Felipe Oyarzun-Ampuero, Esteban Araya-Hermosilla, Ignacio Moreno-Villoslada, Francesco Picchioni, Patrizio Raffa, Fabián Muñoz-Suescun, José Catalán-Toledo, Lorenzo Massimo Polgar
Amphiphilic aromatic polymers have been synthesized by grafting aliphatic polyketones with 4-(aminomethyl)benzoic acid at different molar ratios via the Paal–Knorr reaction. The resulting polymers, showing diketone conversion degree of 16%, 37%, 53%, and 69%, have been complexed with the redox-active 2,3,5-triphenyl-2H-tetrazolium chloride, a precursor molecule with which aromatic–aromatic interactions are held. Upon addition of ascorbic acid to the complexes, in situ reduction of the tetrazolium salt produced 1,3,5-triphenylformazan nanoparticles stabilized by the amphiphilic polymers. The stabilized nanoparticles display highly negative zeta potential [−(35–70) mV] and hydrodynamic diameters in the submicron range (100–400 nm). Nonaromatic polyelectrolytes or hydrophilic aromatic copolymers showing low linear aromatic density and high linear charge density such as acrylate/maleate and sulfonate/maleate−containing polymers were unable to stabilize formazan nanoparticles synthesized by the same method. The copolymers studied here bear uncharged nonaromatic comonomers (unreacted diketone units) as well as charged aromatic comonomers, which furnish amphiphilia. Thus, the linear aromatic density and the maximum linear charge density have the same value for each copolymer, and the hydrophilic/hydrophobic balance varies with the diketone conversion degree. The amphiphilia of the copolymers allows the stabilization of the nanoparticles, even with the copolymers showing a low linear aromatic density. The method of nanoparticle synthesis constitutes a simple, cheap, and green method for the production of switchable totally organic, redox-active, pH-sensitive nanoparticles that can be reversibly turned into macroprecipitates upon pH changing.