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At least 415 records · Page 23

Leaching of Rare Earth Elements from Central Appalachian Coal Seam Underclays

Rare earth elements (REE) are necessary for advanced technological and energy applications. To support the emerging need, it is necessary to identify new domestic sources of REE and technologies to separate and recover saleable REE product in a safe and economical manner. Underclay rock associated with Central Appalachian coal seams and prevalent in coal utilization waste products is an alternative source of REE to hard rock ores that are mainly composed of highly refractory REE-bearing minerals. This study utilizes a suite of analytical techniques and benchtop leaching tests to characterize the properties and leachability of the coal seam underclays sampled. Laboratory bench-top and flow-through reactor leaching experiments were conducted on underclay rock powders to produce a pregnant leach solution (PLS) that has relatively low concentrations of gangue elements Al, Si, Fe, and Th and is amenable to further processing steps to recover and produce purified REE product. The leaching method described here uses a chelating agent, the citrate anion, to solubilize elements that are adsorbed, or weakly bonded to the surface of clay minerals or other mineral solid phases in the rock. The citrate PLS produced from leaching specific underclay powders contains relatively higher concentrations of REE and lower concentrations of gangue elements compared to PLS produced from sequential digestion using ammonium sulfate and mineral acids. Citrate solution leaching of underclay produces a PLS with lower concentrations of gangue elements and higher concentrations of REE than achieved with hydrochloric acid or sulfuric acid. The results provide a preliminary assessment of the types of REE-bearing minerals and potential leachability of coal seam underclays from the Central Appalachian basin.

58 GEOSCIENCES↗

A High Separation Factor for 165Er from Ho for Targeted Radionuclide Therapy

Background: Radionuclides emitting Auger electrons (AEs) with low (0.02–50 keV) energy, short (0.0007–40 µm) range, and high (1–10 keV/µm) linear energy transfer may have an important role in the targeted radionuclide therapy of metastatic and disseminated disease. Erbium-165 is a pure AE-emitting radionuclide that is chemically matched to clinical therapeutic radionuclide 177Lu, making it a useful tool for fundamental studies on the biological effects of AEs. This work develops new biomedical cyclotron irradiation and radiochemical isolation methods to produce 165Er suitable for targeted radionuclide therapeutic studies and characterizes a new such agent targeting prostate-specific membrane antigen. Methods: Biomedical cyclotrons proton-irradiated spot-welded Ho(m) targets to produce 165Er, which was isolated via cation exchange chromatography (AG 50W-X8, 200–400 mesh, 20 mL) using alpha-hydroxyisobutyrate (70 mM, pH 4.7) followed by LN2 (20–50 µm, 1.3 mL) and bDGA (50–100 µm, 0.2 mL) extraction chromatography. The purified 165Er was radiolabeled with standard radiometal chelators and used to produce and characterize a new AE-emitting radiopharmaceutical, [165Er]PSMA-617. Results: Irradiation of 80–180 mg natHo targets with 40 µA of 11–12.5 MeV protons produced 165Er at 20–30 MBq·µA−1·h−1. The 4.9 ± 0.7 h radiochemical isolation yielded 165Er in 0.01 M HCl (400 µL) with decay-corrected (DC) yield of 64 ± 2% and a Ho/165Er separation factor of (2.8 ± 1.1) · 105. Radiolabeling experiments synthesized [165Er]PSMA-617 at DC molar activities of 37–130 GBq·µmol−1. Conclusions: A 2 h biomedical cyclotron irradiation and 5 h radiochemical separation produced GBq-scale 165Er suitable for producing radiopharmaceuticals at molar activities satisfactory for investigations of targeted radionuclide therapeutics. This will enable fundamental radiation biology experiments of pure AE-emitting therapeutic radiopharmaceuticals such as [165Er]PSMA-617, which will be used to understand the impact of AEs in PSMA-targeted radionuclide therapy of prostate cancer.

165Er↗

Is Genetic Engineering a Route to Enhance Microalgae-Mediated Bioremediation of Heavy Metal-Containing Effluents?

Contamination of the biosphere by heavy metals has been rising, due to accelerated anthropogenic activities, and is nowadays, a matter of serious global concern. Removal of such inorganic pollutants from aquatic environments via biological processes has earned great popularity, for its cost-effectiveness and high efficiency, compared to conventional physicochemical methods. Among candidate organisms, microalgae offer several competitive advantages; phycoremediation has even been claimed as the next generation of wastewater treatment technologies. Furthermore, integration of microalgae-mediated wastewater treatment and bioenergy production adds favorably to the economic feasibility of the former process—with energy security coming along with environmental sustainability. However, poor biomass productivity under abiotic stress conditions has hindered the large-scale deployment of microalgae. Recent advances encompassing molecular tools for genome editing, together with the advent of multiomics technologies and computational approaches, have permitted the design of tailor-made microalgal cell factories, which encompass multiple beneficial traits, while circumventing those associated with the bioaccumulation of unfavorable chemicals. Previous studies unfolded several routes through which genetic engineering-mediated improvements appear feasible (encompassing sequestration/uptake capacity and specificity for heavy metals); they can be categorized as metal transportation, chelation, or biotransformation, with regulation of metal- and oxidative stress response, as well as cell surface engineering playing a crucial role therein. This review covers the state-of-the-art metal stress mitigation mechanisms prevalent in microalgae, and discusses putative and tested metabolic engineering approaches, aimed at further improvement of those biological processes. Finally, current research gaps and future prospects arising from use of transgenic microalgae for heavy metal phycoremediation are reviewed.

Ranjbar, Saeed (ORCID:0000000256518605)↗

Accelerator-Based Production of Scandium Radioisotopes for Applications in Prostate Cancer: Toward Building a Pipeline for Rapid Development of Novel Theranostics

In the field of nuclear medicine, the β + -emitting 43 Sc and β - -emitting 47 Sc are promising candidates in cancer diagnosis and targeted radionuclide therapy (TRT) due to their favorable decay schema and shared pharmacokinetics as a true theranostic pair. Additionally, scandium is a group-3 transition metal (like 177 Lu) and exhibits affinity for DOTA-based chelators, which have been studied in depth, making the barrier to implementation lower for 43/47 Sc than for other proposed true theranostics. Before 43/47 Sc can see widespread pre-clinical evaluation, however, an accessible production methodology must be established and each isotope’s radiolabeling and animal imaging capabilities studied with a widely utilized tracer. As such, a simple means of converting an 18 MeV biomedical cyclotron to support solid targets and produce 43 Sc via the 42 Ca(d,n) 43 Sc reaction has been devised, exhibiting reasonable yields. The Nat Ti(γ,p) 47 Sc reaction is also investigated along with the successful implementation of chemical separation and purification methods for 43/47 Sc. The conjugation of 43/47 Sc with PSMA-617 at specific activities of up to 8.94 MBq/nmol and the subsequent imaging of LNCaP-ENZaR tumor xenografts in mouse models with both 43/47 Sc-PSMA-617 are also presented.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

PET Imaging of the Neurotensin Targeting Peptide NOTA-NT-20.3 Using Cobalt-55, Copper-64 and Gallium-68

Introduction: Neurotensin receptor 1 (NTSR1) is an emerging target for imaging and therapy of many types of cancer. Nuclear imaging of NTSR1 allows for noninvasive assessment of the receptor levels of NTSR1 on the primary tumor, as well as potential metastases. This work focuses on a the neurotensin peptide analogue NT-20.3 conjugated to the chelator NOTA for radiolabeling for use in noninvasive positron emission tomography (PET). NOTA-NT-20.3 was radiolabeled with gallium-68, copper-64, and cobalt-55 to determine the effect that modification of the radiometal has on imaging and potential therapeutic properties of NOTA-NT-20.3. Methods: In vitro assays investigating cell uptake and subcellular localization of the radiolabeled peptides were performed using human colorectal adenocarcinoma HT29 cells. In vivo PET/CT imaging was used to determine the distribution and clearance of the peptide in mice bearing NTSR1 expressing HT29 tumors. Results: Cell uptake studies showed that the highest uptake was obtained with [ 55 Co] Co-NOTA-NT-20.3 (18.70 ± 1.30%ID/mg), followed by [ 64 Cu] Cu-NOTA-NT-20.3 (15.46 ± 0.91%ID/mg), and lastly [ 68 Ga] Ga-NOTA-NT-20.3 (10.94 ± 0.46%ID/mg) (p < 0.001). Subcellular distribution was similar across the three constructs, with the membranous fraction containing the highest amount of radioactivity. In vivo PET/CT imaging of the three constructs revealed similar distribution and tumor uptake at the 1 h imaging timepoint. Tumor uptake was receptor-specific and blockable by co-injection of non-radiolabeled NOTA-NT-20.3. SUV ratios of tumor to heart at the 24 h imaging timepoint show that [ 55 Co] Co-NOTA-NT-20.3 (20.28 ± 3.04) outperformed [ 64 Cu] Cu-NOTA-NT-20.3 (6.52 ± 1.97). In conclusion, our studies show that enhanced cell uptake and increasing tumor to blood ratios over time displayed the superiority of [ 55 Co] Co-NOTA-NT-20.3 over [ 68 Ga] Ga-NOTA-NT-20.3 and [ 64 Cu] Cu-NOTA-NT-20.3 for the targeting of NTSR1.

60 APPLIED LIFE SCIENCES↗

A Facile Aqueous Solution Route for the Growth of Chalcogenide Perovskite BaZrS 3 Films

The prototypical chalcogenide perovskite, BaZrS 3 (BZS), with its direct bandgap of 1.7–1.8 eV, high chemical stability, and strong light–matter interactions, has garnered significant interest over the past few years. So far, attempts to grow BaZrS 3 films have been limited mainly to physical vapor deposition techniques. Here, we report the fabrication of BZS thin films via a facile aqueous solution route of polymer-assisted deposition (PAD), where the polymer-chelated cation precursor films were sulfurized in a mixed CS 2 and Ar atmosphere. The formation of a single-phase polycrystalline BZS thin film at a processing temperature of 900 °C was confirmed by X-ray diffraction and Raman spectroscopy. The stoichiometry of the films was verified by Rutherford Backscattering spectrometry and energy-dispersive X-ray spectroscopy. The BZS films showed a photoluminescence peak at around 1.8 eV and exhibited a photogenerated current under light illumination at a wavelength of 530 nm. Temperature-dependent resistivity analysis revealed that the conduction of BaZrS 3 films under the dark condition could be described by the Efros–Shklovskii variable range hopping model in the temperature range of 60–300 K, with an activation energy of about 44 meV.

36 MATERIALS SCIENCE↗

Zymomonas mobilis oxidative stress transcriptomics

Zymomonas mobilis is an important bioenergy organism that has potential to produce biofuels, including ethanol, in high volumes. Here we examined the response of Zymomonas mobilis to various oxidative stresses using genome-scale transcriptomics data. We first examined the transcrpit abundance in WT aerobic growth compared to aerobic grown in paraquat, which forms superoxide. Under anaerobic growth conditions we compared WT Zymomonas mobilis with strains grown in media lacking iron as well as strains lacking iron that were treated with the iron chelator DIP before collection. Finally we examined transcript abundance in cells lacking ZMO_0422 (Rrf2 family transcription factor homolog) and ZMO_1411 (Fur homolog) grown under anaerobic conditions. Overall design: Transcriptomic analysis of WT, a deletion of ZMO_0422, and a deletion of ZMO_1411 in Zymomonas mobilis ZM4 under aerobic and anaerobic growth conditions along with various oxidative stresses: Paraquate addition, No Iron, and hydrogen peroxide addition.

aerobic↗

Kinetics of the Reaction Between Alcohols and Isocyanates Catalyzed by Ferric Acetylacetonate

The rate and temperature dependence of reaction for the ferric acetylacetonate catalyzed reaction between a-naphthyl, ortho-tolyl, and para-tolyl isocyanates and n-butyl alcohol are investigated. The effect of substituents on the reactivity of isocyanate and hydroxyl group are reported and for substituted isocyanates are correlated by means of the Hammett equation. Several metal chelates were studied and their catalytic activity was compared to that of ferric acetylacetonate. All rate data are interpreted in terms of a mechanism involving simultaneous second-order uncatalyzed and catalyzed reactions between alcohol and isocyanate.

ACETONE↗

Liquid Laser Cavities

Europium chelate liquid laser cavities construction and resonator design for lasing action at room temperatures

Bjorklund, Sven↗

Laser action from a terbium beta-ketoenolate at room temperature

Laser activity is achieved in a solution of terbium tris at room temperature in a liquid solvent of acetonitrile or p-dioxane. After precipitation, the microcrystals of hydrated tris chelate are filtered, washed in distilled water, and dried. They show no signs of deterioration after storage.

Bjorklund, S.↗

A process yields large quantities of pure ribosome subunits

Development of process for in-vitro protein synthesis from living cells followed by dissociation of ribosomes into subunits is discussed. Process depends on dialysis or use of chelating agents. Operation of process and advantages over previous methods are outlined.

Friedman, M.↗

Mechanisms of deterioration of intermediate moisture food systems

A study of shelf stability in intermediate moisture foods was made. Major efforts were made to control lipid oxidation and nonenzymatic browning. In order to determine means of preventing these reactions, model systems were developed having the same water activity content relationship of intermediate moisture foods. Models were based on a cellulose-lipid and protein-lipid system with glycerol added as the humectant. Experiments with both systems indicate that lipid oxidation is promoted significantly in the intermediate moisture range. The effect appeared to be related to increased mobility of either reactants or catalysts, since when the amount of water in the system reached a level where capillary condensation occurred and thus free water was present, the rates of oxidation increased. With added glycerol, which is water soluble and thus increases the amount of mobile phase, the increase in oxidation rate occurs at a lower relative humidity. The rates of oxidation were maximized at 61% RH and decreased again at 75% RH probably due to dilution. No significant non-enzymatic browning occurred in the protein-lipid systems. Prevention of oxidation by the use of metal chelating agents was enhanced in the cellulose system, whereas, with protein present, the lipid soluble chain terminating antioxidants (such as BHA) worked equally as well. Preliminary studies of foods adjusted to the intermediate moisture range bear out the results of oxidation in model systems. It can be concluded that for most fat containing intermediate moisture foods, rancidity will be the reaction most limiting stability.

Labuza, T. P.↗

Semi-organic structural adhesive for aluminum

Structural adhesive consists of titanium chelate polymer, reactive plasticizer, and cure accelerator (phenylsilanetriol). Mixture polymerizes in situ in 65 hours at 170 C.

Kwan, S. C.↗

Storage stability and improvement of intermediate moisture foods

The rates of chemical reactions which deteriorate foods prepared to an intermediate moisture content and water activity (A sub w 0.6 to 0.9) were studied. The phenomenon of sorption hysteresis was used to prepare model systems and foods to similar A sub w's but different moisture levels so that the separate effects of water binding and water content could be elucidated. It was found that water content is the controlling factor for lipid oxidation in model systems comprised of a solid support and an oxidizable liquid. It was proposed that metal chelating agents like EDTA should give good protection to oxidation. EDTA exhibited the highest efficacy, about 10-15 times better than BHA which is a radical scavenger when studied in the model systems.

Labuza, T. P.↗

A search for porphyrin biomarkers in Nonesuch Shale and extraterrestrial samples.

An organic solvent extract of billion year old Nonesuch Shale was examined for porphyrins by means of fluorometry and high resolution mass spectrometry. It appears to contain at least three or more classes of porphyrins, one similar to tetraphenyl porphin and the others more complex. Many are apparently chelated with copper, nickel, zinc, iron and vanadyl and are highly aromatic. We have also examined the extracts of Apollo 11, 12 and 14 surface fines for porphyrins by spectrophotofluorometry, but we found none.

Rho, J. H.↗

Subcellular localization of pituitary enzymes

A cytochemical procedure is reported for identifying subcellular sites of enzymes hydrolyzing beta-naphthylamine substrates, and to study the sites of reaction product localization in cells of various tissues. Investigations using the substrate Leu 4-methoxy-8-naphthylamine, a capture with hexonium pararosaniline, and the final chelation of osmium have identified the hydrolyzing enzyme of rat liver cells; this enzyme localized on cell membranes with intense deposition in the areas of the parcanaliculi. The study of cells in the anterior pituitary of the rat showed the deposition of reaction product on cell membrane; and on the membranes of secretion granules contained within the cell. The deposition of reaction product on the cell membrane however showed no increase or decrease with changes in the physiological state of the gland and release of secretion granules from specific cells.

Smith, R. E.↗