Graphene Quantum Dots based systems as HIV. Inhibitors

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1 Supporting Information to Graphene Quantum Dots based systems as HIV Inhibitors Daniela Iannazzo, *, Alessandro Pistone, Stefania Ferro, Laura De Luca, Anna Maria Monforte, Roberto Romeo, Maria Rosa Buemi and Christophe Pannecouque Department of Engineering, University of Messina, Contrada Di Dio, I Messina, Italy Department of Chemical, Biological, Pharmaceutical and Environmental Sciences, University of Messina, Viale Annunziata, I Messina, Italy KU Leuven, Department of Microbiology and Immunology, Laboratory of Virology and Chemotherapy, Rega Institute for Medical Research, Herestraat 49, B-3000 Leuven, Belgium * Corresponding author. address: diannazzo@unime.it; Fax: ; Tel: Table of Contents Materials.....S2 Chemical, physical and morphological characterization....s2 Figure S1. XRD spectra of MWCNT and GQD S3 Figure S2. AFM image of GQD...S4 Figure S3. UV vis absorption spectrum of GQD...S4 Figure S4. PL spectra of GQDdispersion in deionized water...s5 Figure S5. Raman spectra of MWCNT and GQD.....S5 Scheme S1. Synthesis of CDF119.S6 References..S6 S1

2 Materials Solvents and reagents were obtained from commercial suppliers and used without further purification. Solvents for chromatography were distilled at atmospheric pressure prior to use and dried using standard procedures. MWCNT were produced by catalytic chemical vapor deposition (CCVD) from isobutane on a Fe/Al 2 O 3 catalyst and subjected to purification as previously reported, giving pristine MWCNT with purity >95%. 1 The GQD sample was prepared treating pristine MWCNT with a HNO 3 /H 2 SO 4 mixture in a 1:3 ratio following a previously reported procedure. 2 Chemical, physical and morphological characterization Melting points were determined with a Kofler apparatus and are uncorrected. Elemental analyses were performed with a Perkin-Elmer elemental analyzer and the results were within ±0.4% of the theoretical values. 1 H NMR spectra were measured with a Varian Gemini-300 spectrometer in DMSO-d 6 and chemical shifts are expressed in δ (ppm). Thin-layer chromatography was done on Merck silica gel 60-F254 precoated aluminium plates. Preparative separations were made by flash column chromatography using Merck silica gel mm and mm. The GQD morphology was analyzed using high-resolution transmission electron microscopy (HRTEM) JEOL JEM 2010 analytical electron microscope (LaB 6 electron gun), operating at 200 kv and equipped with a Gatan 794 Multi-Scan CCD camera for digital imaging. HRTEM samples were prepared by placing a drop of the GQD dispersed in isopropanol on 400 mesh holey carbon coated copper grids. UV spectra have been performed by Thermo Nicolet mod, Evolution 500 spectrophotometer. AFM images were performed using an Atomic Force Microscope NT-MDT Smena. operating in the tapping mode on air at room temperature. Thermogravimetrical studies were performed from 100 to 1000 C at 10 C/min under nitrogen on a TA Q500 instrument. The titration analysis performed in order to evaluate the amount of acidic groups present on the nanomaterials, the zeta potential measurements and the intensity size distributions were evaluated using the Zetasizer 3000 instrument (Malvern). The zeta potential measurements were carried out in the ph value range of 4 S2

3 9. Size characterization of the samples was made by dynamic light-scattering (DLS) measurements using a 4 mw He Ne laser operating at a wavelength of 633 nm and a detection angle of 173. Infrared analyses were performed using a Fourier- transform infrared (FT-IR) spectrometer (Perkin- Elmer 2000) by the method of KBr pellets. The photoluminescence (PL) measurements were carried out on a NanoLog modular spectrofluorometer Horiba with a Xe lamp as the excitation light source at room temperature; GQD based nanomaterials used for PL measurement were used at the concentration of 100 ng/ml. Raman spectra were recorded with an InviaRenishaw microspectrometer (50 ) using a laser source at 532 or 633 nm. X-ray powder diffraction (XRD) patters were carried out on a Bruker AXS D8 Advance X-ray diffractometer, using the CuKa1 radiation. Figure S1. XRD spectra of pristine MWCNT and GQD. S3

4 Figure S2. AFM image of GQD. Figure S3. UV vis absorption spectrum of GQD. S4

5 Figure S4. PL spectra of GQDdispersion in deionized water at the excitation wavelengths of 330, 340, 350, 360 and 370. Figure S5. Raman spectra of pristine MWCNT and GQD. S5

6 Scheme S1. Synthesis of CDF119. Reagents and conditions: (i) SnCl 2, EtOH, 2h, then NaOH 10N, r. t., 1h. References 1. Donato, M. G., Galvagno, S., Messina, G., Milone, C., Pistone, A., and Santangelo, S. (2007) Optimisation of gas mixture composition for the preparation of high quality MWCNT by catalytically assisted CVD. Diam. Relat. Mater., 16, Pistone, A., Ferlazzo, A., Milone, C., Iannazzo, D., Piperno, A., Piperopoulos E. and Galvagno, S. (2012) Morphological Modification of MWCNT Functionalized with HNO 3 /H 2 SO 4 Mixtures. J. Nanosci. Nanotechnol., 12, S6