Peroxynitrite (ONOO−) is a critical signaling molecule with a concentration-dependent dual role, yet existing probes struggle to capture its “tipping point” from a physiological messenger to a pathological toxin. To overcome this limitation, we report a pseudo-four-channel fluorescent probe (RS-L) based on a concentration-dependent cascade reaction. At low ONOO− concentrations, the probe’s green (564 nm) and near-infrared (NIR, ∼731 nm) fluorescence channels are synchronously activated, establishing a ratiometric sensing system modulated by Förster resonance energy transfer (FRET). Conversely, at higher pathological concentrations, an irreversible cleavage of the hemicyanine moiety is triggered, causing a dramatic reconfiguration of the fluorescent output comprising the quenching of the NIR channel, a secondary enhancement of the green fluorescence due to FRET blockage, and the emergence of a new blue channel (∼456 nm). This design generates a multi-parametric output, which can be interpreted as a “pseudo-four-channel” information matrix. This matrix comprises three distinct spectroscopic channels (blue, green, and NIR) and an additional analytical pseudo-channel derived from the ratiometric signal (Igreen/INIR) for self-calibrated analysis, enabling the intuitive discrimination of ONOO− levels from functional to damaging overload. We have not only clearly visualized the concentration transition of endogenous ONOO− in cellular models of inflammation and acute kidney injury (AKI), but have also successfully extended this tiered monitoring capability to a zebrafish in vivo model. Therefore, RS-L not only provides a promising tool for investigating the concentration-dependent effects of ONOO− but also, its multi-parametric cascade response design paradigm provides a new design paradigm for smart probes capable of decoding complex biological signals.
Owing to their appealing properties and versatile reactivity, sulfonyl fluorides have attracted considerable attention across numerous fields, with aromatic sulfonyl fluorides playing a pivotal role in chemical biology and molecular pharmacology. The introduction of -SO2F groups via direct C-H fluorosulfonylation of arenes, circumventing the need for prefunctionalization, represents an effective and concise approach for the synthesis of aromatic sulfonyl fluorides; however, this radical variant has remained an unsolved challenge. Herein, we report the first example of a direct radical fluorosulfonylation of aromatics with fluorosulfonyl radicals, enabled by a benzimidazolium-type radical precursor and an iridium photocatalyst under photoredox catalytic conditions. This reaction provides a new and straightforward method for synthesizing a range of aryl and heteroaryl sulfonyl fluorides from readily available arenes and heteroarenes. Furthermore, density functional theory (DFT) calculations and detailed mechanistic studies were performed to afford deeper insight into the reaction mechanism, and the superiority of introducing -SO2F groups for diversity synthesis is demonstrated through further transformation via sulfur(VI) fluoride exchange (SuFEx) click reactions and drug molecule ligation.
The electrochemical carbon dioxide reduction reaction (CO2RR) converts CO2 into value-added fuels and chemicals. Traditionally, research on carbon-based electrocatalysts has focused primarily on tailoring the intrinsic properties of specific active sites. However, carbon materials are now recognized not merely as inert supports, but as multifunctional platforms that actively participate in electronic modulation, mass transport, and even catalysis itself. Here, we systematically review the control of the catalytic environment via carbon materials, spanning from electronic regulation at the microscopic scale to macroscopic structural design. This ranges from defect engineering and heteroatom doping at the atomic scale, to the stabilization of metal clusters at the nanoscale, and finally to hierarchical pore engineering and gas diffusion electrode design at the micro-macro scale to manage mass transport and stabilize the triple-phase interface. This review proposes a comprehensive design scheme for multi-scale carbon carriers. By leveraging this multi-scale collaborative strategy, the adsorption energy barriers of key intermediates can be precisely adjusted and the local reaction microenvironment optimized, thereby directing the reaction pathway and improving overall efficiency. Ultimately, this work provides valuable insights for the future structural and functional optimization of carbon-based catalysts.
Under mild continuous-flow gas-solid conditions, the direct conversion of gaseous nitric oxide (NO) in flue gas to pure ammonia (NH3) is hindered by the challenges of sustaining continuous proton-electron coupling and transfer. Here, we develop a PtOx-TiO2 photocatalyst featuring ultrafine PtOx clusters that sustain continuous electron transfer via dynamic PtOx/PtO(x−δ) redox cycling. Upon illumination, PtOx continuously captures photogenerated electrons to form PtO(x−δ) and injects them into NO antibonding orbitals, while the PtOx-TiO2 interface simultaneously drives H2O dissociation to provide a steady proton flux. This persistent electron-proton coupling orchestrated by PtOx/PtO(x−δ) cluster interface promotes exciton dissociation, interfacial charge separation, and stepwise hydrogenation of NO to NH3. Under continuous-flow conditions with 200 ppm NO, PtOx-TiO2 achieves 76.0
The failure of stretchable optical materials under extreme conditions, such as fire, poses a serious threat to human safety during disaster response. However, conventional systems cannot ensure reliable optical communication in life-threatening scenarios like smoke-filled environments. Here, we present a class of novel organic long-persistent luminescent (OLPL) ionogels designed to bridge this gap. By synergistically integrating amino-aromatic luminophores and a rigid hydroxypropyl methylcellulose scaffold into a conductive network, we achieve a material platform with exceptional resilience. These ionogels exhibit ultrastretchability (>1900
