Thermoresponsive Semi-IPN Hydrogel Microfibers from Continuous Fluidic Processing with High Elasticity and Fast Actuation

Hydrogels with rapid and strong response to external stimuli and possessing high elasticity and strength have been considered as platform materials for numerous applications, e.g., in biomaterials engineering. Thermoresponsive hydrogels based on semi-interpenetrating polymer networks (semi-IPN) featuring <i>N</i>-isopropylacrylamide with copolymers of poly­(<i>N</i>-isopropylacrylamide-<i>co</i>-hydroxyethyl methacrylate) p­(NIPAM-HEMA) chains are prepared and described. The copolymer was characterized by FTIR, NMR, and GPC. The semi-IPN structured hydrogel and its responsive properties were evaluated by dynamic mechanical measurements, SEM, DSC, equilibrium swelling ratio, and dynamic deswelling tests. The results illustrate that the semi-IPN structured hydrogels possess rapid response and high elasticity compared to conventional pNIPAM hydrogels. By using a microfluidic device with double coaxial laminar flow, we succeeded in fabricating temperature responsive (“smart”) hydrogel microfibers with core–shell structures that exhibit typical diameters on the order of 100 μm. The diameter of the fibers can be tuned by changing the flow conditions. Such hydrogel fibers can be used to fabricate “smart” devices, and the core layer can be potentially loaded with cargos to incorporate biological function in the constructs. The platforms obtained by this approach hold promise as artificial “muscles”, and also “smart” hydrogel carriers providing a unique biophysical and bioactive environment for regenerative medicine and tissue engineering

Hydrogels with a Memory: Dual-Responsive, Organometallic Poly(ionic liquid)s with Hysteretic Volume-Phase Transition

We report on the synthesis and structure–property relations of a novel, dual-responsive organometallic poly­(ionic liquid) (PIL), consisting of a poly­(ferro­cenyl­silane) backbone of alternating redox-active, silane-bridged ferrocene units and tetra­alkyl­phosphonium sulfonate moieties in the side groups. This PIL is redox responsive due to the presence of ferrocene in the backbone and also exhibits a lower critical solution temperature (LCST)-type thermal responsive behavior. The LCST phase transition originates from the interaction between water molecules and the ionic substituents and shows a concentration-dependent, tunable transition temperature in aqueous solution. The PIL’s LCST-type transition temperature can also be influenced by varying the redox state of ferrocene in the polymer main chain. As the polymer can be readily cross-linked and is easily converted into hydrogels, it represents a new dual-responsive materials platform. Interestingly, the as-formed hydrogels display an unusual, strongly hysteretic volume-phase transition indicating useful thermal memory properties. By employing the dispersing abilities of this cationic PIL, CNT-hydrogel composites were successfully prepared. These hybrid conductive composite hydrogels showed bi-stable states and tunable resistance in heating–cooling cycles

Synchrotron SAXS and Impedance Spectroscopy Unveil Nanostructure Variations in Redox-Responsive Porous Membranes from Poly(ferrocenylsilane) Poly(ionic liquid)s

Nanostructured cellular polymeric materials with controlled cell sizes, dispersity, architectures, and functional groups provide opportunities in separation technology, smart catalysts, and controlled drug delivery and release. This paper discusses porous membranes formed in a simple electrostatic complexation process using a NH₃ base treatment from redox responsive poly­(ferrocenysilane) (PFS)-based poly­(ionic liquid)­s and poly­(acrylic acid) (PAA). These porous membranes exhibit reversible switching between more open and more closed structures upon oxidation and reduction. The porous structure and redox behavior that originate from the PFS matrix are investigated by small-angle X-ray scattering (SAXS) using synchrotron radiation combined with electrochemical impedance spectroscopy. In order to gain more insight into structure variations during electrochemical treatment, the scattering signal of the porous membrane is detected directly from the films at the electrode surface in situ, using a custom-built SAXS electrochemical cell. All experiments confirm the morphology changing between more “open” and more “closed” cells with approximately 30% variation in the value of the equivalent radius (or correlation length), depending on the redox state of ferrocene in the polymer main chain. This property may be exploited in applications such as reference-electrode-free impedance sensing, redox-controlled gating, or molecular separations