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Results for “adsorptive chromatography”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 19 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS2003

Enhancement of anion-exchange chromatography of DNA using compaction agents

The use of adsorptive chromatography for preparative nucleic acid separations is often limited by low capacity. The possibility that the adsorbent surface area sterically accessible to nucleic acid molecules could be increased by reducing their radius of gyration with compaction agents has been investigated. The equilibrium adsorption capacity of Q Sepharose anion-exchange matrix for plasmid DNA at 600 mM NaCl was enhanced by up to ca. 40% in the presence of 2.5 mM spermine. In addition, compaction agent selectivity has been demonstrated. Spermine, for example, enhances the adsorption of both plasmid and genomic DNA, spermidine enhances binding only of plasmid, and hexamine cobalt enhances only the binding of genomic DNA. Compaction may be generally useful for enhancing adsorptive separations of nucleic acids.

NASA Discipline Environmental Health↗
NASA NTRS1991

Evaluation of Fungal Metabolic Compounds Released to the Air in a Restricted Environment

The metabolic action of selected fungi species on common components of the interior of Space Station Freedom (SSF) will be tested. When present, volatile organic chemicals will be collected on porous polymer adsorbent columns. Using thermal desorption, the volatile compounds will be passed onto a gas chromatographic column for analysis. The Space Station Freedom (SSF) modular complex will largely be individually self contained and the established air environment will not be easily adjusted. The development and maintenance of a safe working environment offers a considerable challenge. Present plans for use of SSF acknowledge periods of manned activities and alternate times when the station is unmanned. The obvious necessity for clean and safe air and water during periods of use have been pursued as fundamental systems to SSF success. Somewhat less obvious, although perhaps of no less importance to the success of long term cyclic usage, are those periods of inactivity. It is during these periods when spores from microorganisms may be afforded the best conditions to germinate and in the vegetative form react with the complex synthetic chemical polymers which compose the furnishings and hardware of SSF nodes. Biodegradation could constitute a real hygiene problem, if the organisms form and release volatile organic chemicals. Similar problems have been documented in closed and improperly ventilated buildings and work spaces. Many of the metabolic products of fungi and bacterial growth create a variety of health problems. Analytical chemical techniques will first be used to document the growth of Aspergillus, Penicillium, and Cladosporium fungal species on the potential substrates Nomex and Kevlar. Any volatile organics that are released will be measured using the spectrum of gas adsorption chromatography. The level of microbial contamination that is necessary to produce such volatile compounds and the relative amounts expected to accumulate will be estimated.

Ferebee, Robert N.↗
NASA NTRS1966

Electrostatic interactions in gas-solid chromatography.

Electrostatic theory of physical adsorption applied to gas-solid chromatography, discussing chromatographic inseparability of argon and oxygen at room temperature, prediction of elution order of many gases, etc

GAS-SOLID INTERFACE↗
DOE OSTI2023

Chemically Stable Styrenic Electrospun Membranes with Tailorable Surface Chemistry

Membranes with tailorable surface chemistry have applications in a wide range of industries. Synthesizing membranes from poly(chloromethyl styrene) directly incorporates an alkyl halide surface-bound initiator which can be used to install functional groups via SN2 chemistry or graft polymerization techniques. In this work, poly(chloromethyl styrene) membranes were synthesized through electrospinning. After fabrication, membranes were crosslinked with a diamine, and the chemical resistance of the membranes was evaluated by exposure to 10 M nitric acid, ethanol, or tetrahydrofuran for 24 h. The resulting membranes had diameters on the order of 2–5 microns, porosities of >80%, and permeance on the order of 10,000 L/m2/h/bar. Crosslinking the membranes generally increased the chemical stability. The degree of crosslinking was approximated using elemental analysis for nitrogen and ranged from 0.5 to 0.9 N%. The poly(chloromethyl styrene) membrane with the highest degree of crosslinking did not dissolve in THF after 24 h and retained its high permeance after solvent exposure. The presented chemically resistant membranes can serve as a platform technology due to their versatile surface chemistry and can be used in membrane manufacturing techniques that require the membrane to be contacted with organic solvents or monomers. They can also serve as a platform for separations that are performed in strong acids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Investigating the Role of Silver Oxidation State on the Thermodynamic Interactions between Xenon and Silver-Functionalized Zeolites

The molecular level understanding of the strong adsorption of Xe to silver-modified zeolites remains elusive. Here, we probe the effect of silver oxidation state on the thermodynamics of Xe sorption in silver-functionalized zeolites by measuring the enthalpies of adsorption after various treatments using inverse gas chromatography (IGC). The enthalpy of adsorption was measured for silver-functionalized chabazites (AgCHA) before and after hydrogen reduction and subsequent reoxidation. The sorption enthalpy (ΔH) for AgCHA was 35.2 kJ/mol, which decreased to 25.8 kJ/mol with hydrogen reduction. After reoxidation (O 2 -AgCHA), 95% of the binding strength was restored. Hydrogen reduction of the base chabazite (CHA) did not influence Xe adsorption. Henry’s law constant for Xe adsorption increased in the order AgCHA > O 2 -AgCHA > H 2 -AgCHA > CHA. A decrease in enthalpy and Henry’s constant with silver reduction and increase with reoxidation suggest that ionic silver is playing a role in Xe binding. The effect of reduction and reoxidation on the zeolite microstructure was analyzed using surface area analysis, powder X-ray diffraction (p-XRD), scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM/EDS), and X-ray photoelectron spectroscopy (XPS). Finally, these results lay the groundwork for better material design of strong noble gas adsorbents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

A New Process for Small-Batch Purification of the Medical Isotope Molybdenum-99: Non-Technical Overview

The U.S. medical community depends on a reliable supply of the radioisotope molybdenum-99 (Mo-99) for nuclear medical diagnostic procedures. Mo-99's decay product, technetium-99m (Tc-99m), is used in over 40,000 medical procedures in the United States each day to diagnose heart disease and cancer, to study organ structure and function, and to perform other important medical applications. For example, patients undergoing a common procedure—the cardiac “stress test”—likely have benefited from Tc-99m. Historically, Mo-99 was primarily produced through the fission of uranium-235, in the form of highly enriched uranium (HEU) targets irradiated in research and test reactors. HEU is a proliferation-sensitive material that, if diverted or stolen, could be used as a component of a nuclear weapon. NNSA’s Office of Material Management and Minimization (M3) manages the Molybdenum-99 (Mo-99) Program as part of its mission to minimize the use of HEU in civilian applications. The Mo-99 Program assists global Mo-99 production facilities in converting to non-HEU processes and supports the establishment of domestic supplies of Mo-99 without the use of proliferation-sensitive HEU. As part of this program, M3 funds U.S. national laboratories to provide non-proprietary technical support to U.S. companies working to establish non-HEU-based Mo-99 production capabilities. The results of this research are published on OSTI.gov for the benefit of the Mo-99 community and the public. However, it can be difficult for readers without a scientific background to understand and interpret these publications. In order to increase public understanding of the work being done in M3’s Mo-99 Program, this paper aims to provide an overview of a key, recent national laboratory technical publication in terms that can be understood by readers without a technical background. To accomplish this, the paper first explains key scientific concepts—primarily related to chemistry—that provide a foundation for understanding research in this area. This includes chromatography, absorption vs. adsorption, dissolution and precipitation, and liquid-liquid extraction. Drawing on these concepts, the paper then provides an explanation for non-technical audiences of the Argonne National Laboratory publication entitled Recovery of High Specific Activity Molybdenum-99 from Accelerator-Induced Fission on Low-Enriched Uranium for Technetium-99m Generators (Brown, M.A. et al., 2021) and related article Separation and Purification of Mo-99 Produced from Natural U3O8 Targets via Photo-Fission (Brown, M.A. et al., 2021).

Stamler, Bradley↗
DOE OSTI2024

Group hexavalent actinide separation from lanthanides using sodium bismuthate chromatography

Advanced used nuclear fuel (UNF) reprocessing strategies are limited by the complex radiochemical separations and engineering required to achieve the separation of actinides (An) from neutron scavenging lanthanides (Ln). The accessibility of the hexavalent oxidation state for the actinides (U – Am) provides a pathway to achieving a group hexavalent actinide separation from the trivalent lanthanides and Cm. The solid oxidant and ion exchanger, sodium bismuthate (NaBiO 3 ), has been demonstrated to quantitatively oxidize and separate Am from trivalent Cm in a column chromatographic system. This work expands on the use of NaBiO 3 chromatography to characterize the adsorption, kinetic, and elution behavior of U, Pu, and Eu. Separation factors over 200 with rapid kinetics were observed at dilute nitric acid concentrations with a complete An/Ln separation achieved in under an hour. In conclusion, the adsorption and chromatographic behavior of key fission products present in various reprocessing raffinates was characterized which demonstrated potential application of a NaBiO 3 -based separation following a TRUEX process.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2024

Extraction and separation of rare earth elements using LN resins in hydrochloric acid

The separation of the rare earth elements is essential for numerous scientific applications but remains a significant challenge due to the nearly identical chemical properties of the adjacent lanthanide elements. Eichrom’s LN series of extraction chromatographic resins feature organophosphorus extractants and are widely used to achieve adjacent lanthanide separations. While extensive characterization of these resins has been completed for nitric acid matrices, the use of hydrochloric acid is preferred for a variety of applications. Further, the extraction of the rare earth elements, La–Lu and Y, has been characterized on LN and LN2 resins in hydrochloric acid via batch uptake and column chromatographic studies.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
NASA NTRS1981

Possible selective adsorption of enantiomers by Na-montmorillonite

Racemic amino acids including (D,L) alpha-alamine, (D,L) alpha-aminobutyric acid, (D,L) valine, and (D,L) norvaline were incubated with Na-montmorillonite at 100% CEC at three hydrogen ion concentrations, and amino acid adsorption was determined by ion exchange chromatography. Enantiomers were analyzed by gas chromatography. Differences in the quantities of D and L enantiomers in any of the fractions was no larger than a few percent. Although a large difference in the adsorption of the amino acid enantiomers was not observed, the analysis may indicate a small preferential adsorption (0.5-2%) of L-amino acids by Na-montmorillonite.

Friebele, E.↗
DOE OSTI2024

Adsorption of terbium (III) on DGA and LN resins: Thermodynamics, isotherms, and kinetics

Two commercially available extraction chromatography (EXC) resins containing N,N,N’,N’-tetra-n-octyldiglycolamide (DGA Resin, Normal, 50 – 100 μm) and Bis(2-ethylhexyl) phosphate (LN Resin, 100 – 150 μm) were used as adsorbents to study fundamental adsorption properties such as thermodynamic values, equilibrium isotherms, and kinetic uptake models for terbium(III) adsorption. Weight distribution ratios (D w ) for terbium on DGA and LN resins were measured using a [ 160 Tb]Tb 3+ radiometric tracer in nitric acid as a function of acidity, temperature, initial analyte concentration, and equilibrium time. The D w values showed increasing binding affinity for DGA resin at high nitric acid concentrations and decreasing binding affinity for LN resins. Thermodynamic studies for DGA and LN resins revealed that the Gibbs free energy (ΔG) increased consistently with temperature. To model equilibrium data, increasingly higher parameter equilibrium isotherm models (Henry (1) < Langmuir, Freundlich (2) < Redlich-Peterson (3) < Fritz-Schluender (4)) were compared on their root mean squared errors (RMSE) and adjusted determination coefficients to determine the most applicable model. In all cases, the empirical four-parameter Fritz-Schluender isotherm demonstrated a superior fit. Similar comparisons for reaction-based kinetic models (Pseudo-first-order < Pseudo-second-order < Pseudo-n-order) revealed that the higher-order PNO model yielded a superior fit of kinetic data for both resins. Furthermore, in some cases, adsorption isotherms and kinetic models could also be modeled by a lower-order model with minimal change in error parameters. Weber-Morris plots revealed that two linear sections are observed for each resin, where the first linear segment is attributed to fast (film diffusion) adsorption of terbium, followed by slower intraparticle diffusion of terbium through the pores as the rate-limiting step. Based on the Weber-Morris plot, both film and intraparticle diffusion are involved in controlling the kinetic rate of adsorption for DGA and LN resins.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2024

Characterizing cobalt sequestration in manganese-rich coal mine drainage treatment solids

This study investigates Co adsorption on synthesized birnessites over a wide pH range and in sulfate-rich solution to simulate CMD treatment conditions. Langmuir and Freundlich adsorption isotherms of Co at pH values of 3.5, 4.5, and 6.5 at 25°C onto Na-and H-birnessite were generated. Cobalt concentrations in supernatants were determined by ICP-MS and chelation ion chromatography. Mineralogy and morphology of pre- and post-adsorption experiment solids characterization by X-ray diffraction and scanning electron microscopy will be presented. These experiments suggest that cobalt sulfate complexes and pH of CMD, as well as the Mn-oxide mineral structures present in treatment beds, will impact cobalt adsorption in CMD solids, and can be used as calibration points for equilibrium and kinetic modeling approaches that are critical for developing effective and implementable remediation processes and to better inform future Co recovery efforts from CMD solids.

Schaffer, Camille↗
DOE OSTI2025

MCCCS-MN

The MCCCS‒MN (Monte Carlo for Complex Chemical Systems‒Minnesota) software is developed by the Siepmann research group at the University of Minnesota. MCCCS‒MN allows for the simulation of multi-component molecular systems in the canonical, isobaric-isothermal (including constant stress for solids), grand-canonical, semi-grand, and Gibbs (NVT, NPT, and more than two simulation boxes) ensembles. It uses the configurational-bias Monte Carlo method to efficiently sample phase space for linear, branched and cyclic chain molecules, the adiabatic nuclear and electronic sampling Monte Carlo method to treat many-body polarization effects, and the aggregation-volume-bias Monte Carlo algorithm to efficiently sample the spatial distribution of associating molecules. MCCCS-MN employs a molecular representation of the system where force fields contain bonded and non-bonded terms. Funding for the development of MCCCS-MN through grants from the National Science Foundation (simulation of fluid phase equilibria and chromatography) and the Department of Energy (simulation of adsorption equilibria) is gratefully acknowledged.

Siepmann, J.Ilja [University of Minnesota - Twin C↗
NASA NTRS1998

Polymerization on the rocks: beta-amino acids and arginine

We have studied the accumulation of long oligomers of beta-amino acids on the surface of minerals using the 'polymerization on the rocks' protocol. We find that long oligopeptides of beta-glutamic acid which cannot be formed in homogeneous aqueous solution are accumulated efficiently on the surface of hydroxylapatite using 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDAC) as condensing agent. The EDAC-induced oligomerization of aspartic acid on hydroxylapatite proceeds even more efficiently. Hydroxylapatite can also facilitate the ligation of the tripeptide (glu)3. The 'polymerization on the rocks' scenario is not restricted to negatively-charged amino acids. Oligoarginines are accumulated on the surface of illite using carbonyldiimidizole (CDI) as condensing agent. We find that FeS2 catalyzes the CDI-induced oligomerization of arginine, although it does not adsorb oligoarginines. These results are relevant to the formation of polypeptides on the primitive earth.

NASA Discipline Exobiology↗
DOE OSTI2021

Influence of polycarboxylate superplasticizer, citric acid and their combination on the hydration and workability of calcium sulfoaluminate cement

Highlights: • The dispersion efficiency of polycarboxylate superplasticizers drops quickly over time. • Citric acid maintains the dispersion efficiency of PCE over time. • Competitive adsorption between citric acid and PCE occurs. • The combination of citric acid with PCE decreases the initial dispersion efficiency of PCE. PCEs are well known to improve the initial fluidity of CSA. However, their dispersion efficiency drops quickly over time. This issue can be solved by incorporating retarders. In this context, this paper deals with the influence of citric acid, used as a retarder, PCE and their combination on the hydration and workability of CSA. Isothermal calorimetry, XRD and TG analysis were used to describe the hydration process, while workability was characterized with the mini-cone test. Adsorption behavior was investigated using total organic carbon analyzer coupled with ion chromatography. Results show that the introduction of citric acid retained the dispersion efficiency of PCE over time. However, the initial dispersion efficiency of PCE was decreased by citric acid as the latter tend to adsorb first on the surface of cement grains, inhibiting the adsorption of PCE. A dispersion model was proposed to describe the acting mechanism of these admixtures on CSA.

36 MATERIALS SCIENCE↗