Photoactive Earth‐Abundant Iron Pyrite Catalysts for Electrocatalytic Nitrogen Reduction Reaction

The generation of ammonia, hydrogen production, and nitrogen purification are considered as energy intensive processes accompanied with large amounts of CO₂ emission. An electrochemical method assisted by photoenergy is widely utilized for the chemical energy conversion. In this work, earth‐abundant iron pyrite (FeS₂) nanocrystals grown on carbon fiber paper (FeS₂/CFP) are found to be an electrochemical and photoactive catalyst for nitrogen reduction reaction under ambient temperature and pressure. The electrochemical results reveal that FeS₂/CFP achieves a high Faradaic efficiency (FE) of ≈14.14% and NH₃ yield rate of ≈0.096 µg min^?1 at ?0.6 V versus RHE electrode in 0.25 m LiClO₄. During the electrochemical catalytic reaction, the crystal structure of FeS₂/CFP remains in the cubic pyrite phase, as analyzed by in situ X‐ray diffraction measurements. With near‐infrared laser irradiation (808 nm), the NH₃ yield rate of the FeS₂/CFP catalyst can be slightly improved to 0.1 µg min^?1 with high FE of 14.57%. Furthermore, density functional theory calculations demonstrate that the N₂ molecule has strong chemical adsorption energy on the iron atom of FeS₂. Overall, iron pyrite‐based materials have proven to be a potential electrocatalyst with photoactive behavior for ammonia production in practical applications.     

Design of Trehalose-Based Amide/Sulfonamide C-type Lectin Receptor Signaling Compounds

Mincle agonists have been shown to induce inflammatory cytokine production, such as tumor necrosis factor-alpha (TNF) and promote the development of a Th1/Th17 immune response that might be crucial to development of effective vaccination against pathogens such as Mycobacterium tuberculosis. As an expansion of our previous work, a library of 6,6′-amide and sulfonamide α,α-d -trehalose compounds with various substituents on the aromatic ring was synthesized efficiently in good to excellent yields. These compounds were evaluated for their ability to activate the human C-type lectin receptor Mincle by the induction of cytokines from human peripheral blood mononuclear cells. A preliminary structure–activity relationship (SAR) of these novel trehalose diamides and sulfonamides revealed that aryl amide-linked trehalose compounds demonstrated improved activity and relatively high potency cytokine production compared to the Mincle ligand trehalose dibehenate adjuvant (TDB) and the natural ligand trehalose dimycolate (TDM) inducing dose-dependent and human-Mincle-specific stimulation in a HEK reporter cell line.     

Advanced Postirradiation Characterization of Nuclear Fuels Using Pulsed Neutrons

Methods for postirradiation characterization of bulk (cm³) irradiated materials or even spent nuclear fuels are sparse due to their extremely radioactive nature. While several methods exist to characterize smaller volumes (<?1 mm³) of such samples, selecting these volumes from larger samples is challenging. X-ray-based methods are prohibitive due to the strong γ-radiation from the sample flooding the detectors. Neutron-based methods available in the proximity of irradiation reactors allow for thermal neutron radiography or computed tomography using a small reactor source, but one cannot assess isotope distributions or microstructural features such as phases, texture, or strain from diffraction measurements due to flux limitations. We present herein a pathway to provide pulsed neutron characterization of bulk irradiated samples using time-of-flight neutron diffraction for microstructural characterization and energy-resolved neutron imaging for assessment of isotopic densities and distributions. Ultimately, laser-driven pulsed neutron sources may allow deployment of these techniques pool-side at irradiation reactors.

     

Outlier accommodation in moving-horizon state estimation: A risk-averse performance-specified approach

This paper presents a novel state estimation approach for linear dynamic systems when measurements are corrupted by outliers. Since outliers can degrade the performance of state estimation, outlier accommodation is critical. The standard approach combines outlier detection utilizing Neyman-Pearson (NP) type tests with a Kalman filter (KF). This approach ignores all residuals greater than a designer-specified threshold. When measurements with outliers are used (ie, missed detections), both the state estimate and the error covariance matrix become corrupted. This corrupted state and covariance estimate are then the basis for all subsequent outlier decisions. When valid measurements are rejected (ie, false alarms), potentially using the corrupted state estimate and error covariance, measurement information is lost. Either using invalid information or discarding too much valid information can result in divergence of the KF. An alternative approach is moving-horizon (MH) state estimation, which maintains all recent measurement data within a moving window with a time horizon of length L. In MH approaches, the number of measurements available for state estimation is affected by both the number of measurements per time step and the number of time steps L over which measurements are retained. Risk-averse performance-specified (RAPS) state estimation works within an optimization setting to choose a set of measurements that achieves a performance specification with minimum risk of outlier inclusion. This paper derives and formulates the MH-RAPS solution for outlier accommodation. The paper also presents implementation results. The MH-RAPS application uses Global Navigation Satellite Systems measurements to estimate the state of a moving platform using a position, velocity, and acceleration model. In this application, MH-RAPS performance is compared with MH-NP state estimation.     

Insight into the Mechanism of Phenylacetate Decarboxylase (PhdB), a Toluene-Producing Glycyl Radical Enzyme

We recently reported the discovery of phenylacetate decarboxylase (PhdB), representing one of only ten glycyl-radical-enzyme reaction types known, and a promising biotechnological tool for first-time biochemical synthesis of toluene from renewable resources. Here, we used experimental and computational data to evaluate the plausibility of three candidate PhdB mechanisms, involving either attack at the phenylacetate methylene carbon or carboxyl group [via H-atom abstraction from COOH or single-electron oxidation of COO⁻ (Kolbe-type decarboxylation)]. In vitro experimental data included assays with F-labeled phenylacetate, kinetic studies, and tests with site-directed PhdB mutants; computational data involved estimation of reaction energetics using density functional theory (DFT). The DFT results indicated that all three mechanisms are thermodynamically challenging (beyond the range of many known enzymes in terms of endergonicity or activation energy barrier), reflecting the formidable demands on PhdB for catalysis of this reaction. Evidence that PhdB was able to bind α,α-difluorophenylacetate but was unable to catalyze its decarboxylation supported the enzyme's abstraction of a methylene H atom. Diminished activity of H327A and Y691F mutants was consistent with proposed proton donor roles for His327 and Tyr691. Collectively, these and other data most strongly support PhdB attack at the methylene carbon.     

Oxidative removal of bisphenol A using zero valent aluminum-acid system

Bisphenol A (BPA), a controversial endocrine disruptor, is ubiquitous in the aquatic environment. In this study, the oxidative degradation of BPA and its mechanism using zero valent aluminum (ZVAl)-acid system under air-equilibrated conditions was investigated. Under pH <3.5 acidic conditions, ZVAl demonstrated an excellent capacity to remove BPA. More than 75% of BPA was eliminated within 12 h in pH 1.5 reaction solutions initially containing 4.0 g/L aluminum and 2.0 mg/L BPA at 25 ± 1 °C. The removal of BPA was further accelerated with increasing aluminum loadings. Higher temperature and lower initial pH also facilitated BPA removal. The addition of Fe²⁺ into the ZVAl-acid system significantly accelerated the reaction likely due to the enhancing transformation of H₂O₂ to HO via Fenton reaction. Furthermore, the primary products or intermediates including monohydroxylated BPA, hydroquinone, 2-(4-hydroxyphenyl)propane and 4-isopropenylphenol, were identified and a possible reaction scheme was proposed. The remarkable capacity of the ZVAl-acid system in removing BPA displays its potential application in the treatment of organic compound-contaminated water.     

Arsenic-sulfides confound anion exchange resin speciation of aqueous arsenic

A field-portable anion exchange resin method (often cited as the Ficklin method (1983)) has been extensively used to distinguish between dissolved arsenite (As(III)) and arsenate (As(V)) species in natural waters. As(III) occurs largely as As(OH)(3), which is uncharged at ca. pH 7, while As(V) is negatively charged and will sorb to the resin. However, we show that negatively charged As(III)-sulfide (thioarsenite) species, important at sulfide concentrations >10 microM, also bind to the anion exchange resins, and therefore might be interpreted incorrectly as As(V). Furthermore, we show that nitrogen-purging, which results in a conversion of As(III)-sulfides to arsenite, can be used to obtain accurate arsenic speciation when resins are used on sulfidic water samples.     

Anaerobic microbial mobilization and biotransformation of arsenate adsorbed onto activated alumina

Due to the enactment of a stricter drinking water standard for arsenic in the United States, larger quantities of arsenic will be treated resulting in larger volumes of treatment residuals. The current United States Environmental Protection Agency recommendation is to dispose spent adsorbent residuals from arsenic treatment into non-hazardous municipal solid waste (MSW) landfills. The potential of microorganisms to alter the speciation affecting the mobility of arsenic in the disposal environment is therefore a concern. The purpose of this paper was to evaluate the potential of an anaerobic microbial consortium to biologically mobilize arsenate (As(V)) adsorbed onto activated alumina (AA), a common adsorbent used for treating arsenic in drinking water. Three anaerobic columns (0.27 l) packed with 100 g dry weight of AA containing 0.657 mg adsorbed As(V) (expressed as arsenic) per gram dry weight were continuously flushed with synthetic landfill leachate for 257 days. The fully biologically active column was inoculated with methanogenic anaerobic sludge (10 g volatile suspended solids l(-1) column) and was operated with a mixture of volatile fatty acids (VFA) in the feed (2.5 g chemical oxygen demand l(-1) feed). At the end of the experiment, 37% of the arsenic was removed from the column, of which 48% was accounted for by arsenical species identified in the column effluent. The most important form of arsenic eluted was arsenite (As(III)), accounting for nearly all of the identified arsenic in periods of high mobilization. Additionally, two methylated metabolites, methylarsonic acid and dimethylarsinic acid were observed. Mobilization of arsenic is attributed to the biological reduction of As(V) to As(III) since literature data indicates that As(III) is more weakly adsorbed to AA compared to As(V). Batch and continuous assays confirmed that VFA, present in landfill leachates, served as an electron donating substrate supporting enhanced rates of As(V) reduction to As(III). Two control columns, lacking inoculum and/or VFA in the feed displayed low mobilization of arsenic compared to the fully biologically active column. Therefore, leachates generated in MSW landfills could potentially result in the biologically catalyzed mobilization of arsenic from As(V)-laden drinking water residuals.