Photothermal amplification of Cu-porphyrin redox chemistry on Ti₃C₂ MXene for NIR-activated reactive oxygen species generation for the treatment of hepatocellular carcinoma.

Authors

Ushmita Dey, Antara Ghosh, Nilanjan Das, Archana Singh, Sumanta Kumar Sahu

Published in

Dalton transactions (Cambridge, England : 2003). Volume 55. Issue 22. Pages 8489-8507. Jun 09, 2026. Epub Jun 09, 2026.

Abstract

Controlled generation and regulation of reactive oxygen species (ROS) remains challenging when photochemical and redox processes are combined for cancer-related applications. Photothermal regulation of metal-centred redox kinetics provides a route to amplified ROS (¹O₂, ˙OH, O₂˙^-, etc.) generation in hybrid inorganic systems. In such systems, transition metal-mediated ROS generation is intrinsically governed by local coordination environments, redox kinetics, and energy-transfer pathways. Herein, we report a stepwise-assembled Ti₃C₂@UCNP@Cu-TCPP@LA system in which the redox chemistry of Cu(II)-tetrakis(4-carboxyphenyl)porphyrin (Cu-TCPP) is kinetically regulated by plasmon-assisted photothermal activation of Ti₃C₂ MXene under near-infrared (808 nm) irradiation. Ti₃C₂ nanosheets were integrated with aminated NaYF₄:Yb³⁺/Er³⁺/Nd³⁺ upconversion nanoparticles (UCNPs) through interfacial hydrogen bonding. UCNPs serve as NIR-to-visible photonic intermediates for activating spatially segregated Cu-TCPP moieties covalently attached to the UCNP surface. This architecture suppresses π-π aggregation-induced ROS quenching, preserves the excited-state dynamics of Cu-TCPP, and facilitates efficient Förster resonance energy transfer (FRET) from the UCNPs. Under 808 nm irradiation, the integrated Ti₃C₂ component exhibits pronounced plasmon-derived photothermal behaviour (photothermal conversion efficiency ≈57%), which kinetically accelerates singlet oxygen (¹O₂) generation from photoexcited Cu-TCPP. Simultaneously, photothermal heating promotes intracellular Cu²⁺/Cu⁺ redox cycling and accelerates glutathione depletion and Fenton-like hydroxyl radical (˙OH) production, collectively amplifying chemodynamic reactivity. Ti₃C₂-mediated photothermal activation yields ∼4-fold higher ¹O₂ and ∼3-fold greater ˙OH generation than the UCNP@Cu-TCPP@LA system. Beyond photothermal activation, Ti₃C₂ serves as a conductive support that facilitates interfacial charge and energy transfer processes under NIR irradiation. Functionalisation with lactobionic acid (LA) improves aqueous dispersibility and enables receptor-mediated cellular uptake. In vitro studies confirm pH-responsive behaviour, efficient intracellular ROS generation, and significant cancer cell apoptosis (∼78%) under 808 nm excitation, highlighting the functional relevance of plasmon-assisted photothermal amplification of Cu-porphyrin redox chemistry on Ti₃C₂.

PMID:
42306814
Bibliographic data and abstract were imported from PubMed on 17 Jun 2026.

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