Competitive photooxidation of small colorless organics controlled by oxygen vacancies under visible light.

Visible-light photooxidation sensitized by surface attachment of small colorless organics on semiconductor photocatalysts has emerged as an economical method for photocatalytic synthesis or degradation. In particular, heteroatom (X = N and Cl)-containing substrates could undergo either C-N coupling or dechlorination degradation sensitizing TiO, but the mechanism in conducting the competitive visible-light sensitized photooxidations is still vague. Herein, the visible-light photooxidation of colorless 4-chlorobenzene-1,2-diamine (-CAN) on TiO was revealed, contributing to selective C-N coupling rather than dechlorination.

A dynamic cascade DNA nanocomplex to synergistically disrupt the pyroptosis checkpoint and relieve tumor hypoxia for efficient pyroptosis cancer therapy.

Pyroptosis has attracted widespread concerns in cancer therapy, while the therapeutic efficiency could be significantly restricted by using the crucial pyroptosis checkpoint of autophagy and tumor hypoxia. Herein, a DNA nanocomplex (DNFs@ZnMn), containing cascade DNAzymes, promoter-like ZnO-Mn nanozymes and photosensitizers, was constructed in one pot through rolling circle amplification reactions to induce pyroptosis through disrupting autophagy. After targeting cancer cells with a high expression of H and glutathione, DNFs@ZnMn decomposed to expose DNAzymes and promoter-like ZnO-Mn nanozymes.

Synergistically remodulating H/Ca gradients to induce mitochondrial depolarization for enhanced synergistic cancer therapy.

The remodulation of H/Ca gradients in the mitochondria matrix could be effective to induce mitochondria depolarization for the enhancement of cancer therapy. However, it is still challenged by H homeostasis, insufficient Ca, uncoordinated regulations, and inefficient loading/delivery strategies. Herein, a supramolecular DNA nanocomplex (Ca@DNA-MF) was prepared to synergistically remodulate H/Ca gradients for mitochondrial depolarization.

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

Single electron transfer (SET) has made great contributions to a broad range of chemical processes, whose radical cation and carbocation intermediates are important for mechanism studies. Herein, hydroxyl radical (˙OH)-initiated SET was revealed in accelerated degradations, the online examination of radical cations and carbocations by electrosonic spray ionization mass spectrometry (ESSI-MS). In the green and efficient non-thermal plasma catalysis system (MnO-plasma), hydroxychloroquine was efficiently degraded upon SET carbocations.

Modular and hierarchical self-assembly of siRNAs into supramolecular nanomaterials for soft and homogeneous siRNA loading and precise and visualized intracellular delivery.

siRNA therapeutics are challenged by homogeneous and efficient loading, maintenance of biological activities, and precise, dynamic and monitorable site-release. Herein, supramolecular nanomaterials of WP5⊃G-siRNA were constructed by modular and hierarchical self-assembly of siRNA with guest (3,6-di(thiophen-2-yl)pyrrolo[3,4-]pyrrole-1,4(2,5)-dione derivative, G) and host (pillar[5]arene, WP5) molecules in the same system. Demonstrated by experiments and theoretical calculations, WP5⊃G-siRNA was constructed comprehensive weak interactions including electrostatic, hydrophobic-hydrophilic, host-guest and π-π interactions.

SiRNA-templated 3D framework nucleic acids for chemotactic recognition, and programmable and visualized precise delivery for synergistic cancer therapy.

Developments in framework nucleic acids (FNAs) are limited by complicated synthesis, by-product interference, and low framework utilization. Herein, simple core-shell spherical 3D FNAs (ST-SFNAs) preparation is presented based on siRNA-templated linear polymerization followed by hybridization chain reaction branched polymerization. Without by-products, all components exhibited their special functions to obtain high space utilization of ST-SFNAs.