S1.2. Synthesis details of HBPSi-R
The synthesis of hyperbranched polysiloxanes (HBPSi-R) is straightforward using A2+B3transesterification co-polymerization,[1-5] where R represents their terminal groups of amino (HBPSi-NH2), epoxy (HBPSi-EP), vinyl group (HBPSi-V). Siloxane monomers including KH-550, A-1871 and A-151 were used as the B3 monomers with similar molecular structure but different functional groups, and a simple diol (PDO) was used as the B2 reactant. The feed ratio follows in accordance from the Florey-Carothers law to avoid over-crosslinking. Briefly, 0.16 mol of siloxanes and 0.35 mol of PDO were put into a three-necked flask equipped with a mechanical stirrer, a N2 inlet and a thermometer. The mixtures were heated from 120 °C to 180 °C at a heating rate of 5 °C h-1, then maintain stirring until no more distillate generated. Theoretically, the distillates from all three reactions should be the same ethanol with low-boiling point, which could be consistently separated from the reaction system by a condenser to drive the polymerization proceeded. The distillates were collected for IR detection. Taking a rough purification by pressure-reduce drying to remove the small molecules from reaction, the liquid products can be final obtained (Figure 1 ).