## 2 Materials and Methods
### Synthesis of ligands
#### 2.2.8 2-(2-(2-(Pent-4-en-1-yloxy)ethoxy)ethoxy)ethyl-4-methylbenzenesulfonate **14**
2-(2,3,4-Tri-O-benzyl-6-(1-thioacetylpentyl-(5-(2-(2-(2-(2-(2-hydroxyethyl)ethoxy))ethoxy)))-\(\alpha\)-D-glucopyranosyl)-1-azidoethane **16**  
Compound **15** (384 mg, 0.545 mmol) was dissolved in CH\({}_{2}\)Cl\({}_{2}\) (5.4 mL, 0.1 M) and the solution transferred into a sealed glass vial; thioacetic acid (0.656 mmol) and DPAP (0.055 mmol) were added and the reaction was stirred at r.t. under UV light exposure at 365 nm (using a UVA lamp of 4 W located 2 cm away from the glass vial). The progress of the reaction was followed by TLC (Hexane/EtOAc 7:3). After 2 h, TLC indicated the disappearance of the starting material; the crude was directly subjected to flash chromatography (silica gel, eluent Hexane/EtOAc 7:3), which afforded pure thioester **16** (357 mg, 0.46 mmol, 85% yield). \({}^{1}\)H NMR (400 MHz, CDCl\({}_{3}\)) \(\delta\) 7.36-7.27 (m, 15H, CH Ar), 4.91 (d, J = 10.9 Hz, 1H, CH\({}_{2}\)Ph), 4.85 (d, J = 10.9 Hz, 1H, CH\({}_{2}\)Ph), 4.81 (d, J = 10.9 Hz, 1H, CH\({}_{2}\)Ph), 4.70 (d, J = 11.6 Hz, 1H, CH\({}_{2}\)Ph), 4.67-4.58 (m, 2H, CH\({}_{2}\)Ph), 4.16-4.07 (m, 1H, H1), 3.75-3.71 (m, 2H, H2, H3), 3.69-3.47 (m, 16H, H4, H5, H6a,b, CH\({}_{2}\)CH\({}_{2}\)O-), 3.44-3.27 (m, 4H, H7a,b, H2\({}^{2}\),a,b), 2.85 (t, J = 7.3 Hz, 2H, H11a,b), 2.31 (s, 3H, CH\({}_{3}\)C(O)S), 2.00-1.90 (m, 2H, H1\({}^{1}\)a,b), 1.62-1.52 (m, 4H, H110a,b, H8a,b) and 1.46-1.34 (m, 2H, H9a,b). \({}^{13}\)C NMR (101 MHz, CDCl\({}_{3}\)) \(\delta\) 196.10 (CH\({}_{3}\)C(O)S), 138.73, 138.37 and 138.12 (Cq Ar), 128.61, 128.58, 128.52, 128.07, 128.03, 128.01, 127.91 and 127.76 (C Ar), 82.34 (C3), 79.67 (C2), 78.02 (C4), 75.61 (CH\({}_{2}\)Ph), 75.19 (CH\({}_{2}\)Ph), 73.40 (CH\({}_{2}\)Ph), 71.71 (C1), 71.46 (C5), 71.22, 71.12, 70.75, 70.70, 70.61, 70.34 and 70.18 (C6 sugar, CH\({}_{2}\)CH\({}_{2}\)O-), 48.06 (C2), 30.79 (CH\({}_{3}\)C(O)S), 29.49 (C8), 29.23 (C10), 29.16 (C11), 25.49 (C9) and 24.51 (C1\({}^{\prime}\)). MS: \(m/z\) = 780.6 [M+H]\({}^{+}\), 752.6 [M-N\({}_{2}\)+H]\({}^{+}\), 802.6 [M+Na]\({}^{+}\), 818.6 [M+K]\({}^{+}\). 2.2.11. 2-(2,3,4-Tri-O-benzyl-6-(1-thio-(5-(2-(2-(2-(2-hydroxyethyl)ethoxy)ethoxy)ethyl)))-\(\alpha\)-D-glucopyranosyl)-1-azidoethane (dimer) **16**  
Pure thioester **16** (38 mg, 0.049 mmol) was dissolved in MeOH (1 mL, 0.05 M) and 1.3 mg (0.024 mmol) of solid sodium methylate was added. The reaction was stirred at r.t. whilst exposed to air to promote the oxidation of the thiol group into a disulfide bond. After 24 h, TLC (Hexane/EtOAc 6:5:3.5) indicated the completion of the reaction. The reaction mixture was concentrated to dryness; \({}^{1}\)H-NMR analysis of the crude sample indicated the complete removal of the acetyl group and the formation of a disulfide bond (triplet signal at 2.65 ppm). The residue was re-suspended in CH\({}_{2}\)Cl\({}_{2}\), and the undissolved material was filtered off and discarded; the filtrate was concentrated to dryness and directly used for the next reaction. \({}^{1}\)H NMR (crude sample) (500 MHz, CDCl\({}_{3}\)) 8 7.37-7.24 (m, 15H, CH Ar), 4.94-4.90 (m, 1H, CH\({}_{2}\)Ph), 4.85 (d, J = 10.9 Hz, 1H, CH\({}_{2}\)Ph), 4.81 (d, J = 10.9 Hz, 1H, CH\({}_{2}\)Ph), 4.72-4.68 (m, 1H, CH\({}_{2}\)Ph), 4.65-4.59 (m, 2H, CH\({}_{2}\)Ph), 4.12 (dt, J = 9.8, 5.0 Hz, 1H, H1), 3.73 (dd, J = 8.5, 6.0 Hz, 2H, H2, H3), 3.70-3.49 (m, 16H, CH\({}_{2}\)CH\({}_{2}\)O-, H4, H5, H6a,b), 3.44-3.29 (m, 4H, H7a,b, H2\({}^{\prime}\)a,b), 2.71-2.62 (t, 2H, J = 7.3 Hz, H11a,b), 2.01-1.89 (m, 2H, H1\({}^{\prime}\)a,b), 1.68 (dt, J = 15.0, 7.5 Hz, 2H, H10a,b), 1.62-1.52 (m, 2H, H8a,b) and 1.47-1.37 (m, 2H, H9a,b). 2.2.12. 2-(6-(1-Thio-(5-(2-(2-(2-(2-(2-hydroxyethyl)ethoxy)ethyl)))-amino-dimcer) **18**  
Compound **18** was prepared following a Birch reduction protocol on protected derivative **17**, according to a procedure described in [63], with slight modifications. Some drops of liquid ammonia were collected in a two-necked round-bottomed flask cooled to \(-\)78 \({}^{\circ}\)C and a small piece of sodium (approx. 20-30 mg) was added.