Xiaojing Li

Photodynamic therapy (PDT) is a promising antitumor treatment that is based on the photosensitizers that inhibit cancer cells by yielding reactive oxygen species (ROS) after irradiation of light with specific wavelengths. As a potential photosensitizer, titanium dioxide (TiO2) exhibits minimal dark cytotoxicity and excellent ultraviolet (UV) light triggered cytotoxicity, but is challenged by the limited tissue penetration of UV light. Herein, a novel near-infrared (NIR) light activated photosensitizer for PDT based on TiO2-coated upconversion nanoparticle (UCNP) core/shell nanocomposites (UCNPs@TiO2 NCs) is designed. NaYF4:Yb(3+),Tm(3+)@NaGdF4:Yb(3+) core/shell UCNPs can efficiently convert NIR light to UV emission that matches well with the absorption of TiO2 shells. The UCNPs@TiO2 NCs endocytosed by cancer cells are able to generate intracellular ROS under NIR irradiation, decreasing the mitochondrial membrane potential to release cytochrome c into the cytosol and then activating caspase 3 to induce cancer cell apoptosis. NIR light triggered PDT of tumor-bearing mice with UCNPs@TiO2 as photosensitizers can suppress tumor growth efficiently due to the better tissue penetration than UV irradiation. On the basis of the evidence of in vitro and in vivo results, UCNPs@TiO2 NCs could serve as an effective photosensitizer for NIR light mediated PDT in antitumor therapy.

Abstract Multifunctional nanocarriers based on the up‐conversion luminescent nanoparticles of NaYF 4 :Yb 3+ /Er 3+ core (UCNPs) and thermo/pH‐coupling sensitive polymer poly[( N ‐isopropylacrylamide)‐ co ‐(methacrylic acid)] (P(NIPAm‐ co ‐MAA)) gated mesoporous silica shell are reported for cancer theranostics, including fluorescence imaging, and for controlled drug release for therapy. The as‐synthesized hybrid nanospheres UCNPs@mSiO 2 ‐P(NIPAm‐ co ‐MAA) show bright green up‐conversion fluorescence under 980 nm laser excitation and the thermo/pH‐sensitive polymer is active as a “valve” to moderate the diffusion of the embedded drugs in‐and‐out of the pore channels of the silica container. The anticancer drug doxorubicin hydrochloride (DOX) can be absorbed into UCNPs@mSiO 2 ‐P(NIPAm‐ co ‐MAA) nanospheres and the composite drug delivery system (DDS) shows a low level of leakage at low temperature/high pH values but significantly enhanced release at higher temperature/lower pH values, exhibiting an apparent thermo/pH controlled “on‐off” drug release pattern. The as‐prepared UCNPs@mSiO 2 ‐P(NIPAm‐ co ‐MAA) hybrid nanospheres can be used as bioimaging agents and biomonitors to track the extent of drug release. The reported multifunctional nanocarriers represent a novel and versatile class of platform for simultaneous imaging and stimuli‐responsive controlled drug delivery.

Multifunctional nanocarriers for targeted bioimaging and drug delivery have attracted much attention in early diagnosis and therapy of cancer. In this work, we develop a novel aptamer-guided nanocarrier based on the mesoporous metal-organic framework (MOF) shell and up-conversion luminescent NaYF4:Yb(3+)/Er(3+) nanoparticles (UCNPs) core for the first time to achieve these goals. These UCNPs, chosen as optical labels in biological assays and medical imaging, could emit strong green emission under 980 nm laser. The MOF structure based on iron (III) carboxylate materials [MIL-100 (Fe)] possesses high porosity and non-toxicity, which is of great value as nanocarriers for drug storage/delivery. As a unique nanoplatform, the hybrid inorganic-organic drug delivery vehicles show great promising for simultaneous targeted labeling and therapy of cancer cells.

In this article, Eu-activated CaYAlO4 aluminate phosphors were synthesized by a solid-state reaction. Under UV light excitation, characteristic red line emission of Eu(3+) was detected in the range of 570-650 nm. In addition, we introduced crystal-site engineering approach into the CaYAlO4 host through incorporation of Si(4+)-Ca(2+) to replace Al(3+)-Y(3+), which would shrink the AlO6 octahedrons, accompanied by the expansion of CaO9 polyhedron, and then enable the partial reduction of Eu(3+) to Eu(2+). The crystal structure and underlying mechanism have been clarified on the basis of the Rietveld refinement analysis. The PL spectra of Ca0.99+xY1-xAl1-xSixO4:Eu0.01 (x = 0-0.30) exhibit both green emission of Eu(2+) (4f(6)5d(1)-4f(7), broadband around 503 nm) and red-orange emission of Eu(3+) ((5)D0-(7)F1,2, 593 and 624 nm) under UV light excitation with a quantum yield of 38.5%. The CIE coordinates of Ca0.99+xY1-xAl1-xSixO4:Eu0.01 (x = 0-0.30) phosphors are regularly shifted from (0.482, 0.341) to (0.223, 0.457) with increasing x, which would expand the application of Eu. Furthermore, this investigation reveals the correlations of structure and property of luminescent materials, which would shed light on the development of novel phosphors suitable for lighting and display applications.