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Electrochemical approaches to form C(sp2)−C(sp3) bonds have focused on coupling C(sp3) electrophiles that form stabilized carbon‐centered radicals upon reduction or oxidation. Whereas alkyl bromides are desirable C(sp3) coupling partners owing to their availability and cost‐effectiveness, their tendency to undergo radical‐radical homocoupling makes them challenging substrates for electroreductive cross‐coupling. Herein, we disclose a metal‐free regioselective cross‐coupling of 1,4‐dicyanobenzene, a useful precursor to aromatic nitriles, and alkyl bromides. Alkyl bromide reduction is mediated directly by 1,4‐dicyanobenzene radical anions, leading to negligible homocoupling and high cross‐selectivity to form 1,4‐alkyl cyanobenzenes. The cross‐coupling scheme is compatible with oxidatively sensitive and acidic functional groups such as amines and alcohols, which have proven difficult to incorporate in alternative electrochemical approaches using carboxylic acids as C(sp3) precursors. [ABSTRACT FROM AUTHOR]

Electrochemical approaches to form C(sp 2 )-C(sp 3 ) bonds have focused on coupling C(sp 3 ) electrophiles that form stabilized carbon-centered radicals upon reduction or oxidation. Whereas alkyl bromides are desirable C(sp 3 ) coupling partners owing to their availability and cost-effectiveness, their tendency to undergo radical-radical homocoupling makes them challenging substrates for electroreductive cross-coupling. Herein, we disclose a metal-free regioselective cross-coupling of 1,4-dicyanobenzene, a useful precursor to aromatic nitriles, and alkyl bromides. Alkyl bromide reduction is mediated directly by 1,4-dicyanobenzene radical anions, leading to negligible homocoupling and high cross-selectivity to form 1,4-alkyl cyanobenzenes. The cross-coupling scheme is compatible with oxidatively sensitive and acidic functional groups such as amines and alcohols, which have proven difficult to incorporate in alternative electrochemical approaches using carboxylic acids as C(sp 3 ) precursors., (© 2023 Wiley-VCH GmbH.)

Intracellular cargo delivery is a critical and challenging step in controlling cell states. Silicon nanowire (NW) arrays have emerged as a powerful platform for accessing the intracellular space through a combination of their nanoscale dimensions and electrical properties. Here, we develop and characterize a conductive polypyrrole (PPy)-NW device for temporally controlled intracellular delivery. Fluorescent cargos, doped in electroresponsive PPy matrices at wire tips as well as entire NW arrays, are released with an applied reducing potential. Intracellular delivery into endothelial cells from PPy-Si substrates demonstrated comparable kinetics to solution-based delivery methods while requiring an order of magnitude less cargo loading. This hybrid polymer-semiconductor platform extends methods available for intracellular delivery and links electrical signaling from artificial systems with living molecular transduction.

Polyphosphates (polyPs) are ubiquitous polymers in living organisms from bacteria to mammals. They serve a wide variety of biological functions, ranging from energy storage to stress response. In the last two decades, polyPs have been primarily viewed as linear polymers with varying chain lengths. However, recent biochemical data show that small metaphosphates, cyclic oligomers of [PO 3 ] (-) , can bind to the enzymes ribonuclease A and NAD kinase, raising the question of whether metaphosphates can occur naturally as products of biological activity. Before the 1980s, metaphosphates had been reported in polyPs extracted from various organisms, but these results are considered artifactual due to the extraction and purification protocols. Here, we employ nondestructive 31 P solid-state NMR spectroscopy to investigate the chemical structure of polyphosphates in whole cells as well as insoluble fractions of the bacterium Xanthobacter autotrophicus. Isotropic and anisotropic 31 P chemical shifts of hydrated whole cells indicate the coexistence of linear and cyclic phosphates. Under our cell growth conditions and the concentrated conditions of the solid-state NMR samples, we found substantial amounts of cyclic phosphates in X. autotrophicus , suggesting that in fresh cells metaphosphate concentrations can be significant. The cellular metaphosphates are identified by comparison with the 31 P chemical shift anisotropy of synthetic metaphosphates of known structures. In X. autotrophicus , the metaphosphates have a chemical shift anisotropy that is consistent with an average size of 3-8 phosphate units. These metaphosphates are enriched in insoluble and electron-dense granules. Exogenous hexametaphosphate added to X. autotrophicus cell extracts is metabolized to trimetaphosphates, supporting the presence and biological role of metaphosphates in cells. The definitive evidence for the presence of metaphosphates, reported here in whole bacterial cells for the first time, opens the path for future investigations of the biological function of metaphosphates in many organisms.