A biomimetic cuproptosis amplifier for targeted NIR-II fluorescence/photoacoustic imaging-guided synergistic NIR-II photothermal immunotherapy.

The therapeutic efficacy of cuproptosis combined with phototheranostics is still hindered by easy copper efflux, nonspecific accumulation and limited light penetration depth. Here, a high-performance NIR-II semiconductor polymer was first synthesized through dual-donor engineering. Then a biomimetic cuproptosis amplifier (PCD@CM) was prepared by Cu(II)-mediated coordinative self-assembly of NIR-II ultrasmall polymer dots and the chemotherapeutic drug DOX, followed by camouflaging of tumor cell membranes. After homologous targeting delivery to tumor cells, overexpressed GSH in the tumor microenvironment (TME) triggers the disassembly of the amplifier and the release of therapeutic components through the reduction of Cu(II) to Cu(I), which enable NIR-II fluorescence/photoacoustic imaging-guided NIR-II photothermal therapy (PTT) and chemotherapy. The released Cu(I) induces the aggregation of lipoylated mitochondrial proteins accompanied by the loss of iron-sulfur proteins, leading to severe proteotoxic stress and eventually cuproptosis. NIR-II PTT and GSH depletion render tumor cells more sensitive to cuproptosis. The amplified cuproptosis sensitization provokes significant immune surveillance, triggering the immunogenic cell death (ICD) to promote cytotoxic T lymphocyte infiltration together with aPD-L1-mediated immune checkpoint blockade. This work proposes a new strategy to develop cuproptosis sensitization systems enhanced by NIR-II phototheranostics with homologous targeting and anti-tumor immune response capabilities.

Fabrication of Pickering emulsions stabilized by citrus pectin modified with ß-cyclodextrin and its application in 3D printing.

Pickering emulsions stabilized by polysaccharide particles have received increasing attention because of their potential applications in three-dimensional (3D) printing. In this study, the citrus pectins (citrus tachibana, shaddock, lemon, orange) modified with ß-cyclodextrin (ß-CD) were used to stabilize Pickering emulsions reaching the requirements of 3D printing. In terms of pectin chemical structure, the steric hindrance provided by the RG I regions was more conducive to the stability of the complex particles. The modification of pectin by ß-CD provided the complexes a better double wettability (91.14 ± 0.14°-109.43 ± 0.22°) and a more negative ζ-potential, which was more beneficial for complexes to anchor at oil-water interface. In addition, the rheological properties, texture properties and stability of the emulsions were more responsive to the ratios of pectin/ß-CD (Rß/C). The results showed that the emulsions stabilized at a φ = 65 % and a Rß/C = 2:2 achieved the requirements (shear thinning behavior, self-supporting ability, and stability) of 3D printing. Furthermore, the application in 3D printing demonstrated that the emulsions under the optimal condition (φ = 65 % and Rß/C = 2:2) displayed excellent printing appearance, especially for the emulsions stabilized by ß-CD/LP particles. This study provides a basis for the selection of polysaccharide-based particles to prepare 3D printing inks which may be utilized in food manufacturing.