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At least 973 records · Page 54

RNA isolation and fractionation with compaction agents

A new approach to the isolation of RNA from bacterial lysates employs selective precipitation by compaction agents, such as hexammine cobalt and spermidine. Using 3.5 mM hexammine cobalt, total RNA can be selectively precipitated from a cell lysate. At a concentration of 2 mM hexammine cobalt, rRNA can be fractionated from low molecular weight RNA. The resulting RNA mixture is readily resolved to pure 5S and mixed 16S/23S rRNA by nondenaturing anion-exchange chromatography. Using a second stage of precipitation at 8 mM hexammine cobalt, the low molecular weight RNA fraction can be isolated by precipitation. Compaction precipitation was also applied to the purification of an artificial stable RNA derived from Escherichia coli 5S rRNA and to the isolation of an Escherichia coli-expressed ribozyme. Copyright 2001 Academic Press.

Non-NASA Center↗

Identification of Ser-543 as the major regulatory phosphorylation site in spinach leaf nitrate reductase

Spinach leaf NADH:nitrate reductase (NR) responds to light/dark signals and photosynthetic activity in part as a result of rapid regulation by reversible protein phosphorylation. We have identified the major regulatory phosphorylation site as Ser-543, which is located in the hinge 1 region connecting the cytochrome b domain with the molybdenum-pterin cofactor binding domain of NR, using recombinant NR fragments containing or lacking the phosphorylation site sequence. Studies with NR partial reactions indicated that the block in electron flow caused by phosphorylation also could be localized to the hinge 1 region. A synthetic peptide (NR6) based on the phosphorylation site sequence was phosphorylated readily by NR kinase (NRk) in vitro. NR6 kinase activity tracked the ATP-dependent inactivation of NR during several chromatographic steps and completely inhibited inactivation/phosphorylation of native NR in vitro. Two forms of NRk were resolved by using anion exchange chromatography. Studies with synthetic peptide analogs indicated that both forms of NRk had similar specificity determinants, requiring a basic residue at P-3 (i.e., three amino acids N-terminal to the phosphorylated serine) and a hydrophobic residue at P-5. Both forms are strictly calcium dependent but belong to distinct families of protein kinases because they are distinct immunochemically.

NASA Discipline Plant Biology↗

The anion exchange properties of AFm (hydrocalumite-group) minerals defined from solubility experiments and crystallographic information

Solubility experiments with binary series of OH-, Cl-, SO{sub 4}- and CO{sub 3}-AFm were re-examined with a non-ideal, multicomponent solid solution model. The electrical double layer on the mineral's outer surface, which neutralizes about 5% of the anionic charge, can be included. The choice of the end-members in the solid solution and the reaction formulation can help to eliminate the ‘non-ideality’ for OH-SO{sub 4} and Cl-OH exchange. CO{sub 3}-Cl-OH exchange is not ideal in the solubility experiments, nor can it be, because the mineral volume is not a linear combination of the end-members. The solubilities of the end-members are related to the anion charge and inversely to the anion-layer thickness. OH is part of the anion-charge, even when a pure, other anion form is the target of the synthesis. Pure OH-AFm is unstable and converts into hydrogarnet and portlandite, depending on the precipitation rate of hydrogarnet.

36 MATERIALS SCIENCE↗

Ammonium-Coordinated Exchanger (ACE) Sorbents for Aqueous Oxyanion Metal Recovery/Removal

Ammonium coordinated exchanger (ACE) sorbents recovery/remove anionic contaminant/critical metals from water. Heavy reliance of the U.S. on foreign critical mineral (CM) supplies presents national security and economics risks. This prompted government action. Domestically recovering CM from unconventional water sources, largely through adsorption processes, could alleviate this problem. Acid mine drainage and mineral leachates are viable sources

amines↗

Cation uptake by fine aggregate in hardened cement mortar and its effect on electrical properties

Electrical resistivity tests can be used to evaluate the transport properties of concrete and provide a durability assessment. However, the electrical resistivity is largely dependent on the pore solution composition and recent work suggests that some aggregates have the capacity for cation uptake. This study first aims to provide further evidence for adsorption of cations on aggregate surfaces, without formation of reaction products (e.g. alkali-silica reaction). Secondly, hardened mortar samples were prepared using a fine aggregate with a high alkali affinity and a non-reactive fine aggregate as a control. The electrical resistivity of mortars was measured, and the pore solution of these mortars was obtained through high-pressure extraction. The effect of aggregate moisture dilution on the pore solution was decoupled by using a pore partitioning model. The results indicate that aggregate minerology can influence the pore solution composition through cation uptake. Specific minerals of minor quantity, like biotite, may be responsible for cation exchange. While adsorbed cations strongly affected pore solution and formation factor measurement, the bulk resistivity measurements on hardened mortar were only marginally influenced. Research on other implications of similar aggregate interactions with pore solutions are an intriguing area for future research.

Alkali-aggregate reaction↗

Pseudospin versus magnetic dipole moment ordering in the isosceles triangular lattice material K 3 Er(VO 4 ) 2

Spin- 1 / 2 antiferromagnetic triangular lattice models are paradigms of geometrical frustration, revealing very different ground states and quantum effects depending on the nature of anisotropies in the model. Due to strong spin orbit coupling and crystal field effects, rare-earth ions can form pseudospin- 1 / 2 magnetic moments with anisotropic single-ion and exchange properties. Thus, rare-earth-based triangular lattices enable the exploration of this interplay between frustration and anisotropy. Here we study one such case, the rare-earth double vanadate glaserite material K 3 Er ( VO 4 ) 2 , which is a quasi-two-dimensional (2D) isosceles triangular antiferromagnet. Our specific heat and neutron powder diffraction data from K 3 Er ( VO 4 ) 2 reveal a transition to long range magnetic order at T N = 155 ± 5 mK which accounts for all R ln 2 entropy. Furthermore, we observe what appears to be a coexistence of three-dimensional (3D) and quasi-2D order below T N . The quasi-2D order leads to an anisotropic Warren-like peak profile for ( h k 0 ) reflections, while the 3D order is best-described by layers of antiferromagnetic b -aligned moments alternating with layers of zero moment. Our magnetic susceptibility data reveal that Er 3 + takes on a strong X Y single-ion anisotropy in K 3 Er ( VO 4 ) 2 , leading to vanishing moments when pseudospins are oriented along c . Thus, the magnetic structure, when considered from the pseudospin point of view could comprise of alternating layers of b -axis and c -axis aligned antiferromagnetism.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Morphology and Transport of Multivalent Cation-Exchanged Ionomer Membranes Using Perfluorosulfonic Acid–Ce Z+ as a Model System

Perfluorosulfonic acids (PFSAs) are commonly used as solid polymer electrolyte membranes (PEMs) in electrochemical energy devices, where they are vulnerable to attack by radical species during operation. A popular strategy to combat this problem is to introduce radical scavengers like cerium (Ce) ions that neutralize these species before they attack the PFSA. Such cation doping creates a multi-ion system, in which understanding the mechanisms of cation solvation and transport becomes important for the effective design and utilization of PFSA–cation systems. Ce ions also provide a representative model system for multication-exchanged ionomers in electrochemical systems. In this study, hydration and conductivity measurements, along with X-ray fluorescence and scattering, are employed to elucidate how Ce ion exchange alters PFSA’s ionic solvation, as well as nano- and mesoscale morphologies, which ultimately control its ion transport properties. A molecular transport model is used to deconvolute the impact of Ce ions on the local solvation structure of water in the membrane from mesoscale changes of the transport pathways. The combined experimental and theoretical analysis reveals a nonlinear decrease in conductivity driven by cation solvation at the molecular level and morphological changes at longer length scales. Migration–diffusion coupling, its nonlinear dependence on ion exchange and hydration, and its overall implications for ionomer performance are also discussed. Finally, these findings have the potential to be translated into other mixed cation–ionomer systems for a wide range of energy and environmental devices.

36 MATERIALS SCIENCE↗

Ammonium-coordinated exchanger (ACE) functionalized silica sorbents for recovering/removing aqueous anionic contaminants

There are limited studies of functionalized silica anion exchange sorbents used for critical/heavy metal recovery/removal relative to polymeric and other inorganic materials. This work features ammonium-coordinated exchanger (ACE) anion exchange particle sorbents prepared by either acid-washing epoxy-crosslinked polyethylenimine (PEI) hydrogen bonded within/to a silica particle sorbent (two-step method) or reacting a di-chlorinated crosslinker, α,α-dichloro-p-xylene (DPX), with PEI within silica (single-step method). Energy dispersive X-ray spectroscopy (EDS) and infrared spectroscopy confirmed the presence of -NH 2 + ···Cl - and -NH 3 + ···Cl - groups, which removed oxyanionic species –arsenate, selenate, chromate, sulfate, phosphate, and nitrate– plus bromide from ideal solutions, authentic acid mine drainage (AMD), and authentic flue gas desulfurization (FGD) wastewater. Affinity of the anions for ACE varied across single- and mixed-element solutions. However, affinity for CrO 4 2- was among the highest in both cases. Total anion uptake by the optimized ACE, PEI-E3-HCl_1.1, reached 1.2 mmol anion/g-sorb. (0.56 mmol CrO 4 2- /g), or ∼2.3 mmol negative charge/g-sorb. This was close to the 0.52 mmol CrO 4 2- /g of a commercial anion exchange resin. Near-consistent removal of 20–80 % of each anion from FGD during an eight-cycle adsorption-desorption (1 M NaCl) test predicted good ACE viability for testing under practical conditions at larger scale.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Performance and Durability Investigation of Thin, Low Crossover Proton Exchange Membranes for Water Electrolyzers

The goal of this project was to fabricate and study the performance and durability implications of thin, mechanically reinforced membranes containing gas recombination catalysts (GRCs) for advanced proton exchange membrane water electrolysis (PEMWE) systems. The thinner membranes, optimized for a PEMWE environment, dramatically reduced the proton transport resistance across the membrane, improving the overall efficiency of the PEMWE system. At the same time, the GRC technology was deployed to recombine crossover hydrogen from the cathode with oxygen from the anode to form water within the membrane. This reaction mitigated the buildup of hydrogen in the oxygen stream, ensuring safe operation of the PEMWE system. Capabilities to measure the gas crossover in both an ex-situ screening cell and in operando application testing were developed over the course of the project to track membrane progress and quantify deliverables. State of the art roll to roll manufacturing technologies were leveraged to fabricate the membranes on a commercial scale, where the membrane structure was precisely tuned and GRC distributed within the membrane structure.

08 HYDROGEN↗

PbS/CdS Quantum Dot Room-Temperature Single-Emitter Spectroscopy Reaches the Telecom O and S Bands via an Engineered Stability

We synthesized PbS/CdS core/shell quantum dots (QDs) to have functional single-emitter properties for room-temperature, solid-state operation in the telecom O and S bands. Two shell-growth methods–cation exchange and successive ionic layer adsorption and reaction (SILAR)–were employed to prepare QD heterostructures with shells of 2–16 monolayers. PbS/CdS QDs were sufficiently bright and stable to resolve photoluminescence (PL) spectra representing both bands from single nanocrystals using standard detection methods, and for a QD emitting in the O-band a second-order correlation function showed strong photon antibunching, important steps toward demonstrating the utility of lead chalcogenide QDs as single-photon emitters (SPEs). Irrespective of type, few telecom-SPEs exist that are capable of such room-temperature operation. Access to single-QD spectra enabled a direct assessment of spectral line width, which was ~70–90 meV compared to much broader ensemble spectra (~300 meV). We show inhomogeneous broadening results from dispersity in PbS core sizes that increases dramatically with extended cation exchange. Quantum yields (QYs) are negatively impacted at thick shells (>6 monolayers) and, especially, by SILAR-growth conditions. Time-resolved PL measurements revealed that, with SILAR, initially single-exponential PL-decays transition to biexponential, with opening of nonradiative carrier-recombination channels. Radiative decay times are, overall, longer for core/shell QDs compared to PbS cores, which we demonstrate can be partially attributed to some core/shell sizes occupying a quasi-type II electron–hole localization regime. Finally, we demonstrate that shell engineering and the use of lower laser-excitation powers can afford significantly suppressed blinking and photobleaching. However, dependence on shell thickness comes at a cost of less-than-optimal brightness, with implications for both materials and experimental design

36 MATERIALS SCIENCE↗

Neutral Atom Imaging of the Solar Wind-Magnetosphere-Exosphere Interaction Near the Subsolar Magnetopause

Energetic neutral atoms (ENAs) created by charge-exchange of ions with the Earth's hydrogen exosphere near the subsolar magnetopause yield information on the distribution of plasma in the outer magnetosphere and magnetosheath. ENA observations from the Interstellar Boundary Explorer (IBEX) are used to image magnetosheath plasma and, for the first time, low-energy magnetospheric plasma near the magnetopause. These images show that magnetosheath plasma is distributed fairly evenly near the subsolar magnetopause; however, low-energy magnetospheric plasma is not distributed evenly in the outer magnetosphere. Simultaneous images and in situ observations from the Magnetospheric Multiscale (MMS) spacecraft from November 2015 (during the solar cycle declining phase) are used to derive the exospheric density. The ~11–17 cm –3 density at 10 R E is similar to that obtained previously for solar minimum. Thus, these combined results indicate that the exospheric density 10 R E from the Earth may have a weak dependence on solar cycle.

79 ASTRONOMY AND ASTROPHYSICS↗

Silyl Hot-Injection Versus Thiocyanate Heat-Up Synthesis of Chalcohalides: Pushing the Size and Composition Envelope

Chalcohalide semiconductors are rapidly gaining traction as stable, biocompatible materials for energy conversion applications. While the solid-state synthesis of bulk chalcohalides is relatively well-developed, the colloidal chemistry of these materials is still in its early stages. Colloidal semiconductors are often advantageous in device fabrication due to the cost effectiveness of solution processing. Thus, we aim to increase the utility of chalcohalides in device fabrication by establishing solution phase chemistry of promising compositions. We show that silyl hot-injection is a versatile and effective method of making colloidal PnChI (Pn = Sb, Bi; Ch = S, Se) and Sn 2 PnS 2 I 3 (Pn = Sb, Bi) chalcohalides of tunable sizes and compositions. Furthermore, we demonstrate the preparation of mixed-pnictide chalcohalides through direct hot-injection and/or postsynthetic cation exchange, the latter being one of the few reported instances in chalcohalides. Additionally, we use the thiocyanate heat-up approach in combination with density functional theory to study halide mixing in quaternary tin chalcohalides. By pushing the limits of each synthetic technique, we have designed more soluble chalcohalides with tunable compositions while also gaining a better understanding of the efficacy of each procedure in respect to thin film and subsequent device fabrication. In addition to size and composition tuning, silyl hot-injection can help facilitate the future development and wide-scale application of chalcohalide-based devices by expanding the selection of solution-processable chalcohalides.

halogens↗

Downstream Separation of Formic Acid with Anion-Exchange Resin from Electrocatalytic Carbon Dioxide (CO 2 ) Conversion: Adsorption, Kinetics, and Equilibrium Modeling

The electrocatalytic carbon dioxide reduction reaction (CO 2 RR) that produces liquid formic acid (FA) is one potential route to minimize the CO 2 concentration in the atmosphere by utilizing CO 2 as a feedstock. However, one of the main disadvantages of this route is the high energy demand required for purification through conventional distillation. This method of purification has been shown to result in a large carbon footprint in life-cycle analysis (LCA). Therefore, finding an alternative purification technique that can integrate with an electrochemical CO 2 RR process with the potential to lower the carbon footprint would be of great interest. Under the experimental conditions of the CO 2 RR, FA remains in its basic form as the formate anion in the catholyte. Anion exchange resins with their basic properties can separate the formate anion from the catholyte mixture as an alternative to energy intensive distillation. In this work, three anion exchange resins with increasing basicity order: Amberlite IRA-96 < Amberlite IRA-910 < Ambersep 900 are tested to separate FA in the presence of aqueous solution of potassium bicarbonate catholyte with varying levels of resin and FA. Kinetics and equilibrium studies data for the FA adsorption are interpreted using several kinetics and isotherm models. The kinetics data fit well with a pseudo-first-order model at high initial FA concentrations and a pseudo-second-order model at low initial FA concentrations. The experimental data can be best explained with the Freundlich isotherm model. The fitted results show that strongly basic Ambersep 900 is more effective at separating FA, with a maximum adsorption capacity of 336.7 mg/g compared to Amberlite IRA-96 (275.2 mg/g) and Amberlite IRA-910 (209.2 mg/g) in neutral water. However, weakly basic Amberlite IRA-96 (110.8 mg/g) can separate FA more efficiently from potassium bicarbonate catholyte than Amberlite IRA-910 (99.9 mg/g) and Ambersep 900 (40.0 mg/g). As a result, competitive adsorption occurs in the presence of potassium bicarbonate catholyte, but the formic acid adsorption capacity is still sufficient for adequate separation.

20 FOSSIL-FUELED POWER PLANTS↗

Hybrid Sorbents for 129 I Capture from Contaminated Groundwater

Radioiodine ( 129 I) poses a risk to the environment due to its long half-life, toxicity, and mobility. It is found at the U.S. Department of Energy Hanford Site due to legacy releases of nuclear wastes to the subsurface where 129 I is predominantly present as iodate (IO 3 – ). To date, a cost-effective and scalable cleanup technology for 129 I has not been identified, with hydraulic containment implemented as the remedial approach. Here, novel high-performing sorbents for 129 I remediation with the capacity to reduce 129 I concentrations to or below the US Environmental Protection Agency (EPA) drinking water standard and procedures to deploy them in an ex-situ pump and treat (P&T) system are introduced. Furthermore, this includes implementation of hybridized polyacrylonitrile (PAN) beads for ex-situ remediation of IO 3 – -contaminated groundwater for the first time. Iron (Fe) oxyhydroxide and bismuth (Bi) oxyhydroxide sorbents were deployed on silica substrates or encapsulated in porous PAN beads. In addition, Fe–, cerium (Ce)–, and Bi–oxyhydroxides were encapsulated with anion-exchange resins. The PAN–bismuth oxyhydroxide and PAN–ferrihydrite composites along with Fe- and Ce-based hybrid anion-exchange resins performed well in batch sorption experiments with distribution coefficients for IO 3 – of >1000 mL/g and rapid removal kinetics. Of the tested materials, the Ce-based hybrid anion-exchange resin was the most efficient for removal of IO 3 – from Hanford groundwater in a column system, with 50% breakthrough occurring at 324 pore volumes. The functional amine groups on the parent resin and amount of active sorbent in the resin can be customized to improve the iodine loading capacity. These results highlight the potential for IO 3 – remediation by hybrid sorbents and represent a benchmark for the implementation of commercially available materials to meet EPA standards for cleanup of 129 I in a large-scale P&T system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Iodine Removal from Carbonate-Containing Alkaline Liquids Using Strong Base Resins, Hybrid Resins, and Silver Precipitation

The ability of several material types to remove aqueous iodine from a mildly alkaline, carbonate-rich nuclear waste stream was evaluated: strong base anion exchange resins (SBAR), hybrid resins, Ag-containing materials and Bi-containing hybrid resins. A combination of batch testing and flow through column testing were used in the evaluation. In batch testing, hybrid resins CHM-20, SIR-110-CE and RTBI were shown to have high efficiency for the removal of both iodide and iodate simultaneously, while Ag-containing materials and SBAR demonstrated high capacity for iodide removal. One example of each material type (CHM-20, A532E and Ionex 400) were further evaluated for their sorption isotherms and column performance. The Langmuir isotherm, or a Langmuir-Freundlich hybrid isotherm, best described the sorption of iodide to the CHM-20 hybrid resin and Purolite A532E. The Freundlich isotherm best described the uptake of iodate to CHM-20 and A532E and for both iodide and iodate to the Ag-containing Ionex-400. In column testing the Purolite A532E had exceptional performance for overall iodide removal. With the capacity demonstrated the A532E resin would exceed Class C waste classification before breakthrough initiated, and column change outs in processing would be dictated by eventual waste classification, not breakthrough. The Ionex 400, a Ag-zeolite, was observed to degrade over time in the column in the mild alkaline conditions whereas the hybrid CHM-20 was limited in the single pass through design and would be best suited for applications where iodide and iodate are present and recirculation of the column effluent is feasible. Here this work highlights the feasibility of commercially available materials to separate radioiodine from liquid environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Stability Analysis of Substituted Cobaltocenium [Bis(cyclopentadienyl)cobalt(III)] Employing Chemistry-Informed Neural Networks

Cobaltocenium derivatives are promising components of the anion exchange membranes due to their excellent thermal and alkaline stability under the operating conditions of a fuel cell. Here we present an efficient modeling approach of assessing the chemical stability of substituted cobaltocenium CoCp 2 + based on the computed electronic structure enhanced by machine learning techniques. Within the aqueous environment, the positive charge of the metal cation is balanced by the hydroxide anion through formation of the CoCp 2 + OH¯ complexes, whose dissociation is studied within the implicit solvent employing density functional theory. The data set of about 118 species based on 42 substituent groups characterized by a range of electron- donating (ED) and electron-withdrawing (EW) properties is constructed and analyzed. Given 12 carefully chosen chemistry-informed descriptors of the complexes and relevant fragments, the stability of the complexes is found to strongly correlate with the energies of the highest occupied and lowest unoccupied molecular orbitals, modulated by a switching function of the Hirshfeld charge. The latter is used as a measure of the electron withdrawing-donating character of the substituents. Based on this observation from the conventional regression analysis, two fully connected, feed-forward neural network (FNN) models with different unit structures, called the chemistry-informed (CINN) and the quadratic (QNN) neural networks, are developed. Both models predict the bond dissociation energies of the cobaltocenium complexes with mean relative errors less than 5.40% and average absolute errors less than 0.94 kcal/mol. The results show the potential of QNN to efficiently capture more complex relationships. Here, the concept of incorporating the domain (chemical) knowledge/insight into the neural network structure paves the way to applications of machine learning techniques with small data sets, ultimately leading to better predictive models compared to the conventional regression analysis.

36 MATERIALS SCIENCE↗

Chemical Understanding of Actinide Separations

This work provides a broad overview of the separation processes used to isolate actinides and the experimentally and computationally determined chemical characteristics that define those separations. The redox chemistry of the actinides plays a pivotal role in both aqueous and pyrochemical processing separations. The near-overlapping energies of the 6d and 5f orbitals in the light actinides allow for facile adjustment of actinide oxidation states, which is used in many established separation methods. In contrast, the stable, generally 3+ oxidation states of the mid- and heavy actinides can make it difficult to separate them from the similarly lanthanides(III). In aqueous separations, the tendency of the actinides to form anionic and neutral aqueous complexes with a variety of complexants (especially soft donors) is used to achieve high separation factors between chemically similar elements in both solid–liquid separations and liquid–liquid extraction. This selectivity can be further tuned through the use of specialized organic or solid-phase ligands. Pyroprocessing separations utilize the unique redox behavior of the actinides to adjust their distribution between a molten salt electrolyte and either a solid electrode or molten metal phase. Atomic-level insights into the mechanisms underlying actinide separation processes, with the ultimate goal of predicting separation behavior, can be provided by electronic structure and statistical mechanical-based calculation methods.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Response surface methodology guided adsorption and recovery of free fatty acids from oil using resin

The presence of free fatty acids interferes with the conversion of plant oils to biodiesel. In this work, four strong and weak base resins were evaluated for the removal of free fatty acids (FFA) from oil. Amberlite FPA 51 showed the highest adsorption capacity of FFA. A resin concentration above 3% could enable a higher percentage FFA adsorption. The adsorption process fitted a pseudo-first-order kinetic model and achieved equilibrium in approximately 8 h. A full factorial design was used to optimize the resin and FFA concentrations at a fixed temperature (40°C). A ratio of resin to fatty acid concentrations above 1.875 was sufficient for 70% adsorption and the amount adsorbed continued to increase with further added resin. A two-step washing of resin using hexane and ethanol recovered approximately 67.55%±4.05% of the initially added fatty acid. The resin that was used was regenerated with 5% NaOH and re-used for a minimum of three consecutive cycles. However, the adsorption capacity diminished to 75% of the initial cycle in cycles 2 and 3. Thus, the work presents a resin-based process for deacidification of oil to reduce fatty acid content of oil for biodiesel production.

09 BIOMASS FUELS↗