Polyethyleneimine (PEI)-capped NaYF 4 nanoparticles (NPs) codoped with Yb 3+ , Er 3+ , and Mn 2+ ions (MnUNPs) were synthesized via a solvothermal method. The MnUNPs showed tissue-penetrable over-1000 nm (OTN-) near-infrared (NIR) and strong red upconversion (UC) emission under NIR excitation. Furthermore, the photosensitizers chlorin e6 (Ce6) and biocompatible poly(ethylene glycol) (PEG) were immobilized on the surface of the MnUNPs (PEG/Ce6-MnUNPs). The prepared PEG/Ce6-MnUNPs generated singlet oxygen ( 1 O 2 ) and displayed effective anticancer activity under NIR excitation.
Keywords: Photodynamic therapy | Second biological window | UpconversionPhotodynamic therapy (PDT) is a technique that destroys cancer tissues via photosensitizers and light irradiation.1,2 The photosensitizers absorb the light and produce reactive oxygen species (ROS) that destroy cancer cells. Most current photosensitizers require visible (vis) light for excitation, and their use in cancer treatment suffers from the lack of penetration depth of vis light owing to the scattering it undergoes because of its short wavelength.Because of this drawback of PDT, rare-earth-doped ceramic nanophosphors (RED-CNPs) have attracted much attention as in vivo imaging probes 35 and PDT transducers. 69 The RED-CNPs produce simultaneous tissue-penetrable over-1000 nm near-infrared (OTN-NIR) and vis upconversion (UC) emission under NIR excitation. , Er 3+ NP) showed green and red UC emission under 980-nm NIR excitation and was used as a transducer for PDT. In those studies, the photosensitizer, chlorin e6 (Ce6) ( Figure S1 in Supporting Information (SI)) was immobilized on the surface of the , Mn 2+ NPs (MnUNPs) for the transducer of PDT using a standard solvothermal synthesis method. Ce6 was covalently immobilized on the surface of the polyamine-tethered NPs via amide linkage. Furthermore, for a highly stable PDT probe, the biocompatible polymer poly(ethylene glycol)-blockpoly(acrylic acid) (PEG-b-PAAc) was strongly immobilized on the positive-charged polyamine surface of the NPs via electrostatic interactions (Figure 1).The MnUNPs were synthesized using the solvothermal synthesis method with different nominal Mn 2+ concentrations (4054 mol %)1518 and a fixed concentration of water (4 wt %), as in previous literature. As a control, Mn 2+ -undoped NaYF 4 :Yb 3+ , Er 3+ NPs (UNPs) were also synthesized using the same protocol. X-ray diffraction (XRD) spectroscopy identified the crystal phase of the synthesized MnUNP samples to be pure cubic α-phase NaYF 4 , because all the peaks were indexed to JCPDS data (06- Figure 1. Illustration of NIR-induced PDT and OTN-NIR fluorescence imaging based on PEG/Ce6-MnUNPs.