Temperature-induced aggregation of poly(N-isopropylacrylamide)-stabilized CdS quantum dots in water

Water-soluble nanosized semiconductor CdS particles (quantum dots, QDs) were synthesized with a protective layer of covalently grafting linear thermally sensitive poly(N-isopropylacrylamide) chains. Reversible association and dissociation of these CdS particles can be induced via an alteration of the solution temperature. The formation and fragmentation of the QD aggregates of the CdS particles were systematically investigated by laser light scattering (LLS) and confirmed by transmission electron microscopy (TEM). There exists a hysteresis during one heating-and-cooling cycle. The CdS particles stabilized with shorter PNIPAM chains (Mn=15,000 g/mol) can associate to form larger and denser spherical aggregates with a much higher aggregation number than those grafted with longer PNIPAM chains (Mn=31,000 g/mol) in the heating process. The dissociation (fragmentation) in the cooling process has two stages: initially, the aggregates dissociate as the temperature decreases, and then, the fragmentation stops over a wider temperature range before complete dissociation. We attribute such a two-stage fragmentation to a balanced effect of inter- and intrachain hydrogen bonding as well as the hydrophobic interaction between PNIPAM chains and CdS particles.