ABSTRACT Nonsymmetric stapling of peptides that connects two distinct endogenous residues offers a valuable tool for expanding the structural diversity of peptide macrocycles. However, its development remains challenging due to the high demand for chemo‐ and site‐selectivity while minimizing competing intermolecular peptide crosslinking. In this study, we reported a non‐covalent interaction‐promoted strategy for nonsymmetric stapling of tyrosine‐containing peptides by employing ethenesulfonyl fluoride (ESF) as a bifunctional crosslinker. Once covalently anchored to peptide, the sulfonyl fluoride motif is activated by non‐covalent interactions, which triggers an intramolecular SuFEx click reaction with tyrosine to afford peptide macrocycles. This approach efficiently crosslinks diverse residue pairs, including Cys–Tyr, His–Tyr, and Pro–Tyr. Notably, the protocol is scalable and can be performed in solid‐phase synthesis, providing robust access to tyrosine‐bridged peptide macrocycles with excellent diversity. Nanomolar binding affinity of nonsymmetrically stapled RGD peptide to integrin was also demonstrated.
ABSTRACT Lithium‐rich manganese‐based oxide (LRMO), characterized by distinctive anionic redox activity, has attracted considerable interest as a cathode candidate owing to the low cost and high energy density potential. However, their practical implementation is severely impeded by the intrinsically sluggish kinetics of the anionic redox reaction and the accompanying interfacial side reactions. Herein, a sodium phytate (SP) crosslinked PVDF binder is developed to enhance interfacial ion transport and suppress mechanochemical degradation from surface oxygen inactivation in LRMO. By tailoring the PVDF crystalline phase for Li + transport and introducing polar groups for enhanced binding, SP ensures a more uniform distribution of electrode components. More importantly, the SP suppresses irreversible surface lattice oxygen oxidation in LRMO, and thus quench the release of reactive oxygen species (ROS) and gaseous O 2 . Thereby, the LRMO@PVDF/SP electrode exhibits substantially enhanced chemo‐mechanical stability and an optimized cathode electrolyte interphase (CEI). It delivers exceptional initial Coulombic efficiency (95%) and discharge capacity (322 mAh/g at 0.1 C), as well as markedly improved cycling stability (maintaining ∼90% capacity retention after 400 cycles at 1 C). This work provides a facile yet scalable strategy for stabilizing the surface lattice oxygen of LRMO cathodes, paving the way for their commercial application.
ABSTRACT Organic solar cells (OSCs) hold promise for building‐integrated and wearable photovoltaics, yet excessive H ‐aggregation of non‐fullerene acceptors (NFAs) quenches luminescence and lowers the photoluminescence quantum yield (PLQY), limiting further efficiency gains. Here, we introduce NTCl‐4F, a molecular H ‐aggregation mediator, into the D18:L8‐BO‐C 4 binary system. Designed with an identical backbone to L8‐BO‐C 4 but featuring a rotatable central core that induces steric hindrance (dihedral angle of 4.87° as revealed by single‐crystal diffraction), NTCl‐4F effectively suppresses H ‐aggregation while promoting ordered J ‐aggregation (with average fibril diameters from 20.75 to 17.16 nm). This aggregation‐mode modulation enhances the PLQY from 6.13% to 7.52%. Furthermore, the ordered J ‐aggregation induced by NTCl‐4F enhances the crystallinity of the system with increased crystal coherence lengths (CCL) and decreased fractal dimension ( D f ), achieving synchronous improvement of short‐circuit current. Consequently, the NTCl‐4F‐modified device achieves a power conversion efficiency (PCE) of 20.8% under non‐annealed conditions, which stands among the highest reported efficiencies for non‐annealed OSCs. The strategy proves general, yielding efficiency improvements in PM6:Y6 and D18:Y7 systems. This work establishes aggregation‐mode engineering via an H ‐aggregation mediator as a versatile route to enhance PLQY and crystallinity for high‐performance OSCs.
