The current high-end anticounterfeiting and information encryption technologies have predominantly relied on color-encoded or lifetime-encoded systems. We reason that the integration of multiple afterglow mechanisms, which are mechanism-encoded systems, could fundamentally enhance security levels. Nevertheless, the exploration of mechanism-encoded paradigms remains conspicuously absent in the literature. Here we develop four types of afterglow materials with distinct mechanisms, including room-temperature phosphorescence (RTP, T1 afterglow), thermally activated delayed fluorescence (TADF, S1 afterglow), anti-Kasha T n afterglow (n >= 2), and organic long-persistent luminescence (OLPL), and pioneer a mechanism-encoded anticounterfeiting strategy through systematic material design. Various afterglow patterns, such as security labels, work badges, authentication certificates, and maps, were prepared through ultraviolet printing and melt casting, incorporating multiple afterglow mechanisms that make them highly resistant to counterfeiting. By employing industrial-grade equipment, we successfully achieved the large-scale production of these afterglow patterns, laying the foundation for applications in anticounterfeiting, information encryption, personalization, and aesthetic enhancement.

The development of sterically hindered aryl-alkyl coupling reactions is of great significance in promoting the advancement of organic synthesis and electronic materials. A conformationally well-defined, sterically hindered, electron-rich monophosphorus ligand (P)Ad-AntPhos was designed and synthesized, and its application as a ligand in the palladium-catalyzed Suzuki-Miyaura coupling reaction between sterically hindered aryl halides and cyclic alkylboronic acids were studied. To develop an efficient sterically hindered aryl-alkyl coupling reaction, a more sterically hindered (P)Ad-AntPhos based on the structure of AntPhos was designed and synthesized. In the coupling reaction between 2,4,6-triisopropyl bromobenzene and cyclohexylboronic acid, (P)Ad-AntPhos has shown excellent reactivity, yielding the target product in 80% yield by screening various reaction conditions including ligands, temperature, and bases. A series of sterically hindered aryl-alkyl coupling products have been obtained in unprecedentedly high yields. Compared to AntPhos, (P)Ad-AntPhos has shown good tolerance of steric hindrance.

The pursuit of catalysis capable of forging C(sp(3))& horbar;S bonds is extremely desired because these bonds have substantial importance in pharmaceuticals, functional materials, and organic synthesis. Hydrothiolation and carbothiolation of feedstock alkenes are among the most straightforward and prominent approaches to C(sp(3))& horbar;S bond formations. However, hydrothiolation of alkyl-substituted alkenes typically proceeds in an anti-Markovnikov fashion, and carbothiolation predominantly relies on three-component coupling strategies using highly reactive pre-functionalized electrophilic sulfur sources and nucleophilic carbon sources. Herein, by strategically using heterolytic cleavage of C(sp(3))& horbar;S bond, we report a chemodivergent transfer-hydrothiolation and carbothiolation of alkenes with thioethers serving as bifunctional reagents. The chemo-control is achieved through careful selection of the counteranion associated with the Rh-center. Counteranions with relatively strong coordinating ability, such as TfO-, promote an unusual Markovnikov transfer-thiol-ene reaction. Conversely, noncoordinating counteranions, such as BF4-, enable an unprecedented intermolecular thioether-ene reaction that adds thioethers directly across alkenes. Mechanistic and computational studies elucidated that the coordination or noncoordination of counteranions on Rh can alter the basicity of the thiolate, resulting in chemodivergence.

The mild and practical synthesis of SGLT-2 inhibitors (empagliflozin, dapagliflozin, and canagliflozin) has been achieved via nickel-catalyzed reductive cross-coupling, followed by deprotection. The ligand in this cross-coupling reaction is essential for both the reactivity and stereoselectivity. After conducting several rounds of the ligand design-synthesis-test sequence, a new ligand 4 '-Bu-Terpy with a simple structure and low cost was discovered, affording the C-aryl beta-d-glucoside products in high yields. The decagram-scale synthesis of empagliflozin, dapagliflozin, and canagliflozin through the glycosylation and hydrolysis procedure was also demonstrated, with the products isolated by the recrystallization method.

Understanding the roles and dynamic evolution of active species represents a crucial yet challenging frontier in catalysis research, particularly in systems involving in situ-formed nanoclusters. Owing to the multimetallic nature of soluble nanoclusters, elucidating their distinct catalytic mechanisms, which differ fundamentally from those of conventional homogeneous molecular catalysts or heterogeneous surfaces, has emerged as a critical scientific priority, though this field remains largely unexplored. Herein, we demonstrate a nickel-catalytic system that achieves the regioselective double hydroboration of unsymmetrical internal alkynes with pinacolborane (HBpin), enabling efficient synthesis of sterically congested quaternary 1,1-diboryl alkanes. Mechanistic studies reveal that the catalytic activity originates from in situ-generated Ni nanoclusters, which uniquely activate multiple HBpin simultaneously and enable geminal (H, H) and (B, B) addition to alkynes. This proposed gem-addition mechanism diverges fundamentally from classical sequential double hydroboration pathways mediated by monometallic centers, highlighting the advantages of polynuclear architectures in unlocking unprecedented reactivity and catalytic pathways.

Catalytic enantioselective arylation of disubstituted isatin derivatives with easily accessible arylboronic acids promoted by a chiral phosphine-Co complex is presented. Such a process represents an unprecedented Co-catalyzed approach for direct introduction of a variety of aryl groups onto the isatin derivative motif, affording a range of synthetically useful chiral tertiary alcohols in up to 98% yield with 98:2 er.

Secreted proteins are key mediators of intercellular communication in multicellular organisms. However, progress in secretomics has been hindered by the lack of effective methods for capturing secreted proteins. Here, we present a two-step secretome enrichment method (tsSEM) that integrates unnatural amino acid labeling with click chemistry-based biorthogonal reaction, enabling robust in vitro secretome profiling in the presence of serum. Applying tsSEM, we systematically analyzed the secretome of human induced pluripotent stem cells (iPSCs)-derived astrocytes (iAst) across various disease models and identified a panel of astrocyte-secreted proteins contributing to noncell autonomous neurotoxicity. Among these, we validated two novel neurotrophic factors, FAM3C and KITLG, which enhanced neurite outgrowth, protected neuronal viability, and promoted neural progenitor proliferation. Our findings demonstrate the utility of tsSEM for high-resolution secretome analysis and underscore the potential of iAst-derived secretomes in elucidating disease mechanisms and identifying therapeutic targets.