Radiometallation and photo-triggered release of ready-to-inject radiopharmaceuticals from the solid phase.

The efficient, large-scale synthesis of radiometallated radiopharmaceuticals represents an emerging clinical need which, to date, is inherently limited by time consuming, sequential procedures to conduct isotope separation, radiochemical labeling and purification prior to formulation for injection into the patient. In this work, we demonstrate that a solid-phase based, concerted separation and radiosynthesis strategy followed by photochemical release of radiotracer in biocompatible solvents can be employed to prepare ready-to-inject, clinical grade radiopharmaceuticals. Optimization of resin base, resin loading, and radiochemical labeling capacity are demonstrated with Ga and Cu radioisotopes using a short model peptide sequence and further validated using two peptide-based radiopharmaceuticals with clinical relevance, targeting the gastrin-releasing peptide and the prostate specific membrane antigen.

Versatile Open-Source Photoreactor Architecture for Photocatalysis Across the Visible Spectrum.

Adoption of commercial photoreactors as standards for photocatalysis research could be limited by high cost. We report the development of the Wisconsin Photoreactor Platform (WPP), an open-source photoreactor architecture potentially suitable for general adoption. The WPP integrates inexpensive commercial components and common high-intensity LEDs in a 3D-printed enclosure.

Catalytic Intramolecular Conjugate Additions of Aldehyde-Derived Enamines to α,β-Unsaturated Esters.

We report a pairing of known catalysts that enables intramolecular conjugate additions of aldehyde-derived enamines to α,β-unsaturated esters. Despite extensive prior exploration of conjugate additions of aldehyde-derived enamines, catalytic conjugate additions to unactivated enoate esters are unprecedented. Achieving enantioselective and diastereoselective six-membered ring formation requires the coordinated action of a chiral pyrrolidine, for nucleophilic activation of the aldehyde via enamine formation, and a hydrogen bond donor, for electrophilic activation of the enoate ester.

Tunneling by 16 Carbons: Planar Bond Shifting in [16]Annulene.

Midsized annulenes are known to undergo rapid π-bond shifting. Given that heavy-atom tunneling plays a role in planar bond shifting of cyclobutadiene, we computationally explored the contribution of heavy-atom tunneling to planar π-bond shifting in the major (CTCTCTCT, 5a) and minor (CTCTTCTT, 6a) known isomers of [16]annulene. UM06-2X/cc-pVDZ calculations yield bond-shifting barriers of ca.