Molecular interactions between pyrazine and n-propanol, chloroform, or tetrahydrofuran

The molecular interactions of pyrazine (PZ) with n-propanol, chloroform, and tetrahydrofuran (THF) have been investigated by employing ultraviolet spectroscopy and quantum chemical calculation methods. A new quantity, excess absorption coefficient, was introduced to represent the strength of the interaction. It was found that the interaction decreased in the order: PZ-propanol>PZ-chloroform>PZ-THF. The Benesi-Hildebrand method indicated that the interaction stoichiometries of the PZ-chloroform and PZ-THF systems were both 1:1 and the equilibrium constants were determined to be 2.07 and 0.64M(-1), respectively. Using a nonlinear fitting method, we demonstrated that the PZ-propanol was a two-step 1:2 interaction pair and the equilibrium constants were determined to be 8.8 and 0.19M(-1). Quantum chemical calculations showed the existence of hydrogen-bonding interactions in all the three system: normal Ncdots, three dots, centeredH-O hydrogen bond in the PZ-propanol system, unconventional Ncdots, three dots, centeredH-C hydrogen bond in the PZ-chloroform, and weak N-C-Hcdots, three dots, centeredO hydrogen bond in the PZ-THF system. Methodologically, we pointed out that special care must be taken when the Benesi-Hildebrand method is used to evaluate 1:2 interactions.     

基于D-T紧凑型中子源的快中子照相准直屏蔽体设计及中子束特性模拟研究

中子照相是一种重要的无损检测技术,它能用于火工产品、毒品和核燃料元件等的检测。基于紧凑型D-T中子发生器,完成了一个用于快中子照相的准直屏蔽体系统（BSA）的物理设计。根据D-T中子源的能谱和角分布建立了中子源模型,采用MCNP4C蒙特卡罗程序,模拟了准直屏蔽体系统中中子和γ射线的输运,准直中子束相对于单位源中子的中子注量可以达到9.30×10-6 cm-2,准直中子束中主要是能量大于10 MeV的快中子;在设置的样品平面直径14 cm的照射视野范围,准直束中子注量的不均匀度为4.30%,准直束中中子注量与γ注量的比值为17.20,中子通量和中子注量比值J/Φ为0.992,说明准直中子束有好的平行性;准直屏蔽体外的泄露中子注量率与准直束中子注量率相比降低了2个量级。所设计的准直屏蔽体能满足快中子照相的要求。Neutron radiography is an important nondestructive testing technique. It can be used to detect the explosive devices, drug and the nuclear fuel element, etc. A beam-shaping-assembly (BSA) based on a compact D-T neutron generator is designed for fast neutron radiography in this paper. D-T neutron source model is constructed based on the neutron energy spectrum and angular distribution data. The transportation of neutron and γ-ray in the BSA is simulated using MCNP4C code. The neutron fluence of the collimated neutron beam with respect to the neutron source of the unit source is 9.30×10-6 cm-2. The collimated neutron beams is mainly fast neutrons with energies greater than 10 MeV. In the irradiation field range with a diameter of 14 cm, the neutron fluence uniformity of the collimated beam is 4.3%, the ratio of the neutron fluence to the gamma fluence in the collimated beam is 17.20, and the neutron flux and the neutron fluence ratio (J/Φ) is 0.992 which indicates that the collimated neutron beam has good parallelism. The leakage neutron fluence in outside of BSA is two orders of magnitude lower than that of the collimated neutron beam. The designed BSA can meet the need of fast neutron radiography.     

The role of methyl groups in the formation of hydrogen bond in DMSO-methanol mixtures

When examining the formation energetics of a hydrogen-bonded complex R-X-H...Y-R', focus has been almost always on the atoms directly involved, namely the atoms X, Y, and H. Little attention has been paid to the effects of the secondary alkyl groups R and R'. Taking dimethyl sulfoxide (DMSO)-methanol binary system as an example, we have studied the roles of the alkyl groups in stabilizing the hydrogen bonds by employing FTIR and NMR techniques and quantum chemical calculations. We found that methyl groups play different roles in response to the hydrogen-bonding interactions. The methyl groups of DMSO are electron-donating, whereas that of methanol is electron-withdrawing, both making positive contributions. The findings reveal non-negligible effects of secondary alkyl groups in hydrogen bonding interaction and may shed light on the understanding of other more complicated hydrogen-bonded systems in chemical and biological systems.     

Vibration characteristics of aluminum surface subjected to ultrasonic waves and their effect on wetting behavior of solder droplets

The vibration characteristics of an aluminum surface subjected to ultrasonic waves were investigated with a combination of numerical simulation and experimental testing. The wetting behavior of solder droplets on the vibrating aluminum surface was also examined. The results show that the vibration pattern of the aluminum surface is inhomogeneous. The amplitude of the aluminum surface exceeds the excitation amplitude in some zones, while the amplitude decreases nearly to zero in other zones. The distribution of the zero-amplitude zones is much less dependent on the strength of the vibration than on the location of the vibration source. The surface of the liquid solder vibrates at an ultrasonic frequency that is higher than the vibration source, and the amplitude of the liquid solder is almost twice that of the aluminum surface. The vibration of the surface of the base metal (liquid solder) correlates with the oxide film removal effect. Significant removal of the oxide film can be achieved within 2 s when the amplitude of the aluminum surface is higher than 5.4 μm or when the amplitude of the liquid solder surface is higher than 10.2 μm.     

H-MCM-22沸石分子筛中Brnsted/Lewis酸协同效应的~1H 和~(27)Al双量子魔角旋转固体核磁共振研究

采用各种固体核磁共振 (NMR) 技术详细研究了 H-MCM-22 分子筛中 Brnsted/Lewis 酸的协同效应. 二维 1H 双量子魔角旋转 (DQ-MAS) NMR 结果表明, 在脱铝 H-MCM-22 分子筛中 Brnsted 酸位 (骨架桥式羟基) 和 Lewis 酸位 (非骨架铝羟基) 之间是空间邻近的, 暗示着可能存在 B/L 酸协同效应. 二维 27Al DQ-MAS NMR 结果揭示了各种铝物种之间的空间邻近性, 表明 B/L 酸协同效应优先发生在 H-MCM-22 分子筛超笼中的骨架 T6 位铝和非骨架铝物种之间. 2-13C-丙酮探针分子实验发现, 因 B/L 酸协同效应而导致脱铝 H-MCM-22 分子筛酸性明显增强, 氘代吡啶探针分子实验也证实在 H-MCM-22 分子筛的超笼中发生了 B/L 酸协同效应. 上述结果将有助于我们理解在脱铝 H-MCM-22 分子筛上发生的多相催化机理.     

Light field characteristics of reflective thin-films irradiated by femtosecond laser pulses

The formation of interference field in optical thin-films is a process of unsteady state when irradiated by femtosecond pulses. Based on the methods of plane-wave decomposition and the using of thin-film characteristic matrix, the model is presented focusing on the issues of mirror reflectance and internal light field in femtosecond timescale. The numerical results reveal that with the decrease of the pulse width a reduction of reflection performance occurs. In addition, the traditional approach that simplifies the incident femtosecond pulse to monochromatic continuous wave cannot get the exact value of the light field magnitude and the temporal profile of ultrashort laser pulse should be taken into account to reach more accurate results.     

羧酸衍生物取代甲基苯基聚硅烷制备杂取代聚硅烷

以甲基苯基聚硅烷　(PhSiMe　) n为原料 ,在无水AlCl3 存在下 ,通过与酰氯、酸酐及酯的取代反应合成了氯代聚硅烷及一系列共聚物 .在乙酰氯的作用下 ,　(PhSiMe　) n上的苯基能够被近乎完全的取代而生成氯代聚硅烷 .一元酸酐 (乙酸酐和丙酸酐 )在用酰氧基部分取代聚硅烷上苯基的同时 ,进行得更多的还是Cl取代 .而顺丁烯二酸酐、邻苯二甲酸酐和乙酸乙酯则只进行不完全的Cl取代 ,根据分子活性的不同得到取代比率各不相同的共聚物 .初步分析了各反应的过程 ,讨论了影响反应的因素 ,同时对于各产物的荧光和紫外特性也进行了分析和讨论     

Linear stability and instability of relativistic Vlasov‐Maxwell systems

We consider the linear stability problem for a symmetric equilibrium of the relativistic Vlasov‐Maxwell (RVM) system. For an equilibrium whose distribution function depends monotonically on the particle energy, we obtain a sharp linear stability criterion. The growing mode is proved to be purely growing, and we get a sharp estimate of the maximal growth rate. In this paper we specifically treat the periodic 1½D case and the 3D whole‐space case with cylindrical symmetry. We explicitly illustrate, using the linear stability criterion in the 1½D case, several stable and unstable examples. © 2006 Wiley Periodicals, Inc.     

Air-stable μ2-hydroxyl bridged cationic binuclear complexes of zirconocene perfluorooctanesulfonates: their structures,characterization and application

Three air-stable zirconocene perfluoro-octanesulfonates were successfully synthesized by treatment of C₈F₁₇SO₃Ag with (RCp)₂ZrCl₂ [R?=?H, n-Bu, t-Bu]. According to X-ray analysis, they have μ²-hydroxyl bridged cationic binuclear structures: (i) [CpZr(OH₂)₃]₂(μ²-OH)₂(OSO₂C₈F₁₇)₄·2THF·4H₂O (1a·2THF·4H₂O), (ii) [n-BuCpZr(OH₂)₃]₂(μ²-OH)₂(OSO₂C₈F₁₇)₄·6H₂O (2a·6H₂O), and (iii) [t-BuCpZr(OH₂)₃]₂(μ²-OH)₂(OSO₂C₈F₁₇)₄·2C₃H₆O·8H₂O (3a·2C₃H₆O·8H₂O). The ligands of water and organic molecules in the complexes originated from the moist air and solvent during their recrystallization. These complexes were characterized with different techniques, and found to show water tolerance, air/thermal stability as well as strong Lewis acidity. Moreover, the complexes showed highly catalytic activity in various reactions of CC bond formation. With good recyclability, they should find wide applications in organic chemistry.     

Simultaneous determination of six perylenequinones in Shiraia sp. Slf14 by HPLC

The aim of the study was to develop a rapid and sensitive analytical method for simultaneous determination of the hypocrellin A, hypocrellin B, hypocrellin C, elsinochrome A, elsinochrome B, and elsinochrome C content in the Huperzia serrata endophytic fungus Shiraia sp. Slf14. Separation was performed by high-performance liquid chromatography (HPLC) with an YMC-Triart C18 column (4.6?mm?×?250?mm, 5?µm), elution with acetonitrile and triple-distilled water (volume ratio 70:30) as the mobile phase, a detection wavelength of 460?nm, and a flow rate of 1.0?mL/min. All six pigments were successfully determined with good linear correlations and a precision relative standard deviation <2.3%. The methodology was applied to simultaneously measure the concentration of perylenequinones and their derivatives during submerged fermentation and proved adequate for analysis of the biosynthesis of perylenequinones.