Self-assembly of block copolymers confined in cylindrical nanopores is studied systematically using a simulated annealing technique. For diblock copolymers which form two-dimensional hexagonally packed cylinders with period L0 in the bulk, novel structures such as helices and stacked toroids spontaneously form inside the cylindrical pores. These confinement-induced morphologies have no counterpart in the bulk system and they depend on the pore diameter (D) and the surface-polymer interactions, reflecting the importance of structural frustration and interfacial interactions. On tightening the degree of confinement, transitions from helices to toroids to spheres are observed. Mechanisms of the morphological transitions can be understood based on the degree of structural frustration parametrized by the ratio D/L0.
Self-assembly of AB diblock copolymers confined in cylindrical nanopores is studied using a simulated annealing technique. The pore diameter and surface preference are systematically varied to examine their effects on the self-assembled morphologies and the chain conformations. For bulk lamella-forming and cylinder-forming diblock copolymers, novel structures such as helices and concentric (perforated) lamellae spontaneously form when the copolymers are confined in cylindrical pores. The observed equilibrium morphologies are compared with that obtained from experiments, theory, and other simulations. A simple model is proposed for symmetric diblock copolymers, which gives a reasonable description of the layer thickness for the concentric lamellae. It is found that chains near the pore surfaces are compressed relative to the bulk chains, which can be attributed to the existence of the surfaces. The dependence of the chain conformation on the degree of confinement and strength of the surface preference are reasonably explained. The energetics is discussed qualitatively and used to account for the appearance of the complex phase behavior observed for certain intermediate conditions.
The exciting applications of molecular motion are still limited and are in urgent pursuit, although some fascinating concepts such as molecular motors and molecular machines have been proposed for years. Utilizing molecular motion in a nanoplatform for practical application has been scarcely explored due to some unconquered challenges such as how to achieve effective molecular motion in the aggregate state within nanoparticles. Here, we introduce a class of near infrared-absorbing organic molecules with intramolecular motion-induced photothermy inside nanoparticles, which enables most absorbed light energy to dissipate as heat. Such a property makes the nanoparticles a superior photoacoustic imaging agent compared to widely used methylene blue and semiconducting polymer nanoparticles and allow them for high-contrast photoacoustic imaging of tumours in live mice. This study not only provides a strategy for developing advanced photothermal/photoacoustic imaging nanoagents, but also enables molecular motion in a nanoplatform to find a way for practical application.
Bio-inspired molecular design and synthesis of high-performance and recyclable cross-linked polymers is reported. Reversible cross-links between hard segments are incorporated into linear segmented polyurethane via Diels-Alder reaction between maleimide pendant group and furan cross-linker. The materials form hierarchical structure and exhibit excellent properties with high stiffness, strength and toughness, and can be easily thermally reshaped and re-mended.
Spider silks show unique combinations of strength, toughness, extensibility, and energy absorption. To date, it has been difficult to obtain spider silk-like mechanical properties using non-protein approaches. Here, we report on an artificial spider silk produced by the water-evaporation-induced self-assembly of hydrogel fibre made from polyacrylic acid and silica nanoparticles. The artificial spider silk consists of hierarchical core-sheath structured hydrogel fibres, which are reinforced by ion doping and twist insertion. The fibre exhibits a tensile strength of 895 MPa and a stretchability of 44.3%, achieving mechanical properties comparable to spider silk. The material also presents a high toughness of 370 MJ m−3 and a damping capacity of 95%. The hydrogel fibre shows only ~1/9 of the impact force of cotton yarn with negligible rebound when used for impact reduction applications. This work opens an avenue towards the fabrication of artificial spider silk with applications in kinetic energy buffering and shock-absorbing.
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