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The positive impact of having access to well-defined starting materials for applied actinide technologies - and for technologies based on other elements - cannot be overstated. Of numerous relevant 5f-element starting materials, those in complexing aqueous media find widespread use. Consider acetic acid/acetate buffered solutions as an example. These solutions provide entry into diverse technologies, from small-scale production of actinide metal to preparing radiolabeled chelates for medical applications. However, like so many aqueous solutions that contain actinides and complexing agents, 5f-element speciation in acetic acid/acetate cocktails is poorly defined. Herein, we address this problem and characterize Ac3+ and Cm3+ speciation as a function of increasing acetic acid/acetate concentrations (0.1 to 15 M, pH = 5.5). Results obtained via X-ray absorption and optical spectroscopy show the aquo ion dominated in dilute acetic acid/acetate solutions (0.1 M). Increasing acetic acid/acetate concentrations to 15 M increased complexation and revealed divergent reactivity between early and late actinides. A neutral Ac(H2O)6 (1)(O2CMe)3 (1) compound was the major species in solution for the large Ac3+. In contrast, smaller Cm3+ preferred forming an anion. There were approximately four bound O2CMe1- ligands and one to two inner sphere H2O ligands. The conclusion that increasing acetic acid/acetate concentrations increased acetate complexation was corroborated by characterizing (NH4)2M(O2CMe)5 (M = Eu3+, Am3+ and Cm3+) using single crystal X-ray diffraction and optical spectroscopy (absorption, emission, excitation, and excited state lifetime measurements).

The positive impact of having access to well-defined starting materials for applied actinide technologies - and for technologies based on other elements - cannot be overstated. Of numerous relevant 5f-element starting materials, those in complexing aqueous media find widespread use. Consider acetic acid/acetate buffered solutions as an example. These solutions provide entry into diverse technologies, from small-scale production of actinide metal to preparing radiolabeled chelates for medical applications. However, like so many aqueous solutions that contain actinides and complexing agents, 5f-element speciation in acetic acid/acetate cocktails is poorly defined. Herein, we address this problem and characterize Ac3+ and Cm3+ speciation as a function of increasing acetic acid/acetate concentrations (0.1 to 15 M, pH = 5.5). Results obtained via X-ray absorption and optical spectroscopy show the aquo ion dominated in dilute acetic acid/acetate solutions (0.1 M). Increasing acetic acid/acetate concentrations to 15 M increased complexation and revealed divergent reactivity between early and late actinides. A neutral Ac(H2O)6 (1)(O2CMe)3 (1) compound was the major species in solution for the large Ac3+. In contrast, smaller Cm3+ preferred forming an anion. There were approximately four bound O2CMe1- ligands and one to two inner sphere H2O ligands. The conclusion that increasing acetic acid/acetate concentrations increased acetate complexation was corroborated by characterizing (NH4)2M(O2CMe)5 (M = Eu3+, Am3+ and Cm3+) using single crystal X-ray diffraction and optical spectroscopy (absorption, emission, excitation, and excited state lifetime measurements).

Our lab has developed a new series of self‐immolative MR agents for the rapid detection of enzyme activity in mouse models expressing β‐galactosidase (β‐gal). We investigated two molecular architectures to create agents that detect β‐gal activity by modulating the coordination of water to GdIII. The first is an intermolecular approach, wherein we designed several structural isomers to maximize coordination of endogenous carbonate ions. The second involves an intramolecular mechanism for q modulation. We incorporated a pendant coordinating carboxylate ligand with a 2, 4, 6, or 8 carbon linker to saturate ligand coordination to the GdIII ion. This renders the agent ineffective. We show that one agent in particular (6‐C pendant carboxylate) is an extremely effective MR reporter for the detection of enzyme activity in a mouse model expressing β‐gal. [ABSTRACT FROM AUTHOR]

The promise of 225 Ac targeted alpha therapies has been on the horizon for the last two decades. TerraPower Isotopes are uniquely suited to produce clinically relevant quantities of 225 Ac through the decay of 229 Th. Herein, a rapid processing scheme to isolate radionuclidic and radioisotopically pure 225 Ac in good yield (98%) produced from 229 Th that contains significant quantities of 228 Th activity is described. The characterization of each step of the process is presented along with the detailed characterization of the resulting 225 Ac isotopic starting material that will support the cancer research and development efforts., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Radionuclides find widespread use in medical technologies for treating and diagnosing disease. Among successful and emerging radiotherapeutics, 119 Sb has unique potential in targeted therapeutic applications for low-energy electron-emitting isotopes. Unfortunately, developing 119 Sb-based drugs has been slow in comparison to other radionuclides, primarily due to limited accessibility. Herein is a production method that overcomes this challenge and expands the available time for large-scale distribution and use. Our approach exploits high flux and fluence from high-energy proton sources to produce longer lived 119m Te. This parent isotope slowly decays to 119 Sb, which in turn provides access to 119 Sb for longer time periods (in comparison to direct 119 Sb production routes). We contribute the target design, irradiation conditions, and a rapid procedure for isolating the 119m Te/ 119 Sb pair. To guide process development and to understand why the procedure was successful, we characterized the Te/Sb separation using Te and Sb K-edge X-ray absorption spectroscopy. The procedure provides low-volume aqueous solutions that have high 119m Te-and consequently 119 Sb-specific activity in a chemically pure form. This procedure has been demonstrated at large-scale (production-sized, Ci quantities), and the product has potential to meet stringent Food and Drug Administration requirements for a 119m Te/ 119 Sb active pharmaceutical ingredient., Competing Interests: The authors declare no competing financial interest.

A fundamental challenge in the design of bioresponsive (or bioactivated) Gd III -based magnetic resonance (MR) imaging probes is the considerable background signal present in the "preactivated" state that arises from outer-sphere relaxation processes. When sufficient concentrations of a bioresponsive agent are present (i.e., a detectable signal in the image), the inner- and outer-sphere contributions to r 1 may be misinterpreted to conclude that the agent has been activated, when it has not. Of the several parameters that determine the observed MR signal of an agent, only the electron relaxation time ( T 1e ) impacts both the inner- and outer-sphere relaxation. Therefore, strategies to minimize this background signal must be developed to create a near zero-background (or truly "off" state) of the agent. Here, we demonstrate that intramolecular magnetic exchange coupling when Gd III is coupled to a paramagnetic transition metal provides a means to overcome the contribution of second- and outer-sphere contributions to the observed relaxivity. We have prepared a series of complexes with the general formula LMLn(μ-O 2 CCH 3 )(O 2 CCH 3 ) 2 (M = Co, Cu, Zn). Solid-state magnetic susceptibility measurements reveal significant magnetic coupling between Gd III and the transition metal ion. Nuclear magnetic relaxation dispersion (NMRD) analysis confirms that the observed differences in relaxivity are associated with the modulation of T 1e at Gd III . These results clearly demonstrate that magnetic exchange coupling between Gd III and a transition metal ion can provide a significant decrease in T 1e (and therefore the relaxivity of Gd III ). This design strategy is being exploited to prepare new generations of preclinical bioresponsive MR imaging probes with near zero-background.

Misregulation of extracellular Ca 2+ can indicate bone-related pathologies. New, noninvasive tools are required to image Ca 2+ fluxes and fluorine magnetic resonance imaging ( 19 F-MRI) is uniquely suited to this challenge. Here, we present three, highly fluorinated peptide amphiphiles that self-assemble into nanoribbons in buffered saline and demonstrate these nanostructures can be programmed to change 19 F-NMR signal intensity as a function of Ca 2+ concentration. We determined these nanostructures show significant reduction in 19 F-NMR signal as nanoribbon width increases in response to Ca 2+ , corresponding to 19 F-MR image intensity reduction. Thus, these peptide amphiphiles can be used to quantitatively image biologically relevant Ca 2+ concentrations.

A homologous series of [2]rotaxanes, in which cyclobis(paraquat-p-phenylene) (CBPQT(4+)) serves as the ring component, while the dumbbell components all contain single 4,4'-bipyridinium (BIPY(2+)) units centrally located in the midst of oligomethylene chains of varying lengths, have been synthesized by taking advantage of radical templation and copper-free azide-alkyne 1,3-dipolar cycloadditions in the formation of their stoppers. Cyclic voltammetry, UV/vis spectroscopy, and mass spectrometry reveal that the BIPY(•+) radical cations in this series of [2]rotaxanes are stabilized against oxidation, both electrochemically and by atmospheric oxygen. The enforced proximity between the BIPY(2+) units in the ring and dumbbell components gives rise to enhanced Coulombic repulsion, destabilizing the ground-state co-conformations of the fully oxidized forms of these [2]rotaxanes. The smallest [2]rotaxane, with only three methylene groups on each side of its dumbbell component, is found to exist under ambient conditions in a monoradical state, a situation which does not persist in acetonitrile solution, at least in the case of its longer analogues. (1)H NMR spectroscopy reveals that the activation energy barriers to the shuttling of the CBPQT(4+) rings over the BIPY(2+) units in the dumbbells increase linearly with increasing oligomethylene chain lengths across the series of [2]rotaxanes. These findings provide a new way of producing highly stabilized BIPY(•+) radical cations and open up more opportunities to use stable organic radicals as building blocks for the construction of paramagnetic materials and conductive molecular electronic devices.