Chiral allenes are privileged structural motifs found in numerous natural products and bioactive molecules, consequently, the synthesis of these scaffolds-especially polysubstituted chiral allenes-has garnered significant research interest. Among these methods, direct asymmetric functionalization of allenic sp2 C-H bond has been recognized as a powerful strategy for the modification of allenes, enabling late-stage functionalization (LSF) of allene-containing bioactive compounds. In recent years, Cu(II)-bound nitrogen-centered radicals (NCRs) have been demonstrated to override innate radical preferences to achieve site-selective C-H functionalizations, achieving the site-selective C-H cyanation, arylation and alkynylation of allenes via a copper-catalyzed radical relay process, where the HAA process exclusively occurs at sp2 C-H bonds. Although the enantioselective version has been achieved for the reaction of 1,3-disubstituted allenes, which afforded the chiral trisubstituted allenic nitriles with excellent enantioselectivities, the reactions of trisubstituted allenes exhibited significantly poor enantioselectivity. Herein, we report a copper-catalyzed site- and enantioselective sp2 C-H cyanation of trisubstituted allenes. This reaction was catalyzed by CuOAc and Box ligand L1 in a mixture solvent of tert-amyl alcohol (tAmOH), acetone and (trifluoromethyl)benzene at -40 degrees C. This method efficiently afforded a broad array of tetrasubstituted axially chiral allenic nitriles in good to excellent yields with excellent enantioselectivities.

Cell-cell adhesion is crucial for maintaining cell functions and the integrity of tissue structure in organisms. However, cell-cell adhesion cues have not been effectively replicated in biomaterials and the associated mechanisms that enhance neural regeneration remained largely unexplored. Here, we present a diffusive N-cadherin functionalized hydrogel system, which provided cell-cell adhesion cues to modulate intercellular communications to significantly promote the formation of active neural network via thrombospondin-1 mediated neural communication and activation of TGF-beta/Smad pathway. The dynamic assembly of N-cadherin at cell-hydrogel interface driven by adhered neurons effectively facilitated the reshaping of membrane protrusions to initiate intercellular adherens junctions. Further, this hydrogel system promisingly promoted neurological function recovery in rats following traumatic brain injury. Our study provides the principle of replicating diffusive cell adhesion molecules to mediate cell-cell adhesion in hydrogels, which may have broad applications in developing engineered biomaterials aimed at modulating cell fates in regeneration of various tissues.

The development of pure organic long persistent luminescence (OLPL) materials with hour-scale duration remains a formidable challenge, as their design principles are still elusive. Building upon our donor-sensitizer-acceptor (DSA) system, herein, we report the achievement of hour-long OLPL by engineering the molecular structure of the sensitizer. We designed three difluoroboron beta-diketonate (BF(2)bdk) sensitizers featuring biphenyl-derived motifs with incremental modifications. All corresponding three-component systems exhibited significant room-temperature OLPL with remarkable afterglow durations exceeding 2 h under ambient conditions. This work demonstrates the successful realization of hour-scale OLPL within the DSA system and underscores the pivotal role of sensitizer molecular design in enabling ultralong organic afterglow, providing a clear design blueprint for future materials.

The Bell-Evans-Polanyi (BEP) relationship is a foundational principle linking reaction kinetics and thermodynamics and is widely used to analyze and predict reactivity in group transfer reactions. However, substantial deviations from a single BEP correlation are frequently observed for structurally diverse reagents, limiting its general applicability. Here, by integrating experimental kinetic data with quantum-chemically derived intrinsic barriers obtained from self-exchange reactions, we demonstrate that systematic, reaction-class-dependent variations in intrinsic barriers provide a physically transparent explanation for the breakdown of single BEP correlations across electrophilic fluorination, trifluoromethylthiolation, and hydride transfer reactions. On this basis, we introduce an intrinsic barrier augmented linear free energy framework that diagnostically unifies disparate BEP regimes while remaining consistent with Marcus-type barrier decomposition. This framework captures reaction-class-specific sensitivities to intrinsic barrier and thermodynamic driving force, affording improved quantitative agreement with experiment relative to conventional BEP analysis. Beyond rationalizing outliers and multimodal BEP behavior, this framework enables physically transparent prediction of Mayr electrophilicity and nucleophilicity parameters across structurally diverse reagents. Independent experimental determination of electrophilicity parameters for previously unreported fluorine- and SCF3-transfer reagents provides external validation.