基于大科学装置的空间金属组学和单细胞/单颗粒金属组学

金属组学是综合研究生命体内（(特别是细胞内）)自由或络合的全部金属原子的分布、含量、化学种态及其功能的一门学科,而大科学装置为金属组学研究提供了强有力的工具。本综述本文首先介绍了金属组学发展简史,然后介绍了基于大科学装置的同步辐射技术、中子技术、质子技术及缪子技术等,最后概述了基于大科学装置的空间金属组学、单细胞/单颗粒金属组学的应用示例。基于大科学装置的中子活化技术（NAA）NAA、X-射线荧光光谱（XRF）以及质子激发X射线谱（PIXE ）等技术是开展非原位空间金属组学研究的有力手段,而XRF、PIXE以及缪子X射线荧光谱（MXA）为开展原位空间金属组学提供了有力工具,特别是基于XRF的技术,其空间分辨率可低至10 nm级别,是开展原位单细胞/单颗粒金属组学的利器。 新一代同步辐射光源、质子源及缪子源将为空间金属组学、特别是时空金属组学研究提供更强有力工具。     

放射金属组学：以α核素靶向治疗药物为例

金属组学是综合研究生命体内(特别是细胞内)自由或络合的全部金属和类金属的含量、分布、形态、结构及功能的一门学科。作为金属组学的一个分支，放射金属组学重点研究放射性核素的制备和应用，特别是其在环境和生物体内的含量、分布、化学种态及功能等。靶向α治疗(Targeted alpha therapy, TAT)是一种利用发射α粒子的放射性核素与肿瘤选择性载体分子结合实现靶向癌细胞，进而对肿瘤组织造成杀伤作用的一种医疗方法，是放射金属组学在癌症治疗领域的重要应用方向。α粒子凭借高线性能量传递、短组织射程和较强的相对生物学效应，在放射性免疫和肿瘤治疗方面有着广阔的应用前景。以TAT药物为例，就常用α核素、TAT药物螯合剂及其标记的靶向载体、几种重要α放射性核素靶向治疗进展予以综述，并分析TAT药物研发的挑战和发展前景，从而展示放射金属组学在核医学领域特别是癌症治疗领域的研究进展。随着更多α核素的制备和更多靶向标记方法的建立，TAT药物有望用于多种疾病，这也需要新的放射金属组学方法的建立和应用。因此，放射金属组学在核医学领域具有良好应用前景。     

金属组学：研究生命体系中金属离子的前沿交叉学科

金属组学是一门新兴的前沿交叉学科,是对若干涉及金属相关生命过程的分子机制以及对细胞与组织内全部金属离子和金属配合物进行综合研究的学科．在金属组学中,生命体系中所有的金属蛋白质、金属酶以及其他含金属的生物分子统称为金属组,这个概念与基因组学中的基因组和蛋白质组学中的蛋白质组相类似．本文对金属组学中涉及的若干概念进行阐述,并将着重介绍金属组学中的研究技术和方法,特别是“组和技术”,即把一种高分辨率分离技术如凝胶电泳／激光切除、色谱或者毛细管电泳与一项高灵敏度检测方法,如电感耦合等离子体质谱、电喷雾电离质谱、基质辅助激光解吸附质谱或者X射线荧光／吸收光谱联合起来．并重点分析了这些方法的优缺点以及在分离鉴别金属蛋白、磷酸化蛋白以及硒蛋白、确定金属蛋白的结构与功能的关系和医药中的金属药物活性抗药性方面的研究中的应用．     

金属组学在肝癌诊断及治疗中的应用

金属组学与医学的交叉结合为疾病的诊断及治疗提供了新的研究方向。以肝癌为例，首先介绍了金属组学在肝癌诊断中的应用，包括常用的检测设备和诊断方法；最后介绍了金属组学在肝癌治疗中的应用，除了传统的铂类药物，还发展了钒复合物、钌复合物及砷类药物。金属组学除了用于肝癌的诊断和治疗，也可以预测疗效，如血清Zn与Fe含量的上升，Cu含量下降，提示预后较好。随着新技术的不断发展，金属组学将会在肝癌的诊断及治疗中发挥更大的价值。     

生物和环境样品中硒元素的形态分析研究

金属组学是继基因组学/蛋白质组学和代谢组学后提出的一种新的组学,其研究重点在于对所研究的金属和类金属元素的各种存在形态进行分析。硒是生物环境中存在的一种重要的类金属元素。形态与浓度不同的硒化合物可能是生物体的必需元素,同时也可能导致中毒。本文对目前存在的硒元素形态分析方法的研究现状进行了总结,并对前景进行了展望。     

金属有机配体分析方法及金属组学研究

环境和生物样品中金属与有机酸、氨基酸、多糖、蛋白质、DNA等形成的金属有机物是一系列生物金属。生物金属中参与金属离子配位的有机配基主要是含氧、硫、氮及磷的功能团。金属组学是整合生物金属中金属有机配体的结合形态及其生理功能活性的新概念。文中介绍了目前常用的金属有机配体的分析方法以及金属组学领域的研究技术,并展望了重金属富集和超积累植物的研究前景。     

细菌介导重金属转化过程及金属组学研究方法

重金属污染依然是我国严重的环境问题之一。在重金属胁迫下，微生物可通过复杂的过程，对重金属进行转化，降低重金属的毒性，其中转化涉及的分子机制广受关注。目前，在上述机制相关研究中，对转化过程中重金属的衡量多局限于总量的测定，而对其赋存形态的研究不足，导致难以取得有效进展。对细菌介导重金属的转化过程及金属在其中的赋存形态进行综述，探讨了金属组学研究方法在其中的应用，重点针对重金属的颗粒态与蛋白质结合态进行分析、表征和鉴定，为微生物介导重金属的转化研究提供新视角。     

金属组学、代谢组学及其它

对生命科学方面新近发展起来的两个重要领域，金属组学和代谢组学作了比较深入浅出的介绍，并对这两个领域的主要研究课题和研究方法作了探讨，指出了分析化学家在这两个领域研究中所能够和应该发挥的作用。     

电感耦合等离子体质谱分析

简要综述了我国学者近10年来在电感耦合等离子体质谱(ICP-MS)分析领域的研究工作.在ICP-MS新进样技术和ICP-MS生物分析方法学研究方面,我国科研人员开展了开拓性的研究工作,在元素形态分析和金属组学研究方面富有特色.ICP-MS仪器/部件的设计研制尚待加强;ICP-MS成像研究和在实际生命体系的应用有待进一步强化.     

金属组学——元素生命科学发展的新纪元

对金属组学的概念、研究内容及研究的技术路线和分析技术研究进展进行了综述，主要介绍了对金属蛋白组学研究的相关技术方法，指出了金属组学的发展前景。     

A new spectrometer for grazing incidence X-ray fluorescence for the characterization of Arsenic implants and Hf based high-k layers

Grazing Incidence X-ray Fluorescence Analysis (GIXRF) is a powerful technique for depth-profiling and characterization of thin layers in depths up to a few hundred nanometers. By measurement of fluorescence signals at various incidence angles Grazing Incidence X-ray Fluorescence Analysis provides information on depth distribution and total dose of the elements in the layers. The technique is very sensitive even in depths of a few nanometers. As Grazing Incidence X-ray Fluorescence Analysis does not provide unambigous depth profile information and needs a realistic input depth profile for fitting, in the context of the EC funded European Integrated Activity of Excellence and Networking for Nano and Micro-Electronics Analysis (ANNA) Grazing Incidence X-ray Fluorescence Analysis is used as a complementary technique to Secondary Ion Mass Spectrometry (SIMS) for the characterization of Ultra Shallow Junctions (USJ).     

Analysis of archaeological artefacts: PIXE, XRF or ICP-MS?

Elemental analysis of ancient artefacts is of considerable benefit to the field of Archaeology and of general interest to earth scientists. Several techniques are currently available for this purpose, and in this paper the capabilities of PIXE (Particle Induced X-ray Emission), XRF (X-ray Fluorescence) and ICP-MS (Inductively Coupled Plasma - Mass Spectrometry) were evaluated to establish which of these instrumental methods was best suited especially for routine on-line usage. The elements of interest discussed in this paper are useful in archaeological provenance studies.     

Eignung von Tiefenprofilanalysen zur Charakterisierung von Oxidschichten an Hochtemperaturlegierungen

Summary The characterization of oxide scales by their composition and structure is necessary in order to predict their protective behaviour for the high temperature alloys in various corrosive media. For this purpose information obtained by classical methods, such as metallography, X-ray diffraction and microprobe analysis can be supplemented by depth profiles determined by various spectroscopical methods.In this paper, HASTELLOY X und INCONEL 617 were oxidized for relatively short times in two different atmospheres. Depth profiles were determined by GDOS (Glow Discharge Optical Spectroscopy), SNMS (Secondary Neutral Mass Spectrometry) and SIMS (Secondary Ion Mass Spectrometry).The measured profiles were compared with the results of non-destructive X-ray diffraction analysis to characterize the scales and the oxide-metal interface.     

Trends in metal-binding and metalloprotein analysis

This review describes recent tendencies for metal-binding and metalloprotein analysis, emphasizing metal quantification in proteins through X-ray, atomic absorption, mass spectrometric techniques, and others. Hyphenated techniques such as capillary electrophoresis-synchrotron radiation X-ray fluorescence (CE-SRXRF), laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS), matrix-assisted laser desorption/ionisation-time-of-flight mass spectrometry (MALDI-TOF-MS), etc. are also presented. As protein separation techniques electrophoresis (mainly sodium dodecyl sulphate-polyacrylamide gel electrophoresis, SDS-PAGE), capillary electrophoresis (CE) and high-performance liquid chromatography (HPLC) are indicated, due to their inherent sensitivity, resolution and/or easy implementation. Latest challenges in metallomics are also commented.     

Classical analysis including trace-matrix separation versus solid state mass spectrometry: A comparative study for the analysis of high purity Mo,W and Cr

The applicability of GDMS, SIMS, SSMS, NAA and TMS with AAS, ICP-OES and ICP-MS end determination for routine bulk ultratrace analysis of high purity refractory metals was investigated. Due to the heterogeneous distribution of trace elements in the sub-ppm range, sample consumption and analysis time have a tremendous influence on quantification with procedures of low sample consumption. As an example, GDMS, which is commonly used for ultrapure material certification by most of the manufacturers in Europe and the USA, exhibits discrepancies by more than one order of magnitude for repetitive analyses of a series of trace components in the same sample. Furthermore, results of different laboratories using the same instrument are frequently not comparable. Due to easy standardization and large sample consumption TMS procedures combined with FAAS, GFAAS, ICP-AES and ICP-MS as methods of end determination exhibit better precision and accuracy than GDMS and SIMS. Detection limits are comparably low or even better in case of ICP-MS end determination. TMS procedures are less expensive and less time consuming than highly sophisticated analytical techniques like GDMS, SIMS or NAA. Additionally, they can be easily applied by experienced personnel in a well equipped industrial analytical laboratory.List of Acronyms Used AAS Atomic Absorption Spectrometry - FAAS Flame Atomic Absorption Spectrometry - GDMB Gesellschaft Deutscher Metallhütten- und Bergleute - GDMS Glow Discharge Mass Spectrometry - GFAAS Graphite Furnace Atomic Absorption Spectrometry - ICP-AES Inductively Coupled Plasma Atomic Emission Spectrometry - ICP-MS Inductively Coupled Plasma Mass Spectrometry - IDMS Isotope Dilution Mass Spectrometry - NAA Neutron Activation Analysis - SIMS Secondary Ion Mass Spectrometry - SSMS Spark Source Mass Spectrometry - TMS Trace-Matrix Separation - VLSI Very Large Scale Integration - XRFS X-Ray fluorescence Spectroscopy Dedicated to Professor Günther Tölg on the occasion of his 60th birthday     

Ultratrace and microdistribution analysis in material sciences

Summary All-rounders and experts are two basic types of scientists. A harmonic cooperation between these two groups is essential for today's large study groups engaged in materials development. Materials development programmes in many high-tech countries are major fields of research supported by special financial arrangements (e.g. COST, EURAM or BRITE-programmes in Europe). Modern materials development is not possible without analytical guidance. This is not always realized by all engaged partners and it is a main obligation of analytical chemists to make aware of the role of a potent materials characterization in relevant development programmes. This should be demonstrated in two essential relevant areas: a) Bulk trace and ultra trace analysis of metals. Many important metal properties are directly or indirectly influenced by trace elements. In complex systems like fusion reactors or microelectronic components, trace contents of even minor metal parts might decisively influence system properties. As refractory metals and their silicides gain rising importance in VLSI microelectronic applications, their ultratrace characterization becomes a major challenge. Essential progress was possible by the complementary application of mass-spectrometric methods. Latest results and a critical survey will be given, including GDMS, SIMS, SSMS, IDMS and ICP-MS.Surprisingly, however, highest sensitivities and best detection limits were recently achieved by a combination of trace-matrix separation procedures and final end determination with ICP-MS. This combination also proved to be the most economic and safest approach from the view point of accuracy and precision. b) The analytical characterization of discontinuities and heterogeneities in solid matter. Practical examples are again taken from the study of refractory and hard metals and ceramics. A survey is given as to the manifold effects, heterogeneities and discontinuities exert on modern high-tech materials: as a function of their average diameter, they can either strengthen the material (dispersion strengthening), or they can cause deterioration of material properties e.g. as points of crack initiation, by grain boundary embrittlement etc. Together with most important methods for detection and characterization of heterogeneities and discontinuities, their evaluation and possible prevention during materials fabrication are discussed and pertinent examples are given. The phenomena of heterogeneous particles and pores are elucidated in more detail.

Acronyms used

1 Abbreviations for European research programmes AGATA Advanced Gas Turbines for Automobiles - BRITE Basic Research for Industrial Technologies for Europe - COST Cooperation in Science and Technology - EURAM European Research Activities Programme on Materials 2 Abbreviations in the field of refractory metals technology ADM Ammonium-Di-Molybdate - APT Ammonium-Para-Tungstate - HP High Purity - MHC Molybdenum-based alloy containing 1.2% Hf and 0.1% C - NS Non-sag (tungsten, used for lamp filaments and evaporative metallization techniques) - ODS Oxide Dispersion Strengthened - RM Refractory Metal - TZM Molybdenum-base alloy containing 0.5% Ti, 0.08% Zr and 0.025% C - UHP Ultra High Purity - VLSI Very large scale integration - ZHM Molybdenum-base alloy containing 0.40% Zr, 1.2% Hf and 0.15% C 3 Analytical technique names AA Activation Analysis - AAS Atomic Absorption Spectrophotometry - AES Auger Electron Spectrometry or Atomic Emission Spectrometry (only used in this work where it is clear that Auger Electron Spectrometry is not meant) - EDX(RS) Energy Dispersive X-Ray Spectrometry - EELS Electron Energy Loss Spectrometry - EP(X)MA Electron Probe X-Ray Microanalysis - GDMS Glow Discharge Mass Spectrometry - GFAAS Graphite Furnace Atomic Absorption Spectrometry - ICP-OES, MS Inductively Coupled Plasma — Optical Emission Spectrometry, Mass Spectrometry - ID-MS Isotope Dilution — Mass Spectrometry - LAS Classical photometry (Liquid Absorption — Spectrophotometry) - LEED Low Energy Electron Diffraction - MS Mass Spectrometry - NAA Neutron Activation Analysis - OES Optical Emission Spectrometry - SEM Scanning Electron Microscopy - SIMS Secondary Ion Mass Spectrometry - SSMS Spark Source Mass Spectrometry - TEM Transmission Electron Microscopy - TMS Trace-Matrix Separation (procedure) - WLD(-XRS) Wave Length Dispersive — XRS - XR(F)S X-Ray (Fluorescence) Spectrometry     

Evaluation and comparison of layered titanate nanosheets using TOF‐SIMS and g‐ogram analysis

The evaluation of nanostructure is important to develop the highly controlled nanomaterials. In this study, two kinds of layered titanate nanosheets, which were produced by using hexylamine and laurylamine, respectively, as surfactants were investigated by Gentle Secondary Ion Mass Spectrometry Gentle‐SIMS (G‐SIMS) and g‐ogram, which is the latest Time‐of‐Flight Secondary Ion Mass Spectrometry (TOF‐SIMS) data analysis method for detecting more intact ions and obtaining the information on original chemical structures of samples precisely from complicated TOF‐SIMS spectra. As a result, molecular related ions of the surfactants were detected from each sample, and the structural information of samples was obtained. From both samples, surfactant molecular ions connected with hydrocarbon were detected as more intact ions rather than molecular ions of themselves. It was suggested that hydrophobic domains of their lamellar mesostructure are formed robustly by more than two surfactant molecules connected with each other linearly. After all, important information on the chemical structure of the layered titanate nanosheets, which would be difficult to be found by using typical structural analysis methods such as X‐ray diffraction and transmission electron microscopy, were obtained using G‐SIMS and g‐ogram. Therefore, it was shown that g‐ogram and G‐SIMS are helpful to evaluate the nanostructured materials. And it was also shown that g‐ogram is applicable to organic–inorganic materials which contain long hydrocarbon structures. Copyright © 2015 John Wiley & Sons, Ltd.     

Heterogeneous element distribution: a contribution to quantitative GDOS depth analysis

Summary The apparent enrichment of Cu, Mg, Mn and Si on the surface of Al cast-alloys, as observed by means of glow discharge optical emission spectrometry (GDOS), could be attributed to the heterogeneous distribution of the alloying elements. The samples under investigation were spectrochemical standards and hence assumed to be homogeneous. Different metallurgical phases were identified which induced selective sputtering. The findings point out that quantitative results obtained by GDOS in-depth analysis can be misleading and should be confirmed by other techniques such as Auger Electron Spectrometry and Energy Dispersive X-ray Spectrometry, which are free from sputter effects.