RESUMEN
Ionogels have gained increasing attentions as a flexible conductive material. However, it remains a big challenge to integrate multiple functions into one gel that can be widely applied in various complex scenes. Herein, a kind of multifunctional ionogels with a combination of desirable properties, including transparency, high stretchability, solvent and temperature resistance, recyclability, high conductivity, underwater self-healing ability, and underwater adhesiveness is reported. The ionogels are prepared via one-step photoinitiated polymerization of 2,2,2-trifluoroethyl acrylate and acrylamide in a hydrophobic ionic liquid. The abundant noncovalent interactions including hydrogen bonding and ion-dipole interactions endow the ionogels with excellent mechanical strength, resilience, and rapid self-healing capability at room temperature, while the fluorine-rich polymeric matrix brings in high tolerance against water and various organic solvents, as well as tough underwater adhesion on different substrates. Wearable strain sensors based on the ionogels can sensitively detect and differentiate large body motions, such as bending of limbs, walking and jumping, as well as subtle muscle movements, such as pronunciation and pulse. It is believed that the designed ionogels will show great promises in wearable devices and ionotronics.
RESUMEN
Amphiphilic polymers can self-assemble into various nanostructures in solution, which can find applications in many fields such as nanotechnology, drug delivery, and template synthesis. Herein, we report the controlled self-assembly and dual stimuli-responsive nanostructure transition of a class of three-arm branched amphiphilic polymers (AzoFcPEO) containing ferrocene (Fc) and azobenzene (Azo) moieties in aqueous solution. These amphiphilic polymers were synthesized by an esterification reaction of a variety of polyethylene oxide methyl ethers (Me-PEO) with 3-(6-ferrocenyhexyloxyl)-5-(6-azobenzenehexyloxy) benzoic acid. Both the isomerization of Azo and redox of Fc moieties can respectively change the amphiphilicity of these polymers to different degrees. Consequently, these amphiphilic polymers in aqueous solution can self-assemble into various nanostructures, such as spherical micelle, worm-like micelle, spherical compound micelle, rod-like compound micelle and vesicle dependent on the PEO molecular weight, applied stimuli, and polymer concentration. This work can offer tremendous possibilities not only for the fundamental science of the controlled self-assembly but also for establishing a suitable method for regulating the nanostructures of amphiphilic polymers in aqueous solution.
RESUMEN
Alternating associative polymers (AAPs) containing more than two species of alternating hydrophobic and hydrophilic units can form unique physical network and perform interesting rheological behavior in aqueous solution. In this work, an AAP was prepared through self-assembly assisted dimerization of an anthracene-functionalized telechelic associative polymer (AnTAP) in aqueous solution by light irradiation. It is demonstrated that AnTAP can in situ chain extend to AAP with well-defined linear structure and ultrahigh molecular weight through dimerization reaction of anthracene moieties in the core of micelle under light irradiation. Meanwhile, the solution changes from viscoelastic liquid to a free-standing gel, because a physical network that cannot relax in a finite time window has developed along with the dimerization process. The results are therefore of interest not only for understanding the network structure and rheological properties of AAP solution, but also for preparing AAPs with ultrahigh molecular weight by self-assembly assisted photodimerization reactions.
RESUMEN
Superamphiphilic polymers (SAPs) constructed by host-guest inclusion can self-assemble into various nanostructures in solution, which can find applications in many fields such as nanodevices, drug delivery, and template synthesis. Herein, we report the controlled self-assembly of multiple-responsive SAP based on a selective host-guest inclusion of ß-cyclodextrin (ß-CD) with a modified poly(ethylene glycol) (PEG) (FcC11AzoPEG) consisting of a ferrocene (Fc) end group, a C11 alkyl chain, an azobenzene (Azo) block, and a poly(ethylene glycol)methyl ether (PEG) chain. These SAPs can self-assemble into interesting nanostructures in water upon exposure to different stimuli because ß-CD can be selectively included with different guests, such as Fc, Azo, and C11 alkyl chain, under different stimuli. The inclusion complex of Fc with ß-CD (Fc@ß-CD SAP) can form nanowire micelles in aqueous solution. The nanowire micelles can be transformed into spindle micelles with the addition of oxidant because the majority of ß-CDs dissociated from the complex Fc@ß-CD SAP due to a conversion of Fc to Fc+ and will preferentially include with Azo group to form another dominant inclusion complex (Azo@ß-CD SAP). After UV irradiation, the spindle micelles can be further transformed into spherical micelles because most of ß-CDs are excluded from the complex Azo@ß-CD SAP due to a trans- to cis-Azo conversion and then form a dominant inclusion complex with C11 alkyl chains (C11@ß-CD SAP). This work not only demonstrates the selective host-guest inclusion of stimuli-responsive groups modified PEG with ß-CD but also provides a useful approach for construction of diverse morphologies.
RESUMEN
In this work, we present a novel redox-responsive ferrocene-functionalized hydrophobically modified ethoxylated urethane (Fc-HEUR) model polymer. The effects of a redox-induced hydrophobicity change of ferrocenyl hydrophobes on the self-assembly and rheological properties of Fc-HEUR in aqueous solution were investigated. In view of the redox-induced change in the hydrophilic-lipophilic balance of polymers, the Fc-HEUR polymer in aqueous solution can reversibly self-assemble into spherical micelles and larger micellar aggregates of different nanoscales and also disassemble by redox reactions immediately. Moreover, we have demonstrated that a rearrangement of micellar junctions takes place through a bridge-loop or loop-bridge transition in the concentrated polymer solution followed by redox reactions, which induces a great change in the rheological properties of the polymer solution: a viscoelastic liquid for the reduction state Fc-HEUR and a viscous liquid for the oxidation state Fc+-HEUR, owing to their different relaxation behaviors. Particularly, the associative structures and rheological properties of the Fc-HEUR aqueous solution can be reversibly controlled by redox reactions. This work will be useful not only for understanding of the thickening mechanism of stimuli-responsive HEURs but also for the development of reversible self-assembly and controlled rheological fluids, which may have some special application in drug delivery systems, catalyst supports, sensors, and microfluidic devices.