OH radical-initiated single-electron transfer for accelerated degradation <i>via</i> carbocation intermediates

Ge, Xiyang; Yin, Yiyan; Sun, Jianghui; Ouyang, Jin; Na, Na

doi:10.1039/d2sc06915f

Cited by 3 publications

References 39 publications

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Multienzyme‐Like Polyoxometalate‐Based Single‐Atom Enzymes for Cancer‐Specific Therapy Through Acid‐Triggered Nontoxicity‐to‐Toxicity Transition

Ge,

Yin,

Wang

et al. 2024

Small

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Single‐atom enzymes (SAzymes) exhibit great potential for chemodynamic therapy (CDT); while, general application is still challenged by their instability and unavoidable side effects during delivery. Herein, a manganese‐based polyoxometalate single‐atom enzyme (Mn‐POM SAE) is first introduced into tumor‐specific CDT, which exhibits tumor microenvironment (TME)‐activated transition of nontoxicity‐to‐toxicity. Different from traditional POM materials, the aggregates of low‐toxic Mn‐POM SAE nanospheres are obtained at neutral conditions, facilitating efficient delivery and avoiding toxicity problems in normal tissues. Under acid TME conditions, these nanospheres are degraded into smaller units of toxic Mn(II)‐PW11; thus, initiating cancer cell‐specific therapy. The released active units of Mn(II)‐PW11 exhibit excellent multienzyme‐like activities (including peroxidase (POD)‐like, oxidase (OXD)‐like, catalase (CAT)‐like, and glutathione peroxidase (Gpx)‐like activities) for the synergistic cancer therapy due to the stabilized high valence Mn species (MnIII/MnIV). As demonstrated by both intracellular evaluations and in vivo experiments, ROS is generated to cause damage to lysosome membranes, further facilitating acidification and impaired autophagy to enhance cancer therapy. This study provides a detailed investigation on the acid‐triggered releasing of active units and the electron transfer in multienzyme‐mimic‐like therapy, further enlarging the application of POMs from catalytical engineering into cancer therapy.

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Multienzyme‐Like Polyoxometalate‐Based Single‐Atom Enzymes for Cancer‐Specific Therapy Through Acid‐Triggered Nontoxicity‐to‐Toxicity Transition

Ge,

Yin,

Wang

et al. 2024

Small

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Catalyst-free selective oxidation of C(sp3)-H bonds in toluene on water

Lee,

Cho,

Kim

et al. 2024

Nat Commun

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The anisotropic water interfaces provide an environment to drive various chemical reactions not seen in bulk solutions. However, catalytic reactions by the aqueous interfaces are still in their infancy, with the emphasis being on the reaction rate acceleration on water. Here, we report that the oil-water interface activates and oxidizes C(sp3)-H bonds in toluene, yielding benzaldehyde with high selectivity (>99%) and conversion (>99%) under mild, catalyst-free conditions. Collision at the interface between oil-dissolved toluene and hydroxyl radicals spontaneously generated near the water-side interfaces is responsible for the unexpectedly high selectivity. Protrusion of free OH groups from interfacial water destabilizes the transition state of the OH-addition by forming π-hydrogen bonds with toluene, while the H-abstraction remains unchanged to effectively activate C(sp3)-H bonds. Moreover, the exposed free OH groups form hydrogen bonds with the produced benzaldehyde, suppressing it from being overoxidized. Our investigation shows that the oil-water interface has considerable promise for chemoselective redox reactions on water without any catalysts.

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Catalyst-free selective oxidation of C(sp3)-H bonds in toluene on-water

Choi,

Lee,

Choi

et al. 2024

Preprint

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The anisotropic water interfaces provide a unique environment to drive various chemical reactions not seen in bulk solutions. However, catalytic reactions by the aqueous interfaces are still in their infancy, with the emphasis being on the reaction rate acceleration on-water. Here, we report that the oil-water interface activates and oxidizes C(sp3)-H bonds in toluene, yielding benzaldehyde with high selectivity (> 99%) and conversion (> 99%) under mild, catalyst-free conditions. Collision at the interface between oil-dissolved toluene and hydroxyl radicals spontaneously generated near the water side interfaces is responsible for the unexpectedly high selectivity. Protrusion of free OH groups from interfacial water destabilizes the transition state of the OH-addition by forming π-hydrogen bonds with toluene, while the H-abstraction remains unchanged to effectively activate C(sp3)-H bonds. Moreover, the exposed free OH groups form hydrogen bonds with the produced benzaldehyde, suppressing it from being overoxidized. Our investigation shows that the oil-water interface has considerable promise for chemoselective redox reactions on-water without any catalysts.

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OH radical-initiated single-electron transfer for accelerated degradation via carbocation intermediates

Abstract: Single electron transfer (SET) has exhibited great contributions in broad chemical processes, whose intermediates of radical cations and carbocations are curial for mechanism studies. Herein, hydroxyl radical (·OH)-initiated SET was...

Cited by 3 publications

References 39 publications

Multienzyme‐Like Polyoxometalate‐Based Single‐Atom Enzymes for Cancer‐Specific Therapy Through Acid‐Triggered Nontoxicity‐to‐Toxicity Transition

Multienzyme‐Like Polyoxometalate‐Based Single‐Atom Enzymes for Cancer‐Specific Therapy Through Acid‐Triggered Nontoxicity‐to‐Toxicity Transition

Catalyst-free selective oxidation of C(sp3)-H bonds in toluene on water

Catalyst-free selective oxidation of C(sp3)-H bonds in toluene on-water

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