Structure and reactivity of environmental interfaces: Application of grazing angle X-ray spectroscopy and long-period X-ray standing waves

Chemical processes occurring at environmental interfaces (e.g. mineral–fluid, mineral–organic matter and mineral–biofilm interfaces) have a profound impact on the environmental fate and bioavailability of aqueous metals and other contaminant species. However, the direct analysis of molecular scale structure and properties of environmental interfaces, particularly under “high-pressure” or “wet” conditions is highly challenging. Synchrotron based X-ray scattering and spectroscopic approaches offer numerous advantages, such as the high penetrating power and molecular scale information inherent to X-ray techniques. Yet, the ability to localize information content to environmental interfaces requires challenging experimental configurations. Here, the application of grazing angle X-ray fluorescence techniques is reviewed, including the presentation of a model formalism that allows for quantitative analysis of fluorescent yield profiles and discussion of the experimental setup. Illustrative examples are discussed, particularly in the context of combining results of GI measurements with the results of other complementary interface probes such as crystal truncation rod diffraction and X-ray microprobe spectroscopic studies.     

掠出射X射线荧光分析

掠出射X射线荧光分析技术是全反射X射线荧光分析技术的延伸和发展，文章介绍了掠出射X射线荧光分析技术的形式，特点，基本原理和作者在实验室搭建的实验装置，简述了掠出射X射线荧光分析技术的发展史，以及该技术在化学元素微量和痕量分析及薄膜特性分析等领域中的应用，展望了这种技术今后的发展前景。     

A Review of Application of Total Reflection X-ray Fluorescence Spectrometry to Water Analysis

Abstract

The aim of this article is to review the literature on the application of the total reflection X-ray fluorescence (TXRF) spectrometry for the determination of the chemical composition of aqueous samples. Details of the main stages of the analytical procedures are described. Special attention is given to the sample preparation procedure, current instrumentation, and potential error sources when analyzing the water samples of varying compositions. The examples of matrix effects and spectral interferences as well as the analytical figures of merit are also presented.     

电子在激光驻波场中运动产生的太赫兹及X射线辐射研究

采用单电子模型和经典辐射理论分别对低能和高能电子在线偏振激光驻波场中的运动和辐射过程进行了研究. 结果表明: 垂直于激光电场方向入射的低速电子在激光驻波场中随着光强的增大, 逐渐从一维近周期运动演变为二维折叠运动, 并产生强的微米量级波长的太赫兹辐射; 高能电子垂直或者平行于激光电场方向入射到激光驻波场中, 都会产生波长在几个纳米的高频辐射; 低能电子与激光驻波场作用中, 激光强度影响着电子的运动形式、辐射频率以及辐射强度; 高能电子入射时, 激光强度影响了电子高频辐射的强度, 电子初始能量影响着辐射的频率; 电子能量越高, 产生的辐射频率越大. 研究表明可以由激光加速电子的方式得到不同能量的电子束, 并利用电子束在激光驻波场的辐射使之成为太赫兹和X射线波段的小型辐射源. 研究结果可以为实验研究和利用激光驻波场中的电子辐射提供依据.     

平面镜反射率的标定及修正

 研究了用同步辐射源标定软X光掠入射平面镜的反射率。实验采用北京同步辐射装置(BSRF)-3W1B束线及反射率计靶室,在50~1 500 eV能区,做了C,Si,Ni和Au材料平面镜在1°~7°掠射角下的反射率标定曲线。由于3W1B束线的单色器采用变间距光栅作色散元件,光栅分光必然存在高次谐波,高次谐波严重影响光源的单色性,从而给平面镜的反射率标定值带来误差。前置滤片虽然能有效抵制高次谐波,但不能完全消除高次谐波。为此,利用透射光栅对光源做了单色性研究,给出高次谐波在不同能区所占光源强度的比例,从而对平面镜反射率标定值做出修正。     

极紫外与软X射线用非晶碳膜全反射镜的研究

用高真空磁控溅射设备分别在工作气压为0.40Pa和0.67Pa下制备了非晶碳膜全反射镜样品,利用X射线掠入射反射测量了膜层厚度、粗糙度和膜层密度,用原子力显微镜测量了样品的表面粗糙度,用同步辐射测量了不同工作气压下制备的非晶碳膜全反射镜的反射率,并对测量结果进行了分析讨论.测试结果表明:在0.40Pa工作气压下制备的非晶碳膜反射镜的性能优于在0.67Pa工作气压下制备的反射镜的性能,在掠入射角小于4.5°时,非晶碳膜全反射镜在5nm以上波段有比较平坦的高反射率,在波长小于5nm波段,反射率急剧下降.     

太空育种射干的X射线荧光及X射线衍射分析和表征

联用X射线荧光光谱(XRF)和粉末X射线衍射(PXRD)方法,对我国独创的第4代太空诱变育种射干中多种元素种类和含量及晶态物质进行了研究。结果表明:太空组射干K元素含量比地面组、对照品分别提高了1.03和0.31倍,Mg元素分别提高了1.44和0.06倍,Ca,Mn和Fe元素含量比地面组分别提高了0.95,0.30和0.29倍,Al元素比地面组、对照组分别降低了38.5%和85.5%,并在射干中鉴别出一水草酸钙(CaC2O4.H2O)晶体,晶体含量是地面组<太空组<对照品。从而可得出结论:太空射干中人体必需的矿质元素比地面组都更接近或优于对照品。文章研究结果和方法对筛选品质优良的太空药材籽种和推广种植太空药材以及建立中药材质量评价标准,有积极的作用和重要意义。     

Long period grating in/on planar and channel waveguides: A theory description

A comprehensive, complete theory suitable for a long period grating (LPG) on/in a planar or channel waveguide is described on the basis of coupled mode theory. The theory aims at key characteristic parameters with respect to the effect of the LPG, including resonance wavelength, transmission power of the guided mode in the waveguide, full-width at half-maximum (FWHM) of the power attenuation band in transmission spectrum of the guided mode, and coupling coefficient between a guided and a coupled mode. The type of the grating including relief and index modulation, different polarization state combinations of the guided mode and the resonant mode, and slanted grating structure are considered in this theory. The influences of the coupling between two guided modes and between a guided mode and a substrate mode are discussed. The role of cladding layer in a long period waveguide grating is demonstrated in particular. Finally, the expressions for the sensitivity of resonance wavelength as a function of external temperature, pressure and surrounding refractive index are derived.     

Review of energy-dispersive X-ray fluorescence on food elements detection

Energy-dispersive X-ray fluorescence (EDXRF) is a physical rapid detection method to analyze the types of elements through the energy characteristics of fluorescent X-ray particles. When applied to the detection of food element content, it not only needs simple sample pretreatment but also the element measurement time generally does not exceed 10 min to have the accuracy of μg/g, which can greatly reduce the time and cost of detection. Due to the limitations of the EDXRF instrument and measurement mechanism, it has low sensitivity to light elements in food, and the detection sensitivity varies with elements in food element analysis. For example, the detection sensitivity of Ca, Mg, Fe, Zn, Cu and other elements concerned by people is not high when the content is low, and the measurement accuracy is extremely dependent on the detector resolution. However, with the improvement of detector performance and algorithm optimization of EDXRF, the detection limit of this technology can reach 0.1 μg/g, the detection of trace elements has also been improved, which has made a new breakthrough in the field of food element detection. Therefore, this paper reviews that in recent 20 years, in order to overcome the various difficulties of EDXRF in food detection, the hardware optimization of EDXRF (For example, the development of an analyzer without sample preparation can greatly reduce the time required for the detection of food elements, and a series of instruments combined with EDXRF and cluster capillary technology can greatly improve the excitation efficiency of lighter elements in food. The spectrometer with a high-resolution detector can improve the detection accuracy of target elements with low content in food) and in order to solve the problem of spectrum resolution in food detection, (For example, the wavelet transform method which has good performance in spectrum smoothing, identifying weak peaks and maintaining peak shape is applied to EDXRF spectrum resolution, which can better solve the problem that the X-ray characteristic peaks of elements with a low atomic number in food are submerged) the reform and innovation of spectrum resolution methods are introduced. This paper summarizes and analyzes the representative application examples of EDXRF in food safety detection, discusses the advantages and disadvantages of EDXRF compared with other rapid detection or food detection methods in different situations, concludes its application conditions, and discusses the application prospect of EDXRF technology in the field of food detection.     

X-ray diffraction enhanced imaging study of intraocular tumors in human beings

Diffraction enhanced imaging(DEI) with edge enhancement is suitable for the observation of weakly absorbing objects.The potential ability of the DEI was explored for displaying the microanatomy and pathology of human eyeball in this work.The images of surgical specimens from malignant intraocular tumor of hospitalized patients were taken using the hard X-rays from the topography station of Beamline 4W1A at Beijing Synchrotron Radiation Facility(BSRF).The obtained radiographic images were analyzed in correlation with those of pathology.The results show that the anatomic and pathologic details of intraocular tumors in human beings can be observed clearly by DEI for the first time,with good visualization of the microscopic details of eyeball ring such as sclera,choroids and other details of intraocular organelles.And the best resolution of DEI images reaches up to the magnitude of several tens of μm.The results suggest that it is capable of exhibiting clearly the details of intraocular tumor using DEI method.     

The structures of sulphur on Pd(111) studied by X-ray standing wavefield absorption and surface EXAFS

The surface structures of R30°-S and R19.1°-S on Pd(111) have been investigated by normal incidence X-ray standing wave (NIXSW) absorption and surface extended X-ray absorption fine structure (SEXAFS). NIXSW measurements show that the most likely site of S adsorption in the R30° phase is the threefold “fcc” hollow. The location of the S atoms at the “fcc” hollow site is consistent with S adsorption on the neighbouring fcc (111) transition metal surfaces. SEXAFS analysis revealed a S–Pd nearest neighbour bond distance of 2.28±0.04 Å. The results for the R19.1° phase suggest that the structure involves a mixed S–Pd overlayer, with the S–Pd vertical layer spacing equal to the Pd bulk 111 spacing.     

Investigation of phosphorus surface segregation by X-ray scattering measurements

The surface segregation of phosphorus in silicon at low temperatures is studied by using δ doping structures grown by molecular beam epitaxy. The samples are characterized by X-ray crystal truncation rod (CTR) scattering using synchrotron radiation as the light source. The 1/e decay length of P segregation and segregation barrier energy are obtained by fitting the CTR curves within kinematical approximation of X-ray diffraction theory. The surface segregation of P is strong at a growth temperature of 450 °C, with a 1/e decay length of 14 nm, while for growth temperatures below 350 °C, P segregation is negligible with a 1/e decay length not larger than 4 nm. The segregation barrier energy is determined to be 0.43 eV.     

Sr14-xCaxCu24O41的芯能级光电子发射谱

测量了准一维1/2自旋的反铁磁体系Sr14-xCaxCu24O41(x=0、3.5、6、7、8.4)多晶样品的芯能级光电子发射谱.各样品的Cu2p3/2的光电子发射谱中主峰峰位位于933.8eV左右,半高宽为3.3eV左右,拟合结果表明,当x=0时,Cu2+和Cu3+的质量分数分别为92.13%和7.87%;而Ca对A位Sr的替代对B位Cu芯能级的影响不明显,Cu2+和Cu3+的质量分数变化很小,估算得该体系中Cu离子的平均化合价为2.08;O1s的光电子发射谱中峰位位于531.0eV左右,并由于Ca对Sr的替代导致在低结合能方向出现一个小的台肩,该台肩来自于Ca-O键的贡献;Ca2p3/2的光电子发射谱中峰位位于346.4eV左右,Sr3d5/2的光电子发射谱中峰位位于133.4eV左右,证明在该体系中Ca和Sr的化合价均为+2价,没有混合价态存在.     

拉直的单个DNA分子的全内反射荧光实时成像研究

全内反射荧光(TIRF)成像技术利用穿透深度仅200 nm左右的隐失波来激发诱导荧光,探测灵敏度和图像信噪比大大提高,成为单分子研究的有力工具。分子梳技术利用DNA末端与固体表面的结合力和周围流体流动产生的侧向力将DNA分子拉伸并平铺在表面上。结合这两种技术,对分子梳拉直的单个DNA分子进行了清晰的实时荧光成像,发现TIRF成像条件下DNA分子与荧光探针YOYO-1组成的复合体可自然避免发生光敏断裂现象;实时监测了单个DNA-YOYO-1复合体的光漂白过程,通过对激发光照射时间与探测器曝光时间进行同步控制,可大幅降低光漂白程度,为拉直的单个DNA分子的长时间实时观察和成像研究优化了实验条件,为实时、可视化地研究其与蛋白质相互作用的动力学过程奠定了基础。     

Crystal orientation in poly(ethylene 2,6-naphthalate) ultrathin films revealed by reflection-absorption infrared spectroscopy and grazing incidence X-ray diffraction

Crystal orientation of poly(ethylene 2, 6-naphthalate) (PEN) ultrathin films was investigated by the combination of reflection-absorption infrared spectroscopy (RAIR) and grazing incidence X-ray diffraction (GIXD) techniques. It is concluded that the main-chain of PEN molecule in ultrathin film is prone to alignment parallel to the substrate when compared with thicker films. During the formation of α form crystalline, the naphthalene ring, the CO group in molecular chain of PEN as well as the b axis in crystalline tend to take orientation more parallel to the substrate due to the surface-induced effect. However, such an anisotropic structure could not be observed in the bulk PEN.     

Electronic state observation of inner organic thin films beneath electrodes: Fluorescence-yield X-ray absorption spectra of pentacene derivative films

The electronic states of inner organic thin films have been investigated by X-ray absorption spectroscopy (XAS) in a bulk-sensitive fluorescence-yield (FY) mode with theoretical analysis. The thin films of the synthesized pentacene derivative, i.e., 6,13-dihydrodiazapentacence (C₂₀N₂H₁₄), on SiO₂-covered Si substrates were fabricated and their morphology and crystallinity were characterized by atomic force microscopy (AFM) and X-ray diffraction (XRD) analysis, respectively. The observed N K-edge FY-XAS spectra were different from the surface-sensitive XAS spectra measured in a partial-electron-yield (PEY) mode. The peaks on the FY-XAS spectra were well reproduced by the theoretical calculation of the unoccupied states of an HAPn molecule. In addition, the incident angle dependence of the FY-XAS spectra was consistent with the expected molecular orientation in the thin films. As a result, we successfully obtained the N and C K-edge FY-XAS spectra of the inner HAPn thin films even beneath Au electrodes.     

Qualitative and quantitative analysis of pathological and non-pathological human bone using radioisotope X-ray fluorescence technique

Pathological and non-pathological human elbow bone samples were collected from one male human patient and one female human patient who were undergoing treatment in our University Research Hospital. Pathological and non-pathological human elbow bone samples were analyzed by means of energy-dispersive X-ray fluorescence spectrometry by using standard additions method. Experimental results are presented and discussed in this work.     

Modelling of different TIRM setups by the Discrete Sources Method

Total Internal Reflection Microscopy (TIRM) is an effective technique to measure weak interaction forces between colloidal particles in solution and a flat surface. In this paper the Discrete Sources Method has been applied to model different measuring schemes for TIRM to find the most appropriate one for the determination of the distance between a particle and the filmed surface. It has been found that the placing of a light collector beneath the prism gives a considerable advantage compared with a conventional TIRM design, where the collector is situated above the surface.     

含单负材料的不对称平板波导的传导模

利用图解法系统地研究了由不同类型的单负材料作为包层的三层平板波导的模式特征.研究表明单负介质波导具有一系列奇异的特性,与传统介质波导或左手介质波导相比,此波导的芯区横向振荡导模的模折射率范围较大.除0阶导模外,其它TE,TM导模均为芯区横向振荡模,且同阶的TE、TM模的色散曲线几乎重合,只有0阶的TE,TM模才可以支持表面波的传播.单负介质的结构参数对0阶导模的影响较大.一定条件下,波导中可以出现0阶导模的完伞缺失或仅支持表面波的传输,还会出现超慢波现象,甚至可以共生都是后向波的0阶双模.     

三维超声驻波场的数字全息测量与重建研究

利用数字全息干涉术研究了超声驻波场的三维分布特征,由所记录的不同角度的超声驻波场的数字全息图,经数值再现,得到了超声驻波场的强度和相位差分布图,进而由迭代重建算法重建出超声驻波场的三维分布曲线。结果表明,数字全息干涉术与迭代重建算法相结合是测量与重建三维超声驻波场的一种方便有效方法。