Multi-Stimuli-Responsive Water-Dispersible Magnetite Nanoparticles Using Arylazopyrazole-Modified Polymer Ligands

In order to design new nanomaterials with improved functionalities, magnetite nanoparticles (MNP) modified with arylazopyrazole (AAP) molecular photoswitches are presented. Water dispersibility is achieved by using poly(acrylic acid) (pAA) as a multidentate ligand, which is modified with AAP by amide coupling. The polymer ligand stabilizes the MNP, allows for E-Z isomerization of the photoswitch, and provides pH responsiveness. Three different AAP are synthesized and attached to pAA via amide coupling giving pAA-AAP with photoswitches substituted statistically along the hydrophilic polymer backbone. MNP are synthesized by coprecipitation and pAA-AAP is introduced as a stabilizing agent in situ. Photoisomerization of pAA-AAP and pAA-AAP@MNP is investigated showing good photostationary states and cyclability. The MNP can be assembled and dispersed reversibly in water either by applying a magnetic field or by a change in pH.