Appendix A Cellular Uptake and Cytotoxicity of a Near-IR Fluorescent CorroleTiO2 Nanoconjugates Carl M. Blumenfeld†,‡, Bryce F. Sadtler‡, G. Esteban Fernandez♯, Lily Dara¶, Cathie Nguyen§,δ, Felix Alonso-Valenteenδ, Lali Medina-Kauweδ, Rex A. Moats§, Nathan S. Lewis†,‡, Robert H. Grubbs‡, Harry B. Gray†,‡,*, and Karn Sorasaenee†,‡,§,* † Beckman Institute, California Institute of Technology, Pasadena, CA 91125 USA Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125 USA ♯ Cellular Imaging Core, The Saban Research Institute, Children’s Hospital Los Angeles, Keck School of Medicine of USC, Los Angeles, CA 90027 USA ¶ Division of Gastrointestinal and Liver Diseases, Department of Medicine, Keck School of Medicine of USC, Los Angeles, CA 90089 USA δ Department of Biological Sciences, Cedars-Sinai Medical Center, David Geffen School of Medicine, University of California Los Angeles, Los Angeles, CA 90068 USA § Translational Biomedical Imaging Laboratory, Department of Radiology, The Saban Research Institute, Children’s Hospital Los Angeles, Keck School of Medicine of USC, Los Angeles, CA 90027 USA ‡ Table A.1 Masses of TiO2 nanoparticles, IPA, the PDMS base, and curing agent used to cast PDMS films, weight % TiO2 in the films, film weight, and mass of TiO2 per volume of PDMS. a b Sample Mass TiO2 (mg) Mass IPA (g) Mass PDMS base (g) Mass PDMS curing agent (g) Total weight (g) Est. dry weight (g)a Weight % TiO2 Film weight (g) Etched TiO2 1-Al-TiO2 3.25 3.35 0.3234 0.3683 0.9425 0.9266 0.1154 0.1220 1.3846 1.4203 1.0676 1.0593 0.30 0.32 0.2901 0.2914 Mass TiO2 /volume PDMS (g/L)b 3.2 3.3 Separate measurements showed that 98% of the IPA evaporated during curing of the PDMS film. A value of 0.965 g/cm3 was used for the density of PDMS. Table A.2 Absorption values at 426 and 595 nm and thicknesses for PDMS films containing 1-Alfunctionalized and H2O2-etched TiO2 nanoparticles, and estimated 1-Al loading of the TiO2 particles based on absorption measurements. Wavelength (nm) 426 595 1-Alfunctionalized TiO2 absorbance 0.170 0.048 Film thickness (cm) 0.054 0.054 Est. dye extinction coefficient (M-1cm-1)a 4.08104 7.66103 Etched TiO2 absorbance Film thickness (cm) 1-Al concentration (M) 1-Al loading (mg of dye/g of TiO2) 0.005 0.002 0.054 0.054 7.510-5 1.210-4 23 36 a Extinction coefficients measured in toluene:pyridine (95:5) mixture where the Soret band has an absorption maximum at 436 nm and the Q band has an absorption maximum at 625 nm. Page 1 of 3 Table A.3 ζ Potential measurements for 1-Al-TiO2 suspended in PBS at the concentration of 50 μg/mL. ζ Potential (mV) -24.7 -25.8 -26.2 -27.8 -28.9 -26.3 -26.8 -27.7 -28.3 -28.6 -26.0 -27.3 -29.0 -28.5 -26.9 -27.2 -27.2 -29.8 -27.2 -27.4 -27.4 1.25 Run Number 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 Average Standard Deviation Page 2 of 3 Figure A.1 Hydrodynamic size distribution of 1-Al-TiO2 suspended in PBS: (a) Size distribution plot based the percentage of the aggregates at various sizes. (b) Size distribution plot based on the intensity of the scattered light by the aggregate at various sizes. Page 3 of 3