Supporting Information

Transcription

1 Supporting Information Effect Of TiO 2 Nanoparticle Surface Functionalization On Protein Adsorption, Cellular Uptake and Cytotoxicity: The Attachment Of PEG Comb Polymers Using Catalytic Chain Transfer And Thiol-Ene Chemistry Roslyn Tedja 1, Alexander H. Soeriyadi 2, Michael R. Whittaker 2, May Lim 1, Christopher Marquis 3*, Cyrille Boyer 2*, Thomas P. Davis 2, Rose Amal 1 1 ARC Centre of Excellence for Functional Nanomaterials, School of Chemical Engineering, The University of New South Wales, Sydney NSW 2052, Australia 2 Centre for Advanced Macromolecular Design, School of Chemical Engineering, The University of New South Wales, Sydney NSW 2052, Australia 3 School of Biotechnology and Biomolecular Sciences, The University of New South Wales, Sydney NSW 2052, Australia s: cboyer@unsw.edu.au and c.marquis@unsw.edu.au

2 Additional information: Experimental Synthesis of Model POEGMA dimer Model macromonomer of POEGMA 475 was synthesized via catalytic chain transfer polymerization. The monomer oligo(ethylene glycol) methyl ether methacrylate (OEGMA 475, 2 g, 4.2 mmol) was mixed with acetonitrile (2 ml) and degassed under N 2 gas for at least 30 min. on another round bottom flask, the initiator AIBN ( 5 mg), CoBF (1.3 mg), and magnetic stirrer bar were mixed together and also purged with N2 gas for at least 30 min. The two components were then mix together through cannulation. The reaction was then polymerized at 70 C for 14 hours. The reaction was then stopped by quenching. 1H NMR, GPC, ESI-MS samples were then collected before purification. 1 End group modification of POEGMA model macromonmer The modification of POEGMA model macromonomer was done via Thiolene Michael addition. OEGMA 475 monomer or POEGMA dimer first dissolve in acetonitrile with 1:1 v/v ratio and then mixed with hexylamine and (3-mercaptopropyl) trimetoxysilane in molar ratio of [OEGMA] : [organosilane] : [HA] = 1 : 2 : 2. The reaction mixture was then purged with N 2 and left to react overnight in room temperature. The resulting modification was then monitored via ESI-MS (Figure S2).

3 Additional Information: Result and Discussion Code M n, GPC (g/mol) M n, NMR (g/mol) PDI POEGMA POEGMA POEGMA Table S1. Summary of polymer synthesized and used to modified surface of Titanium dioxide nanoparticle in this study.

4 Figure S1. Gel Permeation Chromatography (GPC) curves and NMR spectrum of three polymers synthesized in this work. Note: NMR was performed using acetone deuterated as solvent.

5 Figure S2. Electrospray ionization mass spectrometry of modification of OEGMA 475 (A) monomer and (B) dimer with 3-mercaptopropyl trimetoxysilane.

6 Figure S3. Wide scan of XPS spectrum of the particle throughout different synthetic stage.

7 Figure S4. ATR-IR spectrum of the bare TiO 2, POEGMA, and surface modified TiO 2.

8 Figure S5. Thermogravimetric analysis (TGA) of nano-tio 2 before and after modification with biocompatible POEGMA.

9 Figure S6. Dynamic Light Scattering (DLS) of nano-tio 2 particle before and after modification in various biological media.

10 Figure S7. Particle effective diameter monitored for 24 hours in RPMI1640 biological media.

11 Additional References (1) Li, G.-Z.; Randev, R. K.; Soeriyadi, A. H.; Rees, G.; Boyer, C.; Tong, Z.; Davis, T. P.; Becer, C. R.; Haddleton, D. M. Polym. Chem. 2010, 1, 1196.