Thiol-Maleimide Click Chemistry: Facile. Fabrication of Targeted Drug Delivery Vehicles

Transcription

1 SUPPORTING INFORMATION Functionalization of Reduced Graphene Oxide via Thiol-Maleimide Click Chemistry: Facile Fabrication of Targeted Drug Delivery Vehicles Yavuz Oz, a Alexandre Barras, b Rana Sanyal, a,c,d Rabah Boukherroub, b Sabine Szunerits *b and Amitav Sanyal *a,c a Department of Chemistry, Bogazici University, Bebek, 34342, Istanbul, Turkey b Univ. Lille, CNRS, Centrale Lille, ISEN, Univ. Valenciennes, UMR IEMN, F Lille, France c Center for Life Sciences and Technologies, Bogazici University, Istanbul, Turkey d RS Research Inc., Teknopark Istanbul, Pendik, 34912, Istanbul, Turkey Corresponding Authors amitav.sanyal@boun.edu.tr, sabine.szunerits@univ-lille1.fr S-1

2 Details of Characterization Techniques UV/Vis absorption spectra were recorded using SAFAS UV/Vis spectrophotometer in quartz cuvettes with an optical path of 10 mm. The wavelength range was nm. Fourier transform infrared spectroscopy (FT-IR) analyses were performed on a Thermo Fisher Scientific Inc, Nicolet H NMR and 13 C NMR spectra were obtained using a Bruker 400 MHz spectrometer. Micro-Raman spectroscopy measurements were performed on a LabRam HR Micro-Raman system (Horiba Jobin Yvon, France) using a 473-nm laser diode as excitation source. Visible light is focused by a 100 objective. The scattered light is collected by the same objective in backscattering configuration, dispersed by a 1800 mm focal length monochromator and detected by a CCD camera. Zeta-potential measurements were performed using a Zeta-sizer Nano-ZS (Malvern Instruments Inc. Worcestershire, UK). Samples were diluted to 10 µg/ml and measured in Milli-Q water at different ph. X-ray photoelectron spectroscopy (XPS) experiments were performed using a PHl 5000 VersaProbe - Scanning ESCA Microprobe (ULVAC-PHI, Japan/USA) instrument at a base pressure below mbar. Core-level spectra were acquired at pass energy of 23.5 ev with a 0.1 ev energy step. All spectra were acquired with 90 between X-ray source and analyzer and with the use of low energy electrons and low energy argon ions for charge neutralization. After subtraction of the Shirley-type background, the core-level spectra were decomposed into their components with mixed Gaussian-Lorentzian (30:70) shape lines using the CasaXPS software. Quantification calculations were conducted using sensitivity factors supplied by PHI. Electrochemical measurements were performed with a potentiostat/galvanostat (Autolab, The Netherlands). A conventional three-electrode configuration was employed using a silver wire and a platinum mesh as reference and auxiliary electrodes, respectively. Thermal images were taken with an IR Camera (Thermovision A40) and images were processed with ThermaCam Researcher Pro 2.9 software. A Gbox model continuous laser (Fournier Medical Solution) S-2

3 was used. PHERAstar FS (BMG LABTECH GmbH, Germany) was used as a plate reader. Optical images of cell lines were recorded using a 10 magnification inverted microscope (Nikon Eclipse TS100, Japan). (A) (B) (C) Figure S1. (A) 1 H-NMR spectrum of Dopa-pMAL in CDCl 3, (B) 1 H-NMR spectrum of Dopa-MAL in (CD 3 ) 2 SO, (C) 13 C-NMR spectrum of Dopa-MAL in (CD 3 ) 2 SO. S-3

4 Compound Characterizations Data: Protected Maleimide Containing Dopamine (dopa-pmal): 1 H NMR (CDCl 3 ) δ (ppm): 6.79 (d, 1H, CH-CH=C-OH), 6.72 (d, 1H, C-CH=C-OH), 6.58 (dd, 1H, C=CH-CH), 6.51 (s, 2H, CH=CH), 5.23 (s, 2H, bridgehead protons), 3.46 (m, 4H, NH-CH 2 -CH 2, N-CH 2 -CH 2 ), 2.84 (s, 2H, CH-CH bridge protons), 2.70 (t, 2H, NH-CH 2 -CH 2 - C), 2.08 (t, 2H, O=C-CH 2 -CH 2 ), 1.87 (m, 2H, CH 2 -CH 2 -CH 2 ). Maleimide Containing Dopamine (dopa-mal): 1 H NMR (DMSO-d6) δ (ppm): 8.69 (s, 2H, C-OH), 7.81 (t, 1H, NH), 7.0 (s, 2H, CH=CH), 6.61 (d, 1H, CH-CH=C-OH), 6.55 (s, 1H, C-CH=C-OH), 6.41 (d, 1H, C=CH-CH), 3.38 (t, 2H, N-CH 2 -CH 2 ), 3.13 (dd, 2H NH-CH 2 -CH 2 ), 2.02 (t, 2H, O=C-CH 2 -CH 2 ), 1.70 (m, 2H, CH 2 -CH 2 -CH 2 ). 13 C NMR (DMSO-d6) δ (ppm): 171.1, 145.0, 143.0, 134.5, 130.2, 119.2, 115.9, 115.5, 40.6, 36.9, 34.7, 32.6, LC MS expected [M + H] m/z = 318 and observed [M + H] m/z = 318. Figure S2. Calibration curve of standard peptide solutions based on UV absorbance values at 562 nm and UV-vis spectrum of rgo/dopa-mal-c(rgdfc) (inset). S-4

5 Figure S3. Doxorubicin calibration curve and UV-vis spectrum of diluted supernatant after doxorubicin loading onto rgo/dopa-mal-c(rgdfc) (inset). S-5