[Show abstract][Hide abstract] ABSTRACT: [L. Chkhartishvili, R. Becker, R. Avci. Relative stability of boron quasi-planar clusters. In: Proc. Int. Conf. “Advanced Materials & Technologies” (Eds. G. Darsavelidze, A. Guldamashvili, R. Chedia, A. Sichinava, M. Kadaria). 2015, Tbilisi: Universal, 42-46]: Nanoboron is a class of advanced materials highly prospective for various technological applications, e.g., in neutron-shielding coatings. Quasi-planar clusters B_n, n = 1, 2, 3, … , consisting of 3-membered rings of B-atoms serve for “building blocks” of nanoboron. Here, small quasi-planar clusters are obtained experimentally in boron vapor and their relative stability is studied theoretically by comparing binding energies per atom E_b. Detected cluster-ions mass-spectra correlate with obtained E_b – n dependence.
[Show abstract][Hide abstract] ABSTRACT: A practical method has been developed for rapidly determining the depth of a corrosion micro-pit from the path lengths of X rays passing through the walls of the pit on their way to an X-ray detector. The method takes advantage of the attenuation of the Bremsstrahlung and characteristic X-ray radiation accompanying each X-ray spectrum, and the results are verified independently using AFM and the special pit geometry surrounding MnS inclusions in 1018 carbon steel. The method has general validity and is especially valuable in those cases where the pit depth-to-width ratio is too steep to measure using the conventional methods.
Full-text · Article · Jan 2015 · Corrosion Science
[Show abstract][Hide abstract] ABSTRACT: [R. Becker, L. Chkhartishvili, R. Avci, I. Murusidze, O. Tsagareishvili, N. Maisuradze. “Metallic” boron nitride. Eur. Chem. Bull., 2015, 4, 1-3, 8-23.]: Boron nitride shell structures of chemical composition BNx with boron excess (x << 1) contaminated with carbon are synthesized in the process of melting of a boron-rich material in a boron nitride crucible with the nitrogen source in the form of high-purity pressed boron nitride rods, which held up the crucible. The obtained material is found to be conductive despite the fact that all the boron nitrides of stoichiometric chemical composition BN are insulators. “Metallic” boron nitride is modeled as a mixture of structural modifications of semiconducting boron and boron carbide heavily doped with nitrogen. First principle calculations performed within the quasi-classical approximation prove that nitrogen impurities, accommodated in large crystallographic voids characteristic of all-boron and boron-rich crystalline lattices, create donor electron-states inside the conduction band and then lead to the local “metallization” of chemical bonds in these initially covalently bonded structures.
[Show abstract][Hide abstract] ABSTRACT: This work focuses on immobilization of living enterhemorrhagic Escherichia coli O157:H7 on a gold surface as a function of the concentration of antibody tethered to the surface in the physiological environment of the organisms. Experiments are conducted using antibodies raised against bacterial surface lipopolysaccharides (LPS) tethered to gold-coated silicon wafers at surface concentrations spanning a range from submonolayers of antibodies to full coverage, an estimated 1 antibody per similar to 100 nm(2). A careful optimization of surface chemistry is conducted to obtain the most efficient tethering of the antibodies to the surface. The mechanism of immobilizing the bacteria is antibody antigen interactions between the tethered antibodies on the surface and the bacterial surface LPS firmly attached to the bacteria. This type of attachment is known as immunoimmobilization. The experiments suggest no noticeable bacterial attachment until the surface antibody concentration reaches similar to 70% of a full monolayer of coverage. Above this critical antibody density, a sharp increase in immunoimmobilized bacteria is observed as they populate nearly 80% to 100% of the available surface area, reaching similar to 1.2 cells/10 mu m(2). This sharp increase in population is tentatively explained in terms of the minimum number of antibody antigen interactions required per bacterium to immobilize the cell. This critical number is estimated to be similar to 6000-8000 antibodies per bacterium (having a 1 mu m(2) footprint on the surface) under the assumption that a full monolayer of antibodies is about 1 antibody per similar to 100 nm(2). However, the large majority of the 6000-8000 antibodies are not expected to participate in antibody antigen interactions, in that the loose LPS in solution will saturate many of these antibodies before bacteria have a chance to interact with them. Furthermore, the geometric considerations will further restrict the majority of the active antibodies from interacting with the surface antigens of the cell, reducing its effective contact area with the antibodies considerably.
[Show abstract][Hide abstract] ABSTRACT: In a saline anaerobic sulfidogenic environment, pitting on 1018 carbon steel was initiated within a 20-30 nm zone at the MnS inclusion boundary. Nanoscale analysis was performed using scanning electron microscopy and a scanning Auger nanoprobe. The pitting was more pronounced in the presence of a biofilm of sulfate-reducing bacteria than in abiotic sulfide medium. It is proposed that initiation of an anodic reaction leading to dissolution of Fe matrix and subsequent pitting of steel in MnS inclusion boundary regions is due to disorder and strain exerted on the Fe matrix by MnS contamination of the interface from metallurgical processes.
[Show abstract][Hide abstract] ABSTRACT: Live attenuated vaccines are adept in stimulating protective immunity. Methods for generating such vaccines have largely adopted strategies used with Salmonella enterica. Yet, when similar strategies were tested in other gram-negative bacteria, the virulence factors or genes responsible to incapacitate Salmonella often failed in providing the desired outcome. Consequently, conventional live vaccines rely on prior knowledge of the pathogen's virulence factors to successfully attenuate them. This can be problematic since such bacterial pathogens normally harbor thousands of genes. To circumvent this problem, we found that overexpression of bacterial appendages, e.g., fimbriae, capsule, and flagella, could successfully attenuate wild-type (wt) Salmonella enterica serovar Typhimurium. Further analysis revealed these attenuated Salmonella strains conferred protection against wt S. Typhimurium challenge as effectively as genetically defined Salmonella vaccines. We refer to this strategy as attenuating gene expression (AGE), a simple efficient approach in attenuating bacterial pathogens, greatly facilitating the construction of live vaccines.
[Show abstract][Hide abstract] ABSTRACT: Two different polymeric materials that are candidate materials for use as binders for mixed uranium-plutonium oxide nuclear fuel pellets were subjected to Li ion beam irradiation, in order to simulate intense alpha irradiation. The materials (a polyethylene glycol 8000 and a microcrystalline wax) were then analyzed using a combination of mass spectrometry (MS) approaches and X-ray photoelectron spectroscopy (XPS). Samples of the irradiated PEG materials were dissolved in H2O and then analyzed using electrospray ionization-MS, which showed the formation of a series of small oligomers in addition to intact large PEG oligomers. The small oligomers were likely formed by radiation-induced homolytic scissions of the C-O and C-C bonds, which furnish radical intermediates that react by radical recombination with H-center dot and OH center dot. Surface analysis using SIMS revealed a heterogeneous surface that contained not only PEG-derived polymers, but also hydrocarbon-based entities that are likely surface contaminants. XPS of the irradiated PEG samples indicated the emergence of different carbon species, with peak shifts suggesting the presence of sp(2) carbon atoms. Analysis of the paraffinic film using XPS showed the emergence of oxygen on the surface of the sample, and also a broadening and shifting of the C1s peak, demonstrating a change in the chemistry on the surface. The paraffinic film did not dissolve in either H2O or a H2O-methanol solution, and hence the bulk of the material could not be analyzed using electrospray. However a series of oligomers was leached from the bulk material that produced ion series in the ESI-MS analyses that were identified octylphenyl ethoxylate oligomers. Upon Li ion bombardment, these shifted to a lower average molecular weight, but more importantly showed the emergence of three new ion series that are being formed as a result of radiation damage. Surface analysis of the paraffinic polymers using SIMS produced spectra that were wholly dominated by hydrocarbon ion series, and no difference was observed between unirradiated and irradiated samples. The studies demonstrate that for the PEG-based polymers, direct evidence for radiolytic scission can be observed using ESI-MS, and suggests that both radiolytic pathways and efficiencies as a function of dose should be measurable by calibrating instrument response to the small oligomeric degradation products. (c) 2012 Elsevier B.V. All rights reserved.
No preview · Article · Feb 2013 · Nuclear Instruments and Methods in Physics Research Section B Beam Interactions with Materials and Atoms
[Show abstract][Hide abstract] ABSTRACT: The speciation and spatial distribution of arsenic on rusted steel surfaces affects both measurement and removal approaches. The chemistry of arsenic residing in the rust of ton containers that held the chemical warfare agents bis(2-chloroethyl)sulfide (sulfur mustard) and 2-chlorovinyldichloroarsine (Lewisite) is of particular interest, because while the agents have been decontaminated, residual arsenic could pose a health or environmental risk. The chemistry and distribution of arsenic in rust samples was probed using imaging secondary ion mass spectrometry (SIMS), X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy, and scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDX). Arsenic in the +3 and or +5 oxidation state is homogeneously distributed at the very top-most layer of the rust samples, and is intimately associated with iron. Sputter depth profiling followed by SIMS and XPS shows As at a depth of several nm, in some cases in a reduced form. The SEM/EDX experiments show that As is present at a depth of several microns, but is inhomogeneously distributed; most locations contained oxidized As at concentrations of a few percent, however several locations showed very high As in a metallic form. These results indicate that the rust material must be removed if the steel containers are to be cleared of arsenic.
No preview · Article · Jan 2013 · Industrial & Engineering Chemistry Research
[Show abstract][Hide abstract] ABSTRACT: Flagella are cell surface appendages involved in a number of bacterial behaviors, such as motility, biofilm formation, and chemotaxis. Despite these important functions, flagella can pose a liability to a bacterium when serving as potent immunogens resulting in the stimulation of the innate and adaptive immune systems. Previous work showing appendage overexpression, referred to as attenuating gene expression (AGE), was found to enfeeble wild-type Salmonella. Thus, this approach was adapted to discern whether flagella overexpression could induce similar attenuation. To test its feasibility, flagellar filament subunit FliC and flagellar regulon master regulator FlhDC were overexpressed in Salmonella enterica serovar Typhimurium wild-type strain H71. The results show that the expression of either FliC or FlhDC alone, and co-expression of the two, significantly attenuates Salmonella. The flagellated bacilli were unable to replicate within macrophages and thus were not lethal to mice. In-depth investigation suggests that flagellum-mediated AGE was due to the disruptive effects of flagella on the bacterial membrane, resulting in heightened susceptibilities to hydrogen peroxide and bile. Furthermore, flagellum-attenuated Salmonella elicited elevated immune responses to Salmonella presumably via FliC's adjuvant effect and conferred robust protection against wild-type Salmonella challenge.
[Show abstract][Hide abstract] ABSTRACT: Enterotoxigenic Escherichia coli CFA/I is a protective antigen and has been overexpressed in bacterial vectors, such as Salmonella Typhimurium H683, to generate vaccines. Effects that overexpressed CFA/I may engender on the bacterial host remain largely unexplored. To investigate, we constructed a high CFA/I expression strain, H683-pC2, and compared it to a low CFA/I expression strain, H683-pC, and to a non-CFA/I expression strain, H683-pY. The results showed that H683-pC2 was less able to migrate into semisolid agar (0.35%) than either H683-pC or H683-pY. Bacteria that migrated showed motility halo sizes of H683-pC2 < H683-pC < H683-pY. In the liquid culture media, H683-pC2 cells precipitated to the bottom of the tube, while those of H683-pY did not. In situ imaging revealed that H683-pC2 bacilli tended to auto-agglutinate within the semisolid agar, while H683-pY bacilli did not. When the cfaBE fimbrial fiber encoding genes were deleted from pC2, the new plasmid, pC2(-), significantly recovered bacterial swimming capability. Our study highlights the negative impact of overexpressed CFA/I fimbriae on bacterial swimming motility.
[Show abstract][Hide abstract] ABSTRACT: Nano-silica particles were deposited on acid-etched hydrophilic aluminum (Al) substrates by immersion in well-dispersed nano-silica aqueous suspension and tetramethylamonium hydroxide, followed by a heat treatment. The surface was then further treated by a reaction with fluorosilane. The hydrophobicity, surface morphology, and mechanical properties of the coated Al substrates were investigated, along with their electrochemical properties over time of exposure to two NaCl solutions (0.3% and 3% by weight). All the coated Al surfaces exhibited a water contact angle of 155–158°, i.e., superhydrophobicity. The use of nano-silica suspension significantly enhanced the hydrophobicity of the coated Al. Artificial neural networks were used to provide quantitative understanding in how the microstructure of the treated Al surface contributed to its superhydrophobicity and electrochemical properties. When Ra, total (nano-roughness + micro-roughness) exceeds 450 nm, WCA is greater than 154°, independent of the nano/micro-roughness ratio (RRNM). FESEM and AFM images of these surfaces suggest that a rough two-length-scale hierarchical structure coupled with the low surface energy of fluorosilane topcoat led to the superhydrophobicity of the formed coatings. The coating prepared with the 0.2% nano-silica suspension (vs. other concentrations) featured the highest Young's modulus and the best corrosion protection to the Al substrate in both NaCl solutions.
[Show abstract][Hide abstract] ABSTRACT: The noble shift in corrosion potential to values between +300 and +400 mV SCE and the accompanying increase in cathodic current density and polarization slope at mild cathodic potentials that develop during microbial colonization of passive metals, are collectively known as ennoblement. This phenomenon is of concern as the noble shift in the corrosion potential may lead to pitting corrosion. We have demonstrated, by growing pure cultures of manganese oxidizing bacteria (MOB) Leptothrix discophora SP-6 under well defined conditions, that microbial deposition of manganese oxides causes ennoblement of 316L stainless steel (SS). Exposing 316L corrosion coupons in lakes and streams supported this conclusion; the rate and extent of ennoblement were positively correlated with the rates of deposition and the amounts of biomineralized manganese oxides deposited on the surfaces of the SS corrosion coupons. X-ray photoelectron spectroscopy (XPS) analyses of the deposits from the ennobled coupons revealed a mixture of manganese oxides, as expected. Many natural waters can support growth of MOB. When manganese-oxidizing biofilms accumulate on surfaces of passive metals there is a potential for manganese redox cycling on the metal surface. This process is initiated by depositing minute amounts of manganese oxides on the metal surface. These microbially deposited manganese oxides are then reduced by the electrons derived from anodic dissolution of the metal; the metal is corroding and the manganese oxides are reduced to divalent manganese ions. However, since the manganese ions are liberated within the manganese-oxidizing biofilm, the manganese ions are immediately reoxidized, and the cycle continues.
Full-text · Article · Apr 2012 · Water Science & Technology Water Supply
[Show abstract][Hide abstract] ABSTRACT: During infection, Yersinia pestis uses its F1 capsule to enhance survival and cause virulence to mammalian host. Since F1 is produced in large quantities and secreted into the host tissues, it also serves as a major immune target. To hold this detrimental effect under proper control, Y. pestis expresses the caf operon (encoding the F1 capsule) in a temperature-dependent manner. However, additional properties of the caf operon limit its expression. By overexpressing the caf operon in wild-type Salmonella enterica serovar Typhimurium under a potent promoter, virulence of Salmonella was greatly attenuated both in vitro and in vivo. In contrast, expression of the caf operon under the regulation of its native promoter exhibited negligible impairment of Salmonellae virulence. In-depth investigation revealed all individual genes in the caf operon attenuated Salmonella when overexpressed. The deleterious effects of caf operon and the caf individual genes were further confirmed when they were overexpressed in Y. pestis KIM6+. This study suggests that by using a weak inducible promoter, the detrimental effects of the caf operon are minimally manifested in Y. pestis. Thus, through tight regulation of the caf operon, Y. pestis precisely balances its capsular anti-phagocytic properties with the detrimental effects of caf during interaction with mammalian host.
[Show abstract][Hide abstract] ABSTRACT: This work is a collaborative effort involving multidisciplinary and multi-institutional scientific groups with a common objective of determining "to what extent the biocorrosion of carbon steel experienced in marine systems can be correlated with anaerobic fuel biodegradation." Within this context our group's specific tasks include but are not limited to understanding the elementary steps of microbially influenced corrosion on carbon steel: This involves developing a versatile experimental platform employing a wide range of surface imaging and surface analytical techniques that address the fundamental mechanisms of the anaerobic carbon steel biodeterioration process resulting from the anaerobic biodegradation of fuel in marine systems in the presence of sulfate, at the nano-, micro- and macroscales. Here we present preliminary data revealing a very rapid degradation of carbon steel surface upon exposure to a culture of fuel-degrading Desulfoglaeba alkanexedens (strain ALDC T) under anaerobic conditions. We also present data on control experiments conducted using Na 2S solutions and compare their effect on the initial degradation of carbon steel surface under high and normal pH conditions and under highly controlled anaerobic conditions. All evidence points to pH playing a key role in the anaerobic corrosion of C steel in the presence of sulfide ions in the solution. Furthermore, the precipitation of the corrosion minerals forms open morphologies with submicron-sized channels, connecting the solution phase to the clean Fe surface and thus enabling sustainable corrosion. The results suggest that the abiotic and biotic general corrosion processes are driven by the same chemical reactions: Fe + 2 H + = Fe 2+ + H 2↑ and Fe 2+ + S 2- = FeS↓, though SRB-mediated MIC may proceed at a very different rate than the abiotic process, which is yet to be quantified.
[Show abstract][Hide abstract] ABSTRACT: Capturing pathogens on a sensor surface is one of the most important steps in the design of a biosensor. The efficiency of a biosensor at capturing pathogens has direct bearing on its sensitivity. In this work we investigated the capturing of Escherichia coli on substrates modified with antibodies targeting different types of fimbriae: K88ab (F4), K88ac (F4), K99 (F5), 987P (F6), F41, and CFA/I. The results suggest that all these fimbriae can be used for the efficient immobilization of living E. coli cells. The immobilization efficiency was affected by the purity and clone type of the antibody and the fimbriae expression level of the bacteria. For a specific fimbriae type, a higher immobilization efficiency was often observed with the monoclonal antibodies. Immunoimmobilization was utilized in an antibody microarray immersed in a mixed culture of pathogens to demonstrate the rapid and simultaneous label-free detection of multiple pathogens within less than 1 h using a single test. The capture rate of living pathogens exceeds a single bacterium per 100 × 100 μm(2) area per 0.5 h of incubation for a bulk concentration of 10(5) cfu/mL.
[Show abstract][Hide abstract] ABSTRACT: Generation of a live attenuated vaccine for bacterial pathogens often requires prior knowledge of the pathogen's virulence factors. We hypothesized an alternative approach of heterologous gene expression would make a wild-type (wt) pathogen more susceptible to host cell killing, thus, resulting in immunization. As proof of concept, the heterologous expression of enterotoxigenic E. coli (ETEC) colonization factor antigen I (CFA/I) was tested to attenuate Salmonella. The overexpression of CFA/I resulted in significant attenuation of wt Salmonella. In-depth studies revealed the attenuation depended on the co-expression of chaperone (CfaA) and usher (CfaC) proteins. Remarkably, the CfaAC-attenuated Salmonella conferred protection against wt Salmonella challenge. Mechanistic study indicated CfaAC made Salmonella outer membranes permeable, causing Salmonella to be vulnerable to host destruction. Thus, enhancing bacterial permeability via CfaAC represents an alternative method to attenuate pathogens despite the presence of unknown virulence factors.