There is a growing interest in the concept of four-dimensional (4D) printing that combines a three-dimensional (3D) manufacturing process with dynamic modulation for bioinspired soft materials exhibiting more complex functionality. However, conventional approaches have drawbacks of low resolution, control of internal micro/nanostructure, and creation of fast, complex actuation due to a lack of high-resolution fabrication technology and suitable photoresist for soft materials. Here, we report an approach of 4D printing that develops a bioinspired soft actuator with a defined 3D geometry and programmed printing density. Multiphoton lithography (MPL) allows for controlling printing density in gels at pixel-by-pixel with a resolution of a few hundreds of nanometers, which tune swelling behaviors of gels in response to external stimuli. We printed a 3D soft actuator composed of thermoresponsive poly(N-isopropylacrylamide) (PNIPAm) and gold nanorods (AuNRs). To improve the resolution of printing, we synthesized a functional, thermoresponsive macrocrosslinker. Through plasmonic heating by AuNRs, nanocomposite-based soft actuators undergo nonequilibrium, programmed, and fast actuation. Light-mediated manufacture and manipulation (MPL and photothermal effect) offer the feasibility of 4D printing toward adaptive bioinspired soft materials.
Cells feel the forces exerted on them by the surrounding extracellular matrix (ECM) environment and respond to them. While many cell fate processes are dictated by these forces, which are highly synchronized in space and time, abnormal force transduction is implicated in the progression of many diseases (muscular dystrophy, cancer). However, material platforms that enable transient, cyclic forces in vitro to recreate an in vivo-like scenario remain a challenge. Here, we report a hydrogel system that rapidly beats (actuates) with spatio-temporal control using a near infra-red light trigger. Small, user-defined mechanical forces (~nN) are exerted on cells growing on the hydrogel surface at frequencies up to 10 Hz, revealing insights into the effect of actuation on cell migration and the kinetics of reversible nuclear translocation of the mechanosensor protein myocardin related transcription factor A, depending on the actuation amplitude, duration and frequency.
Under vigorous stirring, 875 µL of (II) was added to (I) and left at high stirring speed for 5 min. The authors would like to apologize for any inconvenience this mistake may have caused.
The self‐diffusion of various nano‐objects investigated by high‐resolution nuclear magnetic resonance diffusometry proves to be an efficient method for the characterization of dynamics, aggregation kinetic, and matrix morphology. This study investigates how the two‐state model and Boltzmann function approach can be used for the evaluation of the thermodynamic parameters of temperature‐induced phase transition encoded in polymer diffusivity. The characteristics of the phase transition given by the transition temperature, change of entropy, and width of transition are obtained for poly(N‐isopropylacrylamide) (PNIPAm) linear polymers with hydrophilic and hydrophobic end‐group functionalization. The effect of end groups upon the polymer diffusivity is investigated as a function of molecular weight (M
n), from which fractal dimensions and hydrodynamic drag coefficients are obtained. The PNIPAm diffusivity is affected strongly by the end groups, and it is reflected in the hydrodynamic radius dependence upon molecular weight that obeys different power‐law relations. In this study, the synthesis of α‐ω‐heterotelechelic PNIPAm of different molecular weights with a thiol end group and a hydrophilic NIPAm‐like as well as a hydrophobic benzyl end group are described by reversible addition–fragmentation chain‐transfer polymerization.
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