Effects of substituents on activation parameters in SN2 reactions at aliphatic carbon in solution

Changes of the activation parameters in aliphatic S_N2 reactions with anionic and neutral nucleophiles in various solvents, ΔH^≠ and ΔS^≠, were correlated with σ constants of the substituents. The resultant δΔH^≠ and δΔS^≠ reaction constants are linearly related for variations of substituents at the substrate, leaving group and nucleophile. Correlations of δΔH^≠ versus δΔS^≠ allow the estimation of the contribution of changes of the internal enthalpy, δΔH, to the enthalpy reaction constant, δΔH^≠, which gives a single linear dependence on the Hammett ρ reaction constants. The deviations from the dependence of δΔH versus ρ can be interpreted in terms of changes in the transition state structure in S_N2 reactions. The results obtained show that the substituent effects on the charge development in the transition state are governed by the magnitude of δΔH. Copyright © 2009 John Wiley & Sons, Ltd.     

当量比对圆盘结构下旋转爆震波传播的影响

为研究反应物当量比对旋转爆震波传播过程的影响,在圆盘形旋转爆震发动机上进行H₂/air的旋转爆震实验研究,并统计分析了当量比对爆震波传播模态及参数的影响规律.实验结果表明,固定质量流率,同一种传播模态下,随着当量比的增大,爆震波的压力峰值及传播速度增大,且旋转爆震波的传播过程更加稳定.不同质量流率条件下,当量比对传播模态的影响规律不同.空气质量流率小于100 g/s时,旋转爆震波皆以单波模态传播.空气质量流率大于150 g/s时,随着当量比的增大,旋转爆震波的传播模态由单波模态向双波模态转变,再转变为不对称双波模态,最后又回到单波模态.并且在不对称双波模态中发现了低频振荡现象,振荡频率约为300 Hz.质量流率继续增大,燃烧室中发现了同向三波传播模态.随着质量流率的增加,双波模态的当量比下限降低,不对称双波模态的当量比上限增大,而双波与不对称双波模态的分界线受质量流率的影响较小.      

Exchange charge model and analysis of the microscopic crystal field effects in KAl(MoO4)2:Cr

In the present paper, we report on consistent crystal field calculations of the Cr³⁺ ions energy levels in KAl(MoO₄)₂ using actual D_3d site symmetry of the Cr³⁺ position and employing the exchange charge model (ECM) of the crystal field. In addition to the energy level calculations, the Huang-Rhys factor S=5.7 and effective phonon energy ?ω=268 cm^-1 were evaluated in the single configurational coordinate model. Detailed treatment of the microscopic crystal field effects in the ECM framework allowed to obtain analytical dependence of the crystal field strength 10Dq on the Cr-O interionic distance and extracting from it the values of some parameters of the electron-vibrational interaction (EVI) in the KAl(MoO₄)₂:Cr³⁺ system. All obtained results are compared with experimental data and discussed; agreement between the calculated and experimental parameters is good.     

DC conductivity of new single and mixed alkali oxyfluorovanadate glasses

New glasses have been prepared according to these formulas (70-x)V₂O₅-30BaF₂-xAF, where AF=LiF or NaF and (60-x)V₂O₅-30BaF₂-10LiF-xAF, where AF=NaF and x=10, 15, 20, 25 and 30 mol%. Density of the glasses was measured and molar volume calculated and they correlated with the AF content. The dc conductivity has been measured in the temperature range from 302 to 453 K. The dc conductivity increases with temperature and V₂O₅ content, while it decreases with the alkali fluoride content. Conductivity has been correlated with the calculated polaron distance, R, and glass transition temperature, T_g. The activation energy, W, increases with the increase in the alkali fluoride, while it decreases with the V₂O₅ content. Some parameters like polaron distance, R, polaron radius, r_p, ion concentrations, n(V), n(Li) or n(Na), hopping energy, W_H, density of localized states at Fermi level, N(E_F), polaron coupling constant, γ_p, polaron band width, J, hopping mobility, μ, and carrier density for electronic conduction, N_c, were calculated to explain the conduction mechanism and behavior of the present glasses.     

Universal scaling for the dilemma strength in evolutionary games

Why would natural selection favor the prevalence of cooperation within the groups of selfish individuals? A fruitful framework to address this question is evolutionary game theory, the essence of which is captured in the so-called social dilemmas. Such dilemmas have sparked the development of a variety of mathematical approaches to assess the conditions under which cooperation evolves. Furthermore, borrowing from statistical physics and network science, the research of the evolutionary game dynamics has been enriched with phenomena such as pattern formation, equilibrium selection, and self-organization. Numerous advances in understanding the evolution of cooperative behavior over the last few decades have recently been distilled into five reciprocity mechanisms: direct reciprocity, indirect reciprocity, kin selection, group selection, and network reciprocity. However, when social viscosity is introduced into a population via any of the reciprocity mechanisms, the existing scaling parameters for the dilemma strength do not yield a unique answer as to how the evolutionary dynamics should unfold. Motivated by this problem, we review the developments that led to the present state of affairs, highlight the accompanying pitfalls, and propose new universal scaling parameters for the dilemma strength. We prove universality by showing that the conditions for an ESS and the expressions for the internal equilibriums in an infinite, well-mixed population subjected to any of the five reciprocity mechanisms depend only on the new scaling parameters. A similar result is shown to hold for the fixation probability of the different strategies in a finite, well-mixed population. Furthermore, by means of numerical simulations, the same scaling parameters are shown to be effective even if the evolution of cooperation is considered on the spatial networks (with the exception of highly heterogeneous setups). We close the discussion by suggesting promising directions for future research including (i) how to handle the dilemma strength in the context of co-evolution and (ii) where to seek opportunities for applying the game theoretical approach with meaningful impact.     

Landau damping of ion-acoustic waves with simultaneous effects of non-extensivity and non-thermality in the presence of hybrid Cairns-Tsallis distributed electrons

The dispersion properties and Landau damping rate of ion-acoustic waves (IAWs) with the hybrid Cairns-Tsallis distributed (CTD) electrons and Maxwellian ions are investigated using the plasma kinetic model based on Vlasov-Poisson's equations. For both super-extensive (q < 1) and sub-extensive (q > 1) plasmas, the dielectric response function, real frequency, and Landau damping rate of IAWs are derived. By taking the effect of θ_{i, e} (ion-to-electron temperature ratio) into account, it is found that with the increase of ion temperature, the real frequency and wave dispersion effects increase as well (for both super-extensive and sub-extensive cases). Exploring the properties of the Landau damping rate of IAWs with the simultaneous presence of non-thermal parameter α and non-extensive parameter q, a comparison of numerical and analytical results is presented. It is found that in different ranges of θ_{e, i} (electron-to-ion temperature ratio), on decreasing the values of the non-extensive parameter and increasing values of the non-thermal parameter, the weak damping rate is observed (vice versa) in super-extensive or super-thermal plasma, although the trend of the damping rate in sub-thermal plasma is similar (as in the case of super-thermal plasma) but is less weak. It is further revealed that the damping rate of IAWs in thermal plasmas (Maxwellian) is stronger than the damping rate of IAWs in the case of non-thermal plasmas (CTD). The current study is applicable to provide deep insight and further allow the exploration of electrostatic plasma modes in different space and laboratory plasma environments where the hybrid CTD plasma exists.     

C6v对称TIR-PCF结构参数对基模零色散点的调节数值研究

用多极方法数值研究构成六重对称全内反射型光子晶体光纤各种结构参数对基模零色散点的调节.数值结果表明,在相对孔径较大时,包层空气孔柱层数不影响零色散点,在其它结构参数相同的条件下,空气孔直径越大,零色散点波长越短,而在其它结构参数相同的条件下,空气孔孔距越大,零色散点波长越长,当空气孔直径与空气孔孔距都很小时,零色散点出现在长波区域,当空气孔直径与空气孔孔距大到一定程度时,色散曲线在零色散线出现振荡特性,并出现多个零色散点,在包层空气柱层数一定的条件下,中央纤芯缺省空气孔层数对零色散点的调节范围大.     

Study on the interaction between promethazine hydrochloride and bovine serum albumin by fluorescence spectroscopy

The interaction between promethazine hydrochloride (PMT) and bovine serum albumin (BSA) in vitro was investigated by means of fluorescence spectroscopy and absorption spectroscopy. The fluorescence of BSA was quenched remarkably by PMT and the quenching mechanism was considered as static quenching by forming a complex. The association constants K_a and the number of binding sites n were calculated at different temperatures. The BSA-PMT binding distance was determined to be less than 8 nm, suggesting that energy transfer from BSA to PMT may occur. The thermodynamic parameters of the interaction between PMT and BSA were measured according to the van’t Hoff equation. The enthalpy change (ΔH) and entropy change (ΔS) were calculated to be −23.62 kJ mol⁻¹ and −0.10 J mol⁻¹ K⁻¹, respectively, which indicated that the interaction of PMT with BSA was driven mainly by van der Waals forces and hydrogen bonds. The binding process was a spontaneous process in which Gibbs free energy change (ΔG) was negative. In addition, the results of synchronous fluorescence spectra and three-dimensional fluorescence spectra showed that binding of PMT with BSA can induce conformational changes in BSA.