Responsive polymer materials can adapt to surrounding environments, regulate transport of ions and molecules, change wettability and adhesion of different species on external stimuli, or convert chemical and biochemical signals into optical, electrical, thermal and mechanical signals, and vice versa. These materials are playing an increasingly important part in a diverse range of applications, such as drug delivery, diagnostics, tissue engineering and 'smart' optical systems, as well as biosensors, microelectromechanical systems, coatings and textiles. We review recent advances and challenges in the developments towards applications of stimuli-responsive polymeric materials that are self-assembled from nanostructured building blocks. We also provide a critical outline of emerging developments.

To investigate how substrate properties influence stem-cell fate, we cultured single human epidermal stem cells on polydimethylsiloxane (PDMS) and polyacrylamide (PAAm) hydrogel surfaces, 0.1 kPa-2.3 MPa in stiffness, with a covalently attached collagen coating. Cell spreading and differentiation were unaffected by polydimethylsiloxane stiffness. However, cells on polyacrylamide of low elastic modulus (0.5 kPa) could not form stable focal adhesions and differentiated as a result of decreased activation of the extracellular-signal-related kinase (ERK)/mitogen-activated protein kinase (MAPK) signalling pathway. The differentiation of human mesenchymal stem cells was also unaffected by PDMS stiffness but regulated by the elastic modulus of PAAm. Dextran penetration measurements indicated that polyacrylamide substrates of low elastic modulus were more porous than stiff substrates, suggesting that the collagen anchoring points would be further apart. We then changed collagen crosslink concentration and used hydrogel-nanoparticle substrates to vary anchoring distance at constant substrate stiffness. Lower collagen anchoring density resulted in increased differentiation. We conclude that stem cells exert a mechanical force on collagen fibres and gauge the feedback to make cell-fate decisions.

When oppositely charged polyelectrolytes are mixed below a critical salt concentration, their mixtures show macroscopic phase separation into a dilute and a dense, polyelectrolyte complex phase. Binodal compositions of the polyelectrolyte complexes have been measured experimentally using fluorescently labeled polyelectrolytes. We used fluorescein-labeled poly(acrylic acid) (PAA) of four different chain lengths (N = 20, 50, 150, and 510) to determine the binodal compositions of polyelectrolyte complexes of PAA and poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) of similar chain lengths. The water content of polyelectrolyte complexes obtained has a lower limit of about 65%, practically independent of chain length, and increases with increasing salt concentration. We interpret our results on binodal compositions, water content and critical salt concentration as a function of chain length using the mean-field model of Voorn and Overbeek and find good quantitative agreement with our experiments using only one adjustable parameter. We believe that such a model can be used to predict equilibrium concentrations also for other strongly charged flexible polyelectrolytes.

Catechols play an important role in many natural systems. They are known to readily interact with both organic (e.g., amino acids) and inorganic (e.g., metal ions, metal oxides) compounds, thereby providing a powerful system for protein curing. Catechol crosslinked protein networks, such as sclerotized cuticle and byssal threads of the mussel, have been shown to exhibit excellent mechanical properties. A lot of effort has been devoted to mimicking the natural proteins using synthetic catechol-functionalized polymers. Despite the success in developing catechol-functionalized materials, the crosslinking chemistry of catechols is still a subject of debate. To develop materials with controlled and superior properties, a clear understanding of the crosslinking mechanism of catechols is of vital importance. This review describes the crosslinking pathways of catechol and derivatives in both natural and synthetic systems. We discuss existing pathways of catechol crosslinking and parameters that affect the catechol chemistry in detail. This overview will point towards a rational direction for further investigation of the complicated catechol chemistry.

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