理论研究F2BN3多聚体的结构特色和热力学稳定性

在密度泛函理论（DFT）B3LYP/6-311+G*水平上计算研究了叠氮二氟硼多聚体(F2BN3)n (n=1-4),获得了它们的结构和热力学性质,讨论了几何参数随聚合度的变化趋势。多聚体(F2BN3)2-4的优化构型均为由不同子体系的叠氮基α−N和B原子相连形成的环状结构。三聚体的船扭式构象比椅式构象的结合能低10.54 kJ•mol-1;四个新获得的四聚体的结合能差异较大,大小为3.1~45.65 kJ•mol-1。由焓变可知,单体形成二聚体在热力学上是不利的,而形成三聚体和四聚体在高达1200 K的温度下是有利的,同时分析比较了后续反应的热力学参数。     

带缺陷结构的二维磁性光子晶体的数值模拟分析

利用频域有限差分方法分析了多种带缺陷结构二维磁性光子晶体（二重对称,四重对称和六重对称结构）的法拉第旋转角与椭圆率的变化特性.结果表明：在这些结构中,光波均被局域在中心缺陷处;同时,对于具有四重对称轴结构的材料,在其法拉第旋转角增加的同时,出射光波的椭圆率没有明显的增加;但对于不具有四重对称轴结构的材料,其法拉第旋转角增加的同时,出射光波的椭圆率也在增加.因此,只有在具有四重对称轴结构的二维磁性光子晶体中引入缺陷,才能很好地抑制光波偏振态的变化.这种带缺陷的二维磁性光子晶体结构有可能用于制作磁性光子晶体光 关键词： 磁光效应 二维磁性光子晶体 缺陷 频域有限差分法     

微型平像场近红外光谱仪的消杂散光设计

设计和研制了结构紧凑、杂散光低的微型平像场近红外光谱仪。在分光系统设计中不采用附加杂散光遮挡装置的常规方法,而是在准直物镜前设置一块直径为8．5mm的平面反射镜,通过调节平面反射镜改变入射光束的空间角,使光束全部被准直镜接收,不再产生旁光,从而有效地消除系统内的杂散光,使仪器整体杂散光水平降低了1．13％。另外,该光谱仪选择线阵CCD作为探测器件,不再设置冷却系统也避免了平面光栅带有扫描旋转机构。由于使用CCD作探测器和新的消杂散光设计方法,该光谱仪实现了微型化。     

SOLEIL shining on the solution‐state structure of biomacromolecules by synchrotron X‐ray footprinting at the Metrology beamline

Synchrotron X‐ray footprinting complements the techniques commonly used to define the structure of molecules such as crystallography, small‐angle X‐ray scattering and nuclear magnetic resonance. It is remarkably useful in probing the structure and interactions of proteins with lipids, nucleic acids or with other proteins in solution, often better reflecting the in vivo state dynamics. To date, most X‐ray footprinting studies have been carried out at the National Synchrotron Light Source, USA, and at the European Synchrotron Radiation Facility in Grenoble, France. This work presents X‐ray footprinting of biomolecules performed for the first time at the X‐ray Metrology beamline at the SOLEIL synchrotron radiation source. The installation at this beamline of a stopped‐flow apparatus for sample delivery, an irradiation capillary and an automatic sample collector enabled the X‐ray footprinting study of the structure of the soluble protein factor H (FH) from the human complement system as well as of the lipid‐associated hydrophobic protein S3 oleosin from plant seed. Mass spectrometry analysis showed that the structural integrity of both proteins was not affected by the short exposition to the oxygen radicals produced during the irradiation. Irradiated molecules were subsequently analysed using high‐resolution mass spectrometry to identify and locate oxidized amino acids. Moreover, the analyses of FH in its free state and in complex with complement C3b protein have allowed us to create a map of reactive solvent‐exposed residues on the surface of FH and to observe the changes in oxidation of FH residues upon C3b binding. Studies of the solvent accessibility of the S3 oleosin show that X‐ray footprinting offers also a unique approach to studying the structure of proteins embedded within membranes or lipid bodies. All the biomolecular applications reported herein demonstrate that the Metrology beamline at SOLEIL can be successfully used for synchrotron X‐ray footprinting of biomolecules.     

铽与两种不同结构羧酸配合物的低温固相合成及发光性质研究

以两种不同结构的羧酸苯乙酸和苯基羟基乙酸与氯化铽为原料,采用低温固相反应合成了两种羧酸铽配合物。经元素分析、稀土络合滴定、摩尔电导确定了配合物的组成为： Tb(L₁)₃·H₂O,Tb(L₂)₃·4H₂O(L₁= C₆H₅ CH COO- ,L₂=C₆H₅CH(OH)COO-)。测定了配体及配合物的IR谱、1H NMR及配体的磷光光谱和铽配合物荧光激发和发射光谱。根据磷光发射光谱数据计算了配体的三重态能级值。比较两个配合物的荧光发射主峰5D₄→7F₅强度： 苯基羟基乙酸铽为苯乙酸铽的5倍。由此可见在配体亚甲基上引入拉电子基团羟基,将会扩大共轭体系π电子的离域范围,提高能量传递效率,提高稀土离子的发光强度。     

石英玻璃微球吸收光谱上的结构共振

通过CO2激光器熔融不同直径的熔锥光纤以得到相应直径的石英玻璃微球,利用此微球和熔锥光纤,构造了球微腔耦合系统。实验中利用光腰直径为3.1μm的熔锥光纤与直径为143.1μm的石英玻璃微球进行耦合,通过最大分辨力为1pm的可调谐半导体激光器对该耦合系统进行光谱扫描,发现石英玻璃微球的吸收光谱中出现分立的结构共振峰。利用光学微球腔理论讨论了石英玻璃微球吸收光谱中的结构共振,并用米氏散射理论公式对一阶TE模共振峰的位置以及它们的间隔进行了计算,共振峰位置实验结果与理论结果的误差仅为0.03%,表明实验与计算结果相符。     

Aspects of Pre-quantum Description of Deformed Theories

We discuss deformations of the classical systems in the phase space and show that one can use non-canonical transformations to relate regular and deformed models. On the other hand some of the models can be obtained as a classical limit of the deformed quantum models, i.e. as the result of the dequantization procedure. Nonrelativistic deformations are described.     

Elliptic Linear Problem for Painlevé VI Equation with Spectral Parameter

We introduce a linear problem with a spectral parameter for the elliptic form of the Painlevé VI equation. The corresponding nonautonomous version produces the Lax pair with spectral parameter for the Calogero-Inozemtsev model with a single degree of freedom.     

Vibrational spectroscopic study of budesonide

The Raman spectrum of budesonide is reported for the first time, and molecular assignments are proposed on the basis of ab initio BLYP DFT calculations with a 6‐31 G* basis set and vibrational wavenumbers predicted on a quasi‐harmonic approximation. Comparison with previously published infrared data has explained several spectral features, and the relative band intensities in the CO and CC stretching regions are interpreted. The results from this study provide data that can be used for the preparative process monitoring of budesonide, an important steroidal pharmaceutical in various dosage forms, and its interaction with excipients and other components. Copyright © 2007 John Wiley & Sons, Ltd.     

[ONSO]型Salen化合物的合成、单晶结构及金属离子识别

一些重金属离子即使在较低浓度时也会对环境、生物体产生毒性,所以研究痕量金属离子识别具有重大意义。荧光传感器由于具有选择性好、灵敏度高、成本低、实时响应等优点, 得到了广泛关注。以2,4-二叔丁基苯酚,3,5-二叔丁基水杨醛和邻氨基苯硫酚为原料合成了类Salen配体L1, 并用1H NMR,13C NMR,IR,元素分析及X射线单晶衍射等手段对其进行了表征。并通过自由挥发法得到了配体L1的单晶结构,实验表明L1是三斜晶、P-1空间群的一个空穴平面[ONSO]四配位环境。通过荧光光谱考察了类Salen配体与金属离子(Li+,Na+,K+,Cd2+,Cs+,Co2+,Cu2+,Hg2+,Mn2+,Ni2+,Zn2+,Ag+)的识别与配位性能。光谱滴定分析表明L1与Zn2+以1∶1的化学计量数配位。另外,L1与Zn2+结合后荧光显著增强,荧光检测限达到5.01×10-5 mol·L-1,而上述提到的其他常见金属离子不引起荧光光谱变化。结果表明L1是一个对检测Zn2+的选择性高,灵敏度强的荧光增强型探针。