Construction of multifunctional stimuli-responsive nanotherapeutics enabling improved intratumoral penetration of therapeutics and reversal of multiple-drug resistance (MDR) is potent to achieve effective cancer treatment. Herein, we report a general method to synthesize pH-dissociable calcium carbonate (CaCO3) hollow nanoparticles with amorphous CaCO3 as the template, gallic acid (GA) as the organic ligand, and ferrous ions as the metallic center via a one-pot coordination reaction. The obtained GA–Fe@CaCO3 exhibits high loading efficiencies to both oxidized cisplatin prodrug and doxorubicin, yielding drug loaded GA–Fe@CaCO3 nanotherapeutics featured in pH-responsive size shrinkage, drug release, and Fenton catalytic activity. Compared to nonresponsive GA–Fe@silica nanoparticles prepared with silica nanoparticles as the template, such GA–Fe@CaCO3 confers significantly improved intratumoral penetration capacity. Moreover, both types of drug-loaded GA–Fe@CaCO3 nanotherapeutics exhibit synergistic therapeutic efficacies to corresponding MDR cancer cells because of the GA–Fe mediated intracellular oxidative stress amplification that could reduce the efflux of engulfed drugs by impairing the mitochondrial-mediated production of adenosine triphosphate (ATP). As a result, it is found that the doxorubicin loaded GA–Fe@CaCO3 exhibits superior therapeutic effect towards doxorubicin-resistant 4T1 breast tumors via combined chemodynamic and chemo-therapies. This work highlights the preparation of pH-dissociable CaCO3-based nanotherapeutics to enable effective tumor penetration for enhanced treatment of drug-resistant tumors.
A simple template‐free high‐temperature evaporation method was developed for the growth of crystalline Si microtubes for the first time. As‐grown Si microtubes were characterized using X‐ray diffraction, scanning electron microscopy, transmission electron microscopy, and room‐temperature photoluminescence. The lengths of the Si tubes can reach several hundreds of micrometers; some of them have lengths on the order of millimeters. Each tube has a uniform outer diameter along its entire length, and the typical outer diameter is ≈ 2–3 μm. Most of the tubes have a wall thickness of ≈ 400–500 nm, though a considerable number of them exhibit a very thin wall thickness of ≈ 50 nm. Room‐temperature photoluminescence measurement shows the as‐synthesized Si microtubes have two strong emission peaks centered at ≈ 589 nm and ≈ 617 nm and a weak emission peak centered at ≈ 455 nm. A possible mechanism for the formation of these Si tubes is proposed. We believe that the present discovery of the crystalline Si microtubes will promote further experimental studies on their physical properties and smart applications. 相似文献