Self-Assembly of Gold Nanoparticles With Oppositely Charged, Long, Linear Chains of Periodic Copolymers
Abstract
We studied the assembly of nanoparticles with oppositely charged linear and periodic copolymers (CPs), alternating ionic and polar sequences, in the dilute range of polymer concentration. For the first time, we considered CPs displaying a contour length much higher than the AuNP perimeter. We assumed that such CPs will enable to collect a finite number of NPs into linear nanostructures with a gain of colloidal stability and a better structural control compared to electrostatic complexes obtained with homo polyelectrolytes. As a case study, we synthesized anionic gold nanoparticles (AuNPs) and CPs consisting of alternated cationic poly-L-lysine (PLL) blocks and polar sequences of poly(ethyleneglycol) (PEG). We showed that complexation of AuNPs with CPs is quite similar to that observed with homo PLL. In that respect, finite size nanometric clusters, of less than 30 NPs, outside the electro neutrality domain and a fast phase separation occurs at the electro neutrality. Nevertheless, the presence of PEG blocks allowed us to highlight some specific effects. First, the global charge of the positively charged clusters was found to be always lower for CP based clusters than for homo PLL with a dependence of the charge with the number and the mass of the PEG blocks. Second, in spite of this effect which should have promoted the formation of dense structure, the fractal dimension characterizing the structure of the clusters in bulk was found to be always below 1.8. Finally, we showed…
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