Solution and microbial controls on the formation of reduced U(IV) species

Reduction of U(VI) to U(IV) as the result of direct or indirect microbial activity is currently being explored for in situ remediation of subsurface U plumes, under the assumption that U(IV) solubility is controlled by the low-solubility mineral uraninite (U(IV)-dioxide). However, recent characterizations of U in sediments from biostimulated field sites, as well as laboratory U(VI) bioreduction studies, report on the formation of U(IV) species that lack the U═O(2)═U coordination of uraninite, suggesting that phases other than uraninite may be controlling U(IV) solubility in environments with complexing surfaces and ligands. To determine the controls on the formation of such nonuraninite U(IV) species, the current work studied the reduction of carbonate-complexed U(VI) by (1) five Gram-positive Desulfitobacterium strains, (2) the Gram-negative bacteria Anaeromyxobacter dehalogenans 2CP-C and Shewanella putrefaciens CN32, and (3) chemically reduced 9,10-anthrahydroquinone-2,6-disulfonate (AH(2)QDS, a soluble reductant). Further, the effects of 0.3 mM dissolved phosphate on U(IV) species formation were explored. Extended X-ray absorption fine structure (EXAFS) spectroscopy analysis demonstrated that the addition of phosphate causes the formation of a nonuraninite, phosphate-complexed U(IV) species, independent of the biological or abiotic mode of U(VI) reduction. In phosphate-free medium, U(VI) reduction by Desulfitobacterium spp. and by AH(2)QDS resulted in nonuraninite, carbonate-complexed U(IV) species, whereas reduction by Anaeromyxobacter or Shewanella yielded nanoparticulate uraninite. These findings suggest that the Gram-positive Desulfitobacterium strains and the Gram-negative Anaeromyxobacter and Shewanella species use distinct mechanisms to reduce U(VI).     

Binding of HgII to high-affinity sites on bacteria inhibits reduction to Hg0 by mixed FeII/III phases

Magnetite and green rust have been shown to reduce aqueous Hg(II) to Hg(0). In this study, we tested the ability of magnetite and green rust to reduce Hg(II) sorbed to 2 g · L(-1) of biomass (Bacillus subtilis), at high (50 μM) and low (5 μM) Hg loadings and at pH 6.5 and 5.0. At high Hg:biomass loading, where Hg(II) binding to biomass is predominantly through carboxyl functional groups, Hg L(III)-edge X-ray absorption spectroscopy showed reduction of Hg(II) to Hg(0) by magnetite. Reduction occurred within 2 h and 2 d at pH 6.5 and 5.0, respectively. At low Hg:biomass loading, where Hg(II) binds to biomass via sulfhydryl functional groups, Hg(II) was not reduced by magnetite at pH 6.5 or 5.0 after 2 months of reaction. Green rust, which is generally a stronger reductant than magnetite, reduced about 20% of the total Hg(II) bound to biomass via sulfhydryl groups to Hg(0) in 2 d. These results suggest that Hg(II) binding to carboxyl groups does not significantly inhibit the reduction of Hg(II) by magnetite. However, the binding of Hg(II) to biomass via sulfhydryl groups severely inhibits the ability of mixed Fe(II/III) phases like magnetite and green rust to reduce Hg(II) to Hg(0). The mobility of heavy metal contaminants in aquatic and terrestrial environments is greatly influenced by their speciation, especially their oxidation state. In the case of Hg, reduction of Hg(II) to Hg(0) can increase Hg mobility because of the volatility of Hg(0). Since Hg is typically present in aquatic and terrestrial systems at low concentrations, binding of Hg(II) to high-affinity sites on bacteria could have important implications for the potential reduction of Hg(II) to Hg(0) and the overall mobility of Hg in biostimulated subsurface environments.     

Uniform graphene oxide films fabrication via spray-coating for sensing application

Abstract

A spray-coating technique for deposition of thin uniform graphene oxide films with a thickness of several tens of nanometers was developed. Among distinctive features of the technique is the low substrate heating temperature, which allows preserving most oxygen-containing functional groups and coat a wide range of substrates. The morphology of the spray-coated graphene oxide films with flakes of different lateral sizes was investigated. The local laser-induced photo-thermal reduction of thin graphene oxide thin films was demonstrated. The sensitivity of reduced graphene oxide to water vapor was also measured. Spray-coating and laser reduction techniques can be further applied for humidity sensor fabrication.     

Characterization of cross‐linking depth for thin polymeric films using atomic force microscopy

Thin polymeric films made with various elastomers, like polyisoprene, and elastomer composites were prepared for characterization of cross‐linking depth in this study. Various cross‐linking methods have been applied to get mechanically stronger, more thermally stable and chemically resistant polymer coatings. However, there is no existing approach that could effectively characterize the degree or depth of cross‐linking for thin polymer films. The objective of this work is to use atomic force microscopy to characterize cross‐linking depth in a precise way. Hyperthermal hydrogen bombardment‐induced cross‐linking was employed as a cross‐linking method and the depth of cross‐linking was estimated via local change of the elastic modulus along the sample cross‐section with precise force measurement and high spatial resolution. It is found that the cross‐linking depth is closely related to the chemical composition of thin films. Understanding the depth of cross‐linking is vital for a broad range of applications. It is believed that the developed technique is also applicable for studying other cross‐linkable materials. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41493.     

Optimized EPI for fMRI using a slice-dependent template-based gradient compensation method to recover local susceptibility-induced signal loss

Object  

Most functional magnetic resonance imaging (fMRI) experiments use gradient-echo echo planar imaging (GE EPI) to detect the blood oxygenation level-dependent (BOLD) effect. This technique may fail in the presence of anatomy-related susceptibility-induced field gradients in the human head. In this work, we present a novel 3D compensation method in combination with a template-based correction that can be optimized over particular regions of interest to recover susceptibility-induced signal loss without acquisition time penalty.     

Convergence of the discrete dipole approximation. I. Theoretical analysis

We perform a rigorous theoretical convergence analysis of the discrete dipole approximation (DDA). We prove that errors in any measured quantity are bounded by a sum of a linear term and a quadratic term in the size of a dipole d when the latter is in the range of DDA applicability. Moreover, the linear term is significantly smaller for cubically than for noncubically shaped scatterers. Therefore, for small d, errors for cubically shaped particles are much smaller than for noncubically shaped ones. The relative importance of the linear term decreases with increasing size; hence convergence of DDA for large enough scatterers is quadratic in the common range of d. Extensive numerical simulations are carried out for a wide range of d. Finally, we discuss a number of new developments in DDA and their consequences for convergence.     

Designing solution-processable air-stable liquid crystalline crosslinkable semiconductors

Organic electronics technology, in which at least the semiconducting component of the integrated circuit is an organic material, offers the potential for fabrication of electronic products by low-cost printing technologies, such as ink jet, gravure offset lithography and flexography. The products will typically be of lower performance than those using the present state of the art single crystal or polysilicon transistors, but comparable to amorphous silicon. A range of prototypes are under development, including rollable electrophoretic displays, active matrix liquid crystal (LC) displays, flexible organic light emitting diode displays, low frequency radio frequency identification tag and other low performance electronics. Organic semiconductors that offer both electrical performance and stability with respect to storage and operation under ambient conditions are required. This work describes the development of reactive mesogen semiconductors, which form large crosslinked LC domains on polymerization within mesophases. These crosslinked domains offer mechanical stability and are inert to solvent exposure in further processing steps. Reactive mesogens containing conjugated aromatic cores, designed to facilitate charge transport and provide good oxidative stability, were prepared and their liquid crystalline properties evaluated. The organization and alignment of the mesogens, both before and after crosslinking, were probed by grazing incidence wide-angle X-ray scattering of thin films. Both time-of-flight and field effect transistor devices were prepared and their electrical characterization reported.     

Optical vortices in twisted elliptical optical fibers with torsional stress

In the present paper we have derived the analytical expressions for the modes of twisted elliptical fibers with torsional mechanical stress at various relationships of the fiber parameters. It was shown that circularly polarized optical vortices with the topological charges ±1 can propagate in elliptical fibers as generic modes if ellipticity and the twist-induced circular birefringence suppress the spin-orbit interaction. A comparison of the obtained results with the corresponding results for spun elliptical fibers is made.     

Pathogen‐Mimicking MnO Nanoparticles for Selective Activation of the TLR9 Pathway and Imaging of Cancer Cells

Here, design of the first pathogen‐mimicking metal oxide nanoparticles with the ability to enter cancer cells and to selectively target and activate the TLR9 pathway, and with optical and MR imaging capabilities, is reported. The immobilization of ssDNA (CpG ODN 2006) on MnO nanoparticles is performed via the phosphoramidite route using a multifunctional polymer. The multifunctional polymer used for the nanoparticle surface modification not only affords a protective organic biocompatible shell but also provides an efficient and convenient means for loading immunostimulatory oligonucleotides. Since fluorescent molecules are amenable to photodetection, a chromophore (Rhodamine) is introduced into the polymer chain to trace the nanoparticles in Caki‐1 (human kidney cancer) cells. The ssDNA coupled nanoparticles are used to target Toll‐like receptors 9 (TLR9) receptors inside the cells and to activate the classical TLR cascade. The presence of TLR9 is demonstrated independently in the Caki‐1 cell line by western blotting and immunostaining techniques. The magnetic properties of the MnO core make functionalized MnO nanoparticles potential diagnostic agents for magnetic resonance imaging (MRI) thereby enabling multimodal detection by a combination of MR and optical imaging methods. The trimodal nanoparticles allow the imaging of cellular trafficking by different means and simultaneously are an effective drug carrier system.