Mass spectrometry imaging for the proteomic study of clinical tissue

Over the last decade, MALDI-MS imaging has been used by researchers to explore areas of proteomics, lipidomics and metabolomics in samples of clinical origin for both targeted and global biomarker analysis. Numerous technological advancements in MS and clinical tissue MS imaging have been accomplished; hence, in this article we aim to critically discuss whether MS imaging has now in fact become a true champion of the ‘Omics Era’. In order to assess the potential for it to be routinely used in the clinical setting, it is pertinent to discuss some of its limitations, and to examine how these have been addressed by researchers. The key limitations of the technique we will discuss in this viewpoint article are as follows: sample throughput; relevance to patients, the availability of validated/standardised techniques; and integration with conventional pathology and other medical imaging techniques. Good progress has been made over the last 5 years in overcoming these limitations that had previously restricted the use of this technology in the clinical setting.     

Interphase Formation and the Characterisation of Polymer/Ceramic Adhesion

The adhesion of photocured resins to ceramic substrates has been investigated using a variety of surface analytical techniques. Work has been aimed at establishing the physical and chemical interactions between resin and substrate in the interphase region and the effect of environmental exposure on these Analysis was aided by use of specially-designed, in-situ fracture facilities attached by an X-ray photoelectron spectrometer. Specific attention was focused on identification of localised regions of varying chemical composition in adhesive and adherend by imaging spectroscopies (imaging XPS and ToF SIMS imaging) and the study of the significance of such heterogeneities on adhesion and subsequent failure mechanisms.     

Adhesion Promotion by Silanes: A Study of their Interfacial Chemistry in a Model Polystyrene Coating by XPS and SIMS

Adhesion of a polystyrene coating to solvent cleaned steel is increased two-fold by addition of 0.5% wt/wt of aminosilane (A1120). A study has been carried out on the coating-substrate interfacial chemistry to gain an understanding of the mechanism of adhesion promotion. It is shown that in peel experiments the coating fails adhesively between the polystyrene and an adsorbed layer of aminosilane on the steel surface. The improvement in adhesion results from displacement by the silane of the 1.4 nm thick layer of residual carbonaceous contamination on the steel surface. It is proposed that this leads to a stronger substrate-coating interaction either through improved intermolecular contact between the segregated silane and the polymer or through secondary bonding between the amine groups of the silane and the polarisable aromatic rings of the polystyrene.     

Desorption of large molecules with light-element clusters: Effects of cluster size and substrate nature

This contribution focuses on the conditions required to desorb a large hydrocarbon molecule using light-element clusters. The test molecule is a 7.5 kDa coil of polystyrene (PS61). Several projectiles are compared, from C₆₀ to 110 kDa organic droplets and two substrates are used, amorphous polyethylene and mono-crystalline gold. Different aiming points and incidence angles are examined. Under specific conditions, 10 keV nanodrops can desorb PS61 intact from a gold substrate and from a soft polyethylene substrate. The prevalent mechanism for the desorption of intact and ‘cold’ molecules is one in which the molecules are washed away by the projectile constituents and entrained in their flux, with an emission angle close to ∼70°. The effects of the different parameters on the dynamics and the underlying physics are discussed in detail and the predictions of the model are compared with other published studies.     

Factors controlling the time evolution of the corrosion potential of aluminum in alkaline solutions

The mechanism of corrosion of 99.99% purity aluminum in alkaline solutions was investigated, through detailed examination of open-circuit potential transients. These transients displayed a characteristic time dependence, in which the potential first decreased over a few seconds to a minimum of −1.7 to −1.9 V vs. Ag/AgCl, and then slowly increased over a period of hours. The value of the minimum potential of electropolished foils, along with its dependence on pH and aluminate ion concentration, indicated that it was determined by the Nernst potential for the oxidation of surface aluminum hydride (AlH₃). This finding supports the direct role of hydride in the dissolution process. The increase of anodic polarization after the minimum potential occurred in two stages, the first correlated with the buildup of surface hydride, and the second with surface enrichment of Cu and Fe impurities.     

Limitation of Na-H codoping in achieving device-quality p-type ZnO

Na-H in-situ codoping in single crystalline ZnO films was carried out by plasma assisted molecular beam epitaxy. It is found that Na-H codoping dramatically enhances the formation of substitutional Na (Na_Zn) in ZnO lattice due to the unchanged Fermi level. The annealing temperature needed to kick out H, however, is very high, which would concurrently result in a notable decrease of Na concentration to its solution limit in ZnO, namely, in the range of 10¹⁷ cm⁻³. Our results suggest that Na-H codoping method has a limited effect on enhancing the p-type conductivity of ZnO.     

Analytical investigations concerning the wear behaviour of cutting tools used for the machining of compacted graphite iron and grey cast iron

Compacted graphite iron (CGI) is the material for the upcoming new generation of high-power diesel engines. Due to its increased strength compared to grey cast iron (CI) it allows an increase in the cylinder-pressures and therefore a better fuel economy and a higher power output are possible. First examples of such engines are the 3.3 L Audi V8 TDI and the 4.0 L BMW V8. The reason why CGI is not used to a larger extent in large scale production up to now is its much more difficult machinability as compared to conventional CI, especially at high cutting speeds. In modern transfer lines high cutting speeds are used in the cylinder-boring operation. And especially in these continuous cutting operations the tool life decreased due to the change from CI to CGI by about a factor of 20. As was found out previously by us, the difference in tool lifetime can be explained by the formation of a MnS-layer on the tool surface in the case of CI. This layer cannot form when machining CGI because the formation of MnS-inclusions is not possible in this material due to the higher magnesium content which in turn is responsible for the formation of the graphite vermicles. The MnS-layer acts as a lubricant and prevents the adhesion of workpiece particles. This is the reason for the greatly reduced wear of CI in high speed machining operations. This MnS-layer is inspected closer by X-ray diffraction, X-ray induced photoelectron spectrometry, atomic force microscopy and secondary ion mass spectrometry in this work. Furthermore, available information on the performance of MnS as lubricant in PM-steels is comparatively discussed. This knowledge led to an economic solution of high productivity machining of CGI. The key was to reduce the cutting speed, replacing single insert tools with multiple insert tools. This allowed to increase the feed rate. By increasing the feed rate in the same amount as decreasing the cutting speed, the same productivity can be realized. This concept is leading to a number of multiple insert tools thus realizing a high productivity machining of CGI cylinder-bores with multi-layer-coated carbide tools.     

Correlative high-resolution imaging of hydrogen in Mg2Ni hydrogen storage thin films

Nanometer scale imaging of hydrogen in solid materials remains an important challenge for the characterization of advanced materials, such as semiconductors, high-strength metallic alloys, and hydrogen storage materials. Within this work, we demonstrate high-resolution imaging of hydrogen and deuterium within Mg₂Ni/Mg₂NiH₄ hydrogen storage thin films using an in-house developed secondary ion mass spectrometer (SIMS) system attached to a commercially available dual-beam focused ion beam - scanning electron microscope (FIB-SEM) instrument. We further demonstrate a novel approach to measure the size, shape, and distribution of the hydride phase in partially transformed films using laser scanning confocal microscopy (LSCM) to measure surface topography changes from the hydride phase volume expansion. Combining these techniques provides new insights on hydride nucleation and growth within the Mg₂NiH_x system. Finally, we demonstrate the efficacy of tracking deuterium as a hydrogen analog to reduce the background for SIMS imaging of hydrogen in high-vacuum chambers (∼10⁻⁶ mbar).     

XPS and SIMS characterization

XPS study V₂O₅–WO₃/TiO₂ mixed oxide catalysts for Selective Catalytic Reduction (SCR) of NO_x carried out by researchers from ten different laboratories shows good reproducibility of the chemical shift results. The binding energies of the corresponding core level spectra allow us to identify the chemical states of main elements as Ti(IV), V(V) and W(VI). No other oxidation states for these elements were observed both for fresh/used and for crushed/monolith samples. Discrepancy in quantitative data can be proposed to arise from the heterogeneity of their composition as a function of depth. This suggestion is confirmed by SIMS data and ion etching experiments which indicate surface location of V₂O₅ phase, as well as impurity ones, with respect to TiO₂ and WO₃ and their redistribution as result of catalyst operation.     

Low-temperature atomic layer deposition of Al2O3 thin coatings for corrosion protection of steel: Surface and electrochemical analysis

ToF-SIMS, XPS, voltammetry and EIS investigation of the anti-corrosion properties of thin (10, 50 and 100 nm) alumina coatings grown by atomic layer deposition at 160 °C on steel is reported. Surface analysis shows a thickness-independent Al₂O₃ stoichiometry of the coating and trace contamination by the growth precursors. The buried coating/alloy interface has iron oxide formed in ambient air and/or resulting from the growth of spurious traces in the initial stages of deposition. Electrochemical analysis yields an exponential decay of the coating porosity over four orders of magnitude with increasing thickness, achieved by sealing of the more defective first deposited 10 nm.