Spectroscopic and Microscopic Characterization of Microbial Biofouling on Aircraft Fuel Tanks.

Avoiding microbial contamination and biofilm formation on the surfaces of aircraft fuel tanks is a major challenge in the aviation industry. The inevitable presence of water in fuel systems and nutrients provided by the fuel makes an ideal environment for bacteria, fungi, and yeast to grow. Understanding how microbes grow on different fuel tank materials is the first step to control biofilm formation in aviation fuel systems. In this study, biofilms of Pseudomonas putida, a model Gram-negative bacterium previously found in aircraft fuel tanks, were characterized on aluminum 7075-T6 surfaces, which is an alloy used by the aviation industry due to favorable properties including high strength and fatigue resistance. Scanning electron microscopy (SEM) coupled with energy-dispersive X-ray (EDX) showed that extracellular polymeric substances (EPS) produced by P. putida were important components of biofilms with a likely role in biofilm stability and adhesion to the surfaces. EDX analysis showed that the proportion of phosphorus with respect to nitrogen is higher in the EPS than in the bacterial cells. Additionally, different morphologies in biofilm formation were observed in the fuel phase compared to the water phase. Micro-Fourier transform infrared spectroscopy (micro-FTIR) analysis suggested that phosphoryl and carboxyl functional groups are fundamental for the irreversible attachment between the EPS of bacteria and the aluminum surface, by the formation of hydrogen bonds and inner-sphere complexes between the macromolecules and the aluminum surface. Based on the hypothesis that nucleic acids (particularly DNA) are an important component of EPS in P. putida biofilms, the impact of degrading extracellular DNA was tested. Treatment with the enzyme DNase I affected both water and fuel phase biofilms─with the cell structure disrupted in the aqueous phase, but cells remained attached to the aluminum coupons.

Molecular Binding of EuIII/CmIII by Stenotrophomonas bentonitica and Its Impact on the Safety of Future Geodisposal of Radioactive Waste.

Microbial communities occurring in reference materials for artificial barriers (e.g., bentonites) in future deep geological repositories of radioactive waste can influence the migration behavior of radionuclides such as curium (CmIII). This study investigates the molecular interactions between CmIII and its inactive analogue europium (EuIII) with the indigenous bentonite bacterium Stenotrophomonas bentonitica at environmentally relevant concentrations. Potentiometric studies showed a remarkably high concentration of phosphates at the bacterial cell wall compared to other bacteria, revealing the great potential of S. bentonitica for metal binding. Infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS) confirmed the role of phosphates and carboxylate groups from the cell envelope in the bioassociation of EuIII. Additionally, time-resolved laser-induced fluorescence spectroscopy (TRLFS) identified phosphoryl and carboxyl groups from bacterial envelopes, among other released complexing agents, to be involved in the EuIII and CmIII coordination. The ability of this bacterium to form a biofilm at the surface of bentonites allows them to immobilize trivalent lanthanide and actinides in the environment.

Highly stable noble metal nanoparticles dispersible in biocompatible solvents: synthesis of cationic phosphonium gold nanoparticles in water and DMSO.

In this work, we report the synthesis of novel cationic phosphonium gold nanoparticles dispersible in water and dimethyl sulfoxide (DMSO) for their potential use in biomedical applications. All the cationic-functionalising ligands currently reported in the literature are ammonium-based species. Here, the synthesis and characterisation of an alternative system, based on phosphonioalkylthiosulfate zwitterions and phosphonioalkylthioacetate were carried out. We have also demonstrated that our phosphonioalkylthiosulfate zwitterions readily disproportionate into phosphonioalkylthiolates in situ during the synthesis of gold nanoparticles produced by the borohydride reduction of gold(III) salts. The synthesis of the cationic gold nanoparticles using these phosphonium ligands was carried out in water and DMSO. UV-visible spectroscopic and TEM studies have shown that the phosphonioalkylthiolates bind to the surface of gold nanoparticles which are typically around 10 nm in diameter. The resulting cationic-functionalised gold nanoparticles are dispersible in aqueous media and in DMSO, which is the only organic solvent approved by the U.S. Food and Drug Administration (FDA) for drug carrier tests. This indicates their potential future use in biological applications. This work shows the synthesis of a new family of phosphonium-based ligands, which behave as cationic masked thiolate ligands in the functionalisation of gold nanoparticles. These highly stable colloidal cationic phosphonium gold nanoparticles dispersed in water and DMSO can offer a great opportunity for the design of novel biorecognition and drug delivery systems.

The effect of environmentally relevant conditions on PVP stabilised gold nanoparticles.

Nanoparticles are a major product from the nanotechnology industry and have been shown to have a potentially large environmental exposure and hazard. In this study, sterically stabilised polyvinyl pyrrolidone (PVP) 7 nm gold nanoparticles (NPs) were produced and characterised as prepared by surface plasmon resonance (SPR), size and aggregation, morphology and surface charge. Changes in these properties with changes in environmentally relevant conditions (pH, ionic strength, Ca concentration and fulvic acid presence) were quantified. These sterically stabilised NPs showed no aggregation with changes in pH or inorganic ions, even under high (0.1 M) Ca concentrations. In addition, the presence of fulvic acid resulted in no observable changes in SPR, size, aggregation or surface chemistry, suggesting limited interaction between the PVP stabilised nanoparticles and fulvic acid. Due to the lack of aggregation and interaction, these NPs are expected to be highly mobile and potentially bioavailable in the environment.

Characterization of cerium oxide nanoparticles-part 1: size measurements.

The present study gives an overview of some of the major aspects for consideration in the characterization of nanomaterials (NMs). Part 1 focuses on the measurement of particle size and size-related parameters using several analytical techniques such as transmission electron microscopy, atomic force microscopy, dynamic light scattering, X-ray diffraction, and Brunauer, Emmett, and Teller surface area measurements as applied to commercially available cerium oxide nanoparticles (NPs) and microparticles (MPs). Part 2 (see companion paper) considers nonsize-related characterization and analysis. The results are discussed in relation to the nature of the sample and preparation, and the analytical principles, limitations, and advantages of each technique. Accurate information on the particle size of the different fractions of a sample can be obtained by using a combination of different types of microscopy, spectroscopy, separation, and other techniques; this should inform ecotoxicological and environmental studies. The good agreement between the measured primary particle size of the NPs (~15 nm) by atomic force microscopy, transmission electron microscopy, X-ray diffraction, and Brunauer, Emmett, and Teller suggests that the primary particles are formed of semispherical single crystals. For MPs, all measurements agree that they are large particles in the range above the NPs (100 nm), with some difference between the measured sizes, possibly as a result of polydispersity effects. Additionally, our findings suggest that atomic force microscopy and transmission electron microscopy prepared by centrifugation methods provide consistent data at low concentrations when dynamic light scattering fails.

Characterization of cerium oxide nanoparticles-part 2: nonsize measurements.

Part 1 (see companion paper) of the present study discussed the application of a multimethod approach in characterizing the size of cerium oxide nanoparticles (NPs). However, other properties less routinely investigated, such as shape and morphology, structure, chemical composition, and surface properties, are likely to play an important role in determining the behavior, reactivity, and potential toxicity of these NPs. The present study describes the measurement of the aforementioned physicochemical properties of NPs (applied also to nanomaterials [NMs]) compared with micrometer particles (MPs). The authors use a wide range of techniques, including high resolution-transmission electron microscopy, scanning electron microscopy, atomic force microscopy, X-ray diffraction, X-ray energy dispersive spectroscopy, electron energy loss spectroscopy, X-ray photoelectron spectroscopy, and electrophoresis, and compare these techniques, their advantages, and their limitations, along with recommendations about how best to approach NM characterization, using an application to commercial cerium oxide NPs and MPs. Results show that both cerium oxide NPs and MPs are formed of single polyhedron or truncated polyhedron crystals. Cerium oxide NPs contain a mixture of Ce(3+) and Ce(4+) cations, whereas the MPs contain mainly Ce(4+) , which is potentially important in understanding the toxicity of cerium oxide NPs. The isoelectric point of cerium oxide NPs was approximately pH 8, which explains their propensity to aggregate in aqueous media (see companion paper).

Interspecies comparisons on the uptake and toxicity of silver and cerium dioxide nanoparticles.

An increasing number and quantity of manufactured nanoparticles are entering the environment as the diversity of their applications increases, and this will lead to the exposure of both humans and wildlife. However, little is known regarding their potential health effects. We compared the potential biological effects of silver (Ag; nominally 35 and 600-1,600 nm) and cerium dioxide (CeO(2;) nominally <25 nm and 1-5 µm) particles in a range of cell (human hepatocyte and intestinal and fish hepatocyte) and animal (Daphnia magna, Cyprinus carpio) models to assess possible commonalities in toxicity across taxa. A variety of analytical techniques were employed to characterize the particles and investigate their biological uptake. Silver particles were more toxic than CeO(2) in all test systems, and an equivalent mass dose of Ag nanoparticles was more toxic than larger micro-sized material. Cellular uptake of all materials tested was shown in C3A hepatocytes and Caco-2 intestinal cells, and for Ag, into the intestine, liver, gallbladder, and gills of carp exposed via the water. The commonalities in toxicity of these particle types across diverse biological systems suggest that cross-species extrapolations may be possible for metal nanoparticle test development in the future. Our findings also suggest transport of particles through the gastrointestinal barrier, which is likely to be an important uptake route when assessing particle risk.

Characterizing manufactured nanoparticles in the environment: multimethod determination of particle sizes.

Sizes of stabilized (24 h) nanoparticle suspensions were determined using several state-of-the-art analytical techniques (transmission electron microscopy; atomic force microscopy; dynamic light scattering; fluorescence correlation spectroscopy; nanoparticle tracking analysis; flow field flow fractionation). Theoretical and analytical considerations were evaluated, results were compared, and the advantages and limitations of the techniques were discussed. No "ideal" technique was found for characterizing manufactured nanoparticles in an environmental context as each technique had its own advantages and limitations.

Manufactured nanoparticles: an overview of their chemistry, interactions and potential environmental implications.

The industrial scale production and wide variety of applications of manufactured nanoparticles (NPs) and their possible release in considerable amounts into the natural aquatic environment have produced an increasing concern among the nanotechnology and environmental science community. In order to address this issue, it is important to understand NP chemistry, preparation, reactivity and possible mechanisms involved in their interaction with the naturally occurring aquatic components, particularly natural colloids and NPs present in the aquatic systems. In this review, an overview of the chemistry of both manufactured and natural aquatic NPs is outlined. This review discusses the physico-chemical aspects of both type of NPs as an essential point to assess possible routes involved in manufactured NP fate in the natural aquatic environment and their toxicity. Key advances related to the characterisation of the manufactured NPs and natural colloids.

Formation of alpha-dicarbonyl compounds in beer during storage of Pilsner.

With the aim of determining the formation of alpha-dicarbonyl intermediates during beer aging on the shelf, alpha-dicarbonyls were identified and quantified after derivatization with 1,2-diaminobenze to generate quinoxalines. The sensory effects of alpha-dicarbonyls were evaluated by the quantification of key Strecker aldehydes and by GC-olfactometry (GCO)analysis of beer headspace using solid phase microextraction. Four alpha-dicarbonyls, reported here for the first time, were detected in fresh and aged beers, three were derived from the 2,3-enolization pathway of mono- and disaccharides, and the fourth was derived from the epimerization of 3-deoxy-2-hexosulose. Ten alpha-dicarbonyls were quantified during beer processing and during different periods of beer aging at 28 degrees C. The aging periods were from 15 to 105 days. During beer aging, 1-deoxydiuloses were produced and degraded, while 1,4-dideoxydiuloses were produced at the highest rates. The GCO analysis indicated that forced beer aging increased the amounts of furaneol, trans-2-nonenal, and phenylacetaldehyde. The blockage of alpha-dicarbonyls inhibited the accumulation of sensory-active aldehydes in the beer headspace.

Phosphonioalkylthiosulfate zwitterions--new masked thiol ligands for the formation of cationic functionalised gold nanoparticles.

We report the synthesis and structural characterisation of a new family of stable phosphonioalkylthiosulfate zwitterions, R3P+ (CH2)nS2O3- (R = Ph or Bu, n = 3,4,6, 8 or 10) which behave as cationic masked thiolate ligands with applications in the functionalisation of gold nanoparticles, having potential as new diagnostic biorecognition systems. The ligands were prepared by treatment of omega-bromoalkylphosphonium salts with sodium thiosulfate. The crystal and molecular structures of the zwitterions (R = Ph, n = 3) and (R = Bu, n = 3) were determined. A series of phosphonioalkanethiolate-capped gold nanoparticles dispersed in water was prepared by borohydride reduction of potassium tetrachloroaurate in the presence of the zwitterions in a dichloromethane-water system. UV-visible spectroscopy and scanning transmission electron-microscopy indicated that capped nanoparticles of ca. 5 nm diameter were present.