Supporting Information. Light Emitting Photon Upconversion Nanoparticles. in the Generation of Transdermal Reactive Oxygen.

Transcription

1 Supporting Information Light Emitting Photon Upconversion Nanoparticles in the Generation of Transdermal Reactive Oxygen Species Martin Prieto a,, Alina Y. Rwei c, d,, Teresa Alejo a, Tuo Wei c, Maria Teresa Lopez-Franco a, Gracia Mendoza a, Victor Sebastian a, b, Daniel S. Kohane c * Manuel Arruebo a,b, * a Department of Chemical Engineering. Aragon Institute of Nanoscience (INA), University of Zaragoza, Campus Río Ebro - Edificio I+D, C/ Poeta Mariano Esquillor S/N, Zaragoza, Spain; Aragon Health Research Institute (IIS Aragón), Zaragoza, Spain b Networking Research Center on Bioengineering, Biomaterials and Nanomedicine, CIBER-BBN, Madrid, Spain. c Laboratory for Biomaterials and Drug Delivery, Department of Anesthesiology, Boston Children s Hospital, Harvard Medical School, Boston, MA d Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA : Both authors contributed equally to this work. S-1

2 *: Corresponding authors: DSK and MA Figure S1. (a) Powder X-ray diffraction pattern of the resulting core-shell nanoparticles and β- NaYF 4 pattern (JCPDS file No ) as reference, (b) EDS spectra of one (bottom) and S-2

3 several (top) nanoparticles and (c) table showing the emission peak assignation, dopants and electronic transitions for the resulting core/shell upconversion nanoparticles. Figure S2. Plots of the luminiscence intensity versus pump power in (a) lineal and (b) double logarithmic scale and (c) lineal fit data. (d) Table showing photon energies at the wavelength of the different emission peaks, the minimum number of photons with a wavelength of 980 nm S-3

4 required to reach this energy and the number of photons involved in the up-conversion process based on the slope. Figure S3. Digital photographs of lyophilized PLGA-PEG nanoparticles containing both upconversion nanoparticles and protoporphyrin IX (top) and PLGA-PEG nanoparticles containing just upconversion nanoparticles (bottom) under 808 nm laser irradiation (530 W/cm ). 2 S-4

5 Figure S4. Fluorescence spectra of upconversion nanoparticles (5 mg/ml) excited at 485 nm in ethanol (top left) and DHR123 (16.5 µm) after 980 nm laser irradiation (11 W/cm ) (top right), 2 heating at 50ºC (bottom left) and suspension of upconversion nanoparticles and DHR123 stirred without laser or heating (bottom right). S-5

6 Figure S5. Control samples for B16F1 before and after irradiation: (a) Control sample not treated and not irradiated; (b) Cells treated with 0.4 mg/ml of PLGA-PEG NPs containing upconversion nanoparticles and Protoporphyrin IX for 24h, not irradiated; (c) Cells not treated with NPs, irradiated; (d-f) Cells treated with PLGA (D), UCNC (E) and Protoporphyrin (F) for 24h, all of them irradiated. The images show the composition of 20 pictures (4X magnification) obtained by fluorescence microscopy in which live cells are stained in green and dead in red. Figure S6. Photodynamic effects of PLGA-PEG NPs containing upconversion nanoparticles and Protoporphyrin IX on human dermal fibroblasts, mouse mesenchymal stem cells and human macrophages. Cells were treated for 24h with these NPs (0.4 mg/ml) and its components to be then irradiated (20 min) and images acquired 24h post-irradiation. Control samples were also S-6

7 run. The pictures show the composition of 20 fields (4X magnification) obtained by fluorescence microscopy in which live cells are stained in green and dead in red. Figure S7. Singlet oxygen generation upon irradiation of nanoparticles. Singlet Oxygen Sensor Green was used as a fluorescent singlet oxygen indicator and added to the nanoparticle dispersion. Irradiation was performed with 808 nm laser light at 800 mw/cm for 15 min. Data 2 are mean ± S.D., N=4. Significant differences (p<0.05) were found between PLGA-UCNP-PPIX and the two other experimental groups assayed. S-7