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51.
在MPW1PW91/6-311G(d,p)水平上优化了标题反应各驻点物种的几何构型,并在相同水平上通过频率计算和内禀反应坐标(IRC)分析对过渡态结构及连接性进行了验证.采用QCISD(T)/6-311G(d,p)方法对所有驻点及反应路径的部分选择点进行单点能校正,分别构建了CH3SO+HO2反应体系的单、三重态反应势能剖面.研究结果表明,CH3SO+HO2反应体系存在6条反应通道7条路径,优势通道(1)R→3IM→P1(CH3SOH+3O2)发生在三重态势能面上,此通道包含两条路径,其表观活化能分别为12.01和-30.04kJ?mol-1,主路径(2)R→3IM→3TS2→P1(CH3SOH+3O2)是一个无势垒氢迁移过程.利用经典过渡态理论(TST)与变分过渡态理论(CVT)并结合小曲率隧道效应模型(SCT),分别计算了主路径(2)在200~2500K温度范围内的速率常数kTST,kCVT和kCVT/SCT,在此温度区间内的表观反应速率常数三参数表达式为kCVT/SCT=4.08×10-24T3.13exp(8012.2/T)cm3imolecule-1is-1,具有负温度系数效应.速率常数计算结果显示,变分效应在计算温度段内影响较小,而量子力学隧道效应在低温段有显著影响. 相似文献
52.
Quantitative structure-activity relationship (QSAR) model was used to predict and explain binding constant (log K) determined by fluorescence quenching. This method allowed us to predict binding constants of a variety of compounds with human serum albumin (HSA) based on their structures alone. Stepwise multiple linear regression (MLR) and nonlinear radial basis function neural network (RBFNN) were performed to build the models. The statistical parameters provided by the MLR model (R2=0.8521, RMS=0.2678) indicated satisfactory stability and predictive ability while the RBFNN predictive ability is somewhat superior (R2=0.9245, RMS=0.1736). The proposed models were used to predict the binding constants of two bioactive components in traditional Chinese medicines (isoimperatorin and chrysophanol) whose experimental results were obtained in our laboratory and the predicted results were in good agreement with the experimental results. This QSAR approach can contribute to a better understanding of structural factors of the compounds responsible for drug-protein interactions, and can be useful in predicting the binding constants of other compounds. 相似文献
53.
Peng Zhou Hongliang Ma Yingying Du Yongmei Han Bo Lu Minjian Zhong 《Applied Physics A: Materials Science & Processing》2011,102(2):295-299
Crystalline TiO2 was induced three dimensionally inside Bi-free glass sample by an 800 nm, 250-kHz femtosecond laser irradiation. Micro-Raman
spectra analysis indicated that the laser-induced crystals in the focal point of the laser beam were monophase TiO2 rutile. Continuous crystalline lines were written through moving the focal point of the laser beam inside the glass. The
results demonstrate that this technique is a convenient method to engrave three-dimensional patterns of crystals for fabricating
integrated optical devices in transparent materials. 相似文献
54.
55.
关于(F,ρ)—不变凸性函数多目标规划的最优性条件 总被引:1,自引:0,他引:1
本文给出了一类更一般的广义凸性函数的定义:(F,ρ)——不变凸性函数,并讨论了其最优性条件。 相似文献
56.
57.
Wenzhuo Li Shuaiyu Huang Dingjia Xu Yingying Zhao Yuchao Zhang Lin Zhang 《Cellulose (London, England)》2017,24(9):3619-3633
Sodium carboxymethyl cellulose (SCMC) with different degrees of substitution (DS) possesses structural characteristics and physicochemical properties that are important in broad areas of industrial applications. This reported work investigated the structural characteristics, including the effective length (L ef), the radius of gyration (R g), and the hydrodynamic radius (R H), and the physicochemical properties, including intrinsic viscosity ([η]) and salt tolerance, of SCMC with a DS more than 1.0 in NaCl solution using molecular dynamics (MD) simulations. In the MD simulations, the DS of SCMC varied from 1.2 to 2.8, and the NaCl concentration varied from 0 to 1.4 mol/L. MD simulation results showed that with the increment of NaCl concentration, the L ef (or R g or R H) of SCMC decreased; with the increment of the DS, the L ef of SCMC increased. Also, the variation tendency of [η] in the NaCl solution was consistent with its L ef (or R g or R H). It was noted that the salt tolerance (represented by D) of SCMC increased as the DS increased. In addition, the sharp variation of the D value of SCMC occurred in the range of DS of 1.6 to 2.0, which agreed with the reported experimental results. Radial distribution function analyses showed that the Na+ cations had a stronger interaction with the carboxyl groups in SCMC with lower DS when it was present in a salt solution of higher concentration, which also reasonably explained the variation of L ef, R g, R H, [η], and D of SCMC in NaCl solution. 相似文献
58.
The article investigates the growth of multiple Dirichlet series.The lower order and the linear order of n-tuple Dirichlet series in C~n are defined and some relations between them and the coefficients and exponents of n-tuple Dirichlet series are obtained. 相似文献
59.
Gels formed by self-association of monomeric guanosine compounds join numerous other agents such as cyclodextrins, crown ethers, chiral surfactants, antibiotics, proteins, and polysaccharides for chiral separations. Guanosine gels (G-gels) are self-assembled networks of hydrogen-bonded tetrads formed by guanosine nucleotides and their derivatives. The tetrads stack upon themselves to form columnar, helical aggregates that are stabilized by π-π interactions and centrally located cations. Previous work showed the effectiveness of G-gels formed by guanosine-5'-monophophate for separation of the enantiomers of the cationic drug propranolol using capillary electrophoresis. Subsequently, it was found that not all chiral compounds could be resolved into their enantiomers, leading us to investigate in this work the structural features that appear to be correlated to enantiomerically selective interactions of chiral compounds with G-gels. For those compounds (anionic 1,1'-binaphthyl-2,2'-diyl hydrogen phosphate and zwitterionic tryptophan) for which enantiomeric resolution was achieved, the effects of experimental conditions and G-gel composition were examined. For other compounds with no net charge (hydrobenzoin and zwitterionic amino acids and derivatives), the migration times were used as an indicator of the extent of interaction with the G-gel run buffer. It was found that the extent of interaction alone does not determine the chiral selectivity of the G-gel, indicating that the mechanism of chiral separation involves particular structural characteristics of the chiral compounds. 相似文献
60.
Non-aggregated spherical polystyrene (PS) particles were coated with GdPO4:Tb3+/Ce3+ phosphor layers by a conventional hydrothermal synthesis using poly(vinylpyrrolidone) (PVP) as an additive without further
annealing treatment. X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy
(TEM), photoluminescence (PL), as well as luminescence decay experiments were used to characterise the resulting core-shell
structured PS@GdPO4:Tb3+/Ce3+ samples. The results of XRD indicated that the PS particles were successfully coated with the GdPO4:Tb3+/Ce3+ phosphor layers, which could be further verified by the images of FESEM. Under ultraviolet excitation, the PS@GdPO4:Tb3+/Ce3+ phosphors show Tb3+ characteristic emission, i.e. 5D4-7FJ (J = {6, 5, 4, 3}) emission lines with green emission 5D4-7F5 (543 nm) as the most prominent group. The core-shell phosphors so obtained have potential applications in field emission
display (FED) and plasma display panels (PDP). 相似文献