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At least 235 records · Page 13

3D Printed Microfluidic Supported Liquid Membrane Module for Radionuclide Separations

Microfluidic supported liquid membrane extraction is a promising technique for microliter-scale radionuclide separations because it requires very small reagent volumes and combines extraction and stripping in a single unit operation. Flat sheet supported liquid membrane (FS-SLM) modules with 100, 200, 300, and 400 μm deep channels were fabricated at a cost of less than 5 USD in material using a commercially available resin three-dimensional (3D) printer. The performance of these modules was characterized by quantifying uranium transport across a 15 v/v% tributyl phosphate (TBP) liquid membrane at flow rates between 5 and 60 μL min –1 and developing a two-dimensional (2D) numerical transport model for the system. The extent of uranium extraction was found to increase with increasing residence time and decreasing channel depth, with quantitative extraction occurring at the slowest flow rates and shallowest channel depths. The numerical model agreed well with the experimental extraction results. Time-dependent calculations showed that the modules reach steady state in fewer than 9 min and that there is a considerable buildup of uranium in the membrane during that time.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Sample processor for the automatic extraction of families of compounds from liquid samples and/or homogenized solid samples suspended in a liquid

A sample processor and method for the automatic extraction of families of compounds, known as extracts, from liquid and/or homogenized solid samples are disclosed. The sample processor includes a tube support structure which supports a plurality of extraction tubes, each containing a sample from which families of compounds are to be extracted. The support structure is moveable automatically with respect to one or more extraction stations, so that as each tube is at each station a solvent system, consisting of a solvent and reagents, is introduced therein. As a result an extract is automatically extracted from the tube. The sample processor includes an arrangement for directing the different extracts from each tube to different containers, or to direct similar extracts from different tubes to the same utilization device.

Jahnsen, Vilhelm J.↗

Techno-Economic Analysis of Gas-Liquid Contactors for Tritium Extraction from Lead-Lithium

To enable a sustainable fuel cycle, any deuterium-tritium fusion reactor must breed its tritium fuel onsite. Lead-lithium (PbLi), a eutectic metal, is a leading liquid breeder material for tritium generation. One challenge with PbLi blanket technology is the extraction of tritium from the molten eutectic. Three technologies are the focus of worldwide research: the vacuum permeator, the vacuum sieve tray, and the gas-liquid contactor (GLC). The present work offers a methodology for designing, sizing, optimizing, and costing a trickle-bed GLC. Here, we analyzed tritium extraction from PbLi using MELODIE experimental data by applying traditional packed bed mass transfer efficiency models along with supplementary models, like film theory. Our analysis revealed that traditional packed bed mass transfer efficiency models do not fit the MELODIE loop experimental data. Moreover, uncertainty in PbLi solubility resulted in a 325-fold increase in required gas flow rates when comparing identical packing heights. The film theory liquid mass transfer coefficient, Delt-Olujic wettability model, and Reiter tritium solubility values fit the MELODIE data best and were used both in the design and to conduct the economic analysis. Techno-economic analysis of the GLC was performed to evaluate three design sizes, all achieving a minimum extraction efficiency of 90 [%] for a total tritium extraction of 31 [kg/yr].

Fusion Fuel Cycle↗

High‐throughput screening of aqueous biphasic systems with ionic liquids as additives for extraction and purification of enveloped virus‐like particles

Due to their unique properties, virus‐like particles (VLPs) have been portrayed as a promising high‐value biopharmaceutical in VLP‐based vaccination and cancer therapy. Nevertheless, due to limited physical and economical capabilities of the current downstream processing of VLPs, their production is still difficult and seen as a major problem that needs to be tackled. In this work, high‐throughput screening on a liquid handling station (LHS) has been implemented for efficient selection of adequate polymer‐salt aqueous biphasic systems (ABS) for extraction and purification of enveloped Hepatitis C virus pseudoparticles (HCVpp). The effect of polyethylene glycol (PEG) molecular weight and salt type (citrate, sulfate, and phosphate) was first evaluated. Furthermore, to optimize extraction parameters, the effect of pH and tie‐line lengths (TLL) was also addressed. For the most promising ABS and extraction conditions, the addition of ten ionic liquids (ILs) as adjuvants was investigated. Insights on the chemical features of ILs that impact HCV‐VLPs partitioning are highlighted. Finally, the potential of studied ABS containing ILs as adjuvants in the extraction and purification of VLPs from cell culture supernatants was addressed. The 100% extraction efficiency of VLPs in the PEG‐rich phase was achieved, and VLP purity was increased compared to the system without IL. In conclusion, these promising results show that ILs can be very effective in modulating the phase properties of polymer‐salt ABS, achieving high HCV‐VLP purification.

Marchel, Mateusz↗

Molecular Analyzer for Complex Refractory Organic-Rich Surfaces (MACROS)

The Molecular Analyzer for Complex Refractory Organic-rich Surfaces, MACROS, is a novel instrument package being developed at NASA Goddard Space Flight Center. MACROS enables the in situ characterization of a sample's composition by coupling two powerful techniques into one compact instrument package: (1) laser desorption/ionization time-of-flight mass spectrometry (LDMS) for broad detection of inorganic mineral composition and non-volatile organics, and (2) liquid-phase extraction methods to gently isolate the soluble organic and inorganic fraction of a planetary powder for enrichment and detailed analysis by liquid chromatographic separation coupled to LDMS. The LDMS is capable of positive and negative ion detection, precision mass selection, and fragment analysis. Two modes are included for LDMS: single laser LDMS as the broad survey mode and two step laser mass spectrometry (L2MS). The liquid-phase extraction will be done in a newly designed extraction module (EM) prototype, providing selectivity in the analysis of a complex sample. For the sample collection, a diamond drill front end will be used to collect rock/icy powder. With all these components and capabilities together, MACROS offers a versatile analytical instrument for a mission targeting an icy moon, carbonaceous asteroid, or comet, to fully characterize the surface composition and advance our understanding of the chemical inventory present on that body.

Getty, Stephanie A.↗

Evaluation of DNA extraction protocols from liquid-based cytology specimens for studying cervical microbiota

Cervical microbiota (CM) are considered an important factor affecting the progression of cervical intraepithelial neoplasia (CIN) and are implicated in the persistence of human papillomavirus (HPV). Collection of liquid-based cytology (LBC) samples is routine for cervical cancer screening and HPV genotyping and can be used for long-term cytological biobanking. We sought to determine whether it is possible to access microbial DNA from LBC specimens, and compared the performance of four different extraction protocols: (ZymoBIOMICS DNA Miniprep Kit; QIAamp PowerFecal Pro DNA Kit; QIAamp DNA Mini Kit; and IndiSpin Pathogen Kit) and their ability to capture the diversity of CM from LBC specimens. LBC specimens from 20 patients (stored for 716 ± 105 days) with CIN values of 2 or 3 were each aliquoted for each of the four kits. Loss of microbial diversity due to long-term LBC storage could not be assessed due to lack of fresh LBC samples. Comparisons with other types of cervical sampling were not performed. We observed that all DNA extraction kits provided equivalent accessibility to the cervical microbial DNA within stored LBC samples. Approximately 80% microbial genera were shared among all DNA extraction protocols. Potential kit contaminants were observed as well. Variation between individuals was a significantly greater influence on the observed microbial composition than was the method of DNA extraction. We also observed that HPV16 was significantly associated with community types that were not dominated by Lactobacillus iners.

59 BASIC BIOLOGICAL SCIENCES↗

Profiling of adrenocorticotropic hormone and arginine vasopressin in human pituitary gland and tumor thin tissue sections using droplet-based liquid-microjunction surface-sampling-HPLC–ESI-MS–MS

Described here are the results from the profiling of the proteins arginine vasopressin (AVP) and adrenocorticotropic hormone (ACTH) from normal human pituitary gland and pituitary adenoma tissue sections using a fully automated droplet-based liquid microjunction surface sampling-HPLC-ESI-MS/MS system for spatially resolved sampling, HPLC separation, and mass spectral detection. Excellent correlation was found between the protein distribution data obtained with this droplet-based liquid microjunction surface sampling-HPLC-ESI-MS/MS system and those data obtained with matrix assisted laser desorption ionization (MALDI) chemical imaging analyses of serial sections of the same tissue. The protein distributions correlated with the visible anatomic pattern of the pituitary gland. AVP was most abundant in the posterior pituitary gland region (neurohypophysis) and ATCH was dominant in the anterior pituitary gland region (adenohypophysis). The relative amounts of AVP and ACTH sampled from a series of ACTH secreting and non-secreting pituitary adenomas correlated with histopathological evaluation. ACTH was readily detected at significantly higher levels in regions of ACTH secreting adenomas and in normal anterior adenohypophysis compared to non-secreting adenoma and neurohypophysis. AVP was mostly detected in normal neurohypophysis as anticipated. This work demonstrates that a fully automated droplet-based liquid microjunction surface sampling system coupled to HPLC-ESI-MS/MS can be readily used for spatially resolved sampling, separation, detection, and semi-quantitation of physiologically-relevant peptide and protein hormones, such as AVP and ACTH, directly from human tissue. In addition, the relative simplicity, rapidity and specificity of the current methodology support the potential of this basic technology with further advancement for assisting surgical decision-making.

59 BASIC BIOLOGICAL SCIENCES↗

Micro-Raman technology to interrogate two-phase extraction on a microfluidic device

Microfluidic devices provide ideal environments to study solvent extraction. When droplets form and generate plug flow down the microfluidic channel, the device acts as a microreactor in which the kinetics of chemical reactions and interfacial transfer can be examined. Among the many benefits of microreactors is the ability to maintain small sample volumes, which is especially important when studying solvent extraction in harsh environments, such as in separations related to the nuclear fuel cycle. In solvent extraction, the efficiency of the process depends on complex formation and rates of transfer in biphasic systems. Thus, it is important to understand the kinetic parameters in an extraction system to maintain a high efficiency and effectivity of the process. Here we present a methodology that combines chemometric analysis with on-line micro-Raman spectroscopy to monitor biphasic extractions within a microfluidic device. This monitoring provided concentration measurements in both organic and aquoeus plugs as they flowed through the microfluidic channel. The biphasic system studied was comprised of HNO3 as the aqueous phase and 30 % (v/v) tributyl phosphate in n-dodecane comprised the organic phase, which simulated the Plutonium Uranium Redox EXtraction (PUREX) process. Using pre-equilibrated solutions (post extraction) the validity of the technique and methodology is illustrated. Following this validation, solutions that were not equilibrated were examined and the kinetics of interfacial mass transfer within the biphasic system were established. Results were compared to kinetics already determined on a macro scale to prove the efficacy of the technique

extraction, interfacial transport, liquid:liquid e↗

Liquid microjunction surface sampling of acetaminophen, terfenadine and their metabolites in thin tissue sections

The aim of this paper was to evaluate the analytical performance of a fully automated droplet-based surface-sampling system for determining the distribution of the drugs acetaminophen and terfenadine, and their metabolites, in rat thin tissue sections. The following are the results: The rank order of acetaminophen concentration observed in tissues was stomach > small intestine > liver, while the concentrations of its glucuronide and sulfate metabolites were greatest in the liver and small intestine. Terfenadine was most concentrated in the liver and kidney, while its major metabolite, fexofenadine, was found in the liver and small intestine. In conclusion, the spatial distributions of both drugs and their respective metabolites observed in this work were consistent with previous studies using radiolabeled drugs.

59 BASIC BIOLOGICAL SCIENCES↗

Novel Diglycolamide Extractant?s Performance in Liquid-Liquid Separations for Pilot Scale Application

Modified diglycolamide (DGA) extractants show high affinity for light lanthanides and improved separation factors compared to phosphonic acids used commercially. Previous studies with DGAs included flowsheet design and implementation into solvent extraction equipment but with low extractant concentration. Modifications on the alkyl chains of previous DGA extractants led to a competitive product for light rare earth separation with a higher extractant concentration. The scope of this project is to test a recently developed DGA extractant for application in pilot scale solvent extraction equipment with single stage testing, by narrowing down scrubbing conditions, and collecting distribution values for flowsheet planning.

42 ENGINEERING↗

Surface-functionalized polyolefin fibers and their use in methods for extracting metal ions from liquid solutions

A fiber useful in the absorption of metal ions from aqueous solutions, the fiber comprising a polyolefin backbone having a diameter of at least 1 micron and having covalently appended on its surface halogen atoms and vinyl-addition polymeric grafts functionalized with metal-binding groups, such as at least one functional group selected from carboxylate, keto, aldo, amino, imino, nitrile, amido, oxime, amidoxime, imide dioxime, and hydroxamate groups. The vinyl-addition polymeric grafts may also be further functionalized with hydrophilic groups different from the metal-binding groups, wherein the hydrophilic groups may be selected from carboxylate, sulfone, sulfonate, phosphonate, alkylammonium, iminium, amide, pyrrolidone, and polyalkyleneglycol groups. Also described are methods for producing the functionalized fibers, and methods for using the functionalized fiber, particularly in extracting metal ions from metal-containing solutions.

Dai, Sheng↗

Structural characterization of sugarcane lignins extracted from different protic ionic liquid pretreatments

Previous studies based on protic ionic liquids have shown them to be effective for extracting lignins from biomass. Moreover, ILs synthesized with amine cations can promote the insertion of nitrogen into lignin, favoring its valorization for industrial applications. Here, lignins extracted from sugarcane bagasse by eight different PILs were analyzed. Several techniques of characterization were employed (2D HSQC NMR, 31P NMR, GPC, Py-GC/MS, TGA, FTIR, and elemental analysis), seeking a deeper understanding of lignin structure post-PILS treatment. In particular, lignin obtained with acetate and lactate anions with monoethanolamonium cations showed similar structural compositions. Lignins obtained from ethylenediamonium cation combined anions acetate and lactate exhibited relatively higher molecular weights compared to the other lignins studied. The elemental analysis of these lignins further revealed the presence of nitrogen in their structures, suggesting that amination occurred. In this work we used PILs not yet reported in the literature for this purpose, and consequently obtained lignins with specific structures. Overall, our results demonstrated that depending on the PILs used, lignins with distinct properties could be obtained which might be used for value-added applications. This work covered new advances in elucidation of lignin chemical structure and opened a new path for lignin valorization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Influence of Metal Ion Complexation on the Radiolytic Longevity of Butyramide Extractants under Direct Dissolution Process Conditions

The direct dissolution of voloxidized used nuclear fuel (UNF) into an organic solution–comprised of diluent and specialized extractants–poses a promising alternative to the traditional liquid–liquid solvent extraction approach to reprocessing UNF. However, moving to direct dissolution removes the presence of a concentrated nitric acid aqueous phase, which has been shown to significantly influence the radiolytic longevity of extractants in conventional extraction flowsheets. Given the limited knowledge of radiation effects under direct dissolution conditions, here we present a time-resolved and dose-accumulation study on the impact of direct dissolution conditions on the radiolytic longevity of two candidate butyramide extractants, N,N-di(2-ethylhexyl) butyramide (DEHBA) and N,N-di(2-ethylhexyl)isobutyramide (DEHiBA), in pre-equilibrated n-dodecane solvent in the presence and absence of process-relevant metal ions, specifically, uranium and rhenium. Loss G(DEHBA) and G(DEHiBA) values were found to be comparable to each other, with an average of 0.37 ± 0.02 μmol J –1 , and to previous data from the γ irradiation of DEHBA and DEHiBA under conventional solvent extraction conditions. Rhenium, and by extension technetium, extraction had a modest decrease (~10%) in the overall radiolytic stability of DEHiBA only, despite >2× observed increases in chemical kinetic reactivity of the corresponding complexes with the n-dodecane radical cation. Uranium loading, on the other hand, significantly improved the lifetime of both ligands (>30%) under γ irradiation, with a greater stabilization observed for DEHBA over DEHiBA. The observed radioprotective effect afforded by uranium loading is fortuitous for the longevity of direct dissolution solvent.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Electron extraction efficiency study for dual-phase xenon dark matter experiments

Dual-phase xenon detectors are widely used in dark matter direct detection experiments, and have demonstrated the highest sensitivities to a variety of dark matter interactions. However, a key component of the dual-phase detector technology—the efficiency of charge extraction from liquid xenon into gas—has not been well characterized. We report a new measurement of the electron extraction efficiency (EEE) in a small xenon detector using two monoenergetic decay features of $^{37}\mathrm{Ar}$. By achieving stable operation at very high voltages, we measured the EEE values at the highest extraction electric field strength reported to date. For the first time, an apparent saturation of the EEE is observed over a large range of electric field; between 7.5 and $10.4\text{ }\text{ }\mathrm{kV}/\mathrm{cm}$ extraction field in the liquid xenon the EEE stays stable at the level of 1% $(\mathrm{kV}/\mathrm{cm}{)}^{{-}1}$. In the context of electron transport models developed for xenon, we discuss how the observed saturation may help calibrate this relative EEE measurement to the absolute EEE values. In addition, we present the implications of this result not only to current and future xenon-based dark matter searches, but also to xenon-based searches for coherent elastic neutrino-nucleus scatters.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

A New Triketone Ligand for Extraction of Lithium from Brines**

Recovery of lithium from brines by liquid-liquid solvent extraction (LLE) with diketones and synergistic co-ligands has been investigated for decades, but industrial application has been limited. In pursuit of a ligand with improved properties, a series of ketonamides with beta-carbonyl groups were designed, synthesized, and tested in extraction of lithium from sulfate and carbonate simulants of clay mineral tailing leachates. The best performing ligand, a novel tricarbonyl amide, was characterized for lithium extraction with and without four synergistic co-ligands. Further, the tricarbonyl amide combined with the synergistic co-ligand Cyanex-923 was absorbed on a resin support. The ligand-modified resin was tested for performance in extraction of dilute brine simulants and up to 60 % recovery of lithium was achieved.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of hydrophobic ionic liquids aqueous solubility on metal extraction from hydrochloric acid media: Mathematical modelling and trivalent thallium behavior

A mathematical model to explain cations’ solubility of both protic and aprotic ionic liquids in a wide range of hydrochloric acid solutions has been developed. The concept of this model is based on an assumption of the mineral acid extraction into the organic phase, formation of a salt there between an ionic liquid cation and chloride-anion due to ions recombination and partial salt back-extraction. The proposed approach allows estimating corresponding extraction constants. Comparison of calculated and experimentally measured solubility product constants shows that they are in good agreement. It has been determined also that the more the hydrophilicity of the ionic liquids’ cation the more hydrochloric acid is extracted. Furthermore, this model has been utilized to facilitate analysis of thallium transfer into hydrophobic ionic liquids providing insights into the mechanism of metal extraction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Relationship between liquid nanoscale structure in solvents and the strength of the Hofmeister effect in extraction experiments

In this study, we used mixtures of carboxylic acids and amines as solvents for the liquid–liquid extraction of copper salts with various anions from aqueous phase, and systematically varied the acid/amine ratio to determine its influence on extraction efficiency. The organic phases resulting from these extraction experiments were studied using small-angle X-ray scattering (SAXS), establishing a connection between the extraction process and the liquid structure. Furthermore, a relationship is found between the extent of extraction for the metal salt, the strength of the Hofmeister effect of the anions of the salt, and the characteristic lengthscale of the observed liquid nanoscale structure before and after extraction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗