Dynamic hydrogel crosslinking captures network reorganization and self‐healing of natural materials, yet is often accompanied by reduced mechanical properties compared to covalent analogs. Toughening is possible in certain materials with processing by directional freeze‐casting and salting‐out, producing hierarchically organized networks with directionally enhanced mechanical properties. The implications of including dynamic supramolecular crosslinking alongside such processes are unclear. Here, a supramolecular hydrogel prepared from homoternary crosslinking by pendant guests with a free macrocycle is subsequently processed by directional freeze‐casting and salting‐out. The resulting hydrogels tolerate multiple cycles of compression. Excitingly, supramolecular affinity dictates the mechanical properties of the bulk hydrogels, with higher affinity interactions producing materials with higher Young's modulus and enhanced toughness under compression. The importance of supramolecular crosslinking is emphasized with a supramolecular complex that is converted in situ into a covalent crosslink. While supramolecular hydrogels do not fracture and spontaneously self‐heal when cut, their covalent analogs fracture under moderate strain and do not self‐heal. This work shows a molecular‐scale origin of bulk hydrogel toughening attributed to affinity and dynamics of supramolecular crosslinking, offering synergy in combination with bulk post‐processing techniques to yield materials with enhanced mechanical properties tunable at the molecular scale for the needs of specific applications.
Achieving a simple yet sustainable printing technique with minimal instruments and energy remains challenging. Here, a facile and sustainable 3D printing technique is developed by utilizing a reversible salting-out effect. The salting-out effect induced by aqueous salt solutions lowers the phase transition temperature of poly(N-isopropylacrylamide) (PNIPAM) solutions to below 10 °C. It enables the spontaneous and instant formation of physical crosslinks within PNIPAM chains at room temperature, thus allowing the PNIPAM solution to solidify upon contact with a salt solution. The PNIPAM solutions are extrudable through needles and can immediately solidify by salt ions, preserving printed structures, without rheological modifiers, chemical crosslinkers, and additional post-processing steps/equipment. The reversible physical crosslinking and de-crosslinking of the polymer through the salting-out effect demonstrate the recyclability of the polymeric ink. This printing approach extends to various PNIPAM-based composite solutions incorporating functional materials or other polymers, which offers great potential for developing water-soluble disposable electronic circuits, carriers for delivering small materials, and smart actuators.
more » « less- Award ID(s):
- 2011924
- PAR ID:
- 10506093
- Publisher / Repository:
- Nature Publishing Group
- Date Published:
- Journal Name:
- Nature Communications
- Volume:
- 15
- Issue:
- 1
- ISSN:
- 2041-1723
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
more » « less
Abstract -
Abstract Almost all commercial proteins are purified using ammonium sulfate precipitation. Protein-polymer conjugates are synthesized from pure starting materials, and the struggle to separate conjugates from polymer, native protein, and from isomers has vexed scientists for decades. We have discovered that covalent polymer attachment has a transformational effect on protein solubility in salt solutions. Here, protein-polymer conjugates with a variety of polymers, grafting densities, and polymer lengths are generated using atom transfer radical polymerization. Charged polymers increase conjugate solubility in ammonium sulfate and completely prevent precipitation even at 100% saturation. Atomistic molecular dynamic simulations show the impact is driven by an anti-polyelectrolyte effect from zwitterionic polymers. Uncharged polymers exhibit polymer length-dependent decreased solubility. The differences in salting-out are then used to simply purify mixtures of conjugates and native proteins into single species. Increasing protein solubility in salt solutions through polymer conjugation could lead to many new applications of protein-polymer conjugates.more » « less
-
more » « less
Abstract Inorganic salts present in the atmosphere may affect the composition and abundance of secondary organic aerosol. Here, we quantify the effects of salt identity, salt concentration (ionic strength), and solution pH on the partitioning of ambient water‐soluble organic gases (WSOCg) at a site in the eastern United States. The experimental pH (pH = 1–6) and ionic strengths (10−3–101 mol kg−1) span a wide range of conditions found in atmospheric particles, clouds, and fog droplets. Chloride salts (NaCl, NH4Cl, and KCl) exhibit a strong salting‐out effect at all ionic strengths >0.005 mol kg−1and pH = 1.8–6. In contrast, sulfate salts (Na2SO4, (NH4)2SO4, and K2SO4) induce both salting‐in and salting‐out behaviors, depending on ionic strength and pH. These results suggest that monovalent cations have minimal effect, while ionic strength, pH, and anion identity exert strong effects on the partitioning of ambient organic gases in the atmosphere.
-
more » « less
Abstract Nanostructured materials have enabled new ways of controlling the light–matter interaction, opening new routes for exciting applications, in display technologies and colorimetric sensing, among others. In particular, metallic nanoparticles permit the production of color structures out of colorless materials. These plasmonic structural colors are sensitive to the environment and thus offer an interesting platform for sensing. Here, a self‐assembly of aluminum nanoparticles in close proximity of a mirror is spaced by an ultrathin poly(
N ‐isopropylacrylamide) (PNIPAM) layer. Hybridizing the plasmonic system with the active polymer layer, a thermoresponsive gap‐plasmon architecture is formed that transduces changes in the temperature and relative humidity of the environment into color changes. By harnessing the environmentally induced structural changes of PNIPAM, it was estimated from the finite difference time domain simulation that the resonance can be tuned 7 nm per every 1 nm change in thickness, resulting in color variation. Importantly, these fully reversible changes can be used for reusable powerless humidity and temperature colorimetric sensing. Crucially if condensation on the structure happens, the polymer layer is deformed beyond recovery and the colors are washed away. We leverage this effect to produce tamper‐proof dew labels that a straightforward smartphone app can read by taking a picture. -
more » « less
Abstract A thermally “switchable” liquid‐crystalline (LC) phase is observed in aqueous suspensions of cellulose nanocrystals (CNCs) featuring patchy grafts of the thermoresponsive polymer poly(
N ‐isopropylacrylamide) (PNIPAM). “Patchy” polymer decoration of the CNCs is achieved by preferential attachment of an atom transfer radical polymerization (ATRP) initiator to the ends of the rods and subsequent surface‐initiated ATRP. The patchy PNIPAM‐grafted CNCs display a higher colloidal stability above the lower critical solution temperature (LCST) of PNIPAM than CNCs decorated with PNIPAM in a brush‐like manner. A 10 wt% suspension of the “patchy” PNIPAM‐modified CNCs displays birefringence at room temperature, indicating the presence of an LC phase. When heated above the LCST of PNIPAM, the birefringence disappears, indicating the transition to an isotropic phase. This switching is reversible and appears to be driven by the collapse of the PNIPAM chains above the LCST, causing a reduction of the rods' packing density and an increase in translational and rotational freedom. Suspensions of the “brush” PNIPAM‐modified CNCs display a different behavior. Heating above the LCST causes phase separation, likely because the chain collapse renders the particles more hydrophobic. The thermal switching observed for the “patchy” PNIPAM‐modified CNCs is unprecedented and possibly useful for sensing and smart packaging applications.
