scholarly journals U(VI) Reduction by Diverse Outer Surfacec-Type Cytochromes of Geobacter sulfurreducens

2013 ◽  
Vol 79 (20) ◽  
pp. 6369-6374 ◽  
Author(s):  
Roberto Orellana ◽  
Janet J. Leavitt ◽  
Luis R. Comolli ◽  
Roseann Csencsits ◽  
Noemie Janot ◽  
...  

ABSTRACTEarly studies withGeobacter sulfurreducenssuggested that outer-surfacec-type cytochromes might play a role in U(VI) reduction, but it has recently been suggested that there is substantial U(VI) reduction at the surface of the electrically conductive pili known as microbial nanowires. This phenomenon was further investigated. A strain ofG. sulfurreducens, known as Aro-5, which produces pili with substantially reduced conductivity reduced U(VI) nearly as well as the wild type, as did a strain in which the gene for PilA, the structural pilin protein, was deleted. In order to reduce rates of U(VI) reduction to levels less than 20% of the wild-type rates, it was necessary to delete the genes for the five most abundant outer surfacec-type cytochromes ofG. sulfurreducens. X-ray absorption near-edge structure spectroscopy demonstrated that whereas 83% ± 10% of the uranium associated with wild-type cells correspond to U(IV) after 4 h of incubation, with the quintuple mutant, 89% ± 10% of uranium was U(VI). Transmission electron microscopy and X-ray energy dispersion spectroscopy revealed that wild-type cells did not precipitate uranium along pili as previously reported, but U(IV) was precipitated at the outer cell surface. These findings are consistent with those of previous studies, which have suggested thatG. sulfurreducensrequires outer-surfacec-type cytochromes but not pili for the reduction of soluble extracellular electron acceptors.

2012 ◽  
Vol 79 (3) ◽  
pp. 901-907 ◽  
Author(s):  
Jessica A. Smith ◽  
Derek R. Lovley ◽  
Pier-Luc Tremblay

ABSTRACTGeobacterspecies are important Fe(III) reducers in a diversity of soils and sediments. Mechanisms for Fe(III) oxide reduction have been studied in detail inGeobacter sulfurreducens, but a number of the most thoroughly studied outer surface components ofG. sulfurreducens, particularlyc-type cytochromes, are not well conserved amongGeobacterspecies. In order to identify cellular components potentially important for Fe(III) oxide reduction inGeobacter metallireducens, gene transcript abundance was compared in cells grown on Fe(III) oxide or soluble Fe(III) citrate with whole-genome microarrays. Outer-surface cytochromes were also identified. Deletion of genes forc-type cytochromes that had higher transcript abundance during growth on Fe(III) oxides and/or were detected in the outer-surface protein fraction identified sixc-type cytochrome genes, that when deleted removed the capacity for Fe(III) oxide reduction. Several of thec-type cytochromes which were essential for Fe(III) oxide reduction inG. metallireducenshave homologs inG. sulfurreducensthat are not important for Fe(III) oxide reduction. Other genes essential for Fe(III) oxide reduction included a gene predicted to encode an NHL (Ncl-1–HT2A–Lin-41) repeat-containing protein and a gene potentially involved in pili glycosylation. Genes associated with flagellum-based motility, chemotaxis, and pili had higher transcript abundance during growth on Fe(III) oxide, consistent with the previously proposed importance of these components in Fe(III) oxide reduction. These results demonstrate that there are similarities in extracellular electron transfer betweenG. metallireducensandG. sulfurreducensbut the outer-surfacec-type cytochromes involved in Fe(III) oxide reduction are different.


2020 ◽  
Vol 86 (18) ◽  
Author(s):  
Richard L. Kimber ◽  
Heath Bagshaw ◽  
Kurt Smith ◽  
Dawn M. Buchanan ◽  
Victoria S. Coker ◽  
...  

ABSTRACT Biomineralization of Cu has been shown to control contaminant dynamics and transport in soils. However, very little is known about the role that subsurface microorganisms may play in the biogeochemical cycling of Cu. In this study, we investigate the bioreduction of Cu(II) by the subsurface metal-reducing bacterium Geobacter sulfurreducens. Rapid removal of Cu from solution was observed in cell suspensions of G. sulfurreducens when Cu(II) was supplied, while transmission electron microscopy (TEM) analyses showed the formation of electron-dense nanoparticles associated with the cell surface. Energy-dispersive X-ray spectroscopy (EDX) point analysis and EDX spectrum image maps revealed that the nanoparticles are rich in both Cu and S. This finding was confirmed by X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) analyses, which identified the nanoparticles as Cu2S. Biomineralization of CuxS nanoparticles in soils has been reported to enhance the colloidal transport of a number of contaminants, including Pb, Cd, and Hg. However, formation of these CuxS nanoparticles has only been observed under sulfate-reducing conditions and could not be repeated using isolates of implicated organisms. As G. sulfurreducens is unable to respire sulfate, and no reducible sulfur was supplied to the cells, these data suggest a novel mechanism for the biomineralization of Cu2S under anoxic conditions. The implications of these findings for the biogeochemical cycling of Cu and other metals as well as the green production of Cu catalysts are discussed. IMPORTANCE Dissimilatory metal-reducing bacteria are ubiquitous in soils and aquifers and are known to utilize a wide range of metals as terminal electron acceptors. These transformations play an important role in the biogeochemical cycling of metals in pristine and contaminated environments and can be harnessed for bioremediation and metal bioprocessing purposes. However, relatively little is known about their interactions with Cu. As a trace element that becomes toxic in excess, Cu can adversely affect soil biota and fertility. In addition, biomineralization of Cu nanoparticles has been reported to enhance the mobilization of other toxic metals. Here, we demonstrate that when supplied with acetate under anoxic conditions, the model metal-reducing bacterium Geobacter sulfurreducens can transform soluble Cu(II) to Cu2S nanoparticles. This study provides new insights into Cu biomineralization by microorganisms and suggests that contaminant mobilization enhanced by Cu biomineralization could be facilitated by Geobacter species and related organisms.


2020 ◽  
Author(s):  
Yuta Uetake ◽  
Sachi Mouri ◽  
Setsiri Haesuwannakij ◽  
Kazu Okumura ◽  
Hidehiro Sakurai

<div>Although changing the size of metal nanoparticle (NP) is a reasonable way to tune and/or enhance their catalytic activity, size-selective preparation of NP possessing random-alloy morphology has been challenging because of the differences in the ionization potential of each metal ion. This study demonstrates a time-controlled aggregation–stabilization method for a size-selective preparation of random alloy NPs composed of Au and Pd, which are stabilized by poly(<i>N</i>-vinyl-2-pyrrolidone) (PVP). By adjusting the mixing time in the presence of a small amount of PVP, the aggregation was induced to produce AuPd:PVP with sizes ranging between 1.2 and 8.2 nm at approximately 1 nm intervals. Transmission electron microscopy (TEM), powder X-ray diffraction (PXRD), and extended x-ray absorption fine structure (EXAFS) analyses clearly indicated the formation of various sizes of AuPd nanoalloys with almost the same morphology, and size-dependent catalytic activity was observed when hydrodechlorination of 4-choroanisole was performed using 2-propanol as a reducing agent. AuPd:PVP with a size of 3.1 nm exhibited the highest catalytic activity. A comparison of the absorption edges on x-ray absorption near edge structure (XANES) spectra suggested that the electronic state of the Au and Pd species correlated with their catalytic activity, presumably affecting the rate-determining step.</div><div> </div>


2015 ◽  
Vol 5 (1) ◽  
pp. 20140046 ◽  
Author(s):  
Sami Rtimi ◽  
Jelena Nesic ◽  
Cesar Pulgarin ◽  
Rosendo Sanjines ◽  
Michael Bensimon ◽  
...  

Evidence is presented for radio-frequency plasma pretreatment enhancing the amount and adhesion of TiO 2 sputtered on polyester (PES) and on polyethylene (PE) films. Pretreatment is necessary to attain a suitable TiO 2 loading leading to an acceptable Escherichia coli reduction kinetics in the dark or under light irradiation for PES–TiO 2 and PE–TiO 2 samples. The amount of TiO 2 on the films was monitored by diffuse reflectance spectroscopy and X-ray fluorescence. X-ray electron spectroscopy shows the lack of accumulation of bacterial residues such as C, N and S during bacterial inactivation since they seem to be rapidly destroyed by TiO 2 photocatalysis. Evidence was found for Ti 4+ /Ti 3+ redox catalysis occurring on PES–TiO 2 and PE–TiO 2 during the bacterial inactivation process. On PE–TiO 2 surfaces, Fourier transform infrared spectroscopy (ATR-FTIR) provides evidence for a systematic shift of the n a (CH 2 ) stretching vibrations preceding bacterial inactivation within 60 min. The discontinuous IR-peak shifts reflect the increase in the C–H inter-bond distance leading to bond scission. The mechanism leading to E. coli loss of viability on PES–TiO 2 was investigated in the dark up to complete bacterial inactivation by monitoring the damage in the bacterial outer cell by transmission electron microscopy. After 30 min, the critical step during the E. coli inactivation commences for dark disinfection on 0.1–5% wt PES–TiO 2 samples. The interactions between the TiO 2 aggregates and the outer lipopolysaccharide cell wall involve electrostatic effects competing with the van der Waals forces.


2000 ◽  
Vol 6 (S2) ◽  
pp. 440-441
Author(s):  
D. M. Cao ◽  
J. C. Jiang ◽  
B. Feng ◽  
W. J. Meng

Application of an appropriate ceramic surface coating to mechanical components such as bearings and gears can provide longer life and increased performance reliability. Metal-containing hydrocarbon (Me-C:H) coatings possess high hardness, together with low friction and low wear rate. They have also been suggested to adhere better to metallic substrates. This combination of attractive mechanical/tribological properties makes Me-C:H coatings potentially useful for surface modification of a wide range of mechanical components.Using the technique of inductively coupled plasma (ICP) assisted vapor deposition[1], we have synthesized Ti-containing hydrocarbon (Ti-C:H) coatings with a wide range of Ti compositions[2]. Coating mechanical properties such as modulus and hardness have been measured by the technique of nanoindentation and correlated to Ti and hydrogen compositions[2,3].We have performed detailed microstructural examination of Ti-C:H coatings by transmission electron microscopy (TEM), Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy, and X-ray Absorption Near Edge Structure (XANES) spectroscopy.


2018 ◽  
Vol 70 (3) ◽  
pp. 512-518 ◽  
Author(s):  
Alaa Mohamed ◽  
Mohamed Hamdy ◽  
Mohamed Bayoumi ◽  
Tarek Osman

Purpose To enhance the tribological properties of nanogrease, one of the new technologies was used to synthesize a nanogrease having carbon nanotubes (CNTs) nanoparticles (NPs) with different concentrations. The microstructures of the synthesized NPs were characterized and evaluated by x-ray diffraction spectroscopy (XRD) and transmission electron microscopy (TEM). Tribological properties of the nanogrease were evaluated using a four-ball tester. The worn surface of four steel balls was investigated by scanning electron microscopy (SEM) and energy dispersive x-ray spectroscopy (EDX). Design/methodology/approach Grease was dissolved in chloroform (10 Wt.%), at 25 °C for 1 h. In parallel, functionalized CNTs with different volume concentrations (0.5, 1, 2 and 3 Wt.%) were dispersed in N, N-dimethylformamide. The mixture was stirred for 15 min and then sonicated (40 kHz, 150 W) for 30 min. After that, the mixture was added to the grease solution and magnetically stirred for 15 min and then sonicated for 2 h. Findings The results suggested that CNTs can enhance the antiwear and friction properties of nanogrease at 0.5 Wt.% CNTs to about 57 and 48 per cent, respectively. In addition, the weld load of the base oil containing 0.5 Wt.% CNTs was improved by 17 per cent compared with base grease. Originality/value This work describes the inexpensive and simple fabrication of nanogrease for improving the properties of lubricants, which improve power efficiency and extend lifetimes of mechanical equipment.


2011 ◽  
Vol 77 (16) ◽  
pp. 5584-5590 ◽  
Author(s):  
Liang Shi ◽  
Sara M. Belchik ◽  
Andrew E. Plymale ◽  
Steve Heald ◽  
Alice C. Dohnalkova ◽  
...  

ABSTRACTShewanella oneidensisMR-1 possesses a periplasmic [NiFe]-hydrogenase (MR-1 [NiFe]-H2ase) that has been implicated in H2production and oxidation as well as technetium [Tc(VII)] reduction. To characterize the roles of MR-1 [NiFe]-H2ase in these proposed reactions, the genes encoding both subunits of MR-1 [NiFe]-H2ase were cloned and then expressed in an MR-1 mutant withouthyaBandhydAgenes. Expression of recombinant MR-1 [NiFe]-H2ase intransrestored the mutant's ability to produce H2at 37% of that for the wild type. Following purification, MR-1 [NiFe]-H2ase coupled H2oxidation to reduction of Tc(VII)O4−and methyl viologen. Change of the buffers used affected MR-1 [NiFe]-H2ase-mediated reduction of Tc(VII)O4−but not methyl viologen. Under the conditions tested, all Tc(VII)O4−used was reduced in Tris buffer, while in HEPES buffer, only 20% of Tc(VII)O4−was reduced. The reduced products were soluble in Tris buffer but insoluble in HEPES buffer. Transmission electron microscopy analysis revealed that Tc precipitates reduced in HEPES buffer were aggregates of crystallites with diameters of ∼5 nm. Measurements with X-ray absorption near-edge spectroscopy revealed that the reduction products were a mixture of Tc(IV) and Tc(V) in Tris buffer but only Tc(IV) in HEPES buffer. Measurements with extended X-ray adsorption fine structure showed that while the Tc bonding environment in Tris buffer could not be determined, the Tc(IV) product in HEPES buffer was very similar to Tc(IV)O2·nH2O, which was also the product of Tc(VII)O4−reduction by MR-1 cells. These results shows for the first time that MR-1 [NiFe]-H2ase catalyzes Tc(VII)O4−reduction directly by coupling to H2oxidation.


2013 ◽  
Vol 79 (20) ◽  
pp. 6385-6390 ◽  
Author(s):  
Gudrun Lisa Bovenkamp ◽  
Ulrike Zanzen ◽  
Katla Sai Krishna ◽  
Josef Hormes ◽  
Alexander Prange

ABSTRACTSilver ions are widely used as antibacterial agents, but the basic molecular mechanism of this effect is still poorly understood. X-ray absorption near-edge structure (XANES) spectroscopy at the AgLIII, SK, and PKedges reveals the chemical forms of silver inStaphylococcus aureusandEscherichia coli(Ag+treated). The AgLIII-edge XANES spectra of the bacteria are all slightly different and very different from the spectra of silver ions (silver nitrate and silver acetate), which confirms that a reaction occurs. Death or inactivation of bacteria was observed by plate counting and light microscopy. Silver bonding to sulfhydryl groups (Ag-S) in cysteine and Ag-N or Ag-O bonding in histidine, alanine, anddl-aspartic acid was detected by using synthesized silver-amino acids. Significantly lower silver-cysteine content, coupled with higher silver-histidine content, in Gram-positiveS. aureusandListeria monocytogenescells indicates that the peptidoglycan multilayer could be buffering the biocidal effect of silver on Gram-positive bacteria, at least in part. Bonding of silver to phosphate groups was not detected. Interaction with DNA or proteins can occur through Ag-N bonding. The formation of silver-cysteine can be confirmed for both bacterial cell types, which supports the hypothesis that enzyme-catalyzed reactions and the electron transport chain within the cell are disrupted.


2014 ◽  
Vol 70 (a1) ◽  
pp. C66-C66
Author(s):  
Maria Elena Montero-Cabrera ◽  
Isai Castillo-Sandoval ◽  
Luis Fuentes-Cobas ◽  
Hilda Esparza-Ponce ◽  
Maria Elena Fuentes-Montero ◽  
...  

The Cave of Swords was discovered in 1910 at Naica mine, Chihuahua, Mexico. Its name refers to the look of the 1-2 m long crystals the cave had when it was discovered. Currently the crystals are 0.1-0.3 m long. The crystals surface is opaque and ocher. For over 100 years these crystals continue to amaze and give us clues about their formation. This work is part of a research aimed at the conservation of the Naica Giant Crystals. Thirteen samples from the Cave of Swords were analyzed by Scanning Electron Microscopy with Energy Dispersive Spectroscopy (SEM-EDS), Confocal Laser Microscopy with Differential Interference Contrast (LCM-DIM) and Transmission Electron Microscopy (TEM). X-Ray Fluorescence (μ-XRF) together with X-ray Absorption Near Edge Structure (μ-XANES) and X-ray Photoelectron Spectroscopy (XPS) were employed for elemental analysis. For phase analysis, X-ray diffraction (XRD) in both symmetric and grazing incidence geometries (GI-XRD) and Micro electron diffraction at TEM were used. Impurities on crystals surfaces show a heterogeneous distribution of the present elements. The thickness of impurities ranges from 120 nm to 150 μm. The phases identified were (see figure) gypsum (1, 2, 3, 6, 9, 10, 13), hematite (4, 7, 8), sphalerite (14), chalcopyrite (11), cuprite (15), galena (5), alabandite (12), halite, fluorite and amorphous Pb and Mn oxy-hydroxides. Al, C, Ca, Cl, Cu, F, Fe, Mg, Mn, Na, O, Pb, S, Si and Zn elements were identified. A model for the origin of impurities follows: Selenite stopped growing when the solution became sub-saturated. Then, hematite was deposited as the main phase, which was dissolved or suspended in the solution. Hematite matrix served for the adsorption of other crystalline and amorphous phases. We concluded that humans have not produced the impurities, which are witnesses of the gypsum crystals formation. Acknowledgment: Stanford Synchrotron Radiation Lightsource, Harvard Museum of Natural History and CONACYT CB-183706.


2018 ◽  
Vol 200 (19) ◽  
Author(s):  
Fernanda Jiménez Otero ◽  
Chi Ho Chan ◽  
Daniel R. Bond

ABSTRACTAt least five gene clusters in theGeobacter sulfurreducensgenome encode putative “electron conduits” implicated in electron transfer across the outer membrane, each containing a periplasmic multihemec-type cytochrome, integral outer membrane anchor, and outer membrane redox lipoprotein(s). Markerless single-gene-cluster deletions and all possible multiple-deletion combinations were constructed and grown with soluble Fe(III) citrate, Fe(III) and Mn(IV) oxides, and graphite electrodes poised at +0.24 V and −0.1 V versus the standard hydrogen electrode (SHE). Different gene clusters were necessary for reduction of each electron acceptor. During metal oxide reduction, deletion of the previously describedomcBCcluster caused defects, but deletion of additional components in an ΔomcBCbackground, such asextEFG, were needed to produce defects greater than 50% compared to findings with the wild type. Deletion of all five gene clusters abolished all metal reduction. During electrode reduction, only the ΔextABCDmutant had a severe growth defect at both redox potentials, while this mutation did not affect Fe(III) oxide, Mn(IV) oxide, or Fe(III) citrate reduction. Some mutants containing only one cluster were able to reduce particular terminal electron acceptors better than the wild type, suggesting routes for improvement by targeting specific electron transfer pathways. Transcriptomic comparisons between fumarate and electrode-based growth conditions showed all of theseextclusters to be constitutive, and transcriptional analysis of the triple-deletion strain containing onlyextABCDdetected no significant changes in expression of genes encoding known redox proteins or pilus components. These genetic experiments reveal new outer membrane conduit complexes necessary for growth ofG. sulfurreducens, depending on the available extracellular electron acceptor.IMPORTANCEGram-negative metal-reducing bacteria utilize electron conduits, chains of redox proteins spanning the outer membrane, to transfer electrons to the extracellular surface. Only one pathway for electron transfer across the outer membrane ofGeobacter sulfurreducenshas been linked to Fe(III) reduction. However,G. sulfurreducensis able to respire a wide array of extracellular substrates. Here we present the first combinatorial genetic analysis of five different electron conduits via creation of new markerless deletion strains and complementation vectors. Multiple conduit gene clusters appear to have overlapping roles, including two that have never been linked to metal reduction. Another recently described cluster (ExtABCD) was the only electron conduit essential during electrode reduction, a substrate of special importance to biotechnological applications of this organism.


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