A Study of the Solvation Structure of l‐Leucine in Alcohol–Water Binary Solvents through Molecular Dynamics Simulations and FTIR and NMR Spectroscopy

The solvation structures of l ‐leucine (Leu) in aliphatic‐alcohol–water and fluorinated‐alcohol–water solvents are elucidated for various alcohol contents by using molecular dynamics (MD) simulations and IR, and ¹H and ¹³C NMR spectroscopy. The aliphatic alcohols included methanol, ethanol, and 2‐propanol, whereas the fluorinated alcohols were 2,2,2‐trifluoroethanol and 1,1,1,3,3,3‐hexafluoro‐2‐propanol. The MD results show that the hydrophobic alkyl moiety of Leu is surrounded by the alkyl or fluoroalkyl groups of the alcohol molecules. In particular, TFE and HFIP significantly solvate the alkyl group of Leu. IR spectra reveal that the Leu C?H stretching vibration blueshifts in fluorinated alcohol solutions with increasing alcohol content, whereas the vibration redshifts in aliphatic alcohol solutions. When the C?H stretching vibration blueshifts in the fluorinated alcohol solutions, the hydrogen and carbon atoms of the Leu alkyl group are magnetically shielded. Consequently, TFE and HFIP molecules may solvate the Leu alkyl group through the blue‐shifting hydrogen bonds.     

Influence of Ag+ on the Magnetic Response of [2.2.2]Paracyclophane: NMR Properties of a Prototypical Organic Host for Cation Binding Based on DFT Calculations

The complexation of metal cations into a host–guest situation is particularly well exemplified by [2.2.2]paracyclophane and Ag^I, which leads to a strong cation–π interaction with a specific face of the host molecule. Through this study we sought a deeper understanding of the effects the metal center has on the NMR spectroscopic properties of the prototypical organic host, generating theoretical reasons for the observed experimental results with an aim to determine the role of the cation–π interaction in a host–guest scenario. From an analysis of certain components of the induced magnetic field and the ¹³C NMR shielding tensor under its own principal axis system (PAS), the local and overall magnetic behavior can be clearly described. Interestingly, the magnetic response of such a complex exhibits a large axis-dependent behavior, which leads to an overall shielding effect for the coordinating carbon atoms and a deshielding effect for the respective uncoordinated counterparts, evidence that complements previous experimental results. This proposed approach can be useful to gain further insight into the local and overall variation of NMR shifts for host–guest pairs involving both inorganic and organic hosts.     

The role of induced current density in Steroelectronic effects: Perlin effect

The normal and reverse Perlin effect is usually explained by the redistribution of electron density produced by hyperconjugative mechanisms, which increases the electron population within axial or equatorial proton in normal or reverse effect, respectively. Here an alternative explanation for the Perlin effect is presented on the basis of the topology of the induced current density, which directly determines the nuclear magnetic shielding. Current densities around the C? H bond critical point and intra‐atomic and interatomic contributions to the magnetic shielding explain the observed Perlin effect. The balance between intra‐atomic and interatomic contributions determines the difference in the total atomic shielding. Normal Perlin effect is dominated by intra‐atomic part, whereas reverse effect is dominated by interatomic contribution. © 2015 Wiley Periodicals, Inc.     

La(Ⅲ)-乙醇溶液微团簇理论和光谱研究

利用分子光谱和基于密度泛函理论的第一性原理,采用改进的TPSSTPSS泛函方法对C、H、O原子用6-31G基组并添加极化和弥散函数,对La原子选用Def2-SV(P)赝势基组,研究La3+/乙醇溶液微团簇构型。优化计算La3+在水溶液中的溶剂化结构,得出气相中的优化结果可以近似代替液相结果的结论;理论优化计算La3+/乙醇溶液可能存在的结构构型的结果表明,溶剂化数n=6时结构最稳定。采用荧光光谱和核磁共振实验对结果进行了验证,表明La3+的加入使荧光强度显著增强,在高浓度时生成的团簇构型比较稳定,且随着溶剂化数目的增加,O—H键长增大,La3+使其附近的质子产生强大的屏蔽效应,化学位移向高场移动,溶剂化数n=6时绝对误差最小,最稳定,与理论计算结论相吻合。     

Computational, 1H NMR,and X‐ray structural studies on 1‐arylurazole tetrazane dimers

Nitrogen‐centered urazole radicals exist in equilibrium with tetrazane dimers in solution. The equilibrium established typically favors the free‐radical form. However, 1‐arylurazole radicals bearing substituents at the ortho position favor the dimeric form. We were able to determine the structure of one of the dimers (substituted at both ortho positions with methyl groups), namely 1,2‐(2,4‐dimethylphenyl)‐2‐[2‐(2,4‐dimethylphenyl)‐4‐methyl‐3,5‐dioxo‐1,2,4‐triazolidin‐1‐yl]‐4‐methyl‐1,2,4‐triazolidine‐3,5‐dione, C₂₄H₂₈N₆O₄, via X‐ray crystallography. The experimentally determined structure agreed well with the computationally obtained geometry at the B3LYP/6‐311G(d,p) level of theory. The preferred syn conformation of these 1‐arylurazole dimers results in the two aromatic rings being proximate and nearly parallel, which leads to some interesting shielding effects of certain signals in the ¹H NMR spectrum. Armed with this information, we were able to decipher the more complicated ¹H NMR spectrum obtained from a dimer that was monosubstituted at the ortho position with a methyl group.     

Active sound control in composite regions

In active sound control, noise shielding of a target region is achieved via additional sources (called controls) situated at the perimeter of the region. The sources protect the target region by adjusting the acoustic field near the boundary of the region. In the present paper a numerical model of active sound control based on surface potentials in 3D bounded composite regions is numerically studied. In the composite region setup, it is required that the regions be shielded from noise while allowing admissible sound that is generated in the shielded regions to be preserved. The admissible sound is usually required to propagate freely inside the protected regions or in a (selective) predetermined pattern. The adjusting approach used here does not require any knowledge of the sound sources or the properties of the propagation medium in order to obtain the controls. Moreover, the approach differs sharply from some other approaches where the detailed knowledge of the sound sources and the propagation medium is required. For the first time, numerical test cases involving both free communication and predetermined communication pattern between the regions in three dimensions are considered. In all test cases, these regions are effectively shielded from the noise while any present admissible sound is preserved. In addition, selective propagation of the admissible sound between the regions is enforced. The effect of the number of controls on their operation is also studied. Whether admissible sound is present or not, the level of noise cancellation decreases linearly as fewer controls are used. In addition to the increase in size of the interference zone, the controls become individually distinguishable.     

激光防护器材和抗激光损伤薄膜

介绍激光防护滤光片、激光辐射屏蔽和抗激光损伤的光学薄膜的发展情况。     

高能重离子加速器次级中子屏蔽的理论估算

用R.Madey等人提出的由核反应参数计算屏蔽的方法,计算了入射离子单核能为0.6、1.2GeV¹²C束轰击厚Cu靶的次级中子屏蔽.当入射离子束流为1×10¹³ions/s时,其前向和侧向混凝土屏蔽厚度分别为9.8、4.8m(对0.6GeV)和11.5、6.9m(对1.2GeV).     

高超声速飞行器高温流场对激光武器毁伤效应的影响

以美国ABL系统激光武器为例,分析了高超声速飞行器高温流场气体影响激光武器毁伤效应的一些主要因素,包括气体击穿、等离子体屏蔽效应、烧蚀产物颗粒的影响。结果表明:通常情况下,流场电子数密度小于1017cm-3,流场本身等离子体特性不会引起对激光的等离子体屏蔽效应;只有在0.5 km射程以内和宽脉冲激光引起的高压流场(约10 MPa以上)气体击穿,才会导致明显的等离子体屏蔽效应,但在实际战场条件下这种情况一般不会发生;对采用烧蚀手段进行防热的飞行器而言,飞行高度大于10 km,并且基于自由来流流量的无量纲化烧蚀流量小于10-2左右时,烧蚀产物颗粒不会引起激光的衰减。