ELECTRONIC SUPPLEMENTARY MATERIAL T. Biver a*, A. Corti b, N. Eltugral a, E. Lorenzini b, M. Masini b, A. Paolicchi b, A. Pucci a,c, G. Ruggeri a, F. Secco a, M. Venturini a. Analysis of dimethylaminopyridine (DMAP)-gold nanoparticles behaviour in solution and of their interaction with calf thymus DNA and living cells a Chemistry and Industrial Chemistry Department - University of Pisa – Via Risorgimento 35 – 56126 Pisa (Italy) b Experimental Pathology Department BMIE - University of Pisa – Via Roma, 55 – 56126 Pisa (Italy) c CNR NANO Nanoscience-CNR Institute, piazza S. Silvestro 12, 56127 Pisa (Italy) T. Biver () e-mail: tarita@dcci.unipi.it; tel. +39-050-2219259; fax. +39-050-2219260 0.8 pH = 6.5 pH = 6 A 0.6 pH = 7 pH = 10 0.4 0.2 0.0 400 500 600 700 (nm) Fig. 1S LS corrected absorbance spectra of aqueous dispersions of DMAP-Au NPs at different pH values in phosphate buffer, Na2HPO4/NaH2PO4 (0.02 M/0.02 M), CAu = 1.6×10-4 M, I = 0.08 M, T = 25 oC. The slight blue-shift from pH 10 to pH 7 indicates some NP destabilization that turns, for pH < 6.5, in a large red-shift indicating nanoparticles aggregation. Fig. 2S Picture of aqueous dispersions of DMAP-Au NPs at different pH values in phosphate buffer, Na2HPO4/NaH2PO4 (0.02 M/0.02 M), CAu = 1.6×10-4 M, I = 0.08 M, T = 25 oC. Color shift to blue indicates nanoparticles aggregation. 1.0 1.0 A B 0.8 0.6 0.6 A A 0.8 0.4 0.4 0.2 0.2 0.0 400 0.0 500 600 700 800 0 1 2 C (nm) Au 3 4 (M) Fig. 3S LS corrected absorbance spectra of DMAP-Au NPs at different concentrations (A) and relevant absorbance vs. concentration plot at 520nm (B). CAu = 4.1×10-6 to 3.8×10-4 M, I = 0.08 M (Na2HPO4/NaH2PO4 buffer), pH = 8.0, T = 25 °C. 0.4 A 0.3 0.2 0.1 0.0 200 250 300 350 400 (nm) Fig. 4S UV-vis absorption spectra of the DMAP/DNA system, CDMAP = 2.0×10-5 M, CDNA = 0 – 8.2×10-5 M, pH = 8.0, T = 25 oC. Spectra invariability indicates no interaction takes place between DMAP and DNA. 0.6 c A b B 3 -1 10 A/C Au (M ) 0.5 0.4 A a 0.3 -2 0.2 2 1 0.1 0.0 400 0 500 600 (nm) 700 800 0 2 4 6 C DNA 8 10 (M) Fig. 5S (A) LS corrected absorption spectra of the DMAP-Au NPs/DNA system, CAu = 1.5×10-4 M, CDNA = 0 (a), 3.1×10-6 M (b), 9.8×10-5 M (c), pH = 8.0, T = 25 oC; (B) corresponding binding isotherm at = 525 nm, Fig. 6S Picture of DMAP-Au NPs/DNA mixtures at t = 0 (on the top) and after 72 h (at the bottom) at the various DNA concentrations given in Table 2 (DNA concentration is zero in A and increases until 9.8×10-5 M from B to G). Significant precipitation together with colour blue-shift is observed in experiments B and C, whereas return to red and samples stability is observed for experiments D to G.