3.1.1. Synthesis of PGAβCyDArg1

βCyD3NH<sup>2</sup> (50 mg in 1 mL of H2O), and DMTMM (18.26 mg in 350 µL) were added to PGA (6.61 mg in 350 µL) every 30 min in three aliquots. The pH of the reaction mixture was adjusted to 8. After 24 h, ArgOCH3(2 mg) and DMTMM (18 mg) were added to the solution (during 30 min). The reaction mixture was stirred at r.t. for 24 h.

The polymer was isolated with Sephadex G-15 column chromatography. The various fractions collected were examined using TLC, (eluent PrOH/AcOEt/H2O/NH<sup>3</sup> 5:2:3:1). The main product was characterised by NMR spectroscopy.

<sup>1</sup>H NMR (500, in D2O) δ (ppm): 5.20-4.80 (H-1 of CyD); 4.28 (s, CH Glu); 4.2 (m, CH Arg); 4.2–3.2 (m, H-3, -6, -5, -2,-4 of CyD, OCH3); 3.2 (m, γ CH<sup>2</sup> Arg); 2.60–1.50 (m, β- and γ-CH<sup>2</sup> PGA); 1.35 (m, CH<sup>2</sup> butyl chain of PGA); 1.26 (m, CH<sup>2</sup> butyl chain of PGA), 0.88 (m, CH<sup>3</sup> butyl chain of PGA).

<sup>13</sup>C NMR (125 MHz, in D2O) δ (ppm): 24.5 (β-CH<sup>2</sup> of Arg), 26.8 (α-CH<sup>2</sup> of Arg), 31.8 (β-CH<sup>2</sup> of PGA), 40.5 (δ CH<sup>2</sup> butyl chain of PGA), 52.3 (CH Arg), 52.9 (C-2 of CyD and OCH<sup>3</sup> of Arg), 53.0 (CH of Glu), 60.0 (C-6 of CyD), 71.6 (C-3 of CyD ), 73.0 (C-5 of CyD), 80.4 (C-4 of CyD), 101–105 (C-1 of CyD), 160 (C=N of Arg), 173–174 (CNH PGA-CyD, PGA-Arg), 174.72 (CO methyl ester of Arg).

Dimension (DLS, Z average): 49 ± 5; PDI (DLS): 0.4; Zeta potential: 8 ± 1 mV (pH = 7.4). The other polymers were synthesised in the same manner as PGAβCyDArg1 with different amounts of the reagents.
