Organic electroactive materials that can be processed using simple alcohols, such as ethanol and 1-butanol, are highly desired, since these solvents can be sourced from biomass and present lower hazards for human and environmental health. Herein, we report the first class of poly­(3-alkylamidethiophenes) (P3AAT) synthesized via the sustainable method of direct arylation polymerization (DArP) that can be processed using green, sustainable solvents. The unprecedented synthesis of P3AAT reveals the superiority of DArP, as P3AAT can be readily prepared in only three simple steps with an M n of up to 15.4 kDa and yields of up to 90% exclusively with this methodology. The tertiary amide, poly­(N-hexyl-N-methylthiophene-3-carboxamide-2,5-diyl) (P1), has excellent solubility in the green solvents ethanol, 1-butanol, and anisole. Processing of P1 in 1-butanol is shown to provide comparable space-charge-limited current (SCLC) hole mobility versus dichlorobenzene and commensurate photophysical properties. Also, the secondary amide, poly­(N-(2-ethylhexyl)­thiophene-3-carboxamide-2,5-diyl) (P2), was successfully synthesized, demonstrating excellent functional group tolerance for DArP, while showing hydrogen-bonding features and similar SCLC hole mobility as P1. This study provides a facile synthetic strategy for a novel structural motif that can be processed in sustainable solvents without a compromise in performance, which can easily be extended to other valuable areas of organic electronics and bioelectronics.

Several protic ionic liquids (PILs) with a wide range of pK(a) differences (ΔpK(a)) between the parent acid and base molecules were thermally evaporated in vacuum, trapped on a CsI plate by a cryogenic neon matrix-isolation method, and studied by Fourier transform infrared spectroscopy and density functional theory calculations. The parent neutral molecules and proton-transferred cation-anion pair species were identified as chemical components evaporated from the PILs with lower and higher ΔpK(a) values, respectively. The ΔpK(a)-dependent vaporization mechanism is discussed in terms of thermodynamic equilibrium between acid-base and anion-cation systems in the liquid phase.

This report describes a copper-mediated radiocyanation of aryl halides that is applicable to complex molecules. This transformation tolerates an exceptionally wide range of functional groups, including unprotected amino acids. As such, it enables the site-specific introduction of [11C]­CN into peptides at an iodophenylalanine residue. The use of a diamine-ligated copper­(I) mediator is crucial for achieving high radiochemical yield under relatively mild conditions, thus limiting racemization and competing side reactions of other amino acid side chains. The reaction has been scaled and automated to deliver radiolabeled peptides, including analogues of adrenocorticotropic hormone 1–27 (ACTH) and nociceptin (NOP). For instance, this Cu-mediated radiocyanation was leveraged to prepare >40 mCi of [11C]­cyano-NOP to evaluate biodistribution in a primate using positron emission tomography. This investigation provides preliminary evidence that nociceptin crosses the blood–brain barrier and shows uptake across all brain regions (SUV > 1 at 60 min post injection), consistent with the known distribution of NOP receptors in the rhesus brain.

Liquid-liquid interfacial reactions between FeSO4 (aq.) and benzenehexathiol (BHT) in chloroform at room temperature and at 45 °C give bis(dithiolato)iron nanosheets 1-RT and 1-H, respectively. Nanosheets were characterized by IR, UV-Vis, SEM-EDS, TEM, XPS and PXRD. 1-H is remarkably more crystalline than 1-RT and its chemical structure resembles not the porous nickel-BHT nanosheet ([Ni3(C6S6)2]n, “Type 1”) but the non-porous copper-BHT nanosheet ([Cu3(C6S6)]n, “Type 2”), evidenced by PXRD data. Electrical conductivity of 1-H is 0.68 S cm−1 with Ea = 270 meV.

This report describes a comparison of four different routes for the clinical-scale radiosynthesis of the κ-opioid receptor antagonist [11C]LY2795050. Palladium-mediated radiocyanation and radiocarbonylation of an aryl iodide precursor, as well as copper-mediated radiocyanation of an aryl iodide and an aryl boronate ester, have been investigated. Full automation of all four methods is reported, each of which provides [11C]LY2795050 in sufficient radiochemical yield, molar activity, and radiochemical purity for clinical use. The advantages and disadvantages of each radiosynthesis method are compared and contrasted.