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.

In this paper, an asymmetric plasmonic structure composed of a MIM (metal-insulator-metal) waveguide and a rectangular cavity is reported, which can support double Fano resonances originating from two different mechanisms. One of Fano resonance originates from the interference between a horizontal and a vertical resonance in the rectangular cavity. And the other is induced by the asymmetry of the plasmonic structure. Just because the double Fano resonances originate from two different mechanisms, each Fano resonance can be well tuned independently by changing the parameters of the rectangular cavity. And during the tuning process, the FOMs (figure of merit) of both the Fano resonances can keep unchanged almost with large values, both larger than 650. Such, the transmission spectra of the plasmonic structure can be well modulated to form transmission window with the position and the full width at half maximum (FWHM) can be tuned freely, which is useful for the applications in sensors, nonlinear and slow-light devices.

Thermoresponsive hydrogel-based actuators are highly important for fundamental research and industrial applications, while the preparation of temperature-driven bilayer hydrogel actuators with rapid response to bend and recover properties remains a challenge. To date, most temperature-driven bilayer hydrogel actuators are based on polymers only with a lower critical solution temperature (LCST) or with an upper critical solution temperature (UCST), which need more time to bend and recover just in a small range of bending angle. Herein, we propose a new strategy to design and synthesize a fully temperature-driven bilayer hydrogel actuator, which consists of a poly­(N-acryloyl glycinamide) (NAGA) layer with a UCST-type volume phase change and a poly­(N-isopropyl acrylamide) (NIPAM)-Laponite nanocomposite layer with an LCST-type volume phase change. Due to the complementary UCST and LCST behavior of the two selected polymers, both layers have opposite thermoresponsive swelling and shrinkage properties at low and high temperatures; this imbues the hydrogel actuator with rapid thermoresponsive bending and recovery ability, as well as a large bending angle. In addition, the incorporation of Laponite nanosheets in PNIPAM layer not only improves the mechanical property of actuators but also provides the excellent bonding ability of the two-layer interface, which prevents delamination caused by excessive local stress on the interface during the bending process. Thanks to high-performance behavior, the actuator can act as an effective and sensitive actuator, such as a gripper to capture, transport, and release an object, or as an electrical circuit switch to turn on and off a light-emitting diode (LED). Overall, such hydrogel actuator may provide new insights for the design and fabrication of artificial intelligence materials.

Polymeric materials combining good mechanical performances with self-healing ability and malleability have attracted dramatic attention, but it presently remains a challenge for the facile fabrication of such high-performance materials, not to mention the atomic-level characterization for understanding the molecular origin of the macroscopic properties. Herein, we proposed a facile strategy to fabricate a dual-cross-linked poly­(n-butyl acrylate) polymer material, in which the self-complementary quadruple hydrogen bonding interactions between 2-ureido-4­[1H]-pyrimidinone (UPy) dimers were utilized as the dynamic sacrificial cross-linkages, and thus to enhance the mechanical strength and toughness. The hydrogen bonding interactions between UPy dimers in such synthetic cross-linked polymer material were revealed in detail by selective saturation double-quantum (DQ) solid-state NMR spectroscopy under ultrafast magic-angle-spinning beyond 60 kHz. In the meantime, the self-healing capability and recyclability were achieved by utilizing dynamic fast boronic ester transesterification at an elevated temperature. A novel symmetrical diboronic ester cross-linker was developed and employed to enhance the probability of bornoic ester transesterification at an elevated temperature. The boronic ester transesterification was verified on a small molecular model and polymer materials by solution 1H NMR spectroscopy and swelling experiments, respectively, and the cross-linking structure of polymer materials was addressed by low-field proton multiple-quantum NMR spectroscopy and T 2 relaxometry. Overall, it is well demonstrated that a combination of diboronic ester bonds and UPy dimers as the chemical and physical cross-linkage, respectively, can impart the rubbery materials with enhanced mechanical stiffness and toughness, good healing and recycling efficiency, and elucidation of the structure–property relationship here can further provide piercing insights into the development of high-performance polymeric materials.

Vitrimers are fascinating thermoset polymers to the industry since they can be recycled and reprocessed without compromising their mechanical strength and solvent resistance. Particularly, transesterification reaction in the epoxy resin (ER) vitrimers usually requires the incorporation of a catalyst, whereas most reports only focused on investigating the catalytic effect of small molecules, such as zinc acetate (Zn­(OAc)2) and triazabicyclodecene (TBD). In this work, a polymer catalyst, poly­(acrylonitrile-co-zinc methacrylate) (Zn-PAM), was synthesized by the random copolymerization of zinc methacrylate and acrylonitrile, where the transesterification catalysis efficiency of Zn-PAM was systematically investigated and compared to that of Zn­(OAc)2 and TBD by temperature-dependent stress relaxation experiments. It was revealed that Zn-PAM has a higher catalysis efficiency than Zn­(OAc)2 and TBD under the same loading between Zn2+ and TBD. Besides, only a tiny amount of polymer catalyst is needed to efficiently catalyze the transesterification reaction while in the meantime enhance the mechanical properties of ER.