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.

Combined bioreduction and volatilization of SeVI by Stenotrophomonas bentonitica: Formation of trigonal selenium nanorods and methylated species.

Nowadays, metal pollution due to the huge release of toxic elements to the environment has become one of the world's biggest problems. Bioremediation is a promising tool for reducing the mobility and toxicity of these contaminants (e.g. selenium), being an efficient, environmentally friendly, and inexpensive strategy. The present study describes the capacity of Stenotrophomonas bentonitica to biotransform SeVI through enzymatic reduction and volatilization processes. HAADF-STEM analysis showed the bacterium to effectively reduce SeVI (200 mM) into intra- and extracellular crystalline Se0 nanorods, made mainly of two different Se allotropes: monoclinic (m-Se) and trigonal (t-Se). XAS analysis appears to indicate a Se crystallization process based on the biotransformation of amorphous Se0 into stable t-Se nanorods. In addition, results from headspace analysis by gas chromatography-mass spectometry (GC-MS) revealed the formation of methylated volatile Se species such as DMSe (dimethyl selenide), DMDSe (dimethyl diselenide), and DMSeS (dimethyl selenenyl sulphide). The biotransformation pathways and tolerance are remarkably different from those reported with this bacterium in the presence of SeIV. The formation of crystalline Se0 nanorods could have positive environmental implications (e.g. bioremediation) through the production of Se of lower toxicity and higher settleability with potential industrial applications.

Enhanced hydrogenation catalyst synthesized by Desulfovibrio desulfuricans exposed to a radio frequency magnetic field.

Desulfovibrio desulfuricans reduces Pd(II) to Pd(0)-nanoparticles (Pd-NPs) which are catalytically active in 2-pentyne hydrogenation. To make Pd-NPs, resting cells are challenged with Pd(II) ions (uptake), followed by addition of electron donor to promote bioreduction of cell-bound Pd(II) to Pd(0) (bio-Pd). Application of radiofrequency (RF) radiation to prepared 5 wt% bio-Pd catalyst (60 W power, 60 min) increased the hydrogenation rate by 70% with no adverse impact on selectivity to cis-2-pentene. Such treatment of a 5 wt% Pd/carbon commercial catalyst did not affect the conversion rate but reduced the selectivity. Lower-dose RF radiation (2-8 W power, 20 min) was applied to the bacteria at various stages before and during synthesis of the bio-scaffolded Pd-NPs. The reaction rate (µ mol 2-pentyne converted s-1 ) was increased by ~threefold by treatment during bacterial catalyst synthesis. Application of RF radiation (2 or 4 W power) to resting cells prior to Pd(II) exposure affected the catalyst made subsequently, increasing the reaction rate by 50% as compared to untreated cells, while nearly doubling selectivity for cis 2-pentene. The results are discussed with respect to published and related work which shows altered dispersion of the Pd-NPs made following or during RF exposure.

The Bioreduction of Selenite under Anaerobic and Alkaline Conditions Analogous to Those Expected for a Deep Geological Repository System.

The environmental conditions for the planned geological disposal of radioactive waste -including hyper-alkaline pH, radiation or anoxia-are expected to be extremely harsh for microbial activity. However, it is thought that microbial communities will develop in these repositories, and this would have implications for geodisposal integrity and the control of radionuclide migration through the surrounding environment. Nuclear waste contains radioactive isotopes of selenium (Se) such as 79Se, which has been identified as one of the main radionuclides in a geodisposal system. Here, we use the bacterial species Stenotrophomonas bentonitica, isolated from bentonites serving as an artificial barrier reference material in repositories, to study the reduction of selenite (SeIV) under simulated geodisposal conditions. This bacterium is able to reduce toxic SeIV anaerobically from a neutral to alkaline initial pH (up to pH 10), thereby producing elemental selenium (Se0) nanospheres and nanowires. A transformation process from amorphous Se (a-Se) nanospheres to trigonal Se (t-Se) nanowires, through the formation of monoclinic Se (m-Se) aggregates as an intermediate step, is proposed. The lesser solubility of Se0 and t-Se makes S. bentonitica a potential candidate to positively influence the security of a geodisposal system, most probably with lower efficiency rates than those obtained aerobically.

Synthesis of Pd/Ru Bimetallic Nanoparticles by Escherichia coli and Potential as a Catalyst for Upgrading 5-Hydroxymethyl Furfural Into Liquid Fuel Precursors.

Escherichia coli cells support the nucleation and growth of ruthenium and ruthenium-palladium nanoparticles (Bio-Ru and Bio-Pd/Ru NPs). We report a method for the synthesis of these monometallic and bimetallic NPs and their application in the catalytic upgrading of 5-hydroxymethyl furfural (5-HMF) to 2,5 dimethylfuran (DMF). Examination using high resolution transmission electron microscopy with energy dispersive X-ray microanalysis (EDX) and high angle annular dark field (HAADF) showed Ru NPs located mainly at the cell surface using Ru(III) alone but small intracellular Ru-NPs (size ∼1-2 nm) were visible only in cells that had been pre-"seeded" with Pd(0) (5 wt%) and loaded with equimolar Ru. Pd(0) NPs were distributed between the cytoplasm and cell surface. Cells bearing 5% Pd/5% Ru showed some co-localization of Pd and Ru but chance associations were not ruled out. Cells loaded to 5 wt% Pd/20 wt% Ru showed evidence of core-shell structures (Ru core, Pd shell). Examination of this cell surface material using X-ray photoelectron spectroscopy (XPS) showed Pd(0) and Pd(II) and Ru(IV) and Ru(III), with confirmation by analysis of bulk material using X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) analyses. Both Bio-Ru NPs and Bio-Pd/Ru NPs were active in the conversion of 5-HMF into 2,5-DMF but commercial Ru on carbon catalyst outperformed 5 wt% bio-Ru by fourfold. While 5 wt% Pd/20 wt% Ru achieved 20% yield of DMF the performance of the 5 wt% Pd/5 wt% Ru bio-catalyst was higher and comparable to the commercial 5 wt% Ru/C catalyst in a test reaction using commercial 5-HMF (>50% selectivity). 5-HMF was prepared by thermochemical hydrolysis of starch and cellulose with solvent extraction of 5-HMF into methyltetrahydrofuran (MTHF). Here, with MTHF as the reaction solvent the commercial Ru/C catalyst had little activity (100% conversion, negligible selectivity to DMF) whereas the 5 wt% Pd/5 wt% Ru bio-bimetallic gave 100% conversion and 14% selectivity to DMF from material extracted from hydrolyzates. The results indicate a potential green method for realizing increased energy potential from biomass wastes as well as showing a bio-based pathway to manufacturing a scarcely described bimetallic material.

Characterization of Palladium Nanoparticles Produced by Healthy and Microwave-Injured Cells of Desulfovibrio desulfuricans and Escherichia coli.

Numerous studies have focused on the bacterial synthesis of palladium nanoparticles (bio-Pd NPs), via uptake of Pd (II) ions and their enzymatically-mediated reduction to Pd (0). Cells of Desulfovibrio desulfuricans (obligate anaerobe) and Escherichia coli (facultative anaerobe, grown anaerobically) were exposed to low-dose radiofrequency (RF) radiation(microwave (MW) energy) and the biosynthesized Pd NPs were compared. Resting cells were exposed to microwave energy before Pd (II)-challenge. MW-injured Pd (II)-treated cells (and non MW-treated controls) were contacted with H2 to promote Pd(II) reduction. By using scanning transmission electron microscopy (STEM) associated with a high-angle annular dark field (HAADF) detector and energy dispersive X-ray (EDX) spectrometry, the respective Pd NPs were compared with respect to their mean sizes, size distribution, location, composition, and structure. Differences were observed following MWinjury prior to Pd(II) exposure versus uninjured controls. With D. desulfuricans the bio-Pd NPs formed post-injury showed two NP populations with different sizes and morphologies. The first, mainly periplasmically-located, showed polycrystalline Pd nano-branches with different crystal orientations and sizes ranging between 20 and 30 nm. The second NPpopulation, mainly located intracellularly, comprised single crystals with sizes between 1 and 5 nm. Bio-Pd NPs were produced mainly intracellularly by injured cells of E. coli and comprised single crystals with a size distribution between 1 and 3 nm. The polydispersity index was reduced in the bio-Pd made by injured cells of E. coli and D. desulfuricans to 32% and 39%, respectively, of the values of uninjured controls, indicating an increase in NP homogeneity of 30-40% as a result of the prior MWinjury. The observations are discussed with respect to the different locations of Pd(II)-reducing hydrogenases in the two organisms and with respect to potential implications for the catalytic activity of the produced NPs following injury-associated altered NP patterning.

Upconversion of Cellulosic Waste Into a Potential "Drop in Fuel" via Novel Catalyst Generated Using Desulfovibrio desulfuricans and a Consortium of Acidophilic Sulfidogens.

Biogas-energy is marginally profitable against the "parasitic" energy demands of processing biomass. Biogas involves microbial fermentation of feedstock hydrolyzate generated enzymatically or thermochemically. The latter also produces 5-hydroxymethyl furfural (5-HMF) which can be catalytically upgraded to 2, 5-dimethyl furan (DMF), a "drop in fuel." An integrated process is proposed with side-stream upgrading into DMF to mitigate the "parasitic" energy demand. 5-HMF was upgraded using bacterially-supported Pd/Ru catalysts. Purpose-growth of bacteria adds additional process costs; Pd/Ru catalysts biofabricated using the sulfate-reducing bacterium (SRB) Desulfovibrio desulfuricans were compared to those generated from a waste consortium of acidophilic sulfidogens (CAS). Methyl tetrahydrofuran (MTHF) was used as the extraction-reaction solvent to compare the use of bio-metallic Pd/Ru catalysts to upgrade 5-HMF to DMF from starch and cellulose hydrolyzates. MTHF extracted up to 65% of the 5-HMF, delivering solutions, respectively, containing 8.8 and 2.2 g 5-HMF/L MTHF. Commercial 5% (wt/wt) Ru-carbon catalyst upgraded 5-HMF from pure solution but it was ineffective against the hydrolyzates. Both types of bacterial catalyst (5wt%Pd/3-5wt% Ru) achieved this, bio-Pd/Ru on the CAS delivering the highest conversion yields. The yield of 5-HMF from starch-cellulose thermal treatment to 2,5 DMF was 224 and 127 g DMF/kg extracted 5-HMF, respectively, for CAS and D. desulfuricans catalysts, which would provide additional energy of 2.1 and 1.2 kWh/kg extracted 5-HMF. The CAS comprised a mixed population with three patterns of metallic nanoparticle (NP) deposition. Types I and II showed cell surface-localization of the Pd/Ru while type III localized NPs throughout the cell surface and cytoplasm. No metallic patterning in the NPs was shown via elemental mapping using energy dispersive X-ray microanalysis but co-localization with sulfur was observed. Analysis of the cell surfaces of the bulk populations by X-ray photoelectron spectroscopy confirmed the higher S content of the CAS bacteria as compared to D. desulfuricans and also the presence of Pd-S as well as Ru-S compounds and hence a mixed deposit of PdS, Pd(0), and Ru in the form of various +3, +4, and +6 oxidation states. The results are discussed in the context of recently-reported controlled palladium sulfide ensembles for an improved hydrogenation catalyst.

Novel catalytically active Pd/Ru bimetallic nanoparticles synthesized by Bacillus benzeovorans.

Bacillus benzeovorans assisted and supported growth of ruthenium (bio-Ru) and palladium/ruthenium (bio-Pd@Ru) core@shell nanoparticles (NPs) as bio-derived catalysts. Characterization of the bio-NPs using various electron microscopy techniques and high-angle annular dark field (HAADF) analysis confirmed two NP populations (1-2 nm and 5-8 nm), with core@shells in the latter. The Pd/Ru NP lattice fringes, 0.231 nm, corresponded to the (110) plane of RuO2. While surface characterization using X-ray photoelectron spectroscopy (XPS) showed the presence of Pd(0), Pd(II), Ru(III) and Ru(VI), X-ray absorption (XAS) studies of the bulk material confirmed the Pd speciation (Pd(0) and Pd(II)- corresponding to PdO), and identified Ru as Ru(III) and Ru(IV). The absence of Ru-Ru or Ru-Pd peaks indicated Ru only exists in oxide forms (RuO2 and RuOH), which are surface-localized. X ray diffraction (XRD) patterns did not identify Pd-Ru alloying. Preliminary catalytic studies explored the conversion of 5-hydroxymethyl furfural (5-HMF) to the fuel precursor 2,5-dimethyl furan (2,5-DMF). Both high-loading (9.7 wt.% Pd, 6 wt.% Ru) and low-loading (2.4 wt.% Pd, 2 wt.% Ru) bio-derived catalysts demonstrated high conversion efficiencies (~95%) and selectivity of ~63% (~20% better than bio-Ru NPs) and 58%, respectively. These materials show promising future scope as efficient low-cost biofuel catalysts.