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.
Bulk and surface properties of proton stability and transportation in Y and Nd co-doped BaCeO3 (BCYN), especially the effect of Nd segregation, were investigated by first-principles calculations. Since the structure of doped BaCeO3 at the operating temperature of proton-conducting has been unclear for a long time, we have summarized the latest experimental results and calculated the structure of the asymmetric BCYN for the first time. The results show that compared with Y, Nd doping promotes oxygen vacancy formation, however reduces proton stability. Our calculation can also provide a possible explanation for the formation of space charge layer at the grain boundary of doped BaCeO3 in experiment. Unlike the stable Y in BCYN, Nd is calculated to be easily segregated, which can facilitate both proton hydration and proton transportation near the surface. Moreover, Nd segregation at the grain boundary is predicted to be beneficial for proton transportation between grains. 相似文献
ZnO/Cu2S nanotube arrays are fabricated firstly by a facile and capping-agent-free method, and the photo-electrochemical performance has been studied systematically. The results show that ZnO/Cu2S nanotube arrays achieve enhanced photo-electrochemical water splitting performance and the photocurrent densities of ZnO/Cu2S are 7.9 times than that of ZnO at 0 V versus Ag/AgCl. The performance of the ZnO/Cu2S nanotube arrays can be adjusted by changing the amount of Cu2S microcrystals. The results confirm that the enhanced photo-electrochemical performance of ZnO/Cu2S is due to the significantly improved visible light absorption, effective separation of photo-induced carriers due to the well band energy match and the formed p-n junction between ZnO and Cu2S. 相似文献