Supporting Information

Transcription

1 1 Supporting Information Synthesis and Characterization of Temperature-sensitive and Chemically Cross-linked Poly(N-isopropylacrylamide)/Photosensitizer Hydrogels for Applications in Photodynamic Therapy Simin Belali, Huguette Savoie, Jessica M. O Brien Atillio A. Cafolla, Barry O Connell, Ali Reza Karimi, Ross W. Boyle, * and Mathias O Senge # * School of Chemistry, SFI Tetrapyrrole Laboratory, Trinity Biomedical Science Institute, Trinity College Dublin, the University of Dublin, Pearse Street, Dublin 2, Ireland. Department of Chemistry, Faculty of Science, Arak University, Arak , Iran. Department of Chemistry, University of Hull, Cottingham Road, Kingston-upon-Hull, HU6 7RX, United Kingdom. School of Physical Sciences, Dublin City University, Glasnevin, Dublin 9, Ireland. Nano Research Facility, Dublin City University, Glasnevin, Dublin 9, Ireland. # Medicinal Chemistry, Trinity Translational Medicine Institute, Trinity Centre for Health Sciences, Trinity College Dublin, The University of Dublin, St. James s Hospital, Dublin 8, Ireland. Content Page FT-IR spectra of Pba and Pba-PNIPAM 2 FT-IR spectra of PpIX-DME and PpIX-DME-PNIPAM 2 1 H NMR spectra of Pba-PNIPAM 3 1 H NMR spectra of PpIX-DME-PNIPAM 3 SEM images of Pba-PNIPAM and PpIX-DME-PNIPAM hydrogel 4 Hydrodynamic diameter of Pba-PNIPAM and PpIX-DME-PNIPAM hydrogel 4 Singlet oxygen production of TPP, PpIX-PNIPAM, Pba-PNIPAM and PpIX-DME-PNIPAM and PpIX PNIPAM 5 Estimate the percentage of covalently bonded PpIX content 5 1

2 2 Figure S1. FT-IR spectra of pheophorbide a (Pba) and poly N-isopropylacrylamide-pheophorbide a (Pba-PNIPAM). Figure S2. FT-IR spectra of protoporphyrin IX dimethyl ester (PpIX-DME) and poly N- isopropylacrylamide-protoporphyrin IX dimethyl ester (PpIX-DME-PNIPAM). 2

3 3 b a H 3 C H CH 3 chn O d e n Figure S MHz 1 H NMR spectrum of poly N-isopropylacrylamide--pheophorbide a (Pba-PNIPAM) in D 2 O. Figure S MHz 1 H NMR spectrum of poly N-isopropylacrylamide-protoporphyrin IX dimethyl ester (PpIX-DME-PNIPAM) in D 2 O. 3

4 4 Figure S5. SEM images of Pba-PNIPAM hydrogel (a,b) and PpIX-DME-PNIPAM hydrogel (c,d) at different magnifications. Figure S6. Hydrodynamic diameter of Pba-PNIPAM hydrogel 3% (a) and PpIX-DME-PNIPAM hydrogel 3% (b) as measured by dynamic light scattering. 4

5 5 Figure. S7. Singlet oxygen production of (a)5,10,15,20-tetraphenylporphyrin, (b) PpIX-PNIPAM nanohydrogel, (c) Pba- PNIPAM nanohydrogel and (d) PpIX-DME-PNIPAM nanohydrogel PpIX-PNIPAM determined by using 1,3- diphenylisobenzofuran (DPBF) in DMSO. For PpIX-PNIPAM Relative Singlet oxygen quantum yield=0.0132/0.0106= 1.24 For Pba-PNIPAM Relative Singlet oxygen quantum yield=0.009/0.0106=0.84 For PpIX-DME-PNIPAM Relative Singlet oxygen quantum yield=0.0107/0.0106=1 Estimation of percentage of covalently bound PpIX To estimate the percentage of real contents of PSs in PNIPAM networks, UV-vis spectroscopy was used. 0.1 mg of PpIX monomer was dissolved it in 10 ml of DMF (concentration = ). The same weight of dry hydrogels were dissolved in 10 ml DMF. The UV-vis absorbance of both monomer and hydrogel were recorded. Then the relative amount of PpIX in hydrogel structure were calculated based on their corresponding absorbance. PNIPAM-PpIX 2%: / 0.98= M PNIPAM-PpIX 3%: / 0.98= M PNIPAM-PpIX 4%: / 0.98= M Relative percentage of PpIX in hydrogel structure based on monomer concentration: PNIPAM-PpIX 2% = PNIPAM-PpIX 3% = = 18.3% 100 = 35.6% 5

6 6 PNIPAM-PpIX 4% = = 42.7% 6