Steric crowding can stabilize a labile molecule: solving the hexaphenylethane riddle

12 not so angry men: Hexaphenylethane is unstable, a phenomenon traditionally attributed to steric repulsion between the six phenyl rings. However, adding 12 bulky tert-butyl groups, one to each of the 12 meta positions, gives a stabile ethane derivative (see space-filling model and potential energy curve for the dissociation of the central C-C bond). This unexpected stabilization is shown to result from attractive dispersion interactions between the substituents.     

Rolling/sliding of a particle on a flat wall in a linear shear flow at finite Re

Recently Lee and Balachandar proposed analytically-based expressions for drag and lift coefficients for a spherical particle moving on a flat wall in a linear shear flow at finite Reynolds number. In order to evaluate the accuracy of these expressions, we have conducted direct numerical simulations of a rolling particle for shear Reynolds number up to 100. We assume that the particle rolls on a horizontal flat wall with a small gap separating the particle from the wall (L = 0.505) and thus avoiding the logarithmic singularity. The influence of the shear Reynolds number and the translational velocity of the particle on the hydrodynamic forces of the particle was investigated under both transient and the final drag-free and torque-free steady state. It is observed that the quasi-steady drag and lift expressions of Lee and Balachandar provide good approximation for the terminal state of the particle motion ranging from perfect sliding to perfect rolling. With regards to transient particle motion in a wall-bounded shear flow it is observed that the above validated quasi-steady drag and lift forces must be supplemented with appropriate wall-corrected added-mass and history forces in order to accurately predict the time-dependent approach to the terminal steady state. Quantitative comparison with the actual particle motion computed in the numerical simulations shows that the theoretical models quite effective in predicting rolling/sliding motion of a particle in a wall-bounded shear flow at moderate Re.     

Bilinear form and new interaction solutions for the sixth-order Ramani equation

By using the Hirota’s bilinear method, the bilinear form of the sixth-order Ramani equation is succinctly obtained. With the aid of the obtained bilinear form, some new interaction solutions which include interaction solutions between exponential and trigonometric functions, interaction solutions between exponential and hyperbolic functions, and interaction solutions between trigonometric and hyperbolic functions are also presented by employing the three wave method.     

A high level computational study of the CH4/CF4 dimer: how does it compare with the CH4/CH4 and CF4/CF4 dimers?

The interaction within the methane–methane (CH₄/CH₄), perfluoromethane–perfluoromethane (CF₄/CF₄) methane–perfluoromethane dimers (CH₄/CF₄) was calculated using the Hartree–Fock (HF) method, multiple orders of Møller–Plesset perturbation theory [MP2, MP3, MP4(DQ), MP4(SDQ), MP4(SDTQ)], and coupled cluster theory [CCSD, CCSD(T)], as well as the PW91, B97D, and M06-2X density functional theory (DFT) functionals. The basis sets of Dunning and coworkers (aug-cc-pVxZ, x?=?D, T, Q), Krishnan and coworkers [6-311++G(d,p), 6-311++G(2d,2p)], and Tsuzuki and coworkers [aug(df, pd)-6-311G(d,p)] were used. Basis set superposition error (BSSE) was corrected via the counterpoise method in all cases. Interaction energies obtained with the MP2 method do not fit with the experimental finding that the methane–perfluoromethane system phase separates at 94.5?K. It was not until the CCSD(T) method was considered that the interaction energy of the methane–perfluoromethane dimer (?0.69?kcal?mol^?1) was found to be intermediate between the methane (?0.51?kcal?mol^?1) and perfluoromethane (?0.78?kcal?mol^?1) dimers. This suggests that a perfluoromethane molecule interacts preferentially with another perfluoromethane (by about 0.09?kcal?mol^?1) than with a methane molecule. At temperatures much lower than the CH₄/CF₄ critical solution temperature of 94.5?K, this energy difference becomes significant and leads perfluoromethane molecules to associate with themselves, forming a phase separation. The DFT functionals yielded erratic results for the three dimers. Further development of DFT is needed in order to model dispersion interactions in hydrocarbon/perfluorocarbon systems.     

1H NMR Studies on the Methylation,Protonation, and Hydration Sites in Some Benzo[b]Naphthyridines (Azaacridines)

Abstract

The 300.13 MHz ¹H NMR spectra of the methylated and protonated 6(9)-methylbenzo[b][1,x] naphthyridines (x=5, 6, 7, 8) (5-methylazaacridines) were collected at 298 K in deuterated dimethyl sulfoxide and chloroform, respectively. The methylation and protonation sites were assigned by comparisons of these data with those of the free bases. The results were compared with similar data for related heterocycles and showed that both methylation and protonation occur at the nitrogen in the outer pyrido ring in all four series.

The hydration site in some 2-and 3-azaacridines was determined by specific line broadening in their ¹H NMR spectra to be the same nitrogen as that involved in methylation and protonation. Variable temperature ¹H NMR demonstrated that the specific line broadening results from some changes of ¹⁴N quadrupolar relaxation produced by the slow chemical exchange between unhydrated and hydrated species. Deuterium exchange experiments indicated that the direct spin-spin interaction of a water proton and the protons alpha to the hydrated nitrogen may also have some contribution.     

有机膨润土结构对吡虫啉吸附热力学和动力学的影响机理

为深入了解有机膨润土结构对农药吸附性能的影响机理,论文制备十六烷基三甲基氯化铵(HTMA)载量系列变化的有机膨润土,通过吸附热力学和动力学研究了新烟碱杀虫剂吡虫啉与改性有机膨润土的相互作用和影响农药分子在有机膨润土层间扩散的结构因素。结果显示,季铵盐改性削弱了膨润土片层与吡虫啉的静电结合,但是增强与吡虫啉的疏水相互作用。吡虫啉吸附动力学与有机膨润土层间结构密切相关,低载量(<0.8′CEC)的HTMA对膨润土层间距的影响很小,但是层间堆积密度的增加导致吡虫啉吸附速率常数急剧下降。HTMA载量的进一步增加导致其层间排列方式由单层平铺向双层平铺的转变,层间距急剧增加使得吡虫啉吸附速率常数略有增大。     

强相互作用理论的渐近自由——2004年诺贝尔物理学奖介绍

瑞典皇家科学院把2004年度的诺贝尔物理学奖授予了美国的戴维·格罗斯(David J. Gross),戴维·玻利泽(H. David Politzer),弗兰克·维里茨克(Frank Wilczek)三位理论物理学家,以表彰他们揭示出了强相互作用的'渐近自由'特性.文章按历史顺序,简要回顾了强相互作用理论——量子色动力学的基本“要素”.介绍了理论上如何得出强相互作用“渐近自由”和“渐近自由”的含义,引述了实验检验理论上的“渐近自由”最典型和最新的情况,展示了强相互作用“渐近自由”的高度正确性.介绍了基于“渐近自由”的微扰量子色动力学.指出“渐近自由”的发现和证实是确立量子色动力学为描述强相互作用的正确理论的依据,同时列举了当前量子色动力学的“色禁闭”等一些前沿问题.“渐近自由”的发现和证实确实深刻地影响了粒子物理,如量子色动力学成了标准模型的重要组成和导致相互作用的大统一理论等.     

光谱法研究甲氨喋呤与牛血清白蛋白的相互作用

用荧光和紫外吸收光谱法,研究了抗癌药物甲氨喋呤(MTX)与牛血清白蛋白(BSA)的相互作用。结果表明：在生理条件下,甲氨喋呤对牛血清白蛋白荧光有较强的猝灭作用,其猝灭方式为静态猝灭。根据猝灭结果,求出了不同温度下反应的结合常数及反应热力学参数,并据此确定了它们相互作用的主要形式。     

变质量质点的动能定理与软绳问题

给出变量质点的动能定理和一对反推内力作功的表达式,并由此给出软绳问题的正确解。     

低聚壳聚糖与角质层蛋白相互作用的体外研究

以脱脂鼠角质层和提取角蛋白为模型,利用电化学交流阻抗谱、SEM、DSC、FTIR等手段,研究了低聚壳聚糖及氨基葡萄糖与角质层蛋白之间的相互作用.结果发现,氨基葡萄糖溶液处理不影响脱脂角质层膜的阻抗,而低聚壳聚糖溶液处理却可明显降低脱脂角质层膜的阻抗,阻抗值由3.79×106Ω·cm2降至8.379×105Ω·cm2.此外,壳聚糖溶液和氨基葡萄糖溶液都可明显破坏角蛋白表面致密均匀的结构,并使得角蛋白二级结构中α-螺旋结构含量减少,同时推动角蛋白α-螺旋结构向β-折叠结构和无规则卷曲结构转变.这些结果表明低聚壳聚糖与角质层蛋白相互作用,一方面可有效降低鼠角质层结构的紧密程度,另一方面可影响角蛋白的微结构,使其结构松散并出现微细孔道,从而为药物的经皮吸收与传送疏通了通道.