We have comparatively studied the association of cyclic- and linear-poly(N-isopropylacrylamide)
(c-PNIPAM and l-PNIPAM) chains with varying chain lengths and end groups in dilute aqueous solutions by
laser light scattering (LLS) and stopped-flow temperature-jump measurements. Dynamic and static LLS results
reveal that the heating leads to a microphase transition. The resultant structures of interchain aggregates depend
on the heating rate and the chain topologies. In comparison with l-PNIPAM chains, a slow heating of c-PNIPAM
chains in the solution results in stable mesoglobules with a lower average aggregation number, a looser structure,
and a smaller average size (∼290 nm). The temperature-jump-induced association of c-PNIPAM chains in the
stopped-flow measurement reveals two kinetic growth stages, which were tentatively ascribed to the loose packing
of contracted c-PNIPAM chains and further contraction-induced fragmentation of initially packed c-PNIPAM
chains due to the lack of interchain entanglements. On the other hand, for l-PNIPAM chains, the intrachain
contraction and interchain penetration/entanglement simultaneously occur as the temperature increases, leading
to larger and more compact aggregates whose size increases with the solution temperature. 快速动力学停流装置与光谱分析系统
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