To verify this hypothesis, we decided to synthesize a new amphiphilic dendron still based on the G1 head but with the incorporation of cholesterol (Chol) as the hydrophobic unit, since we previously observed good performance of cholesterol-based self-assembled dendrons in DNA binding and delivery [13,14]. Thus, starting from the structure of C22G1, we designed CholSG1 (Figure 14a), in which a small spacer (S) between Chol and the triazole ring was inserted to minimize steric hindrance between dendron head and tail and to allow for some conformational mobility [29]. CholSG1 was readily synthesized by modifying Chol with an azide group, followed by conjugation with the alkyne-modified G1 head via click chemistry.