Comparison of a portable micro-X-ray fluorescence spectrometry with inductively coupled plasma atomic emission spectrometry for the ancient ceramics analysis

Two multielement instrumental methods of analysis, micro X-ray fluorescence spectrometry (micro-XRF) and inductively coupled plasma atomic emission spectrometry (ICP-AES) were applied for the analysis of 7th and 5th century B.C. ancient ceramic sherds in order to evaluate the above two methods and to assess the potential to use the current compact and portable micro-XRF instrument for the in situ analysis of ancient ceramics. The distinguishing factor of interest is that micro-XRF spectrometry offers the possibility of a nondestructive analysis, an aspect of primary importance in the compositional analysis of cultural objects. Micro-XRF measurements were performed firstly directly on the ceramic sherds with no special pretreatment apart from surface cleaning (micro-XRF on sherds) and secondly on pressed pellet disks which were prepared for each ceramic sherd (micro-XRF on pellet). For the ICP-AES determination of elements, test solutions were prepared by the application of a microwave-assisted decomposition procedure in closed high-pressure PFA vessels. Also, the standard reference material SARM 69 was used for the efficiency calibration of the micro-XRF instrument and was analysed by both methods. In order to verify the calibration, the standard reference materials NCS DC 73332 and SRM620 as well as the reference materials AWI-1 and PRI-1 were analysed by micro-XRF. Elemental concentrations determined by the three analytical procedures (ICP-AES, micro-XRF on sherds and micro-XRF on pellets) were statistically treated by correlation analysis and Student's t-test (at the 95% confidence level).     

液态金属催化剂:二维材料的点金石

由于石墨烯等二维材料具有独特的结构与优异的性能,其在众多新型电子器件的构建中具有重要的应用前景。然而,其可控生长仍然存在诸多挑战性的问题,这也是制约这类明星材料真正迈向应用的瓶颈所在。化学气相沉积法(CVD)是目前可控制备高质量石墨烯最有效的方法,其中催化基底的设计尤为重要,这将直接决定CVD最为核心的两个过程:催化和传质。相较于改变催化剂的化学组成,近年来我们发现改变催化剂的物态——由固态到液态,对石墨烯等二维材料的CVD过程有质的改变和提升。与固态基底相比,液态基底具有更松散的原子排列、更剧烈的原子迁移,使得液面平滑而各向同性,液相可流动且可包埋异质原子。这使得液态金属在催化石墨烯等二维材料及其异质结生长时表现出很多独特的行为,比如层数严格自限制、超快的生长速度、晶粒拼接平滑等。更重要的是,基底的液态特性给二维材料的自组装和转移带来了突破,实乃二维材料的点金石。本文将梳理液态金属催化剂上二维材料的生长、组装与转移行为,这些关键技术的突破将为二维材料迈向真正应用奠定坚实的基础。     

二维材料插层改性方法研究进展

二维材料凭借其独特的电学、光学、磁学等性质引起了广泛关注,如何处理二维材料使其改性是目前的研究热点。 插层方法是目前调控二维材料性质的主要方法之一。 插层过程中,客体粒子插入主体材料的范德华层间,造成二维材料物理与化学性质的变化。 气相、液相、固相插层均可以使二维材料的性质得到提升。 本文主要介绍二维材料插层方法,分析其不同优势和限制条件,并展望如何综合应用插层方法更好地提升二维材料电学、光学等性能。     

Site‐Targeted Interfacial Solid‐Phase Chemistry: Surface Functionalization of Organic Monolayers via Chemical Transformations Locally Induced at the Boundary between Two Solids

Effective control of chemistry at interfaces is of fundamental importance for the advancement of methods of surface functionalization and patterning that are at the basis of many scientific and technological applications. A conceptually new type of interfacial chemical transformations has been discovered, confined to the contact surface between two solid materials, which may be induced by exposure to X‐rays, electrons or UV light, or by the application of electrical bias. One of the reacting solids is a removable thin film coating that acts as a reagent/catalyst in the chemical modification of the solid surface on which it is applied. Given the diversity of thin film coatings that may be used as solid reagents/catalysts and the lateral confinement options provided by the use of irradiation masks, conductive AFM probes or stamps, and electron beams in such solid‐phase reactions, this approach is suitable for precise targeting of different desired chemical modifications to predefined surface sites spanning the macro‐ to nanoscale.     

Three-dimensional micro-XRF under cryogenic conditions: a pilot experiment for spatially resolved trace analysis in biological specimens

Three-dimensional micro-XRF is a recently developed microprobe which facilitates three-dimensional resolved chemical analyses with a resolution of around 20 μm. Arbitrary sites or sections of samples can be investigated without the need to section specimens physically. In this paper we demonstrate the use of the microprobe in combination with a cold nitrogen gas stream for the cryogenic fixation of specimens. A 3D micro-XRF setup at the new microfocus beamline at BESSY II was equipped with a nitrogen cryogenic stream. The distribution of Ca, Fe, Zn and Cu across virtual cross sections of a water-rich sample, the root of common duckweed, could be investigated without further sample preparation. This paper demonstrates the capabilities of 3D micro-XRF under cryogenic conditions for investigations of biological specimens.     

Grazing-exit and micro X-ray fluorescence analyses for chemical microchips.

Grazing-exit x-ray fluorescence (GE-XRF) and micro x-ray fluorescence (micro-XRF) methods were applied to chemical microchips as a detection method. Since an energy-dispersive x-ray detector was used, the simultaneous detection of multiple elements was possible. An analyzing region was especially designed on the microchip so that a sample solution could be dried and concentrated in a suitable area corresponding to the size of the primary x-ray beam. Finally, it was confirmed that both analytical methods could be combined well for use with a microchip. In GE-XRF, the background intensity in the XRF spectrum was reduced at grazing-exit angles. In addition, a good relationship between the x-ray fluorescence intensities and the concentrations of standard solutions that were introduced into the microchip was obtained. This indicates that the GE-XRF method is feasible for trace elemental analysis in chemical microchip systems. In micro-XRF, an attempt was made to concentrate and dry the analyte within a small analyzing region. The preliminary results indicated that the micro-XRF method could be applied for the analysis of microchips.     

锂硫银锗矿固态电解质研究进展

全固态电池因其较高的安全性和能量密度而成为下一代电动汽车和智能电网用储能器件的重点研究方向之一。开发具有高室温锂离子电导率、化学/电化学稳定性优异、对电极材料兼容性优异等特点的固态电解质材料是推动全固态电池发展的重要研究课题之一。硫化物电解质因其相对较高的室温电导率(~10⁻³ S∙cm⁻¹)、较低的电解质/电极固-固界面阻抗等优点而在众多无机固体电解质材料中成为研究热点。本文基于作者多年研究成果和当前国内外发表的相关工作,从电解质的结构、离子传导、合成、综合性能改善及在全固态电池中的应用等方面系统总结了锂硫银锗矿固态电解质材料研究,并分析了该类电解质面临的问题和挑战,最后探讨了其未来可能的研究方向和发展趋势。     

Derivatization of azaspiracid biotoxins for analysis by liquid chromatography with fluorescence detection

Azaspiracids (AZAs) are an important group of regulated lipophilic biotoxins that cause shellfish poisoning. Currently, the only widely available analytical method for quantitation of AZAs is liquid chromatography-mass spectrometry (LC-MS). Alternative methods for AZA analysis are needed for detailed characterization work required in the preparation of certified reference materials (CRMs) and by laboratories not equipped with LC-MS. Chemical derivatization of the amine and carboxyl groups on AZAs was investigated for the purpose of facilitating analysis by LC with fluorescence detection (FLD). Experiments towards chemical modification of AZA1 at the amine achieved only limited success. Derivatization of the carboxyl group, on the other hand, proved successful using the 9-anthryldiazomethane (ADAM) method previously applied to the okadaic acid (OA) group toxins. Extraction and clean-up methods were investigated for shellfish tissue samples and a post-reaction solid phase extraction procedure was developed for the AZA ADAM derivatives. Chromatographic separations were developed for the LC-FLD analysis of derivatized AZAs alone or in the presence of other derivatized toxins. This new analytical method for analysis of AZAs enabled verification of AZA1-3 concentrations in recently certified reference materials. The method demonstrated good linearity, repeatability and accuracy showing its potential as an alternative to LC-MS for measurement of AZAs.     

Hard X-ray micro-spectroscopy at Berliner Elektronenspeicherring für Synchrotronstrahlung II

The capabilities of the X-ray beamlines at Berliner Elektronenspeicherring für Synchrotronstrahlung II (BESSY II) for hard X-ray measurements with micro- and nanometer spatial resolution are reviewed. The micro-X-ray fluorescence analysis (micro-XRF), micro-extended X-ray absorption fine structure (micro-EXAFS), micro-X-ray absorption near-edge structure (micro-XANES) as well as X-ray standing wave technique (XSW), X-ray beam induced current (XBIC) in combination with micro-XRF and micro-diffraction as powerful methods for organic and inorganic sample characterization with synchrotron radiation are discussed. Mono and polycapillary optical systems were used for fine X-ray focusing down to 1 µm spot size with monochromatic and white synchrotron radiation. Polycapillary based confocal detection was applied for depth-resolved micro-XRF analysis with a volume resolution down to 3.4 · 10^− 6 mm³. Standing wave excitation in waveguides was also applied to nano-EXAFS measurements with depth resolution on the order of 1 nm. Several examples of the methods and its applications in material research, biological investigations and metal-semiconductor interfaces analysis are given.     

Laser pyrolysis micro-spectroscopy for modelling fire-induced degradation of ethylene-vinyl acetate systems

A recently developed laser pyrolysis (LP)-Raman/ATR micro-spectroscopic method was applied for analyzing the degradation of polymer systems. The concept behind the method is to combine the micro-scale modelling of fire circumstances with analytical monitoring of the chemical changes in the solid phase of the sample. Samples were irradiated with the infrared beam of a CO₂ laser. The chemical changes were determined by micro-Raman/ATR spectroscopy methods in 200 ms intervals. The applicability of the method is demonstrated here through the pyrolysis of EVA and EVA composites containing metal-modified clays. Rapid depth profiling of few milligrams of sample is feasible with Raman detection, while the ATR sensor is applicable for analysis of fluorescent samples such as Fe coated sepiolite. The acceleration effect of montmorillonite and sepiolite minerals on the degradation of EVA is more pronounced if their surface is coated with Fe atoms. The effects of laser and the cone heater on the ratio of characteristic Raman bands of the polymer are compared and found to be in good correlation.     

Electrochemistry of marmatite-carbon paste electrode in the presence of bacterial strains

The electrochemical behaviors of a marmatite-carbon paste electrode with the chemical leaching of Fe3+ ions, or the microbial leaching using Acidithiobacillus ferrooxidans, were compared. The cyclic voltammograms of the electrode in the presence and absence of bacterial strains showed that the leaching process of marmatite was carried out by the different reactions occurring in the interface of the marmatite electrode-leach liquid. The polarization currents of the electrode under the differently applied potentials suggested that the microbial leaching of marmatite could be accelerated by the applied potential. The SEM observations indicated that the corrosion pits formed in the electrode surface were similar to the attached bacterial cells in shape and size, other than that by the chemical leaching of Fe3+ ions. The contact leaching of the attached cells on the mineral substrate played an important role on the dissolution of marmatite in addition to the chemical leaching of Fe3+ ions.     

Three-dimensional micro-XRF investigations of paint layers with a tabletop setup

The non-destructive investigation of art and archaeological objects with depth sensitivity is now possible using 3D micro-XRF spectroscopy. More detailed answers for questions on painting techniques, on the pigment palette, on the production processes and indirectly on dating or provenancing of objects are accessible now. This was already illustrated by the investigation of Mughal miniatures with a confocal setup at the synchrotron source BESSY.In this paper we demonstrate the feasibility of 3D micro-XRF spectroscopy with a tabletop setup and discuss its sensitivity in comparison to the synchrotron-based setup. Investigated objects are glass standards and also prepared paint layers. Perspectives for other types of studies are proposed.     

保健食品中非法添加物检测的前处理及分析方法研究进展

保健食品作为一种特定的食品种类,能调节人体的机能,适用于特定人群食用.但是在保健食品中添加化学药物和非法添加物的现象也层出不穷,因此迫切需要建立多指标的有效检测方法,为保健食品的质量安全提供技术保障.高效的前处理方法和高灵敏的分析方法为检测非法添加物提供了有效的技术手段.综述了近三年来溶剂萃取和固相萃取样品前处理方法,以及高效液相色谱、实时直接分析质谱、表面增强拉曼光谱及色谱-质谱串联技术等分析方法在微量及痕量非法添加物检测中的应用,为进一步研究建立高效简便的前处理方法和检测新方法、新技术提供理论参考.     

Recent developments in microextraction techniques based on crown ethers

Sample preparation is essential for isolating desired components from complex matrices and greatly influences their reliable and accurate analysis. Microextraction techniques such as solid phase micro extraction and liquid–liquid–liquid micro extraction based on hollow fiber and also single drop micro extraction methods are new and effective sample preparation techniques. Crown ethers are heterocyclic chemical compounds that consist of a ring containing several ether groups. Recently crown ethers have been applied in these methods and increase efficiency and selectivity of these techniques. Here we review the application of crown ethers in various micro extraction techniques.     

固液界面双电层的理论计算模拟

固液界面双电层在电化学中处于核心地位. 如何发展一个理论方法,在该方法的框架下计算双电层的平衡性质和动力学性质一直以来都是理论研究的难点和热点. 本文总结了最近十几年第一性原理计算方法在计算双电层平衡性质和电催化反应的进展,如热力学方法、反应中心模型以及双参考方法. 并进一步详细地阐述了基于周期性均匀介质溶剂化模型 ( DFT/CM-MPB)对于固液界面双电层的研究,该方法能够计算双电层的平衡性质(零电荷电势和微分电容)和表面相图,在此基础上能深入研究基元反应的电荷转移系数,并结合微观动力学推导出宏观的Tafel(电流-电势)曲线. 并列举了该方法对于重要电化学反应(如氢电极反应)的应用实例.     

脉冲激光轰击固体靶制备纳米材料

综述了近年来脉冲激光轰击固体靶制备纳米材料。按介质种类和性质,脉冲激光轰击固体靶制备纳米材料的方法可分为六种:在气相、静态液相、动态液相三种惰性状态及其反应性状态下的反应。本文对以上六种制备方法及其优缺点作了较详细的阐述。其中最近发展起来的脉冲激光轰击处于流动液相中固体靶技术具有明显的优势,所制得的纳米产物分布均匀,重现性高,适用范围广泛。通过改变靶材和流动相的组分可制备各种各样具有新奇光、电、磁特性的纳米材料或纳米杂化材料,因而该技术有望成为脉冲激光轰击固体靶技术的一个重要的发展方向。     

Development of air‐assisted dispersive micro‐solid‐phase extraction‐based supramolecular solvent‐mediated Fe3O4@Cu–Fe–LDH for the determination of tramadol in biological samples

A simple method, air‐assisted dispersive micro‐solid‐phase extraction‐based supramolecular solvent was developed for the preconcentration of tramadol in biological samples prior to gas chromatography–flame ionization detection. A new type of carrier liquid, supramolecular solvent based on a mixture of 1‐dodecanol and tetrahydrofuran was combined with layered double hydroxide coated on a magnetic nanoparticle (Fe₃O₄@SiO₂@Cu–Fe–LDH). The supramolecular solvent was injected into the solution containing Fe₃O₄@SiO₂@Cu–Fe–LDH in order to provide high stability and dispersion of the sorbent without any stabilizer agent. Air assisted was applied to enhance the dispersion of the sorbent and solvent. A number of analytical techniques such as Fourier transform‐infrared spectrometry, field emission scanning electron microscope, energy‐dispersive X‐ray spectroscopy and X‐ray diffraction measurements were applied to assess the surface chemical characteristics of Fe₃O₄@SiO₂@Cu–Fe–LDH nanoparticles. The effects of important parameters on the extraction recovery were also investigated. Under optimized conditions, the limits of detection and quantification were obtained in the range of 0.9–2.4 and 2.7–7.5 μg L^?1 with preconcentration factors in the range of 450–472 in biological samples. This method was used for the determination of tramadol in biological samples (plasma, urine and saliva samples) with good recoveries.     

Square planar coordinate iron oxides

We will provide an overview of the synthesis, structures, chemical and physical properties of novel iron oxides bearing FeO(4) square planar coordination, such as SrFeO(2) and Sr(3)Fe(2)O(5). The preparation of these materials relies on topotactic low-temperature reduction using metal hydrides. For instance, a simple 3D perovskite structure SrFeO(3) converts to a 2D structure SrFeO(2)via SrFeO(2.5). SrFeO(2) shows a remarkable stability against temperature and chemical substitution (for both A- and B-sites) and also tolerates distortions of square planes toward tetrahedra to adapt different A sites. Such structural stability and flexibility arise from strong covalent interactions not only through the in-plane Fe-O-Fe superexchange interactions but also through the out-of-plane Fe-Fe direct exchange interactions, and explains why SrFeO(2) exhibits magnetic order far beyond room temperature. The application of pressure on SrFeO(2) and Sr(3)Fe(2)O(5) further enhances the Fe-Fe direct exchange interactions and eventually induces striking transitions at around 34 GPa: spin-state transition from S = 2 to S = 1, insulator-to-metal transition, and antiferro-to-ferromagnetic transition. The high mobility of oxide ions at relatively low temperatures, during the reduction and reoxidation reaction process would offer an important challenge to tailor and design new solid oxide fuel cells/membranes toward lowering working temperatures.