RESUMO
The key of heterostructure is the combinations created by stacking various vdW materials, which can modify interlayer coupling and electronic properties, providing exciting opportunities for designer devices. However, this simple stacking does not create chemical bonds, making it difficult to fundamentally alter the electronic structure. Here, we demonstrate that interlayer interactions in heterostructures can be fundamentally controlled using hydrostatic pressure, providing a bonding method to modify electronic structures. By covering graphene with boron nitride and inducing an irreversible phase transition, the conditions for graphene lattice-matching bonding (IMB) were created. We demonstrate that the increased bandgap of graphene under pressure is well maintained in ambient due to the IMB in the interface. Comparison to theoretical modeling emphasizes the process of pressure-induced interfacial bonding, systematically generalizes, and predicts this model. Our results demonstrate that pressure can irreversibly control interlayer bonding, providing opportunities for high-pressure technology in ambient applications and IMB engineering in heterostructures.
RESUMO
Although research on photodynamic therapy (PDT) of malignant tumor has made considerable progress in recent years, it is a remaining challenge to extend PDT to the second near-infrared window (NIR-II) along with real-time and accurate NIR-II fluorescence imaging to determine drug enrichment status and achieve high treatment efficacy. In this work, lanthanide nanoparticles (Ln NPs)-based nanoplatform (LCR) equipped with photosensitizer Chlorin e6 (Ce6) and targeting molecular NH2-PEG1000-cRGDfK are developed, which can achieve NIR-II photodynamic therapy (PDT) and NIR-II fluorescence imaging by dual channel excitation. Under 808 nm excitation, Nd3+ in the outer layer can absorb the energy and transfer inward to emit strong NIR-II emissions (1064 and 1525 nm). Due to the low background noise of NIR-II light and the targeting effect of NH2-PEG1000-cRGDfK, LCR can recognize tiny tumor tissue (≈3 mm) and monitor drug distribution in vivo. Under 1530 nm excitation, internal Er3+ can be self-sensitized, generating intense upconversion emission (662 nm) that can effectively activate Ce6 for in vivo PDT due to the deep tissue penetration of NIR-II light. This study provides a paradigm of theranostic nanoplatform for both real-time fluorescence imaging and PDT of orthotopic breast tumor in NIR-II window.
RESUMO
Sonodynamic therapy (SDT) has been recognized as a promising treatment for cancer due to its advantages of superior specificity, non-invasiveness, and deep tissue penetration. However, the antitumor effect of SDT remains restricted by the limited generation of reactive oxygen species (ROS) due to the lack of highly efficient sonosensitizers. In this work, we developed the novel sonosensitizer Pt/CeO2-xSx by constructing oxygen defects through S doping and Pt loading in situ. Large amounts of oxygen defects have been obtained by S doping, endowing Pt/CeO2-xSx with the ability to suppress electron-hole recombination, further promoting ROS production. Moreover, the introduction of Pt nanoparticles can not only produce oxygen in situ for relieving hypoxia but also form a Schottky heterojunction with CeO2-xSx for further inhibiting electron-hole recombination. In addition, Pt/CeO2-xSx could effectively deplete overexpressed glutathione (GSH) via redox reactions, amplifying oxidative stress in the tumor microenvironment (TME). Combined with the excellent POD-mimetic activity, Pt/CeO2-xSx can achieve highly efficient synergistic therapy of SDT and chemodynamic therapy (CDT). All these findings demonstrated that Pt/CeO2-xSx has great potential for cancer therapy, and this work provides a promising direction for designing and constructing efficient sonosensitizers.
Assuntos
Antineoplásicos , Cério , Cério/química , Cério/farmacologia , Humanos , Animais , Antineoplásicos/farmacologia , Antineoplásicos/química , Camundongos , Espécies Reativas de Oxigênio/metabolismo , Terapia por Ultrassom , Platina/química , Platina/farmacologia , Ensaios de Seleção de Medicamentos Antitumorais , Proliferação de Células/efeitos dos fármacos , Tamanho da Partícula , Linhagem Celular Tumoral , Microambiente Tumoral/efeitos dos fármacos , Sobrevivência Celular/efeitos dos fármacos , Camundongos Endogâmicos BALB C , Neoplasias/tratamento farmacológico , Neoplasias/terapiaRESUMO
A pH-responsive charge-convertible drug delivery nanocarrier (MSN-TPZ-GOx@ZnO@PAH-PEG-DMMA, abbreviated as MTGZ@PPD) was prepared, which could specifically release hypoxia-activated chemotherapeutic Tirapazamine (TPZ) and glucose oxidase (GOx) in the tumor site for precise starvation and chemo synergistic oncotherapy. Acid-responsive Schiff base structure modified mesoporous silica nanoparticles (MSN) co-load with GOx and TPZ, then link with ZnO quantum dots (QDs). PAH-PEG-DMMA (PPD) polymer makes MTGZ@PPD with biocompatibility and charge-convertible feature. MTGZ@PPD is negatively charged at physiological pH, and the charge reversal of PPD and acidolysis of the Schiff base structure under the acidic tumor microenvironment (TME) induce a positively charged surface, which could potentiate the cell internalization. ZnO QDs could decompose at acidic TME, achieving controllable drug release. GOx could starve the tumor cells and enhance hypoxia level, thus initiates the activation of TPZ to realize synergistic starvation therapy and chemotherapy. This intelligent MTGZ@PPD has shown great potential for starvation and chemo synergistic oncotherapy.
Assuntos
Doxorrubicina , Óxido de Zinco , Doxorrubicina/química , Óxido de Zinco/química , Bases de Schiff , Concentração de Íons de HidrogênioRESUMO
Graphene with atomic thickness possesses excellent mechanical and electrical properties, which hold great potential for high performance pressure sensing. The exposed electron of graphene is always cross-sensitive to any pollution absorbed or desorbed on the surface, from which the long-term stability of the graphene pressure sensor suffers a lot. This is one of the main obstacles towards graphene commercial applications. In this paper, we utilized polymethylmethacrylate (PMMA)/graphene heterostructure to isolate graphene from the ambient environment and enhance its strength simultaneously. PMMA/graphene pressure sensors, with the finite-depth cavity and the through-hole cavity separately, were made for comparative study. The through-hole device obtained a comparable sensitivity per unit area to the state of the art of the bare graphene pressure sensor, since there were no leaking cracks or defects. Both the sensitivity and stability of the through-hole sensor are better than those of the sensor with 285-nm-deep cavities, which is due to the sealed gas effect in the pressure cavity. A modified piezoresistive model was derived by considering the pressure change of the sealed gas in the pressure cavity. The calculated result of the new model is consistent with the experimental results. Our findings point out a promising route for performance optimization of graphene pressure sensors.