General procedure for the NPA preparation

FM 1a (0.0032 mmol), DMPA (10 μL of a 12.8 mg/mL solution in DMSO, 0.0005 mmol), and MBAm (0.04 mmol) were added to a micellar solution of 3 (9.3 mg, 0.02 mmol) in water (2.0 mL). The reaction mixture was ultrasonicated for 10 min, followed by the addition of 4 (3.4 mg, 0.02 mmol), CuCl₂ (10 μL of a 6.7 mg/mL solution in H₂O, 0.0005 mmol), and sodium ascorbate (10 μL of a 99 mg/mL solution in H₂O, 0.005 mmol). The mixture was stirred slowly at room temperature for 12 h before the protein template (0.0004 mmol) was added. After another 12 h of stirring at room temperature, the mixture was transferred to a glass vial and purged with nitrogen for 15 min. After the sample was irradiated in a Rayonet reactor (300 W/m², 365 nm) for 12 h, 5 (10.6 mg, 0.04 mmol), CuCl₂ (10 μL of a 6.7 mg/mL solution in H₂O, 0.0005 mmol), and sodium ascorbate (10 μL of a 99 mg/mL solution in H₂O, 0.005 mmol) were added. After the mixture was stirred at room temperature for another 6 h, the aqueous reaction mixture was poured into 8 mL of acetone. The precipitate was collected by centrifugation (2500×g for 10 min) and washed with a mixture of acetone/water (3 × 5 mL/1 mL), methanol/acetic acid (3 × 5 mL/0.1 mL), and excess methanol before air-dried. Typical yields for NP_A were ~80%. Removal of the template was confirmed by MALDI MS analysis (Supplementary Fig. ⁸).