Quadrupole transitions revealed by Borrmann spectroscopy

The Borrmann effect-a dramatic increase in transparency to X-ray beams-is observed when X-rays satisfying Bragg's law diffract through a perfect crystal. The minimization of absorption seen in the Borrmann effect has been explained by noting that the electric field of the X-ray beam approaches zero amplitude at the crystal planes, thus avoiding the atoms. Here we show experimentally that under conditions of absorption suppression, the weaker electric quadrupole absorption transitions are effectively enhanced to such a degree that they can dominate the absorption spectrum. This effect can be exploited as an atomic spectroscopy technique; we show that quadrupole transitions give rise to additional structure at the L(1), L(2) and L(3) absorption edges of gadolinium in gadolinium gallium garnet, which mark the onset of excitations from 2s, 2p(1/2) and 2p(3/2) atomic core levels, respectively. Although the Borrmann effect served to underpin the development of the theory of X-ray diffraction, this is potentially the most important experimental application of the phenomenon since its first observation seven decades ago. Identifying quadrupole features in X-ray absorption spectroscopy is central to the interpretation of 'pre-edge' spectra, which are often taken to be indicators of local symmetry, valence and atomic environment. Quadrupolar absorption isolates states of different symmetries to that of the dominant dipole spectrum, and typically reveals orbitals that dominate the electronic ground-state properties of lanthanides and 3d transition metals, including magnetism. Results from our Borrmann spectroscopy technique feed into contemporary discussions regarding resonant X-ray diffraction and the nature of pre-edge lines identified by inelastic X-ray scattering. Furthermore, because the Borrmann effect has been observed in photonic materials, it seems likely that the quadrupole enhancement reported here will play an important role in modern optics.     

同步辐射XANES方法对FeCl3 水溶液的研究

利用X 射线近边吸收谱学(X-ray Absorption Near Edge Structure, XANES)方法研究了不同浓度的FeCl₃ 水溶液中Fe³⁺离子的电子结构和近邻结构. 在不同浓度的FeCl₃ 水溶液的XANES 谱中, XANES 谱的形状随着FeCl₃ 浓度的不同而发生改变. 在XANES 谱的边前结构中观测到边前锋的分裂, 其分裂的能量差约为1.6 eV, 随着浓度的降低约有0.2 eV 的高能方向的位移, 此边前结构由1s-3d 轨道的电子跃迁引起, 双峰分裂来源于配位体配位引起的3d 轨道分裂. 随着FeCl₃ 浓度的改变, XANES 谱的主峰也发生变化, 此变化来源于溶液中Fe—Cl 配位与Fe—O 配位的比例变化. 另外, 利用量子化学计算的方法对于Fe³⁺与不同数目的H₂O 和Cl^?配位体络合时的构型进行了计算, 得到了Fe³⁺在水溶液中近邻结构的信息, 从另一方面解释了FeCl₃ 溶液中Fe³⁺离子3d 轨道分裂能的变化     

利用XANES谱研究凝聚态物质的电子结构

讨论了利用XANES谱研究凝聚态物质费米能附近空态电子结构的要点，给出了XANESD谱多次散射计算的概要，并列举了探测凝取态物质电子结构的XANES谱学方法的几个实例。     

核磁共振技术测定DNA在溶液中的三维结构

综述了现代二核磁共振技术测定ＤＮＡ结构的进展、方法及其原理和一般步骤，从ＤＮＡ的基本结构出发，应用二维ＮＯＥ谱及其它ＮＭＲ方法，获得大量的质子间距离、键长和键角数据，再经距离几何学、分子动力学等数据处理手段、可获得知ＤＮＡ在溶液中的三维结构。     

Molecular dynamics studied by analysis of the X-ray diffuse scattering from lysozyme crystals

It is now well established that the biological activity of proteins is related not only to their mean molecular structure, but also to their intramolecular mobility. Nearly all techniques sensitive to dynamics have given evidence for intramolecular mobility in proteins: NMR, ESR, Raman spectroscopy, fluorescence quenching, M?ssbauer spectroscopy, neutron scattering, measurements of elastic constants and hydrogen-deuterium exchange. The dynamics of proteins has also been approached by theoretical calculations. We report here investigations of the atomic and molecular displacements in hen egg-white lysozyme crystals using a new technique. This technique, based on the X-ray diffuse scattering analysis (scattering out of the Bragg reflections), can yield information on the atomic displacements, provided that they are correlated. Rigid-body molecular displacements, correlated along short rows of aligned molecules in two perpendicular directions, have been detected and analysed (mean square amplitude of the order of 5 X 10(-4) nm2). This technique can be also applied to the detection and analysis of intramolecular displacements.     

仅由原子散射因子虚部引起的布拉格情况的衍射特征

本文给出任意厚度平板晶体布拉格情况的Ｘ射线动力学衍射通式，并以之详细研究原子散射因子实部为零时晶体对Ｘ射线的衍射特征。     

用XANES研究Ga_(1-x)Mn_xN稀磁半导体的Mn原子的局域结构

利用基于实空间多重散射的XANES研究了Ga1-xMnxN(x=0.01,0.25,0.10)稀磁半导体中Mn原子的局域结构.结果表明在低Mn含量(摩尔浓度)的Ga0.990Mn0.010N样品中,Mn原子替代了GaN中的Ga,以替位形式存在.当Mn含量增加到0.025时,部分Mn原子处于被4个Ga所包围的间隙位,并与替位Mn原子形成了MnGa-MnI二聚体.当Mn含量进一步增加到0.100时,样品中的Mn原子主要以Mn团簇形式存在.     

Ni_(100-x)P_x合金的X射线谱学研究

利用X射线吸收精细结构(XAFS)和X射线衍射(XRD)研究了化学还原法制备的不同磷含量的Ni_(100-x)P_x合金的原子和电子结构.结果表明,当x=10时,磷元素的掺入导致了NiP样品中fcc结构的镍晶格扭曲和膨胀,Ni-Ni第一近邻配位的键长约增加0.03 A.随着磷含量的增加,膨胀和扭曲加剧,当x达到14左右时,样品的fcc-Ni晶格被完全破坏,从而形成非晶态NiP合金.X射线吸收近边结构(XANES)的结果表明,低磷含量(x≤10)时NiP样品的电子结构没有明显的变化,随着磷含量的增加,Ni4p态的分布变得宽化和越来越弥散.而当x达到26时,有大量电荷从Ni原子转移到P原子.     

Liquid-like movements in crystalline insulin

Diffuse X-ray scattering from protein crystals provides information about molecular flexibility and packing irregularities. Here we analyse diffraction patterns from insulin crystals that show two types of scattering related to disorder: very diffuse, liquid-like diffraction, and haloes around the Bragg reflections. The haloes are due to coupled displacements of neighbouring molecules in the lattice, and the very diffuse scattering results from variations in atomic positions that are only locally correlated within each molecule. The measured intensity was digitally separated into three components: the Bragg reflections and associated haloes; the water and Compton scattering; and the scattering attributed to internal protein movements. We extend methods used to analyse disorder in membrane structures to simulate the diffuse scattering from crystalline insulin in terms of (1) the Patterson (autocorrelation) function of the ideal, ordered crystal structure, (2) the root-mean-square (r.m.s.) amplitude of the atomic movements, and (3) the mean distance over which these displacements are coupled. Movements of the atoms within the molecules, with r.m.s. amplitudes of 0.4-0.45 A, appear to be coupled over a range of approximately 6 A, as in a liquid. These locally coupled movements account for most of the disorder in the crystal. Also, the protein molecules, as a whole, jiggle in the lattice with r.m.s. amplitudes of approximately 0.25 A that appear to be significantly correlated only between nearest neighbours.     

Coexistence of A- and B-form DNA in a single crystal lattice

It is well known that DNA can exist in a variety of conformations which can be interconverted by relatively mild changes in conditions. The in vivo conformation of DNA is usually thought to be the B form, but there is recent evidence that other conformations may be important in DNA-protein recognition. Different fragments of DNA crystallized under virtually identical conditions can form A, B or Z helices. A fragment that adopted an A conformation in a crystal was found in the B conformation in solution, whereas NMR spectroscopy of A-DNA films revealed the presence of a substantial amount of disordered B-DNA. Until now, however, a DNA fragment of a given sequence has not been crystallized in more than one global conformation. We report here an X-ray diffraction study of crystals of the DNA octamer dGGBrUABrUACC. In addition to a 'framework' of A-DNA, which gives discrete X-ray reflections, there are partially disordered B-DNA helices, recognized by their diffuse scattering features.     

基于固/气反应的氧化石墨烯水热还原研究

【目的】对氧化石墨烯的水热还原过程进行系统研究。【方法】采用改进的水热装置,以乙醇为还原剂,通过固/气反应成功实现了水热条件下氧化石墨烯的还原,制备得到石墨烯。通过透射电子显微镜(TEM)、X射线衍射(XRD)、X射线光电子能谱(XPS)、X射线近边吸收谱(XANES)和热重分析(TGA)对石墨烯材料的结构和性质进行了测试,探讨水热条件下乙醇蒸汽对氧化石墨烯的还原效果。【结果】研究结果表明,水热环境下的固/气反应还原能够有效地去除氧化石墨烯上的含氧基团,石墨烯的π网格结构得到很好的恢复。还原后的石墨烯材料比氧化石墨烯具有更为优异的热稳定性。【结论】该方法低成本、高效、环保,可用于石墨烯的大规模制备。     

Detection of magnetic circular dichroism using a transmission electron microscope

A material is said to exhibit dichroism if its photon absorption spectrum depends on the polarization of the incident radiation. In the case of X-ray magnetic circular dichroism (XMCD), the absorption cross-section of a ferromagnet or a paramagnet in a magnetic field changes when the helicity of a circularly polarized photon is reversed relative to the magnetization direction. Although similarities between X-ray absorption and electron energy-loss spectroscopy in a transmission electron microscope (TEM) have long been recognized, it has been assumed that extending such equivalence to circular dichroism would require the electron beam in the TEM to be spin-polarized. Recently, it was argued on theoretical grounds that this assumption is probably wrong. Here we report the direct experimental detection of magnetic circular dichroism in a TEM. We compare our measurements of electron energy-loss magnetic chiral dichroism (EMCD) with XMCD spectra obtained from the same specimen that, together with theoretical calculations, show that chiral atomic transitions in a specimen are accessible with inelastic electron scattering under particular scattering conditions. This finding could have important consequences for the study of magnetism on the nanometre and subnanometre scales, as EMCD offers the potential for such spatial resolution down to the nanometre scale while providing depth information--in contrast to X-ray methods, which are mainly surface-sensitive.     

Crystal and electronic structure study of Mn doped wurtzite ZnO nanoparticles

The change in the crystal and electronic structure properties of wurtzite ZnO nanoparticles was studied according to Mn doping in the powder samples. The investigations were conducted by X-ray Absorption Fine Structure Spectroscopy (XAFS) technique for the samples prepared with different heating and doping processes. Electronic analysis was carried out by the collected data from the X-ray Absorption Near-Edge Structure Spectroscopy (XANES) measurements. Additional crystal structure properties were studied by Extended-XAFS (EXAFS) analysis. Longer heating periods for the undoped wurtzite ZnO samples were determined to own stable crystal geometries. However, for some doped samples, the distortions in the crystal were observed as a result of the low doping amounts of Mn which was treated as an impurity. Besides, the changes in oxygen locations were determined to create defects and distortions in the samples.     

Tribological performance and chemistry of films for di-n-butyl dithiocarbamate derivatives in rapeseed oil

Two di-n-butyl dithiocarbamate derivatives were easily synthesized. Their tribological performances as lubricating oil additives in rapeseed oil were evaluated using a four-ball machine, and their chemistry of films was analyzed with X-ray absorption near-edge spectroscopy (XANES). The results indicate that the two compounds possess excellent anti-wear property and good load-carrying capacity. According to the XANES results, for the thermal films, the outer surfaces are mainly composed of N, S-containing polymer and ferric sulfate, and the near-surface and the bulk are composed of ferrous sulfate, while for the anti-wear films, the outer surfaces are only composed of ferric sulfate, but the near-surface and the bulk are mainly composed of ferrous sulfate.     

单晶硅表面有机硅烷/稀土复合自组装膜的摩擦磨损性能

利用分子自组装技术,在单晶硅表面制备了MPTS MPTES /稀土复合自组装膜.利用接触角测定仪、原子力显微镜和X射线光电子能谱仪分析表征了薄膜的组成和结构;采用DF-PM型静-动摩擦系数精密测定仪评价了薄膜的摩擦磨损性能.研究结果表明：稀土元素可以组装到氧化后的硅烷化表面而形成MPTS-MPTES /稀土自组装复合薄膜.在较低载荷下,薄膜不但摩擦系数较低,同时也表现出良好的耐磨性和摩擦稳定性,显示了其在微型机械表面改性的潜在应用前景.     

掺杂Li4SiO4材料的CO2吸附研究

Recycling and utilizing CO2 is very important significance to realizing energy saving and emission reduction. Lithium silicate (Li4SiO4) absorbents for CO2 were prepared by high-temperature solid-state reaction. Thermodynamic equilibrium of Li4SiO4 absorp-tion CO2was discussed using the HSC5.0 code. The capability of Li4SiO4 for absorption CO2 was investigated using the thermobalance instrument. The crystal structure and surface morphologies of the Li4SiO4were also analyzed by X-ray diffraction, SEM. The results showed: the absorption reaction is fast in the temperature range 600～720 ℃, the maximum absorption rate (w) was 29.16% ; and the desorption reaction began in 750 ℃, then Li4SiO4 is regenerated. The concentrations of CO2 obviously affect on the absorption speed and the maximum absorption rate; but the flow rate of CO2 little influences the absorption capability.     

血红素提取品的光谱分析及电化学活性研究

研究了以猪血为原料提取的血红素产品和氯化血红素（ＳＩＧＭＡ公司）的光谱特性和水溶液中玻碳电极上的伏安特性．通过红外吸收光谱、紫外可见吸收光谱、荧光光谱对提取品的化学结构进行了确证．同时采用紫外可见吸收光谱和伏安法测定了提取品的纯度，但是二者的结果有一定的差异，进一步采用原子吸收光谱测定了提取品的铁含量．当提取品的铁含量为理论值的７０％～９７％时，获得了与伏安法测定的纯度基本一致的结果，而光谱分析结果未能完全显示出提取品中铁含量的多少．由此说明，血红素的含铁量及其电化学活性的研究应是全面评价血红素产品的重要指标之一．     

丙烯酰胺/氢氧化铝改性淀粉两性絮凝剂的合成及表征

以玉米淀粉、丙烯酰胺、氯化铝和碳酸铵为主要原料合成了一种新型有机-无机两性絮凝剂,即丙烯酰胺-氢氧化铝改性淀粉絮凝剂.利用红外光谱仪、X-射线衍射仪、热重分析仪和扫描电镜对絮凝剂的结构进行了表征.研究结果表明:在过硫酸铵和亚硫酸氢钠引发剂作用下丙烯酰胺与玉米淀粉发生聚合反应并与氢氧化铝胶体通过离子键键合,絮凝剂明显具有...     

Synthesis and crystal structure of tetranuclear zinc benzoate

A tetranuclear zinc benzoate Zr4O(C6H5CO2)6 was synthesized and characterized by X-ray single crystal determination. It crystallizes in cubic, space group Ia-3d. Its crystal cell is very large, α=4.10063(18)nm, V=68.953(5)nm^3 and Z=48. The structure is composed of discrete Zr4O(C6H5CO2)6 molecules. In each molecule, four zinc atoms are held together by a central oxygen atom, which results in the formation of a regular tetrahedron. All benzoate ligands coordinate to zinc atoms in a bidentate bridging mode. Each zinc atom is in a slightly distorted tetrahedral geometry, coordinated by three benzoate oxygen atoms and the central oxygen atom. The intermolecular interactions result in the formation of a three-dimensional supramolecular framework, with non-intersecting parallel channels.     

X射线质量吸收系数测量中一些问题的研究

作者采用能谱法及蒙特卡罗模拟计算方法，研究了影响测量X射线质量吸收系数的一些问题，并用等效原子序数进行了验证．