Figure S2 The 1H-NMR assignments of a) HBPSi-NH2, b) HBPSi-EP and c) HBPSi-V with their1H-NMR information compared with monomers, respectively.
As given in Figure S2 , 1H-NMR spectra of HBPSi-NH2, HBPSi-EP and HBPSi-V were assigned on by one in accordance with their hyperbranched structures. Due to the different solubility in deuterated reagents, DMSO-d6 was selected for HBPSi-V, and CDCl3 were chosen for HBPSi-NH2 and HBPSi-EP. It is noted that some small offsets as well as emerging new peaks can be recognized in comparison with their reaction monomers, indicating the proceed polymerization. Besides, it could be recognized that the H2 from PDO are separated into three link modes in the resulting hyperbranched polymers, corresponding to H5, H7, H9 in HBPSi-NH2, H7, H9, H11 in HBPSi-EP, and H3, H5, H7 in HBPSi-V. These separated protons in NMR spectra after polymerization are attributed to the various linked modes of dendritic (D), linear (L) and terminal (L) units upon the hyperbranched backbone. Moreover, the protons from amino, epoxy and vinyl groups can be assigned in each HBPSi-R, indicating their characteristic functional groups within the synthetic polymers,