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E/Z reversible photoisomerization of methyl orange doped polyacrylic acid-based polyelectrolyte brush films
The photoswitching behavior of the polyacrylic acid (PAA) doped by methyl orange (MO) brush film was investigated using spectral analysis of UV-Vis absorbance, Fourier Transformation Infrared spectroscopy, 2D electrical conductivity mapping and Atomic Force Microscopy. The kinetics and time evolution of the photoisomerization of the PAA-MO PEBs film from E-state to Z-state by UV-light irradiation, and reverse thermal relaxation to E-state was explored. The results confirm that the photoisomerization kinetics of the overall peak is the superposition of the photoisomerization kinetics of (Formula presented.) transition, low- and high-frequency of the (Formula presented.) transition bands. The E–Z transformation led to transforming the azobenzene from flat with no dipole moment to 3.0 D dipole moment. Hence, the electrical conductivity escalated accordingly. The transformation of E-state to Z-state led to the collapse of the formed brushes because of the angular rotational momentum consequent to E–Z isomerization.
Reconfigurable assembly of charged polymer-modified Janus and non-Janus particles: From half-raspberries to colloidal clusters and chains
Understanding the dynamic and reversible assembly of colloids and particles into complex constructs, inspired by natural phenomena, is of fundamental significance for the fabrication of multi-scale responsive and reconfigurable materials. In this work, we investigate the pH-triggered and reconfigurable assembly of structures composed of binary mixtures of oppositely charged polyacrylic acid (PAA)-modified non-Janus and poly(2-dimethylamino)ethyl methacrylate (PDMAEMA)/poly(N-isopropylacrylamide) (PNIPAM)-modified Janus particles driven by electrostatic interactions. Three different target structures are visible both in dispersions and in dry state: half-raspberry structures, colloidal clusters and colloidal chains depending on the mass, numerical and particle size ratio. All formed structures are well-defined and stable in a certain pH range. Half-raspberry-like structures are obtained at pH 6 and numerical ratios NJP/PAA-HP of 1 : 500 (for 200-PAA-HP), 1 : 44 (for 450-PAA-HP) and 1 : 15 (for 650-PAA-HP), respectively, due to electrostatic interactions between the central JP and the excessive PAA-HP. Colloidal chains and cluster-like structures are generated at numerical ratios NJP/PAA-HP of 4 : 5 (for 200-PAA-HP), 4 : 3 (for 450-PAA-HP), and 4 : 1 (for 650-PAA-HP). Moreover, the smaller the size of a "connecting" PAA colloid, the larger is the average length of a colloidal chain. Depending on the particle size ratio SJP/PAA-HP, some of the observed structures can be disassembled on demand by changing the pH value either close to the IEP of the PDMAEMA (for half-raspberries) or PAA (for colloidal clusters and chains) and then reassembled into new stable structures many times. The obtained results open a pathway to pH-controlled reconfigurable assembly of a binary mixture composed of polymeric-modified non-Janus and Janus particles, which allow the reuse of particle building blocks. © 2019 The Royal Society of Chemistry.