Investigation of the Impacts of Gamma Radiolysis on an Advanced TALSPEAK Separation

The advanced TALSPEAK process is a selective solvent extraction that utilizes 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]) to separate lanthanide elements from trivalent actinides, which are held back in the aqueous phase by N-hydroxylethyl-N,N’,N’-ethylenediamine triacetic acid (HEDTA) buffered by citric acid. Gamma irradiation of an experiment containing Eu(III) and Am(III) as representative lanthanide and actinide elements resulted in higher distribution ratios of both and separation factors which decreased in an exponential fashion with increasing dose. Analysis of the reagents showed that the HEDTA concentration also decreased in an exponential fashion, strongly suggesting that degradation was correlated with loss of separation selectivity. In contrast, the concentration of citrate was unaffected, and while the concentration of HEH[EHP] did decrease, its dose-dependent kinetic profile indicated that it was not limiting partitioning. A second set of experiments were conducted using a citrate concentration that was 7.5 X higher, with the expectation that citrate would protect the HEDTA by scavenging radiolytically formed OH radicals. HEDTA degradation was significantly mitigated at higher gamma doses, but the Eu-Am separation was worse than in the low citrate experiments, presumably because at the high citrate concentrations, the Eu-citrate complexes formed in abundances competitive with the Am complexes, and are more effectively held back in the aqueous phase.     

Phase development and pore stability of yttria- and ytterbia-stabilized zirconia aerogels

High-porosity yttria- and ytterbia-stabilized zirconia aerogels offer the potential of extremely low thermal conductivity materials for high-temperature applications. Yttria- and ytterbia-doped zirconia aerogels were synthesized using a sol-gel approach over the dopant range of 0-20 atomic percent. Surface area, pore volume, and morphology of the as-dried aerogels and materials thermally exposed for short periods of time to temperatures up to 1200°C were characterized by nitrogen physisorption, scanning and transmission electron microscopy, and X-ray diffraction. The aerogels as supercritically dried all were X-ray amorphous. At a 5% dopant level, a tetragonal structure with a smaller monoclinic phase developed on thermal exposure. Mixed tetragonal and cubic phases or predominantly cubic materials were observed at higher dopant levels, depending on the dopant level, temperature and exposure time. The formation of crystalline phases was accompanied by loss of surface area and pore volume, although some mesoporous structure was maintained on short-term exposure to 1000°C. Incorporation of the smaller Yb atom into the lattice structure resulted in smaller lattice dimensions on crystallization than was seen with Y doping and favored a more highly equiaxed structure. Aerogels synthesized with 15% Y maintained the smallest particle size without evidence of sintering at 1100°C. Largest shrinkage and loss of pore volume occurred on crystallization from the amorphous phase, with further loss of pores at temperatures above 1000°C attributable to changes in lattice parameters.     

Cover Image,Volume 66, Issue 10

The cover image, by Bruna A. Bregadiolli et al., is based on the Research Article Towards the synthesis of poly(azafulleroid)s: main chain fullerene oligomers for organic photovoltaic devices, DOI: 10.1002/pi.5419 .

     

Comparison of two size-differentiating air samplers for detecting airborne swine viruses under experimental conditions

Detection and quantification of dilute viral aerosols, as encountered outside animal housing facilities, requires methods that are able to detect small numbers of viruses in large volumes of air. This study compared the performance of two size-differentiating cascade impactors; an Andersen 8-stage (ACI; 28.3 L/min) and a high volume Tisch (TCI; 1,133 L/min) to assess sampling efficiency for detecting porcine reproductive and respiratory syndrome virus (PRRSV) and influenza A virus (IAV). Samples of particles sorted by aerodynamic diameter were analyzed by quantitative polymerase chain reaction (qPCR) and collection efficiency was assessed by particle size. Collection media (minimum essential medium [MEM] and beef extract [BE]), elution technique (active versus passive), and sampling times (10, 20, and 30 min) were variables assessed for the TCI sampler. Extraction efficiency was 35% higher with BE as compared to that of MEM (p = 0.0007); active extraction technique was 19% more efficient than the passive technique (p = 0.03); time of sampling did not significantly affect the amount of virus recovered. The ACI sampler was more efficient in detecting both viruses from small and medium sized airborne particles (≤3 μm) as compared to the TCI sampler (p < 0.001). The latter sampler, however, was more efficient at IAV detection from large airborne particles (>3 μm) (p = 0.0025) indicating the potential of this sampler in detecting the presence of small amounts of viruses in aerosols under field conditions.

© 2017 American Association for Aerosol Research     

Small‐Molecule APOBEC3G DNA Cytosine Deaminase Inhibitors Based on a 4‐Amino‐1,2,4‐triazole‐3‐thiol Scaffold

APOBEC3G (A3G) is a single‐stranded DNA cytosine deaminase that functions in innate immunity against retroviruses and retrotransposons. Although A3G can potently restrict Vif‐deficient HIV‐1 replication by catalyzing excessive levels of G→A hypermutation, sublethal levels of A3G‐catalyzed mutation may contribute to the high level of HIV‐1 fitness and its incurable prognosis. To chemically modulate A3G catalytic activity with the goal of decreasing the HIV‐1 genomic mutation rate, we synthesized and biochemically evaluated a class of 4‐amino‐1,2,4‐triazole‐3‐thiol small‐molecule inhibitors identified by high‐throughput screening. This class of compounds exhibits low‐micromolar (3.9–8.2 μM ) inhibitory potency and remarkable specificity for A3G versus the related cytosine deaminase, APOBEC3A. Chemical modification of inhibitors, A3G mutational screening, and thiol reactivity studies implicate C321, a residue proximal to the active site, as the critical A3G target for this class of molecules.     

Low Dietary c9t11-Conjugated Linoleic Acid Intake from Dairy Fat or Supplements Reduces Inflammation in Collagen-Induced Arthritis

Dietary cis‐9,trans‐11 (c9t11) conjugated linoleic acid (CLA) fed at 0.5 % w/w was previously shown to attenuate inflammation in the murine collagen‐induced (CA) arthritis model, and growing evidence implicates c9t11‐CLA as a major anti‐inflammatory component of dairy fat. To understand c9t11‐CLA's contribution to dairy fat's anti‐inflammatory action, the minimum amount of dietary c9t11‐CLA needed to reduce inflammation must be determined. This study had two objectives: (1) determine the minimum dietary anti‐inflammatory c9t11‐CLA intake level in the CA model, and (2) compare this to anti‐inflammatory effects of dairy fat (non‐enriched, naturally c9t11‐CLA‐enriched, or c9t11‐CLA‐supplemented). Mice received the following dietary fat treatments (w/w) post arthritis onset: corn oil (6 % CO), 0.125, 0.25, 0.375, and 0.5 % c9t11‐CLA, control butter (6 % CB), c9t11‐enriched butter (6 % EB), or c9t11‐CLA‐supplemented butter (6 % SB, containing 0.2 % c9t11‐CLA). Paw arthritic severity and pad swelling were scored and measured, respectively, over an 84‐day study period. All c9t11‐CLA and butter diets decreased the arthritic score (25–51 %, P < 0.01) and paw swelling (8–11 %, P < 0.01). Throughout the study, plasma tumor necrosis factor (TNFα) was elevated in CO‐fed arthritic mice compared to non‐arthritic (NA) mice but was reduced in 0.5 % c9t11‐CLA‐ and EB‐fed mice. Interleukin‐1β and IL‐6 were increased in arthritic CO‐fed mice compared to NA mice but were reduced in 0.5 % c9t11‐CLA‐ and EB‐fed mice through day 42. In conclusion, 0.125 % c9t11‐CLA reduced clinical arthritis as effectively as higher doses, and decreased arthritis in CB‐fed mice suggested that the minimal anti‐inflammatory levels of c9t11‐CLA might be below 0.125 %.     

Aedes aegypti Piwi4 Structural Features Are Necessary for RNA Binding and Nuclear Localization

The PIWI-interacting RNA (piRNA) pathway provides an RNA interference (RNAi) mechanism known from Drosophila studies to maintain the integrity of the germline genome by silencing transposable elements (TE). Aedes aegypti mosquitoes, which are the key vectors of several arthropod-borne viruses, exhibit an expanded repertoire of Piwi proteins involved in the piRNA pathway, suggesting functional divergence. Here, we investigate RNA-binding dynamics and subcellular localization of A. aegypti Piwi4 (AePiwi4), a Piwi protein involved in antiviral immunity and embryonic development, to better understand its function. We found that AePiwi4 PAZ (Piwi/Argonaute/Zwille), the domain that binds the 3′ ends of piRNAs, bound to mature (3′ 2′ O-methylated) and unmethylated RNAs with similar micromolar affinities (K_D = 1.7 ± 0.8 μM and K_D of 5.0 ± 2.2 μM, respectively; p = 0.05) in a sequence independent manner. Through site-directed mutagenesis studies, we identified highly conserved residues involved in RNA binding and found that subtle changes in the amino acids flanking the binding pocket across PAZ proteins have significant impacts on binding behaviors, likely by impacting the protein secondary structure. We also analyzed AePiwi4 subcellular localization in mosquito tissues. We found that the protein is both cytoplasmic and nuclear, and we identified an AePiwi4 nuclear localization signal (NLS) in the N-terminal region of the protein. Taken together, these studies provide insights on the dynamic role of AePiwi4 in RNAi and pave the way for future studies aimed at understanding Piwi interactions with diverse RNA populations.