Tailored stimuli-responsive interaction between particles adjusted by straightforward adsorption of mixed layers of Poly(lysine)-g-PEG and Poly(lysine)-g-PNIPAM on anionic beads

We report a simple and versatile method to functionalize anionic colloid particles and control particle solubility. Poly(lysine)-based copolymers (PLL) grafted with polyethylene oxide (PLL-g-PEG) or poly(N-isopropylacrylamide) (PLL-g-PNIPAM) spontaneously adsorb on bare beads dispersed in aqueous solutions of the copolymers. The final composition of the mixed ad-layers formed (i.e. PEG/PNIPAM ratio) was adjusted by the polymer concentrations in solutions. While the (PLL-g-PEG)-coated particles were stable in a wide range of temperature, the presence of PLL-g-PNIPAM in the outer layer provided a reversible temperature-triggered aggregation at 32±1 °C. In the range of PNIPAM fraction going from 100% (beads fully covered by PLL-g-PNIPAM) down to a threshold 20% weight ratio (with 80% PLL-g-PEG), the particles aggregated rapidly to form micrometer size clusters. Below 20% weight fraction of PLL-g-PNIPAM, the kinetic was drastically lowered. Using PLL derivatives provides a straightforward route allowing to control the fraction of a functional chain (here PNIPAM) deposited on PEGylated particles, and in turn to adjust surface interaction and here the rate of particle-particle aggregation as a function of the density of functional chains. This approach can be generalized to many anionic surfaces onto which PLL is known to adhere tightly, such as glass or silica.