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21.
The association of complex formation with static quenching in CT systems was investigated. Evaluation of the data made evident
that the inner filter effect must be allowed for. Time-resolved and temperature-dependent stationary measurements of fluorescence
led to the separation of dynamic and static quenching components. The static quenching constant is discussed with respect
to the equilibrium constant of complex formation determined by absorption spectroscopy. 相似文献
22.
《Journal of Chemical Sciences》2005,117(5):525-531
The silicon atom may increase its coordination number to values greater than four, to form pentacoordinated compounds. It
has been observed experimentally that, in general, pentacoordinated compounds show greater reactivity than tetracoordinated
compounds. In this work, density functional theory is used to calculate the global softness and the condensed softness of
the silicon atom for SiH
n
F4−n
and SiH
n
F
5−n
1−
. The values obtained show that the global and condensed softness are greater in the pentacoordinated compounds than in the
tetracoordinated compounds, a result that explains the enhanced reactivity. If the results are analysed through a local version
of the hard and soft acids and bases principle, it is possible to suggest that in nucleophilic substitution reactions, soft
nucleophiles preferably react with SiH
n
F
5−n
1−
, and hard nucleophiles with SiH
n
F4−n
. 相似文献
23.
24.
Quantitative H–Al distances in acid sites of two zeolites with MFI and IFR framework topology were obtained by numerical simulation of 1H{27Al} rotational echo adiabatic passage double resonance (REAPDOR) experiments. A 27Al offset-dependent data set yields for each resolved 1H NMR line a corresponding nuclear electric quadrupole coupling constant of the neighboring 27Al site. This information is used for analyzing a second data set for on-resonance irradiation, where the dipolar evolution time (number of rotor cycles) was varied, to yield the 1H–27Al dipolar coupling constant. Numerical simulations indicate that the REAPDOR method does not depend significantly on the polar angles, defining the orientation of the electric field gradient tensor of 27Al with respect to the Al–H dipolar vector. In contrast, the transfer of populations in double resonance sequence is sensitive to these angles, and it can be thus used to measure them. 相似文献
25.
王胜奎 《数学的实践与认识》2006,36(5):5-10
根据松纵坑切梢小蠹的主要生物学特征,通过分析抚育间伐持续控制松纵坑切梢小蠹虫害的机理,应用复杂适应系统(CA S)理论,建立了模拟松纵坑切梢小蠹虫害的一种动态演化数学模型,并讨论了模型的收敛性.然后选用昆明小哨林场为背景,进行了各种抚育间伐决策的仿真,从中优选抚育间伐决策.结果表明:模拟优化方案与实际调查统计分析结果一致:均为弱度间伐与中弱度间伐控制蠹害效果最好.最后通过森林积材量与虫害程度之间的优化,给出了抚育间伐的优化策略. 相似文献
26.
X. Yang 《Applied Surface Science》2006,252(10):3647-3657
The room-temperature adsorption and thermally induced processes of propionic acid and pyruvic acid on Ni(1 0 0) have been investigated by electron energy loss spectroscopy (EELS). Computational vibrational analysis of the optimized bidentate structures for acid-Ni model complexes (involving the organic acid and a Ni atom) has been performed by using the two-layer ONIOM method with the Density Functional Theory and used to interpret the vibrational EELS data. Dehydrogenation of the hydroxyl group is found to result in bonding of the carboxylate group in the propionate and pyruvate adspecies to either a single Ni surface atom in a bidentate configuration or two neighbouring Ni atoms in a bridge configuration. Given the similarities in the total energies and related vibrational frequencies obtained by the calculations in the case of pyruvate adspecies, it is difficult to differentiate the alternate adsorption structure, in which the keto O and hydroxyl O atoms are bonded to a Ni atom in a five-member chelate ring configuration. Furthermore, temperature-dependent EELS studies show that both the propionate and pyruvate adspecies could decompose upon annealing to above 400 K and further dissociate to CO adspecies above 550 K and to C and/or O above 600 K. 相似文献
27.
功能性丙烯酸/MBAM体系共聚产物的研制 总被引:2,自引:0,他引:2
以丙烯酸和MBAM为主要原料,经聚合,合成了一种高性能的具有良好保水性能的聚合产物,其保水量达到750~1000倍.50℃以下有良好的保水性能,28℃以下有极好的保水性能,并研究了工艺条件对该产品性能的影响因素. 相似文献
28.
We construct a multiplicative group structure in the class of integro-differential operators specific for a polydisk which was introduced by I. I. Bavrin. We indicate two applications of these operators to solution of functional equations. 相似文献
29.
A convenient and large-scale preparation of retinoic acid 1 from β-ionone in five steps with 38% overall yield is described.The key steps are the epoxidization of 2 with a new methylated agent and the condensation 4 with tetraethyl methylenediphophonate in one-pot procedure to prepare 6. 相似文献
30.
Z. J. Yu L. J. Liu R. X. Zhuo 《Journal of polymer science. Part A, Polymer chemistry》2003,41(1):13-21
The ring‐opening polymerization of ε‐caprolactone (ε‐CL), initiated by carboxylic acids such as benzoic acid and chlorinated acetic acids under microwave irradiation, was investigated; with this method, no metal catalyst was necessary. The product was characterized as poly(ε‐caprolactone) (PCL) by 1H NMR spectroscopy, Fourier transform infrared spectroscopy, ultraviolet spectroscopy, and gel permeation chromatography. The polymerization was significantly improved under microwave irradiation. The weight‐average molecular weight (Mw) of PCL reached 44,800 g/mol, with a polydispersity index [weight‐average molecular weight/number‐average molecular weight (Mw/Mn)] of 1.6, when a mixture of ε‐CL and benzoic acid (25/1 molar ratio) was irradiated at 680 W for 240 min, whereas PCL with Mw = 12,100 and Mw/Mn = 4.2 was obtained from the same mixture by a conventional heating method at 210 °C for 240 min. A degradation of the resultant PCL was observed during microwave polymerization with chlorinated acetic acids as initiators, and this induced a decrease in Mw of PCL. However, the degradation was hindered by benzoic acid at low concentrations. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 13–21, 2003 相似文献