Reconfiguration of Langmuir Monolayers of Thermo-Responsive Branched Ionic Polymers with LCST Transition.

Thermo-responsive ionic polymers have the ability to form adaptive and switchable morphologies, which may offer enhanced control in energy storage and catalytic applications. Current thermo-responsive polymers are composed of covalently attached thermo-responsive moieties, restricting their mobility and global dynamic response. Here, we report the synthesis and assembly at the water-air interface of symmetric and asymmetric amphiphilic thermo-responsive branched polymers with weakly ionically bound arms of amine-terminated poly(N-isopropylacrylamide) (PNIPAM) macro-cations. As we observed, symmetric branched polymers formed multimolecular nanosized micellar assemblies, whereas corresponding asymmetric polymers formed large, interconnected worm-like aggregates. Dramatic changes in localized and large-scale chemical composition confirmed the reversible adsorption and desorption of the mobile PNIPAM macro-cations below and above the low critical solution temperature (LCST) and their non-uniform redistribution within polymer monolayer. Increasing the temperature above LCST led to the formation of large interconnected micellar aggregates because of the micelle-centered aggregation of the hydrophobized PNIPAM macro-cationic terminal chains in the aqueous subphase. Overall, this work provides insights into the dynamic nature of the chemical composition of branched ionic polymers with weakly ionically bound thermo-responsive terminal chains and its effect on both morphology and local/surface chemistry of monolayers at LCST transition.

Flexible Sustained Ionogels with Ionic Hyperbranched Polymers for Enhanced Ion-Conduction and Energy Storage.

Flexible and mechanically robust gel-like electrolytes offer enhanced energy storage capabilities, versatility, and safety in batteries and supercapacitors. However, the trade-off between ion conduction and mechanical robustness remains a challenge for these materials. Here, we suggest that the introduction of ionic hyperbranched polymers in structured sustained ionogels will lead to both enhanced ion conduction and mechanical performance because of the hyperbranched polymers' ionically conductive groups and the complementary interfacial interactions with ionic liquids. More specifically, we investigate the effect of hyperbranched polymers with carboxylate terminal groups and imidazolium counterions with various ionic group densities on the properties of ionogels composed of coassembled cellulose nanofibers (CNFs) and cellulose nanocrystals (CNCs) as sustainable open pore frame for ionic liquid immersion. The addition of hyperbranched polymers leads to the formation of highly interconnected openly porous, lightweight, and shape-persistent materials by harnessing hydrogen bonding between the polymers and the CNFs/CNCs "frame". Notably, these materials possess a 2-fold improvement in ionic conductivity combined with many-fold increase in Young's modulus, tensile strength, and toughness, making them comparable to common reinforced nanocomposite materials. Furthermore, the corresponding thin-film gel supercapacitors possess enhanced electrochemical cycling stability upon repeated bending with an 85% capacitance retention after 10 000 cycles, promising new insight in the development of simultaneously conductive and flexible gel electrolytes with sustained performance.

Weakly Ionically Bound Thermosensitive Hyperbranched Polymers.

We synthesized novel amphiphilic hyperbranched polymers (HBPs) with variable contents of weakly ionically tethered thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) macrocations in contrast to traditional covalent linking. Their assembling behavior was studied below and above the lower critical solution temperature (LCST). The HBPs underwent a morphological transition under changing temperature and ionic strength due to the LCST transition of PNIPAM and the reduction in the ionization degree of terminal ionic groups, respectively. We suggest that, in contrast to traditional branched polymers, ionically linked PNIPAM macrocations can reversibly disassociate from the sulfonate groups and form mobile coronas, endowing the dynamic micellar morphologies. In addition, assembly at the air-water interface confined PNIPAM macrocations and resulted in the formation of heterogeneous Langmuir-Blodgett (LB) monolayers with diverse surface morphologies for different peripheral compositions with circular domains formed in the condensed state. The HBPs with 25% PNIPAM showed larger and more stable circular domains that were partially preserved at high compression than those of HBPs with 50% PNIPAM. Moreover, the LB monolayers showed variable surface mechanical and surface charge distribution, which can be attributed to net dipole redistribution caused by the behavior of mobile PNIPAM macrocations and core sulfonate groups.

Transformations of Thermosensitive Hyperbranched Poly(ionic liquid)s Monolayers.

We synthesized amphiphilic hyperbranched poly(ionic liquid)s (HBPILs) with asymmetrical peripheral composition consisting of hydrophobic n-octadecylurethane arms and hydrophilic, ionically linked poly(N-isopropylacrylamide) (PNIPAM) macrocations and studied low critical solution temperature (LCST)-induced reorganizations at the air-water interface. We observed that the morphology of HBPIL Langmuir monolayers is controlled by the surface pressure with uniform well-defined disk-like domains formed in a liquid phase. These domains are merged and transformed to uniform monolayers with elevated ridge-like network structures representing coalesced interdomain boundaries in a solid phase because the branched architecture and asymmetrical chemical composition stabilize the disk-like morphology under high compression. Above LCST, elevated individual islands are formed because of the aggregation of the collapsed hydrophobized PNIPAM terminal macrocations in a solid phase. The presence of thermoresponsive PNIPAM macrocations initiates monolayer reorganization at LCST with transformation of surface mechanical contrast distribution. The heterogeneity of elastic response and adhesion distributions for HBPIL monolayers in the wet state changed from highly contrasted two-phase distribution below LCST to near-uniform mechanical response above LCST because of the hydrophilic to hydrophobic transformation of the PNIPAM phase.