Abstract

Localized surface plasmon resonances arising from the free carriers in copper-deficient copper chalcogenides nanocrystals (Cu2-xE, E=S,Se) enables them with high extinction coefficient in the near-infrared range, which was superior for photothermal related purpose. Although Cu2-xE nanocrystals with different compositions (0< x≪1) all possess NIR absorption, their extinction coefficients were significantly different due to their distinct valence band free carrier concentration. Herein, by optimizing the synthetic conditions, we were able to obtain pure covellite phase CuS nanoparticles with maximized free carrier concentration (x=1), which provides extremely high mass extinction coefficient (up to 60 Lg-1cm-1 at 980 nm and 32.4 Lg-1cm-1 at 800 nm). To the best of our knowledge, these values was maximal among all inorganic nanomaterials. High quality Cu2-xSe can also be obtained with a similar approach. In order to introduce CuS nanocrystals for biomedical applications, we further transferred these nanocrystals into aqueous solution with an amphiphilic polymer and colvalently linked with beta-cyclodextrin. Using host-guest interaction, adamantine-modified RGD peptide can be further anchored on the nanoparticles for the recognition of integrin-positive cancer cells. Together with the high extinction coefficient and outstand photothermal conversion efficiency (determined to be higher than 40%), these CuS nanocrystals were applied for photothermal therapy of cancer cells and photoacoustic imaging. In addition, anticancer drug doxorubicin can also be loading onto the nanoparticles through either hydrophobic or electrostatic interaction for chemotherapy.

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