Microneedle Patch Integrated with Porous Silicon Confined Dual Nanozymes for Synergistic and Hyperthermia‐Enhanced Nanocatalytic Ferroptosis Treatment of Melanoma

Abstract

Superficial melanoma is the deadliest form of skin cancer without desirable clinically therapeutic options. Nanozymes, artificial nanomaterials with physicochemical performance and enzyme catalytic properties, have attracted considerable attention for antitumor therapy. However, the therapeutic efficiency of nanozymes is vulnerable to the tumor microenvironment (TME) and delivery process. Herein, a microneedle (MN) patch that integrates porous silicon (PSi) loaded with dual nanozymes is devised to bidirectionally regulate TME and accurately deliver nanocomplex to initiate ferroptosis for melanoma treatment. Benefitting from the channel confinement effect of PSi, the copper‐doped graphene quantum dots and palladium nanoparticles coloaded PSi (CuGQD/PdNPs@PSi) exhibit synergistic effect with enhanced mimicking peroxidase and glutathione oxidase activities, which are ≈2–3‐fold higher than those of monoconfined nanozyme or nonconfined nanozyme complexes. Additionally, the synergistic catalytic performance of CuGQD/PdNPs@PSi can be improved via photostimuli hyperthermia. The CuGQD/PdNPs@PSi can induce ferroptosis manifested by upregulation of lipid peroxides and inactivation of glutathione peroxidase 4. Furthermore, loading of nanocomplexes into MNs for administration resulted in a satisfactory melanoma growth inhibition of 98.8% within 14 days. Therefore, MNs encapsulated with CuGQD/PdNPs@PSi can provide a potentially nanocatalytic strategy for ferroptosis‐inducing tumor treatment while also meeting the medical needs of eradicating superficial tumors.

Solid Electrochemiluminescence Sensor by Immobilization of Emitter Ruthenium(II)tris(bipyridine) in Bipolar Silica Nanochannel Film for Sensitive Detection of Oxalate in Serum and Urine

“…Porous materials are renowned for their unique structure and properties, characterized by a large surface area, high porosity, tunable pore size and structure, excellent diffusivity, and conductivity [ 31 , 32 , 33 , 34 ]. These features make porous materials widely applicable in various fields such as energy storage, catalysis, adsorption, separation, sensing, and medicine [ 35 , 36 , 37 ]. Utilizing porous molecular sieve film to modify electrodes provides an effective method for constructing solid-state ECL systems.…”

Sensitive Electrochemical Detection of Carcinoembryonic Antigen Based on Biofunctionalized Nanochannel Modified Carbonaceous Electrode

“…In recent years, porous materials have attracted extensive research interest due to their large surface area, demonstrating great applications in adsorption, separation, catalysis, sensors, and other fields [ 20 , 21 , 22 , 23 ]. Unlike bulk porous materials, porous film has a higher compatibility with two-dimensional (2D) planar electrodes.…”

Vertical Silica Nanochannels and o-Phenanthroline Chelator for the Detection of Trace Fe(II)

“…Molecules with different characteristics can show distinct mass transport processes and physical phenomena at the nanoscale, which has been employed for the construction of novel electrochemical and electrochemiluminescence sensors with high sensitivity. , For example, when the size of charged nanochannels or nanopores is comparable to the Debye length (a few or tens of nanometers) in solution, counterions will be electrostatically attracted due to their interaction with the electrical double layer (EDL) near the charged surface of nanochannels or nanopores. − In addition, molecules confined in ultrasmall volume containers can be more easily detected compared to those in bulk solution, which arises from the ultrasmall volume and greatly increased concentration of molecules. − Vertically ordered mesoporous silica film (VMSF) consisting of uniform (commonly 2–3 nm in diameters) and numerous (10 12 pores cm –2 ) nanopores and ultrathin thickness (∼100 nm as usual) has been utilized to modify the electrode for sensitive and antifouling detection of various analytes of interests in real samples, such as metal ions, biomarkers, cells, and drug molecules in complex samples. − Thanks to the deprotonation of abundant silanol groups (p K a ∼ 2) inside nanochannels, ultrasmall volume (∼0.48 zL) of a nanochannel, and adjustable hydrophobic surface, VMSF has become an effective permselective electrode material in terms of charge, size, and complexation effects, which has aroused intensive fundamental research and sensing work so far. − To the best of our knowledge, exploitation of chelating agents for promoting the confined effect inside nanochannels of VMSF and further increasing the analytical performance has not yet been reported.…”