It is demonstrated that light polarization can be used to control photothermal effect‐based shape‐memory polymers (SMPs). Gold nanorods (AuNRs) are embedded in poly(vinyl alcohol) (PVA) and aligned by stretching the composite film. By changing the polarization direction of the incident laser at 785 nm with respect to the film stretching direction, the magnitude of the longitudinal surface plasmon resonance of AuNRs can be varied continuously, which determines the amount of heat generated upon laser exposure and thus the local temperature rise in the composite relative to the glass transition of the PVA matrix. Consequently, the temporary‐to‐permanent shape recovery process of the composite can be made to occur to different extents by tuning the polarization of laser while keeping all other conditions unchanged. This finding enhances the toolbox for controlling light‐triggered SMPs.
A thermo‐, photo‐ and chemoresponsive shape‐memory material is successfully prepared by introducing α‐cyclodextrin (αCD) and azobenzene (Azo) into a poly(acrylate acid)/alginate (PAA/Alg) network. The tri‐stimuli‐responsive formation/dissociation of αCD‐Azo acts as molecular switches freezing or increasing the molecular mobility. The resulting film herein can be processed into temporary shapes as needed and recovers its initial shape upon the application of light irradiation, heating, or chemical agent independently. Furthermore, the agar diffusion test suggests that the α‐CD‐Alg/Azo‐PAA has good biocompatibility for L929 fibroblast‐like cells.
A facile blending strategy to fabricate multishape memory polymers (SMPs) with only one sort of phase transition material has been reported. In this work, olefin block copolymer (OBC) and styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene (SEBS), which are both physically crosslinked, are blended with crystalline paraffin together. Due to the different interactions between polymer matrices and paraffin, the paraffin penetrated in OBC and SEBS exhibit separated melting transitions. It is quite interesting that merely paraffin distributed in OBC also shows two distinct melting transitions with enough OBC content in composites. Therefore, excellent quadruple shape memory effect can be achieved with a maximum of three melting transitions. Furthermore, through adjusting the polymer species and content, the mechanical and rheological properties can be conveniently tuned to a great extent. Compared with the reported strategies, this simple and controllable method sheds light on rapid design of multi‐SMPs using inexpensive raw materials, which greatly paves the way for multi‐SMPs from laboratory to factory.
Conjugation of a hydrophobic poly(2‐oxazoline) bearing tertiary amide groups along its backbone with a short single stranded nucleotide sequence results in an amphiphilic comb/graft copolymer, which organizes in fibrils upon direct dissolution in water. Supported by circular dichroism, atomic force microscopy, transmission electron microscopy, and scattering data, fibrils are formed through inter‐ and intramolecular hydrogen bonding between hydrogen accepting amide groups along the polymer backbone and hydrogen donating nucleic acid grafts leading to the formation of hollow tubes.
Imitating the natural “energy cascade” architecture, we present a single‐molecular rod‐like nano‐light harvester (NLH) based on a cylindrical polymer brush. Block copolymer side chains carrying (9,9‐diethylfluoren‐2‐yl)methyl methacrylate units as light absorbing antennae (energy donors) are tethered to a linear polymer backbone containing 9‐anthracenemethyl methacrylate units as emitting groups (energy acceptors). These NLHs exhibit very efficient energy absorption and transfer. Moreover, we manipulate the energy transfer by tuning the donor–acceptor distance.
A new method for fabricating hydrogels with intricate control over hierarchical 3D porosity using microfiber porogens is presented. Melt electrospinning writing of poly(ε‐caprolactone) is used to create the sacrificial template leading to hierarchical structuring consisting of pores inside the denser poly(2‐oxazoline) hydrogel mesh. This versatile approach provides new opportunities to create well‐defined multilevel control over interconnected pores with diameters in the lower micrometer range inside hydrogels with potential applications as cell scaffolds with tunable diffusion and transport of, e.g., nutrients, growth factors or therapeutics.
The chemical control of cell division has attracted much attention in the areas of single cell‐based biology and high‐throughput screening platforms. A mussel‐inspired cytocompatible encapsulation method for achieving a “cell‐division control” with cross‐linked layer‐by‐layer (LbL) shells is developed. Catechol‐grafted polyethyleneimine and hyaluronic acid are chosen as polyelectrolytes for the LbL process, and the cross‐linking of polyelectrolytes is performed at pH 8.5. Cell division is controlled by the number of the LbL nanolayers and cross‐linking reaction. We also suggest a new measuring unit, , for quantifying “cell‐division timing” based on microbial growth kinetics.
Hierarchical semicrystalline block copolymer nanoparticles are produced in a segmented gas‐liquid microfluidic reactor with top‐down control of multiscale structural features, including nanoparticle morphologies, sizes, and internal crystallinities. Control of multiscale structure on disparate length scales by a single control variable (flow rate) enables tailoring of drug delivery nanoparticle function including release rates.
Moisture or water has the advantages of being green, inexpensive, and moderate. However, it is challenging to endow water‐induced shape memory property and self‐healing capability to one single polymer because of the conflicting structural requirement of the two types of materials. In this study, this problem is solved through introducing two kinds of supramolecular interactions into semi‐interpenetrating polymer networks (semi‐IPNs). The hydrogen bonds function as water‐sensitive switches, making the materials show moisture‐induced shape memory effect. The host–guest interactions (β‐cyclodextrin‐adamantane) serve as both permanent phases and self‐healing motifs, enabling further increased chain mobility at the cracks and self‐healing function. In addition, these polyvinylpyrrolidone/poly(hydroxyethyl methacrylate‐co‐butyl acrylate) semi‐IPNs also show thermosensitive triple‐shape memory effect.
Gold nanoparticles (AuNP) with pyridyl end‐capped polystyrenes (PS‐4VP) as “quasi‐monodentate” ligands self‐assemble into ordered PS‐4VP/AuNP nanostructures with 3D hexagonal spatial order in the dried solid state. The key for the formation of these ordered structures is the modulation of the ratio AuNP versus ligands, which proves the importance of ligand design and quantity for the preparation of novel ordered polymer/metal nanoparticle conjugates. Although the assemblies of PS‐4VP/AuNP in dispersion lack in high dimensional order, strong plasmonic interactions are observed due to close contact of AuNP. Applying temperature as an external stimulus allows the reversible distortion of plasmonic interactions within the AuNP nanocomposite structures, which can be observed directly by naked eye. The modulation of the macroscopic optical properties accompanied by this structural distortion of plasmonic interaction opens up very interesting sensoric applications.
A simple and versatile method is developed for preparing anisotropic polymer particles by pressing polymer microspheres at elevated temperatures. Polystyrene (PS) microspheres are used to demonstrate this approach. Depending on the mechanical deformation and wetting of the polymers on the substrates, polymer structures with special shapes such as barrel‐like or dumbbell‐like shapes can be prepared. The morphology of polymer structures can be controlled by the experimental parameters such as the pressing pressure, the pressing temperature, and the pressing time. The wetting of the polymers on the substrates dominates when the samples are annealing at higher temperatures for longer times.
In this work, syndiotactic polypropylene (sPP) as well as isotactic polypropylene (iPP) are cross‐linked to gain a shape memory effect. Both prepared PP networks exhibit maximum strains of 700%, stored strains of up to 680%, and recoveries of nearly 100%. While x‐iPP is stable for many cycles, x‐sPP ruptures after the first shape‐memory cycle. It is shown by wide‐angle X‐ray scattering (WAXS) experiments that cross‐linked iPP exhibits homoepitaxy in the temporary, stretched shape but in contrast to previous reports it contains a higher amount of daughter than mother crystals.
A novel method for producing monodisperse micro‐ and nanosized shape memory particles from various shape memory polymers (SMPs) is reported. This method uses a polydimethylsiloxane mold to uniformly deform particles from complex shapes to other well‐defined shapes, harvest them without aggressive solvents or heat, and then return them to their original shapes upon heating above a preselected trigger temperature. By manipulating the material properties of both the mold and SMP, monodisperse asymmetric particles are easily achieved. This method is demonstrated with traditional SMPs and polymers with varying degrees of reactive functionality, crystallinity, and transition temperature. This additional reactivity and the robustness of this system allow easy tailoring of the surface with click chemistry to achieve chemical asymmetry.
Anisotropic polymer particles such as Janus particles have attracted significant attention in recent years because of their unique properties and unusual self‐assembly behavior. Most anisotropic polymer particles synthesized so far, however, only have different chemical regions compartmentalized on the particles. It remains a great challenge to fabricate anisotropic polymer particles with different shapes within a single particle. A novel approach is developed to prepare anisotropic polymer particles that contain two hemispheres with different curvatures by annealing polystyrene microspheres on poly(vinyl alcohol) films. During the annealing process, the polymer microspheres gradually sink into the polymer films and transform to asymmetric polymer particles, driven by the surface and interfacial tensions of the polymers. Selective removal techniques are also used to confirm the morphologies of the asymmetric particles.
Inspired by the multifunctionality of vitamin D‐binding protein and the multiple transient‐binding behavior of some intrinsically disordered proteins (IDPs), a polymeric platform is designed, prepared, and characterized for combined delivery of dermal protective and anticancer bioactive cargos on the basis of artificial single‐chain nano‐objects mimicking IDPs. For the first time ever, simultaneous delivery of folic acid or vitamin B9, and hinokitiol, a relevant natural bioactive compound that exhibits anticancer activity against human malignant melanoma cells, from these multidirectionally self‐assembled unimolecular nanocarriers is illustrated.
By anchoring alkynylplatinum(II) terpyridine molecular tweezer/pyrene recognition motif on the chain‐ends of telechelic polycaprolactone, high‐molecular‐weight supramolecular polymers have been successfully constructed via noncovalent chain extension, which demonstrate fascinating rheological and thermal properties. Moreover, the resulting assemblies exhibit interesting temperature‐ and solvent‐responsive behaviors, which are promising for the development of adaptive functional materials.
The functionalization of zinc oxide (ZnO) nanoparticles by poly(3‐hexylthiophene) (P3HT) brush is completed by the combination of a mussel inspired biomimetic anchoring group and Huisgen cyclo‐addition “click chemistry.” Herein, the direct coupling of an azide modified catechol derivative with an alkyne end‐functionalized P3HT is described. This macromolecular binding agent is used to access core@corona ZnO@P3HT with a stable and homogeneous conjugated organic corona. Preliminary photoluminescence measurement proves an efficient electron transfer from the donor P3HT to the acceptor ZnO nanoparticles upon grafting, thus demonstrating the potential of such a combination in organic electronics.
A simple process is developed to fabricate metallo‐supramolecular nanogels (MSNs) by the metallo‐supramolecular‐coordinated interaction between histidine and iron‐meso‐tetraphenylporphin. MSNs are composed of histidine‐modified dextran (DH) and iron‐meso‐tetraphenylporphin (Fe–Por) and exhibit excellent biocompatibility and stability. MSNs show pH responsiveness in the intracellular mildly acidic environment, which has great potential for acid‐triggered drug release delivery. In vitro drug release profiles demonstrate that the pH‐dependent disassembly of MSNs to histidine and Por results in a quicker release rate of loaded‐DOX at pH 5.3, while at pH 7.4 MSNs could hinder the release of loaded‐DOX due to the enhanced stability of MSNs.
Hierarchical self‐assembly of transient composite hydrogels is demonstrated through a two‐step, orthogonal strategy using nanoparticle tectons interconnected through metal–ligand coordination complexes. The resulting materials are highly tunable with moduli and viscosities spanning many orders of magnitude, and show promising self‐healing properties, while maintaining complete optical transparency.
Here, a novel method is demonstrated for the preparation of three‐arm branched microporous organic nanotube networks (TAB‐MONNs) based on molecular templating of three‐arm branched core–shell bottlebrush copolymers and Friedel–Crafts alkylation reaction. The unique three‐arm branched bottlebrush copolymers are synthesized by a combination of atom transfer radical polymerization, reversible addition‐fragmentation chain transfer polymerization, and ring‐opening polymerization techniques. In this approach, the length and diameter of branched tube units can be well‐controlled by rational molecular design. Moreover, the as‐prepared TAB‐MONNs possess a high surface area and exhibit a superior adsorption capacity for Rhodamine 6G (R6G) and p‐cresol.
