High mass and spatial resolution mass spectrometry imaging of Nicolas Poussin painting cross section by cluster TOF‐SIMS

Time‐of‐flight secondary ion mass spectrometry (TOF‐SIMS) imaging using cluster primary ion beams is used for the identification of the pigments in the painting of Rebecca and Eliezer at the Well by Nicolas Poussin. The combination of the high mass resolution of the technique with a sub‐micrometer spatial resolution offered by a delayed extraction of the secondary ions, together with the possibility to simultaneously identifying both minerals and organics, has proved to be the method of choice for the study of the stratigraphy of a paint cross section. The chemical compositions of small grains are shown with the help of a thorough processing of the data, with images of specific ions, mass spectra extracted from small regions of interest, and profiles drawn along the different painting layers. Copyright © 2016 John Wiley & Sons, Ltd.     

Moderated pressure microwave digestion system for preparation of biological samples

A new type closed digestion vessel was constructed for digestion of biological samples. In this the vapour pressure can be maintained on moderated level (150-300 kPa) by means of an internal cooling spiral. During the operation the reflux of the condensed acid and water vapour continuously renews the liquid phase over the sample. By this way a less expensive microwave system may be applied. The performance of this instrument is practically equal to the commercial systems. The digestion time of plant and tissue samples is 5-10 min and the analytical results for reference materials are in good agreement with the reference values.     

Tools for clean preparation of biological samples (reference materials)

Summary Tools made of corundum single crystals (Al₂O₃) grown artificially were found to be excellent for clean preparation of biological samples. Scalpels and knives made in cooperation with the Metallurgical Works at Skawina are described     

Target preparation of biological samples for trace element analysis using nuclear techniques

An easy and rapid method for preparing biological targets for trace element analysis using nuclear techniques involving charged particle beams is described. The targets are thin, homogeneous and uniform. They withstand 100 nA of 1–2 MeV proton beams and of 5–10 MeV alpha beams for about 10 hrs.     

Investigation of ionic liquids under Bi‐ion and Bi‐cluster ions bombardment by ToF‐SIMS

A systematic study of five different imidazolium‐based room temperature ionic liquids, 1‐butyl‐3‐methylimidazolium acetate, 1‐butyl‐3‐methylimidazolium nitrate, 1‐butyl‐3‐methylimidazolium iodide, 1‐butyl‐3‐methylimidazolium hexafluorophosphate and 1‐butyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide were carried out by means of time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) in positive and negative ion mode. The compounds were measured under Bi‐ion and Bi‐cluster ions (Bi_2–7⁺, Bi_{3, 5}²⁺) bombardment, and spectral information and general rules for the fragmentation pattern are presented. Evidence for hydrogen bonding, due to high molecular secondary cluster ions, could be found. Hydrogen bonding strength could be estimated by ToF‐SIMS via correlation of the anionic yield enhancement with solvent parameters. Copyright © 2010 John Wiley & Sons, Ltd.     

Characterizing the impact of preparation method on fullerene cluster structure and chemistry

We examined the physical and chemical characteristics of colloidal dispersions of fullerene materials (nC60) produced through several solvent exchange processes and through extended mixing in water only. The nC60 produced via the different methods were unique from each other with respect to size, morphology, charge, and hydrophobicity. The greatest dissimilarities were observed between the nC60 produced by extended mixing in water alone and the nC60 produced by solvent exchange processes. The role of the respective solvents in determining the characteristics of the various nC60 were attributed to differences in the solvent-C60 interactions and the presence of the solvent as a residual in the nC60 structure, indicating the significance of the solvent properties in determining the ultimate characteristics of the colloidal fullerene. Thus, fullerene C60 that may become mobilized through natural processes (agitation in water) may behave in dramatically different ways than those produced through more artificial means. These results highlight the difficulties in generalizing nC60 properties, particularly as they vary in potential toxicity considerations.     

Infrared and Raman imaging of biological and biomimetic samples

Established methods for imaging of biological or biomimetic samples, such as fluorescence and optical microscopy, magnetic resonance imaging (MRI), X-ray tomography or positron emission tomography (PET) are currently complemented by infrared (both near-IR and mid-IR) as well as Raman spectroscopic imaging, whether it be on a microscopic or macroscopic scale. These vibrational spectroscopic techniques provide a wealth of information without a priori knowledge of either the spectral data or the composition of the sample. Infrared radiation does not harm the organism, no electric potential needs to be applied, and the measurements are not influenced by electromagnetic fields. In addition, no extrinsic labeling or staining, which may perturb the system under investigation, has to be added. The immense volume of information contained in spectroscopic images requires multivariate analysis methodologies in order to effectively mine the chemical and spatial information contained within the data as well as to analyze a time-series of images in order to reveal the origin of a chemical or biochemical process. The promise and limitations of this new analytical tool are surveyed in this review.     

Neutral cesium deposition prior to SIMS analysis of inorganic and organic samples

The enhancement of negative secondary ions yields in SIMS by the use of electropositive primary ions is well known. In previous papers, the authors of this article have reported on the simultaneous use of primary ion bombardment coupled with neutral cesium deposition to optimize the useful yields of negative secondary ions in the steady‐state regime. For electronegative elements, total ionization was achieved while the gain for the other elements attained two orders of magnitude. In this paper, we study the enhancement of negative secondary ion yields in the pre‐equilibrium regime by depositing neutral cesium onto the sample surface prior to the SIMS analysis. The main areas of application of this technique lie in the field of secondary ion imaging of sample surfaces. Of particular interest is the analysis of organic and biological samples on the Cameca NanoSIMS50 instrument. Both inorganic and organic samples will be investigated in this paper. Copyright © 2010 John Wiley & Sons, Ltd.     

Quantification strategies for elemental imaging of biological samples using laser ablation-inductively coupled plasma-mass spectrometry

This review provides analysts with critical insights of current approaches for quantification by laser ablation-inductively coupled plasma-mass spectrometry in the field of elemental imaging. This encompasses both calibration strategies that have been used with success in imaging biological samples, as well as those with potential to improve analytical accuracy and precision if applied to imaging. Methods reviewed include the use of CRMs, laboratory prepared matrix matched standards, internal standardisation, online standard addition and a variety of novel approaches that makes elemental imaging accessible to a wider base of analysts. The importance of quantification and factors affecting its use in imaging will also be considered.     

Automated,feature-based image alignment for high-resolution imaging mass spectrometry of large biological samples

High-resolution imaging mass spectrometry of large biological samples is the goal of several research groups. In mosaic imaging, the most common method, the large sample is divided into a mosaic of small areas that are then analyzed with high resolution. Here we present an automated alignment routine that uses principal component analysis to reduce the uncorrelated noise in the imaging datasets, which previously obstructed automated image alignment. An additional signal quality metric ensures that only those regions with sufficient signal quality are considered. We demonstrate that this algorithm provides superior alignment performance than manual stitching and can be used to automatically align large imaging mass spectrometry datasets comprising many individual mosaic tiles.     

Sample preparation for gas chromatographic determination of halogenated volatile organic compounds in environmental and biological samples

In this review, the wide spectrum of the techniques of isolation and/or preconcentration and final determination of halogenated volatile organic compounds (HVOCs) in water, air, soil, sediment and biological fluids are presented and discussed. The techniques discussed are solvent microextraction, solid phase extraction, gas extraction (static and dynamic techniques), membrane processes and passive sampling. Also, direct techniques, such as direct aqueous injection into gas chromatography (GC) column and membrane inlet mass spectrometry, are presented. Main attention is paid to the practical application of these techniques during all HVOCs determination.     

Non-aqueous capillary electrophoresis of biological samples after at-line solid-phase extraction

Summary Solid-phase extraction (SPE) was coupled at-line to capillary electrophoresis (CE) for the determination of a series of basic test compounds (i. e. tricyclic antidepressants). The analysis was performed using a non-aqueous CE buffer, which resulted in baseline separation of all test compounds. This is in marked contrast with CE using aqueous buffers where hardly any separation was obtained either with or without micelles. The SPE procedure was used to remove simultaneously most of the water from the sample, because no direct analysis of aqueous samples is possible when a non-aqueous CE buffer is used. With the present method the antidepressants can be determined in both urine and serum. Analyte detectability is increased up to 10-fold due to trace enrichment during the extraction process; the limits of detection (LODs; UV 214 nm) are 30–300 ng mL⁻¹ in urine and 300–1000 ng mL⁻¹ in serum. TheRSD values (n=5) of the within-day and between-day precision are below 9% and 11% respectively. Therefore, the present procedure can be used for drug monitoring.     

Automated sequential trace enrichment of dialysates and robotics. A technique for the preparation of biological samples prior to high-performance liquid chromatography

The development of the sample preparation process, the automated sequential trace enrichment of dialysates, in association with a cartesian robotic sampler is described. The system has been applied to the total automation of the preparation of biological samples and high-performance liquid chromatographic analysis. Concepts of the technique are reported together with an examination of its application to free and total analyte estimation. Examples of chromatographic separations obtained from the preparation of a variety of different analytes and sample materials are given.     

Improvement of biological time-of-flight-secondary ion mass spectrometry imaging with a bismuth cluster ion source

A new liquid metal ion gun (LMIG) filled with bismuth has been fitted to a time-of-flight-secondary ion mass spectrometer (TOF-SIMS). This source provides beams of Bi(n)q+ clusters with n = 1-7 and q = 1 and 2. The appropriate clusters have much better intensities and efficiencies than the Au3+ gold clusters recently used in TOF-SIMS imaging, and allow better lateral and mass resolution. The different beams delivered by this ion source have been tested for biological imaging of rat brain sections. The results show a great improvement of the imaging capabilities in terms of accessible mass range and useful lateral resolution. Secondary ion yields Y, disappearance cross sections sigma, efficiencies E = Y/sigma , and useful lateral resolutions deltaL have been compared using the different bismuth clusters, directly onto the surface of rat brain sections and for several positive and negative secondary ions with m/z ranging from 23 up to more than 750. The efficiency and the imaging capabilities of the different primary ions are compared by taking into account the primary ion current for reasonable acquisition times. The two best primary ions are Bi3+ and Bi5(2+). The Bi3+ ion beam has a current at least five times larger than Au3+ and therefore is an excellent beam for large-area imaging. Bi5(2+) ions exhibit large secondary ions yields and a reasonable intensity making them suitable for small-area images with an excellent sensitivity and a possible useful lateral resolution <400 nm.     

Improved spatial resolution in the imaging of biological tissue using desorption electrospray ionization

Desorption electrospray ionization imaging allows biomarker discovery and disease diagnosis through chemical characterization of biological samples in their native environment. Optimization of experimental parameters including emitter capillary size, solvent composition, solvent flow rate, mass spectrometry scan-rate and step-size is shown here to improve the resolution available in the study of biological tissue from 180?μm to about 35?μm using an unmodified commercial mass spectrometer. Mouse brain tissue was used to optimize and measure resolution based on known morphological features and their known relationships to major phospholipid components. Features of approximately 35?μm were resolved and correlations drawn between features in grey matter (principally PS (18:0/22:6), m/z 834) and in white matter (principally ST (24:1), m/z 888). The improved spatial resolution allowed characterization of the temporal changes in lipid profiles occurring within mouse ovaries during the ovulatory cycle. An increase in the production of phosphatidylinositol (PI 38:4) m/z 885 and associated fatty acids such as arachidonic acid (FA 20:4) m/z 303 and adrenic acid (FA 22:4) m/z 331was seen with the postovulatory formation of the corpus luteum.     

Application of microwave digestion to the preparation of sediment samples for arsenic speciation

Several extraction procedures are described allowing arsenic speciation in sediments. The extraction of organometallic compounds such as dimethylarsinic acid or monomethylarsonic acid is quite simple since these compounds are stable in the different extraction media (HCl/ HNO₃, H₃PO₄, ammonium oxalate) and are easily released independent of the extraction mode (magnetic stirring or microwave solubilization). Extraction yields are higher than 96% for these two arsenic forms. An HCl/HNO₃ microwave solubilization procedure allows the quantitative solubilization of mineral arsenic, but the differentiation between the two oxidation states is not possible owing to the oxidation of As(III) to As(V). Extractions with orthophosphoric acid or ammonium oxalate allow the solubilization of mineral arsenic with extraction yields ranging from 90 to 95% and the differentiation between As(III) and As(V). Nevertheless, the amount of As(III) is underestimated owing to its partial oxidation. The usefulness and advantages of microwave solubilization compared with conventional extraction procedures are discussed. Received: 17 May 1996 / Revised: 19 September 1996 / Accepted: 25 September 1996     

Application of microwave digestion to the preparation of sediment samples for arsenic speciation

Several extraction procedures are described allowing arsenic speciation in sediments. The extraction of organometallic compounds such as dimethylarsinic acid or monomethylarsonic acid is quite simple since these compounds are stable in the different extraction media (HCl/ HNO₃, H₃PO₄, ammonium oxalate) and are easily released independent of the extraction mode (magnetic stirring or microwave solubilization). Extraction yields are higher than 96% for these two arsenic forms. An HCl/HNO₃ microwave solubilization procedure allows the quantitative solubilization of mineral arsenic, but the differentiation between the two oxidation states is not possible owing to the oxidation of As(III) to As(V). Extractions with orthophosphoric acid or ammonium oxalate allow the solubilization of mineral arsenic with extraction yields ranging from 90 to 95% and the differentiation between As(III) and As(V). Nevertheless, the amount of As(III) is underestimated owing to its partial oxidation. The usefulness and advantages of microwave solubilization compared with conventional extraction procedures are discussed. Received: 17 May 1996 / Revised: 19 September 1996 / Accepted: 25 September 1996