NIR-Driven Intracellular Photocatalytic O₂ Evolution on Z-Scheme Ni₃S₂/Cu_1.8S@HA for Hypoxic Tumor Therapy

Abstract

Hypoxia in a tumor microenvironment (TME) has inhibited the photodynamic therapy (PDT) efficacy. Here, Ni 3 S 2 /Cu 1.8 S nanoheterostructures were synthesized as a new photosensitizer, which also realizes the intracellular photocatalytic O 2 evolution to relieve hypoxia in TME and enhance PDT as well. With the narrow band gap (below 1.5 eV), the near infrared (NIR) (808 nm) can stimulate their separation of the electron−hole. The novel Z-scheme nanoheterostructures, testified by experimental data and density functional theory (DFT) calculation, possess a higher redox ability, endowing the photoexited holes with sufficient potential to oxide H 2 O into O 2 , directly. Meanwhile, the photostimulated electrons can capture the dissolved O 2 to form a toxic reactive oxygen species (ROS). Moreover, Ni 3 S 2 /Cu 1.8 S nanocomposites also possess the catalase-/peroxidase-like activity to convert the endogenous H 2 O 2 into • OH and O 2 , which not only cause chemodynamic therapy (CDT) but also alleviate hypoxia to assist the PDT as well. In addition, owing to the narrow band gap, they possess a high NIR harvest and great photothermal conversion efficiency (49.5%). It is noted that the nanocomposites also exhibit novel biodegradation and can be metabolized and eliminated via feces and urine within 2 weeks. The present single electrons in Ni/Cu ions induce the magnetic resonance imaging (MRI) ability for Ni 3 S 2 /Cu 1.8 S. To make sure that the cancer cells were specifically targeted, hyaluronic acid (HA) was grafted outside and Ni 3 S 2 /Cu 1.8 S@HA integrated photodynamic therapy (PDT), chemodynamic therapy (CDT), and photothermal therapy (PTT) to exhibit the great anticancer efficiency for hypoxic tumor elimination.

Chemodynamic Therapy via Fenton and Fenton‐Like Nanomaterials: Strategies and Recent Advances

“…In addition, other metal elements have also been exploited for realizing two‐metal‐ion‐based CDT. [ 371–388 ] Yang et al. designed ancient pigment nanosheets (SrCuSi 4 O 10 NSs, abbreviated as SC NSs) and functionalized them with GOx to afford SC@G NSs for the synergistic action of ST, PTT, and CDT ( Figure a).…”

Development of Nickel Selenide@polydopamine Nanocomposites for Magnetic Resonance Imaging Guided NIR‐II Photothermal Therapy

“…In addition, the paramagnetism of nickel ions was due to the two unpaired electrons on its outer layer. And the longitudinal relaxation in MRI is regulated by the spin-lattice interaction mechanism between water protons and the paramagnetic core, so we considered nickel-based nanomaterials might be served as T 1 contrast agents for MRI, such as Ni 3 S 2 /Cu 1.8 S@HA [43] and Niintegrated CuS NCs. [44] In addition, in order to develop a general method to enhance the MRI effect of nickel-based nanomaterials, we designed an universal method through in situ coating the PDA shell on the surface of NiSe NPs.…”

Engineered Nanostructured Photocatalysts for Cancer Therapy

“…The e − from CB I are transferred to VB II , leaving stronger reduction/oxidation potentials and thus improving ROS production [112,119,120]. Different Zscheme configurations have been successfully evaluated for PDT, including Fe 2 O 3 -FeS 2 [112], SbNSs-THPP (namely, 10,15,20-tetrakis(4-hydroxyphenyl)-21H,12H-porphine) [111], Bi 2 S 3 -Bi [113], g-C 3 N 4 -Cu 3 P [114], SnS 1.68 -WO 2.41 [23] or Ni 3 S 2 -Cu 1.8 S [115]. In this case, most of the Z-scheme nanostructures could perform under 808 nm irradiation in comparison with type-II heterostructures, which could work under 650 nm.…”