)06-090-X. All rights reserved.

Relevância:

90.00% 90.00%

Publicador:

Resumo:

Lomefloxacin (LMFX) and terbium ion can form a complex and the sensitized fluorescence of the terbium ion can be observed. It was found that the sensitized fluorescence intensity can be notably enhanced when the terbium complex is exposed to 365 nm ultraviolet light. By the fluorescence spectra, phosphorescence spectra, fluorescence quantum yield and fluorescence lifetime of the system, it was proved that irradiation of the complex made it undergo a photochemical reaction and a new terbium complex which is more favorable to intramolecular energy transfer was formed. This is why the sensitized fluorescence enhancement can be observed. (C) 1999 Elsevier Science S.A. All rights reserved.

Relevância:

90.00% 90.00%

Publicador:

Resumo:

To explore the reactivities of alkene (-CH=CH2) and carboxy (-COOH) group with H-Si under UV irradiation, the addition mechanism for the reactions of SiH3 radical with propylene and acetic acid was studied by using the B3LYP/6-311++ G(d,p) method. Based on the surface energy profiles, the dominant reaction pathways can be established; i.e., SiH3 adds to the terminal carbon atom of the alkene (-CH=CH2) to form an anti-Markovnikov addition product, or adds to the oxygen atom of the carboxy group (-COOH) to form silyl acetate (CH3-COOSiH3). Because the barrier in the reaction of the carboxy group (39.9 kJ/ mol) is much larger than that of alkene (11.97 kJ/mol), we conclude that the reaction of bifunctional molecules (e.g., omega-alkenoic acid) with H-Si under irradiation condition is highly selective; i.e., the alkene group (-CH= CH2) reacts with SiH3 substantially faster than the carboxyl group (-COOH), which agrees well with the experimental results. This provides the possibility of preparing carboxy-terminated monolayers on silicon surface from omega-alkenoic acids via direct photochemical reaction.

Relevância:

80.00% 80.00%

Publicador:

Resumo:

Effects of flame stretch on the laminar burning velocities of near-limit fuel-lean methane/air flames have been studied experimentally using a microgravity environment to minimize the complications of buoyancy. Outwardly propagating spherical flames were employed to assess the sensitivities of the laminar burning velocity to flame stretch, represented by Markstein lengths, and the fundamental laminar burning velocities of unstretched flames. Resulting data were reported for methane/air mixtures at ambient temperature and pressure, over the specific range of equivalence ratio that extended from 0.512 (the microgravity flammability limit found in the combustion chamber) to 0.601. Present measurements of unstretched laminar burning velocities were in good agreement with the unique existing microgravity data set at all measured equivalence ratios. Most of previous 1-g experiments using a variety of experimental techniques, however, appeared to give significantly higher burning velocities than the microgravity results. Furthermore, the burning velocities predicted by three chemical reaction mechanisms, which have been tuned primarily under off-limit conditions, were also considerably higher than the present experimental data. Additional results of the present investigation were derived for the overall activation energy and corresponding Zeldovich numbers, and the variation of the global flame Lewis numbers with equivalence ratio. The implications of these results were discussed. 2010 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

Relevância:

80.00% 80.00%

Publicador:

Resumo:

This paper reports a new method for detection of ROS scavengers including superoxide dismutase, ascorbic acid and glutathione based on a 'probe' of peroxidase-oxidase biochemical oscillator. The oscillation period and amplitude change with different concentrations of scavengers. The linear ranges of superoxide dismutase, ascorbic acid and glutathione are respectively 1.56 x 10(-4)-1.56 x 10(-3) mg mL(-1), 1.75 x 10(-7) -1.75 x 10(-5) mol L-1 and 9.38 x 10(-7) -7.5 x 10(-5) mol L-1. The selectivity, linearity and precision for superoxide dismutase, ascorbic acid, and glutathione are presented and discussed. The results compared well with other standard methods for determination of superoxide dismutase, ascorbic acid and glutathione. Some possible steps in the overall reaction mechanisms are discussed.

Relevância:

80.00% 80.00%

Publicador:

Resumo:

In polymeric films of bacteriorhodopsin (BR) a photoconversion product, which was named the F620 state, was observed on excitation of the film with 532 nm nanosecond laser pulses. This photoproduct shows a strong nonlinear absorption. Such BR films can be used for write-once-read-many (WORM) optical data storage. We demonstrate that a photoproduct similar or even identical to that obtained with nanosecond pulses is generated on excitation with 532 mn femtosecond pulses. This photoproduct also shows strong anisotropic absorption, which facilitates polarization storage of data. The product is thermally stable and is irretrievable to the initial B state either by photochemical reaction or through a thermal pathway. The experimental results indicate that the product is formed by a two-photon absorption process. Optical WORM storage is demonstrated by use of two polarization states, but more polarization states may be used. The combination of polarization data multiplexing and extremely short recording time in the femtosecond range enables very high data volumes to be stored within a very short time. (c) 2005 Optical Society of America.

Relevância:

80.00% 80.00%

Publicador:

Resumo:

Indoly-benzlfulgimide belongs to the photochromic fulgide family and follows photochemical first order kinetics. Its bleaching kinetics is investigated at 633 nm and 640 nm by spectroscopy, by the time dependence of transmission and of diffraction from holographically induced gratings. The non-exponential decay law resulting for diffraction experiments with a Gaussian beam profile is calculated and verified experimentally. For a quasi-homogeneous beam profile the time constant determined from diffraction decay is half the one for absorbance decay. The photochemical reaction rate of indoly-benzylfulgimide in PMMA is (3.9 +/- 0.3) cm(2)/J at 650 nm. (c) 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Relevância:

80.00% 80.00%

Publicador:

Resumo:

Within a chiral constituent quark model approach, η-meson production on the proton via electromagnetic and hadron probes is studied. With few parameters, the differential cross section and polarized beam asymmetry for γp → ηp and differential cross section for π − p → ηn processes are calculated and successfully compared with the data in the center-of-mass energy range from threshold up to 2 GeV. The five known resonances S11(1535), S11(1650), P13(1720),D13(1520), and F15(1680) are found to be dominant in the reaction mechanisms in both channels. Possible roles played by new resonances are also investigated; and in the photoproduction channel, significant contribution from S11 and D15 resonances, with masses around 1715 and 2090 MeV, respectively, are deduced. For the so-called missing resonances, no evidence is found within the investigated reactions. The helicity amplitudes and decay widths of N ∗ → πN, ηN are also presented and found to be consistent with the Particle Data Group values.

Relevância:

80.00% 80.00%

Publicador:

Resumo:

The differential cross sections for elastic scattering products of F-17 on Pb-208 have been measured. The angular dispersion plots of ln(d sigma/d theta) versus theta(2) are obtained from the angular distribution of the elastic scattering differential cross sections. Systematical analysis on the angular dispersion for the available experimental data indicates that there is an angular dispersion turning angle at forward angular range within the grazing angle. This turning angle can be clarified as nuclear rainbow in classical deflection function. The exotic behaviour of the nuclear rainbow angle offers a new probe to investigate the halo and skin phenomena.

Relevância:

80.00% 80.00%

Publicador:

Resumo:

中能重离子碰撞的反应机制及其形成的高激发核的性质研究是当前中能重离子核物理研究的重要领域。本文通过对35 MeV/u~(40)Ar+~(159)Tb/~(197)Au反应中出射的轻粒子、中等质量碎片(IMF)和复合核裂变碎片的符合测量,研究了中等质量碎片的发射机制、类靶核的形成机制及其裂变时标、复合核的温度与激发能以及两者之间的关系等。利用前角探测器组的测量对前角区出射的IMF的单举和关联数据进行了分析。由弹核碎裂理论中的Gozdhaber关系式拟合了类弹碎片的能谱,由此提取的弹核的动量分布约化宽度为σ_0 ≈ 100MevV/c。通过Gemini模拟与IMF-IMF关联数据的对比揭示出激发的类弹碎片的裂变是关联IMF的一个重要来源。由IMF与裂变碎片以及IMF与后角轻粒子的关联数据显示出,在前角区域,当IMF的能量低于10 MeV/u时,复合核的蒸发对较轻IMF有较大的贡献;当IMF能量在10-24 MeV/u的区域时,IMF能量与复合核平均速度以及激发能之间存在着很强的依赖关系,说明这些IMF主要来源与弹靶之间的耗散反应;当IMF的能量超过24 MeV/u后,IMF能量与复合核平均速度以及激发能之间没有关联或关联很弱,说明在弹核碎裂的同时,靶核也发生了碎裂,它们共同贡献出部分核子形成了"中速源"或"颈部"。通过对复合核裂变时出射的关联裂片以及后角轻带电粒子的测量,提取了复合核的激发能以及在不同激发能能下所对应的核温度。对于中心碰撞,Au靶形成了E~* = 4MeV/u、T_(init) = 7.1 MeV的热核,Tb靶形成了E~* = 4.7MeV/u、T_(init) = 7.7MeV的热核。对其量热曲线的研究显示出,在当前入射能下没有观测到原子核液气相变的特征。由类弹碎片(PLF)与类靶核两个裂片的关联数据,提取了类靶核裂变轴在反应平面内的转动角度,并由此计算出类靶核的、裂变时标。在对称裂变时,类靶核的寿命约5 * 10~(-20) s,在非对称裂变(η =0.6)时降为约1.7 * 10~(-21) S。同时我们认为类靶核的裂变存在两种机制,即动力学裂变和统计裂变,分别对应于裂变轴在反应平面内的非各相同性分别和各相同性分布。

Relevância:

80.00% 80.00%

Publicador:

Resumo:

Intramolecular amide hydrolysis of N-methylmaleamic acid is revisited at the B3LYP/6-311G(2df,p)//B3LYP/6-31G(d,p)+ZVPE level, including solvent effects at the CPCM-B3LYP/6-311G(2df,p)//Onsager-B3LYP/6-31G(d,p)+ZPVE level. The concerted reaction mechanism is energetically favorable over stepwise reaction mechanisms in both the gas phase and solution. The calculated reaction barriers are significantly lower in solution than in the gas phase. In addition, it is concluded that the substituents of the four N-methylmaleamic acid derivatives considered herein have a significant effect on the gas-phase reaction barriers but a smaller, or little, effect on the barriers in solution.

Relevância:

80.00% 80.00%

Publicador:

Resumo:

The reaction mechanisms of the H-2 with the homonuclear dimers M-2 (Cu, Ag, Au) and the heteronuclear dimers PdM (M = Cu, Ag, Au) were studied by use of density functional theory. For the H-2 reactions with homonuclear dimers M-2 (Cu, Ag, Au), it was found that it is easier for Au-2 to dissociate the hydrogen molecule compared with Cu-2 and Ag-2. For H-2 reactions with the heteronuclear dimers PdM (M = Cu, Ag, An), the hydrogen molecule can be easily dissociated at Pd site, rather than at noble metal site.

Relevância:

80.00% 80.00%

Publicador:

Resumo:

Blocked isocyanates are widely used in many kinds of one-package coatings, powder coatings and adhesives. They have also been used in water-borne polyurethane. The kinetics and mechanism of the reactions of blocked isocyanates are reviewed and two urethane forming reaction mechanisms by which a blocked isocyanate can react with a nucleophile are provided. Furthermore, effects of isocyanate structure, reaction medium, catalyst and functionality on kinetics of blocked isocyanate are discussed in detail.