Hyperbranched polyamidoamines (HPAs) were directly employed as macroinitiators to initiate the Sn(Oct)

2

catalyzed ring-opening polymerization of

ε

-caprolactone (CL)

resulting in multiarm star copolymers with poly(

ε

-caprolactone) (PCL) as shells and HPA as core (HPA-

b

-PCL). From

1

H-NMR characterization it was deduced that both the primary amines and the secondary amide groups of HPAs could initiate the CL polymerization

and the initiation efficiency increased when more CL monomers were fed. The average arm-numbers of the obtained stars were in the range of 115-353. Differential scanning calorimetry measurements demonstrated that the melting and crystallization temperatures

fusion and crystallization enthalpy and the degree of crystallinity of the star polymers increased as the PCL arm length increased. HPA-

b

-PCL stars could be used as nanocarriers to efficiently accommodate anionic dyes at acidic condition

while load cationic dyes at basic condition. Compared with the dye-loading behavior of multiarm star PCL with the neutral hyperbranched polyglycerol as core

it was deduced that HPA-

b

-PCL nanocarriers accommodated anionic dyes using the HPA core

while loaded cationic dyes using both the HPA core and the PCL shell. Dynamic light scattering analyses also supported such deduction. Furthermore

HPA-b-PCL nanocarriers could selectively load the anionic Eosin Y or the cationic methylene blue from their mixture at pH = 6 or 9

respectively

realizing their separation.