Derong Cao

Enantioselective copper-catalyzed intermolecular radical 1,2-carbosulfenylation of alkenes with readily available alkyl halides provides efficient access to α-chiral alkyl organosulfur compounds, but its development has been hampered by competing side pathways and challenges in enantiocontrol. Herein, we report a general and versatile copper-catalyzed platform for chemo- and enantioselective radical 1,2-carbosulfenylation of a diverse range of alkenes. Central to this strategy is the development of a tunable and readily accessible library of multidentate anionic N,N,N(P)-ligands, which promote the desired transformation while suppressing competing radical pathways, thereby enabling broad compatibility with various alkyl radical precursors and transformable sulfur nucleophiles. The protocol exhibits a broad substrate scope, accommodating electronically diverse alkenes, including monosubstituted and 1,1-disubstituted acrylamides, as well as aryl- or heteroaryl-substituted alkenes, along with alkyl bromides and chlorides as radical precursors. The resulting products can be readily converted into a range of enantioenriched alkyl sulfur-containing building blocks of value in organic synthesis and related fields.

An innovative strategy of aggregation‐induced stabilization is presented to achieve highly stable boron‐containing organic diradicaliods by forming different π–π stacking aggregates through cooperative π bridge and hydrogen bond regulation. Herein, three D‐π‐A‐π‐D crossover shaped molecules (PPCy‐Ph, PPCy‐Th, and PPCy‐Fu) are synthesized with π‐bridge engineering from phenyl‐, thienyl‐to furyl for precisely modulating molecular conformation and aggregation state. As the most stable boron‐containing π‐radicals to date, they all display unprecedentedly stable ESR signals at harsh conditions (300°C in air for 2 h and boiling water for 2 h) and superior photo‐, chemical‐ and thermal stability due to synergistic effect of hydrogen bonding interactions. In particular, PPCy‐Th exhibited best photothermal conversion efficiency, reaching 275°C under 808 nm laser irradiation (1.0 W cm ² ), superior solar‐driven water evaporation rate of 1.42 kg m ⁻² h ⁻¹ and evaporation efficiencies (η) of 98.37%, thermoelectric power generation (256 mV) under 1 sun illumination. The multiple applications in cogeneration of water and electricity, seawater desalination, sewage treatment, laser ignition, and driving electric fan are demonstrated. Moreover, PPCy‐Fu NPs display efficient photothermal & photodynamic synergistic cancer cell killing under hypoxia. This study highlights a novel strategy for developing stable boron‐containing diradicaloids with excellent photo‐thermal conversion efficiency.

A simultaneous donor engineering and boron complexation strategy for boosting photothermal conversion is developed.

Enhancing the efficiency and versatility of supramolecular catalysis remains a central research goal. Water-soluble pillar[6]arenes (H1), per-substituted with quaternary ammonium groups, catalyze the aqueous-phase Kemp elimination of 1,2-benzisoxazole (R1), achieving k_cat/k_uncat ratio up to 1.5 × 10⁵ at pH 8, surpassing previously reported macrocycles for the reaction and rivaling the remarkable rate enhancements (up to 2 × 10⁵-fold) of coordination cages. Orthogonal self-sorting binding enables R1 to anchor in the hydrophobic cavity while OH^– enriches at the positively charged portals, facilitating substrate preorganization and enrichment. Ions, including OH^–, selectively weaken the binding of the anionic product while strengthening substrate R1 association, mitigating product inhibition and boosting turnover. Robust catalysis at pH 6–7 and recyclability provide a sustainable, enzyme-mimetic catalytic strategy.

Hydrazine (N ₂ H ₄ ) and hydrogen sulfide (H ₂ S) play important roles in industrial, agricultural and pharmaceutical fields.

This study presents a novel vinyl sulfide-based radical dynamic chemistry that effectively controls various thiyl radical polymerizations, resulting in sulfur-containing polymers with well-defined architectures.

The detection of aliphatic and aromatic biogenic amines (BAs) is important in food spoilage, environmental monitoring, and disease diagnosis and treatment. Existing fluorescent probes predominantly detect aliphatic BAs with single signal variation and low sensitivity, impairing the adaptability of discriminative sensing platforms. Herein, we present a visual chemosensor (galactose-functionalized pyrrolopyrrole aza-BODIPY, PPAB-Gal) that simultaneously detects eight aliphatic and aromatic BAs in a real-time and intuitive way based on their unique electronic and structural features. Our findings reveal that the dual colorimetric and ratiometric emission changes are rapidly produced in presence of eight BAs through a noncovalent interaction (π–π stacking and hydrogen bond)-assisted chromophore reaction. Specifically, other lone-pair electrons containing compounds, such as secondary amines, tertiary amines, NH₃, and thiol, fail to exhibit these changes. As a result, superior sensing performances with distinctly dual signals (Δλ_ab = 130 nm, Δλ_em = 150 nm), a low LOD (~25 nM), and fast response time (<2 min) were obtained. Based on these advantages, a qualitative and smartphone-assisted sensing platform with a PPAB-Gal-loaded TLC plate is developed for visual detection of putrescine and cadaverine vapor. More importantly, we construct a connection between a standard quantitative index for the TVBN value and fluorescence signals to quantitatively determine the freshness of tuna and shrimp, and the method is facile and convenient for real-time and on-site detection in practical application. Furthermore, since the overexpressed spermine is an important biomarker of cancer diagnosis and treatment, PPAB-Gal NPs can be used to ratiometrically image spermine in living cells. This work provides a promising sensing method for BAs with a novel fluorescent material in food safety fields and biomedical assays.