The primary step in the ultrafast photodissociation of the methyl iodide dimer

This paper shows the results of combined experimental and theoretical work that have unravelled the mechanism of ultrafast ejection of a methyl group from a cluster, the methyl iodide dimer (CH(3)I)(2). Ab initio calculations have produced optimized geometries for the dimer and energy values and oscillator strengths for the excited states of the A band of (CH(3)I)(2). These calculations have allowed us to describe the blue shift that had been observed in the past in this band. This blue shift has been experimentally determined with higher precision than in all previously reported experiments, since it has been measured through its effect upon the kinetic energy release of the fragments using femtosecond velocity map imaging. Observations of the reaction branching ratio and of the angular nature of the fragment distribution indicate that two main changes occur in A-band absorption in the dimer with respect to the monomer: a substantial change in the relative absorption to different states of the band, and, more importantly, a more efficient non-adiabatic crossing between two of those states. Additionally, time resolved experiments have been performed on the system, obtaining snapshots of the dissociation process. The apparent retardation of more than 100 fs in the dissociation process of the dimer relative to the monomer has been assigned to a delay in the opening of the optical detection window associated with the resonant multiphoton ionization detection of the methyl fragment.     

Difluoro-boron-triaza-anthracene: a laser dye in the blue region. Theoretical simulation of alternative difluoro-boron-diaza-aromatic systems

The synthesis, photophysical and laser properties of a difluoro-boron-triaza-anthracene (BTAA) compound are analyzed in the present paper. The molecular structure of this dye is an anthracene-like core with N atoms at 4a, 9 and 10a positions where two of them (4a and 10a) are linked through a BF(2)-bridge group. This structure is reminiscent of aza-BODIPY dye with an s-indacene core, BODIPY being one of the most commonly used laser dye family in the Vis region. The main absorption and emission bands of the new dye are localized in the blue part of the Vis region of the electromagnetic radiation, a spectral region practically unexploited by the BODIPY chromophore. Moreover, the new dye presents a higher laser efficiency and photostability than other commercial laser dyes operating in the same spectral region. In order to look for new molecular structures with potential laser emission covering the whole Vis spectral region, the spectroscopic properties of other different chromophoric systems based on BF(2)-linking aromatic groups are theoretically simulated by quantum mechanical calculations.     

Nusselt-Rayleigh correlations for free convection in 2D air-filled parallelogrammic enclosures with isothermal active walls

In the present study Nu-Ra-α correlations are proposed to calculate the steady-state natural convection heat transfer taking place in 2D air-filled cavities of parallelogrammic section. The thermal conditions and the dimensions of the enclosures permit to cover a large range of Rayleigh numbers, 1.7 × 10³  ≤ Ra ≤ 3.0 × 10⁹, suitable for diverse engineering applications. The two active walls of the cavities are kept vertical and isothermal at hot and cold temperatures T _h and T _c respectively. Separated by a horizontal distance H, they have the same height H and are connected by a closed adiabatic channel whose upper and lower walls can be inclined at an angle α with respect to the horizontal, varying between −60° to +60°. That gives rise to a conducting or insulating cavity, in the convective sense of the term (diode cavity). A computational model based on the finite volume method is used to solve the governing equations. The large number of treated configurations led to propose Nu-Ra-α correlations for large ranges of Ra and α which can be applied to many engineering areas. The results of this numerical study have been successfully compared with calculated and measured available data.     

基于多元高斯声束模型的圆柱体超声检测声场仿真

为了提高圆柱体缺陷检测的准确性,需了解其超声声场分布。针对圆柱体实际检测的要求,本文采用超声水浸检测法。通过多元高斯声束模型分别模拟了实心圆柱体及空心圆柱体中的辐射声场,计算仿真了垂直入射与倾斜入射至圆柱体时的声场,实现了检测声场的可视化。通过计算得出仿真结构与实际理论相符,表明本论文的方法能够应用在圆柱体结构超声声场仿真中。     

旋转薄壁圆柱壳振型进动的非线性振动特性

选取在工程上常用的悬臂旋转薄壁圆柱壳为研究模型,首先推导出考虑阻尼的振型进动因子,然后根据Donnell's简化壳理论建立考虑科氏力,阻尼与几何大变形的非线性波动方程,采用Galerkin方法对波动方程进行离散化,得到模态坐标中相互耦合的三阶非线性微分方程组.应用Runge-Kutta法求解获得非线性幅频特性曲线,分析了不同模态组合下系统主模态(m=1,n=6,k=1)的共振响应.应用谐波平衡法对系统三阶非线性微分方程组解析分析,与数值解比较验证了解析解的正确性和有效性.最后分析了动力系统的运动稳定性.结果表明,节径数n和频率倍数k对于主模态共振响应的影响很小,而轴向半波数m对主共振的影响则相对较大,因此只需选取相邻的两个轴向模态(M=2)即可较为简洁,准确的描述主共振响应;谐波平衡法可以很好的解决三阶微分方程组的非线性问题,并且能够达到较为满意的精度.     

Chord length distributions interpretation using a polydispersed population: Modeling and experiments

Chord length distributions were measured during the crystallization of gas hydrates in a flow loop. The conditions on the flow loop were similar with the conditions in the marine pipelines. The flow loop was filled with water in oil emulsion and pressurized with methane (7 MPa) at low temperature (277 K). During crystallization water droplets crystallize and agglomerate. The CLD measures were interpreted in a preceding work [Le Ba et al., 2010] [1] by constructing random aggregates with known geometrical proprieties from a monodispersed population of droplets and calculating their CLD. Comparing calculated CLD with CLD from the experiment, the geometrical parameters: number of primary particles and fractal dimension of experimental aggregates are identified. However some differences remained between the experiment and the calculated CLD. In the present work the droplets population was considered polydispersed improving the comparison between the model and the experiment.     

Thermodynamics of the Interaction Between Graphene Quantum Dots with Human Serum Albumin and γ-Globulins

As one of the newly emerged nanomaterials, graphene quantum dots (GQDs) have shown great application potential as tracking probes and drug carriers in biological areas. The GQDs synthesized via the nitric acid reflux method in this study turned out to quench the fluorescence of human serum albumin (HSA) and gamma globulin (γ-globulin) in two different functional ways. The fluorescence quenching effect of GQDs on HSA is a static pattern and the predominant interaction forces are hydrogen bonds and van der Waals forces. Distinct from HSA, the interaction between GQDs and γ-globulins belongs to dynamic quenching and is driven by electrostatic forces. Ultraviolet–visible (UV–vis) differential spectrometry and transient state fluorescence spectrometry were also utilized to further confirm their quenching types. Also, thermodynamics parameters, the enthalpy change (ΔH) and entropy change (ΔS) of reaction between GQDs and proteins were obtained through a series of calculations from the van’t Hoff equation. Furthermore, the effect of GQDs on the conformational structure of proteins was characterized by synchronous fluorescence spectra (SFS), three-dimensional (3D) fluorescence and circular dichroism (CD) spectra. In addition, the binding mechanism of GQDs with HSA and γ-globulins were proposed based on the obtained experimental results. The research on the reaction between GQDs with HSA and γ-globulins offers promising insight for the further application of nanomaterials in biomedical fields.     

Decaborane thiols as building blocks for self-assembled monolayers on metal surfaces

Three nido-decaborane thiol cluster compounds, [1-(HS)-nido-B(10)H(13)] 1, [2-(HS)-nido-B(10)H(13)] 2, and [1,2-(HS)(2)-nido-B(10)H(12)] 3 have been characterized using NMR spectroscopy, single-crystal X-ray diffraction analysis, and quantum-chemical calculations. In the solid state, 1, 2, and 3 feature weak intermolecular hydrogen bonding between the sulfur atom and the relatively positive bridging hydrogen atoms on the open face of an adjacent cluster. Density functional theory (DFT) calculations show that the value of the interaction energy is approximately proportional to the number of hydrogen atoms involved in the interaction and that these values are consistent with a related bridging-hydrogen atom interaction calculated for a B(18)H(22)·C(6)H(6) solvate. Self-assembled monolayers (SAMs) of 1, 2, and 3 on gold and silver surfaces have been prepared and characterized using X-ray photoelectron spectroscopy. The variations in the measured sulfur binding energies, as thiolates on the surface, correlate with the (CC2) calculated atomic charge for the relevant boron vertices and for the associated sulfur substituents for the parent B(10)H(13)(SH) compounds. The calculated charges also correlate with the measured and DFT-calculated thiol (1)H chemical shifts. Wetting-angle measurements indicate that the hydrophilic open face of the cluster is directed upward from the substrate surface, allowing the bridging hydrogen atoms to exhibit a similar reactivity to that of the bulk compound. Thus, [PtMe(2)(PMe(2)Ph)(2)] reacts with the exposed and acidic B-H-B bridging hydrogen atoms of a SAM of 1 on a gold substrate, affording the addition of the metal moiety to the cluster. The XPS-derived stoichiometry is very similar to that for a SAM produced directly from the adsorption of [1-(HS)-7,7-(PMe(2)Ph)(2)-nido-7-PtB(10)H(11)] 4. The use of reactive boron hydride SAMs as templates on which further chemistry may be carried out is unprecedented, and the principle may be extended to other binary boron hydride clusters.     

Cross‐Linked‐Polymer‐Supported N‐{2′‐[(Arylsulfonyl)amino][1,1′‐binaphthalen]‐2‐yl}prolinamide as Organocatalyst for the Direct Aldol Intermolecular Reaction under Solvent‐Free Conditions

A bottom‐up strategy was used for the synthesis of cross‐linked copolymers containing the organocatalyst N‐{(1R)‐2′‐{[(4‐ethylphenyl)sulfonyl]amino}[1,1′‐binaphthalen]‐2‐yl}‐D ‐prolinamide derived from 2 (Scheme 1). The polymer‐bound catalyst 5b containing 1% of divinylbenzene as cross‐linker showed higher catalyst activity in the aldol reaction between cyclohexanone and 4‐nitrobenzaldehyde than 5a and 5c . Remarkably, the reaction in the presence of 5b was carried out under solvent‐free, mild conditions, achieving up to 93% ee (Table 1). The polymer‐bound catalyst 5b was recovered by filtration and re‐used up to seven times without detrimental effects on the achieved diastereo‐ and enantioselectivities (Table 2). The catalytic procedure with polymer 5b was extended to the aldol reaction under solvent‐free conditions of other ketones, including functionalized ones, and different aromatic aldehydes (Table 3). In some cases, the addition of a small amount of H₂O was required to give the best results (up to 95% ee). Under these reaction conditions, the cross‐aldol reaction between aldehydes proceeded in moderate yield and diastereo‐ and enantioselectivity (Scheme 2).