Localization of Metabolites of Human Kidney Tissue with Infrared Laser-Based Selected Reaction Monitoring Mass Spectrometry Imaging and Silver-109 Nanoparticle-Based Surface Assisted Laser Desorption/Ionization Mass Spectrometry Imaging.

Infrared (IR) laser ablation-remote-electrospray ionization (LARESI) platform coupled to a tandem mass spectrometer (MS/MS) operated in selected reaction monitoring (SRM) or multiple reaction monitoring (MRM) modes was developed and employed for imaging of target metabolites in human kidney cancer tissue. SRM or MRM modes were employed to avoid artifacts that are present in full scan MS mode. Four tissue samples containing both cancerous and noncancerous regions, obtained from three patients with renal cell carcinoma (RCC), were imaged. Sixteen endogenous metabolites that were reported in the literature as varying in abundance between cancerous and noncancerous areas in various human tissues were selected for analysis. Target metabolites comprised ten amino acids, four nucleosides and nucleobases, lactate, and vitamin E. For comparison purposes, images of the same metabolites were obtained with ultraviolet (UV) desorption/ionization mass spectrometry imaging (UV-LDI-MSI) using monoisotopic silver-109 nanoparticle-enhanced target (109AgNPET) in full-scan MS mode. The acquired MS images revealed differences in abundances of selected metabolites between cancerous and noncancerous regions of the kidney tissue. Importantly, the two imaging methods offered similar results. This study demonstrates the applicability of the novel ambient LARESI SRM/MRM MSI method to both investigating and discovering cancer biomarkers in human tissue.

Metabolomic study of human tissue and urine in clear cell renal carcinoma by LC-HRMS and PLS-DA.

Renal cell carcinoma (RCC) is the most prevalent and lethal malignancy of the kidney. Despite all the efforts made, no tissue biomarker is currently used in the clinical management of patients with kidney cancer. A search for possible biomarkers in urine for clear cell renal cell carcinoma (ccRCC) has been conducted. Non-targeted metabolomic analyses were performed on paired samples of surgically removed renal cancer and normal tissue, as well as on urine samples. Extracts were analyzed by liquid chromatography/high-resolution mass spectrometry (LC-HRMS). Hydroxybutyrylcarnitine, decanoylcarnitine, propanoylcarnitine, carnitine, dodecanoylcarnitine, and norepinephrine sulfate were found in much higher concentrations in both cancer tissues (compared with the paired normal tissue) and in urine of cancer patients (compared with control urine). In contrast, riboflavin and acetylaspartylglutamate (NAAG) were present at significantly higher concentrations both in normal kidney tissue as well as in urine samples of healthy persons. This preliminary study resulted in the identification of several compounds that may be considered potential clear cell renal carcinoma biomarkers. Graphical abstract PLS-DA plot based on LC-MS data for normal and cancer human tissue samples. The aim of this work was the identification of up- and downregulated compounds that could potentially serve as renal cancer biomarkers.

Anaerobic biodegradation of biofuels and their impact on the corrosion of a Cu-Ni alloy in marine environments.

Fuel biodegradation linked to sulfate reduction can lead to corrosion of the metallic infrastructure in a variety of marine environments. However, the biological stability of emerging biofuels and their potential impact on copper-nickel alloys commonly used in marine systems has not been well documented. Two potential naval biofuels (Camelina-JP5 and Fisher-Tropsch-F76) and their petroleum-derived counterparts (JP5 and F76) were critically assessed in seawater/sediment incubations containing a metal coupon (70/30 Cu-Ni alloy). Relative to a fuel-unamended control (1.2 ±â€¯0.4 µM/d), Camelina-JP5 (86.4 ±â€¯1.6 µM/d) and JP5 (77.6 ±â€¯8.3 µM/d) stimulated much higher rates of sulfate reduction than either FT-F76 (11.4 ±â€¯2.7 µM/d) or F76 (38.4 ±â€¯3.7 µM/d). The general corrosion rate (r2 = 0.91) and pitting corrosion (r2 = 0.92) correlated with sulfate loss in these incubations. Despite differences in microbial community structure on the metal or in the aqueous or sediment phases, sulfate reducing bacteria affiliated with Desulfarculaceae and Desulfobacteraceae became predominant upon fuel amendment. The identification of alkylsuccinates and alkylbenzylsuccinates attested to anaerobic metabolism of fuel hydrocarbons. Sequences related to Desulfobulbaceae were highly enriched (34.2-64.8%) on the Cu-Ni metal surface, regardless of whether the incubation received a fuel amendment. These results demonstrate that the anaerobic metabolism of biofuel linked to sulfate reduction can exacerbate the corrosion of Cu-Ni alloys. Given the relative lability of Camelina-JP5, particular precaution should be taken when incorporating this hydroprocessed biofuel into marine environments serviced by a Cu-Ni metallic infrastructure.

Metabolomic and Metagenomic Analysis of Two Crude Oil Production Pipelines Experiencing Differential Rates of Corrosion.

Corrosion processes in two North Sea oil production pipelines were studied by analyzing pig envelope samples via metagenomic and metabolomic techniques. Both production systems have similar physico-chemical properties and injection waters are treated with nitrate, but one pipeline experiences severe corrosion and the other does not. Early and late pigging material was collected to gain insight into the potential causes for differential corrosion rates. Metabolites were extracted and analyzed via ultra-high performance liquid chromatography/high-resolution mass spectrometry with electrospray ionization (ESI) in both positive and negative ion modes. Metabolites were analyzed by comparison with standards indicative of aerobic and anaerobic hydrocarbon metabolism and by comparison to predicted masses for KEGG metabolites. Microbial community structure was analyzed via 16S rRNA gene qPCR, sequencing of 16S PCR products, and MySeq Illumina shotgun sequencing of community DNA. Metagenomic data were used to reconstruct the full length 16S rRNA genes and genomes of dominant microorganisms. Sequence data were also interrogated via KEGG annotation and for the presence of genes related to terminal electron accepting (TEA) processes as well as aerobic and anaerobic hydrocarbon degradation. Significant and distinct differences were observed when comparing the 'high corrosion' (HC) and the 'low corrosion' (LC) pipeline systems, especially with respect to the TEA utilization potential. The HC samples were dominated by sulfate-reducing bacteria (SRB) and archaea known for their ability to utilize simple carbon substrates, whereas LC samples were dominated by pseudomonads with the genetic potential for denitrification and aerobic hydrocarbon degradation. The frequency of aerobic hydrocarbon degradation genes was low in the HC system, and anaerobic hydrocarbon degradation genes were not detected in either pipeline. This is in contrast with metabolite analysis, which demonstrated the presence of several succinic acids in HC samples that are diagnostic of anaerobic hydrocarbon metabolism. Identifiable aerobic metabolites were confined to the LC samples, consistent with the metagenomic data. Overall, these data suggest that corrosion management might benefit from a more refined understanding of microbial community resilience in the face of disturbances such as nitrate treatment or pigging, which frequently prove insufficient to alter community structure toward a stable, less-corrosive assemblage.

Untargeted Metabolomics Approach in Halophiles: Understanding the Biodeterioration Process of Building Materials.

The aim of the study was to explore the halophile metabolome in building materials using untargeted metabolomics which allows for broad metabolome coverage. For this reason, we used high-performance liquid chromatography interfaced to high-resolution mass spectrometry (HPLC/HRMS). As an alternative to standard microscopy techniques, we introduced pioneering Coherent Anti-stokes Raman Scattering Microscopy (CARS) to non-invasively visualize microbial cells. Brick samples saturated with salt solution (KCl, NaCl (two salinity levels), MgSO4, Mg(NO3)2), were inoculated with the mixture of preselected halophilic microorganisms, i.e., bacteria: Halobacillus styriensis, Halobacillus naozhouensis, Halobacillus hunanensis, Staphylococcus succinus, Marinococcus halophilus, Virgibacillus halodenitryficans, and yeast: Sterigmatomyces halophilus and stored at 28°C and 80% relative humidity for a year. Metabolites were extracted directly from the brick samples and measured via HPLC/HRMS in both positive and negative ion modes. Overall, untargeted metabolomics allowed for discovering the interactions of halophilic microorganisms with buildings materials which together with CARS microscopy enabled us to elucidate the biodeterioration process caused by halophiles. We observed that halophile metabolome was differently affected by different salt solutions. Furthermore, we found indications for haloadaptive strategies and degradation of brick samples due to microbial pigment production as a salt stress response. Finally, we detected changes in lipid content related to changes in the structure of phospholipid bilayers and membrane fluidity.

Surface-Transfer Mass Spectrometry Imaging of Renal Tissue on Gold Nanoparticle Enhanced Target.

Renal cell carcinoma (RCC) accounts for several percent of all adult malignant tumor cases and is directly associated with over 120 thousand death cases worldwide annually. Therefore, there is a need for cancer biomarker tests and methods capable of discriminating between normal and malignant tissue. It is demonstrated that gold nanoparticle enhanced target (AuNPET), a nanoparticle-based, surface-assisted laser desorption/ionization (SALDI)-type mass spectrometric method for analysis and imaging, can differentiate between normal and cancerous renal tissue. Diglyceride DG(18:1/20:0)-sodium adduct and protonated octadecanamide ions were found to have greatly elevated intensities in cancerous part of analyzed tissue specimen. Compounds responsible for mentioned ions formation were pointed out as a potential clear cell RCC biomarkers. Their biological properties and localization on the tissue surface are also discussed. Potential application of presented results may also facilitate clinical decision making during surgery for large renal masses.

Anaerobic Biodegradation of Alternative Fuels and Associated Biocorrosion of Carbon Steel in Marine Environments.

Fuels that biodegrade too easily can exacerbate through-wall pitting corrosion of pipelines and tanks and result in unintentional environmental releases. We tested the biological stability of two emerging naval biofuels (camelina-JP5 and Fischer-Tropsch-F76) and their potential to exacerbate carbon steel corrosion in seawater incubations with and without a hydrocarbon-degrading sulfate-reducing bacterium. The inclusion of sediment or the positive control bacterium in the incubations stimulated a similar pattern of sulfate reduction with different inocula. However, the highest rates of sulfate reduction were found in incubations amended with camelina-JP5 [(57.2 ± 2.2)-(80.8 ± 8.1) µM/day] or its blend with petroleum-JP5 (76.7 ± 2.4 µM/day). The detection of a suite of metabolites only in the fuel-amended incubations confirmed that alkylated benzene hydrocarbons were metabolized via known anaerobic mechanisms. Most importantly, general (r(2) = 0.73) and pitting (r(2) = 0.69) corrosion were positively correlated with sulfate loss in the incubations. Thus, the anaerobic biodegradation of labile fuel components coupled with sulfate respiration greatly contributed to the biocorrosion of carbon steel. While all fuels were susceptible to anaerobic metabolism, special attention should be given to camelina-JP5 biofuel due to its relatively rapid biodegradation. We recommend that this biofuel be used with caution and that whenever possible extended storage periods should be avoided.

Metabolomic and high-throughput sequencing analysis-modern approach for the assessment of biodeterioration of materials from historic buildings.

Preservation of cultural heritage is of paramount importance worldwide. Microbial colonization of construction materials, such as wood, brick, mortar, and stone in historic buildings can lead to severe deterioration. The aim of the present study was to give modern insight into the phylogenetic diversity and activated metabolic pathways of microbial communities colonized historic objects located in the former Auschwitz II-Birkenau concentration and extermination camp in Oswiecim, Poland. For this purpose we combined molecular, microscopic and chemical methods. Selected specimens were examined using Field Emission Scanning Electron Microscopy (FESEM), metabolomic analysis and high-throughput Illumina sequencing. FESEM imaging revealed the presence of complex microbial communities comprising diatoms, fungi and bacteria, mainly cyanobacteria and actinobacteria, on sample surfaces. Microbial diversity of brick specimens appeared higher than that of the wood and was dominated by algae and cyanobacteria, while wood was mainly colonized by fungi. DNA sequences documented the presence of 15 bacterial phyla representing 99 genera including Halomonas, Halorhodospira, Salinisphaera, Salinibacterium, Rubrobacter, Streptomyces, Arthrobacter and nine fungal classes represented by 113 genera including Cladosporium, Acremonium, Alternaria, Engyodontium, Penicillium, Rhizopus, and Aureobasidium. Most of the identified sequences were characteristic of organisms implicated in deterioration of wood and brick. Metabolomic data indicated the activation of numerous metabolic pathways, including those regulating the production of primary and secondary metabolites, for example, metabolites associated with the production of antibiotics, organic acids and deterioration of organic compounds. The study demonstrated that a combination of electron microscopy imaging with metabolomic and genomic techniques allows to link the phylogenetic information and metabolic profiles of microbial communities and to shed new light on biodeterioration processes.

Mass Spectrometric Imaging Using Laser Ablation and Solvent Capture by Aspiration (LASCA).

A novel interface for ambient, laser ablation-based mass spectrometric imaging (MSI) referred to as laser ablation and solvent capture by aspiration (LASCA) is presented and its performance demonstrated using selected, unaltered biological materials. LASCA employs a pulsed 2.94 µm laser beam for specimen ablation. Ablated materials in the laser plumes are collected on a hanging solvent droplet with electric field-enhanced trapping, followed by aspiration of droplets and remaining plume material in the form of a coarse aerosol into a collection capillary. The gas and liquid phases are subsequently separated in a 10 µL-volume separatory funnel, and the solution is analyzed with electrospray ionization in a high mass resolution Q-ToF mass spectrometer. The LASCA system separates the sampling and ionization steps in MSI and combines high efficiencies of laser plume sampling and of electrospray ionization (ESI) with high mass resolution MS. Up to 2000 different compounds are detected from a single ablation spot (pixel). Using the LASCA platform, rapid (6 s per pixel), high sensitivity, high mass-resolution ambient imaging of "as-received" biological material is achieved routinely and reproducibly.

Mass spectrometric metabolomic imaging of biofilms on corroding steel surfaces using laser ablation and solvent capture by aspiration.

Ambient laser ablation and solvent capture by aspiration (LASCA) mass spectrometric imaging was combined with metabolomics high-performance liquid chromatography (HPLC) mass spectrometry analysis and light profilometry to investigate the correlation between chemical composition of marine bacterial biofilms on surfaces of 1018 carbon steel and corrosion damage of steel underneath the biofilms. Pure cultures of Marinobacter sp. or a wild population of bacteria present in coastal seawater served as sources of biofilms. Profilometry data of biofilm-free surfaces demonstrated heterogeneous distributions of corrosion damage. LASCA data were correlated with areas on the coupons varying in the level of corrosion attack, to reveal differences in chemical composition within biofilm regions associated with corroding and corrosion-free zones. Putative identification of selected compounds was carried out based on HPLC results and subsequent database searches. This is the first report of successful ambient chemical and metabolomic imaging of marine biofilms on corroding metallic materials. The metabolic analysis of such biofilms is challenging due to the presence in the biofilm of large amounts of corrosion products. However, by using the LASCA imaging interface, images of more than 1000 ions (potential metabolites) are generated, revealing striking heterogeneities within the biofilm. In the two model systems studied here, it is found that some of the patterns observed in selected ion images closely correlate with the occurrence and extent of corrosion in the carbon steel substrate as revealed by profilometry, while others do not. This approach toward the study of microbially influenced corrosion (MIC) holds great promise for approaching a fundamental understanding of the mechanisms involved in MIC.

Identification and characterization of microbial biofilm communities associated with corroded oil pipeline surfaces.

Microbially influenced corrosion (MIC) has long been implicated in the deterioration of carbon steel in oil and gas pipeline systems. The authors sought to identify and characterize sessile biofilm communities within a high-temperature oil production pipeline, and to compare the profiles of the biofilm community with those of the previously analyzed planktonic communities. Eubacterial and archaeal 16S rRNA sequences of DNA recovered from extracted pipeline pieces, termed 'cookies,' revealed the presence of thermophilic sulfidogenic anaerobes, as well as mesophilic aerobes. Electron microscopy and elemental analysis of cookies confirmed the presence of sessile cells and chemical constituents consistent with corrosive biofilms. Mass spectrometry of cookie acid washes identified putative hydrocarbon metabolites, while surface profiling revealed pitting and general corrosion damage. The results suggest that in an established closed system, the biofilm taxa are representative of the planktonic eubacterial and archaeal community, and that sampling and monitoring of the planktonic bacterial population can offer insight into biocorrosion activity. Additionally, hydrocarbon biodegradation is likely to sustain these communities. The importance of appropriate sample handling and storage procedures to oilfield MIC diagnostics is highlighted.

Electric-field-enhanced collection of laser-ablated materials onto a solvent bridge for electrospray ionization mass spectrometry.

RATIONALE: Ambient imaging mass spectrometry methods are critically dependent on the ability to efficiently collect all substances from a well-defined area of the sample. Improvements in this area are critical and enabling. METHODS: Methods for the efficient collection of laser-ablated materials directly into a solvent, for immediate transport to an ion source, have been explored using the application of electric fields. RESULTS: Electric-field-enhanced collection of laser-ablated materials has been demonstrated. Demonstrated increases in collection efficiency are as large as two orders of magnitude, in particular for hydrated biological materials, such as living bacterial colonies. This was achieved by applying approximately 1 kV between the sample and the receiving solvent surface. CONCLUSIONS: Electric-field-enhanced collection of laser-ablated materials holds great promise for ambient sampling and imaging mass spectrometry with rapid and direct interfacing to ionization sources, such as electrospray.

Metagenomic analysis and metabolite profiling of deep-sea sediments from the Gulf of Mexico following the Deepwater Horizon oil spill.

Marine subsurface environments such as deep-sea sediments, house abundant and diverse microbial communities that are believed to influence large-scale geochemical processes. These processes include the biotransformation and mineralization of numerous petroleum constituents. Thus, microbial communities in the Gulf of Mexico are thought to be responsible for the intrinsic bioremediation of crude oil released by the Deepwater Horizon (DWH) oil spill. While hydrocarbon contamination is known to enrich for aerobic, oil-degrading bacteria in deep-seawater habitats, relatively little is known about the response of communities in deep-sea sediments, where low oxygen levels may hinder such a response. Here, we examined the hypothesis that increased hydrocarbon exposure results in an altered sediment microbial community structure that reflects the prospects for oil biodegradation under the prevailing conditions. We explore this hypothesis using metagenomic analysis and metabolite profiling of deep-sea sediment samples following the DWH oil spill. The presence of aerobic microbial communities and associated functional genes was consistent among all samples, whereas, a greater number of Deltaproteobacteria and anaerobic functional genes were found in sediments closest to the DWH blowout site. Metabolite profiling also revealed a greater number of putative metabolites in sediments surrounding the blowout zone relative to a background site located 127 km away. The mass spectral analysis of the putative metabolites revealed that alkylsuccinates remained below detection levels, but a homologous series of benzylsuccinates (with carbon chain lengths from 5 to 10) could be detected. Our findings suggest that increased exposure to hydrocarbons enriches for Deltaproteobacteria, which are known to be capable of anaerobic hydrocarbon metabolism. We also provide evidence for an active microbial community metabolizing aromatic hydrocarbons in deep-sea sediments of the Gulf of Mexico.

Surface-assisted laser desorption/ionization mass spectrometry with a rotating ball interface.

A rotating ball interface for surface-assisted laser desorption/ionization (SALDI) mass spectrometry was designed and tested. One side of the ball was exposed to atmospheric pressure and the other to the vacuum in a time-of-flight mass spectrometer. Analytes (arginine, atenolol, reserpine, tofisopam, and chloropyramine) were applied using electrospray to a silicon substrate on the atmospheric side, the ball was rotated 180°, and the analyte was desorbed on the vacuum side using a pulsed, 200 Hz, 355 nm laser. In order to increase the desorption area, the laser focus was scanned over the substrate in a raster pattern repeated once every second. The design allows for rapid sample throughout with a sample turn-around time as short as 5 s. Newly produced porous silicon substrates initially yielded very low ion signals, and they required several hundred laser shots to attain maximum sensitivity. In contrast, amorphous silicon did not require such 'activation'. Quantitative analysis showed a sample-to-sample reproducibility of about 10%. The sensitivities with model analytes were in the 1000 to 10,000 ions/fmole range and detection limits in the low fg range.

Electrospray droplet impact/secondary ion mass spectrometry: cluster ion formation.

The electrospray droplets that are sampled through an orifice into the vacuum chamber are accelerated by 10 kV and impact on the stainless steel substrate. The mass and the kinetic energy of electrospray droplets are roughly estimated to be a few 10(6) u and approximately 10(6) eV, respectively. The molecular ion M(+.) and the protonated molecule [M+H](+) are observed as secondary ions for chrysene and coronene deposited on the metal substrate (no matrix used). The ionization may take place in the shock wave generated by the high-momentum coherent collision between the droplet projectile and the solid sample. Cluster ions of H(+)(H(2)O)(n) and CF(3)COO(-)(H(2)O)(n), with n up to approximately 150, were observed as secondary ions formed by the electrospray droplet impact ionization (EDI) for 10(-2) M trifluoroacetic acid (TFA) aqueous solution. This indicates that the charged droplets that collide with the metal substrate with the kinetic energy of approximately 10(6) eV do not vaporize completely but are disintegrated into many tiny microdroplets. The ion signal intensity anomalies (i.e. magic numbers) were observed for the cluster ions of H(3)O(+)(H(2)O)(n) and CF(3)COO(-)(H(2)O)(n) for 10(-2) M TFA aqueous solution and of Cs(+)(H(2)O)(n), I(-)(H(2)O)(n), Cs(+)(CsI)(n), and I(-)(CsI)(n) for 10(-2) M CsI aqueous solution.

On the distributions of ion/neutral molecule clusters in electrospray and laser spray -- a cluster division model for the electrospray process.

The clustering of a medium-sized, involatile, neutral molecule, octyl beta-D-glucopyranoside (OG), with Na(+), Ca(2+), and Yb(3+) (M(z+)) ions in electrospray (ESI) was investigated using laser spray (LSI). Extensive distributions of [(M(z+))(i) (OG)(a)](n+)-clusters, extending beyond 50 kDa, were observed. The distributions were highly stable and reproducible and changed only marginally when concentrations of electrolyte or neutral compound were varied by orders of magnitude. Compared with ESI, laser spray yielded superior intensities, particularly of the larger clusters. The cluster distributions demonstrated a range of remarkable features. In particular, the Yb(3+)/OG cluster distribution was unusual. For example, no clusters with 35-52 or with 110-116 OG molecules were observed. The distribution pattern revealed that the clusters were formed as a result of cluster dissociations, such as [(Yb(3+))(3)(OG) ( approximately 110)W](9+) --> [(Yb(3+))(2)(OG)( approximately 90)W](6+) + [(Yb(3+))(1)(OG) ( approximately 20)W](3+), where W represents the water content at the time of dissociation. Based on this study, a cluster division model for electrospray of aqueous solutions of strongly solvated ions is proposed: the Rayleigh droplet disintegration process, which is well-established for the initial stages of electrospray, maintains its general character as it proceeds through a final regime of multiply charged cluster dissociations to the singly and multiply charged ions in mass spectrometry. In the dissociation of multiply charged clusters, the size of each daughter cluster is roughly proportional to the square of the cluster charge. Observed cluster distributions are consistent with a mixture of symmetric and asymmetric cluster dissociations.

Electrospray-assisted laser desorption/ionization mass spectrometry for direct ambient analysis of solids.

A new method of electrospray-assisted laser desorption/ionization (ELDI) mass spectrometry, which combines laser desorption with post-ionization by electrospray, was applied to rapid analysis of solid materials under ambient conditions. Analytes were desorbed from solid metallic and insulating substrata using a pulsed nitrogen laser. Post-ionization produced high-quality mass spectra characteristic of electrospray, including protein multiple charging. For the first time, mass spectra of intact proteins were obtained using laser desorption without adding a matrix. Bovine cytochrome c and an illicit drug containing methaqualone were chosen in this study to demonstrate the applicability of ELDI to the analysis of proteins and synthetic organic compounds.

Microbe-surface interactions in biofouling and biocorrosion processes.

The presence of microorganisms on material surfaces can have a profound effect on materials performance. Surface-associated microbial growth, i.e. a biofilm, is known to instigate biofouling. The presence of biofilms may promote interfacial physico-chemical reactions that are not favored under abiotic conditions. In the case of metallic materials, undesirable changes in material properties due to a biofilm (or a biofouling layer) are referred to as biocorrosion or microbially influenced corrosion (MIC). Biofouling and biocorrosion occur in aquatic and terrestrial habitats varying in nutrient content, temperature, pressure and pH. Interfacial chemistry in such systems reflects a wide variety of physiological activities carried out by diverse microbial populations thriving within biofilms. Biocorrosion can be viewed as a consequence of coupled biological and abiotic electron-transfer reactions, i.e. redox reactions of metals, enabled by microbial ecology. Microbially produced extracellular polymeric substances (EPS), which comprise different macromolecules, mediate initial cell adhesion to the material surface and constitute a biofilm matrix. Despite their unquestionable importance in biofilm development, the extent to which EPS contribute to biocorrosion is not well-understood. This review offers a current perspective on material/microbe interactions pertinent to biocorrosion and biofouling, with EPS as a focal point, while emphasizing the role atomic force spectroscopy and mass spectrometry techniques can play in elucidating such interactions.

Microbe - surface interactions in biofouling and biocorrosion processes / Revisión de las interacciones entre microorganismos y superficies en los procesos de bioensuciamiento y de biocorrosión

The presence of microorganisms on material surfaces can have a profound effect on materials performance. Surface-associated microbial growth, i.e. a biofilm, is known to instigate biofouling. The presence of biofilms may promote interfacial physico-chemical reactions that are not favored under abiotic conditions. In the case of metallic materials, undesirable changes in material properties due to a biofilm (or a biofouling layer) are referred to as biocorrosion or microbially influenced corrosion (MIC). Biofouling and biocorrosion occur in aquatic and terrestrial habitats varying in nutrient content, temperature, pressure and pH. Interfacial chemistry in such systems reflects a wide variety of physiological activities carried out by diverse microbial populations thriving within biofilms. Biocorrosion can be viewed as a consequence of coupled biological and abiotic electron-transfer reactions, i.e. redox reactions of metals, enabled by microbial ecology. Microbially produced extracellular polymeric substances (EPS), which comprise different macromolecules, mediate initial cell adhesion to the material surface and constitute a biofilm matrix. Despite their unquestionable importance in biofilm development, the extent to which EPS contribute to biocorrosion is not well-understood. This review offers a current perspective on material/microbe interactions pertinent to biocorrosion and biofouling, with EPS as a focal point, while emphasizing the role atomic force spectroscopy and mass spectrometry techniques can play in elucidating such interactions (AU)

La presencia de microorganismos en las superficies de materiales puede tener un efecto profundo en el funcionamiento de dichos materiales. El crecimiento microbiano asociado a superficies, por ejemplo un biofilm, se sabe que estimula el desarrollo del bioensuciamiento (biofouling). La presencia de biofilms puede promover en las interfaces reacciones fisicoquímicas no favorecidas en condiciones abióticas. En el caso de materiales metálicos, los cambios no deseados en las características del material y debidos a un biofilm (o a una capa de bioensuciamiento) se denominan biocorrosión o corrosión microbiana (MIC, microbially influenced corrosion). El bioensuciamiento y la biocorrosión se producen en hábitat acuáticos y terrestres con diferentes contenidos de nutrientes, temperatura, presión y pH. En dichos sistemas, la química de las interfaces refleja una gran variedad de actividades fisiológicas realizadas por poblaciones microbianas diversas que crecen muy bien en los biofilms. La biocorrosión puede verse como la consecuencia de un conjunto de reacciones biológicas y abióticas de transferencia de electrones de los metales, por ejemplo reacciones redox, favorecidas por la ecología microbiana. Las sustancias poliméricas extracelulares (EPS) producidas por microorganismos, que comprenden diferentes macromoléculas, median la adherencia inicial de la célula a la superficie del material y constituyen la matriz del biofilm. A pesar de su importancia indiscutible en el desarrollo del biofilm, no se sabe muy bien hasta qué punto contribuyen las EPS a la biocorrosión. Esta revisión describe la percepción actual de las interacciones material/microorganismo relativas a la biocorrosión y al bioensuciamiento, centrándose en las EPS, y destacando el papel que las técnicas de espectroscopia de fuerza atómica y de espectrometría de masas pueden desempeñar en la aclaración de tales interacciones (AU)

Ion/molecule reactions in the orifice-skimmer region of an atmospheric pressure Penning ionization mass spectrometer.

Atmospheric pressure Penning ionization mass spectra of methanol were measured as functions of Ar or He gas pressure in the first vacuum chamber, the position of the skimmer, and the voltage applied between the orifice and the skimmer. When the orifice and the skimmer were coaxial with a distance of 4 mm, the distribution of CH3OH2+(CH3OH)n clusters was only weakly dependent on both Ar pressure (in the range of 19-220 Pa) and orifice-skimmer voltage (in the range of 1-45 V). The ion/molecule reaction CH3OH2+ + CH3OH --> CH3+(CH3OH) + H2O was observed in the free jet expansion, especially at high orifice-skimmer voltage values. When the orifice and the skimmer were off-centered and the distance between them was increased to 18 mm, the formation of large CH3OH2+(CH3OH)n clusters, as well as their dissociation, were seen. The endothermic proton transfer reaction, CH3+(CH3OH) + CH3OH --> CH3OH2+ + CH3OCH3, occurred at high orifice-skimmer voltage. The collision-induced dissociation of cluster ions by He gas in the first vacuum chamber was much more efficient than by Ar. These results demonstrated that the mass spectra are highly dependent on skimmer position and on orifice-skimmer voltage and that ions observed by mass spectrometry do not necessarily reflect the abundance of ions produced in the atmospheric pressure ion source.