Liquid Crystal Elastomer Metamaterials with Giant Biaxial Thermal Shrinkage for Enhancing Skin Regeneration

Liquid crystal elastomers (LCEs) are a class of soft active materials of increasing interest, because of their excellent actuation and optical performances. While LCEs show biomimetic mechanical properties (e.g., elastic modulus and strength) that can be matched with those of soft biological tissues, their biointegrated applications have been rarely explored, in part, due to their high actuation temperatures (typically above 60 °C) and low biaxial actuation performances (e.g., actuation strain typically below 10%). Here, unique mechanics‐guided designs and fabrication schemes of LCE metamaterials are developed that allow access to unprecedented biaxial actuation strain (−53%) and biaxial coefficient of thermal expansion (−33 125 ppm K−1), significantly surpassing those (e.g., −20% and −5950 ppm K−1) reported previously. A low‐temperature synthesis method with use of optimized composition ratios enables LCE metamaterials to offer reasonably high actuation stresses/strains at a substantially reduced actuation temperature (46 °C). Such biocompatible LCE metamaterials are integrated with medical dressing to develop a breathable, shrinkable, hemostatic patch as a means of noninvasive treatment. In vivo animal experiments of skin repair with both round and cross‐shaped wounds demonstrate advantages of the hemostatic patch over conventional strategies (e.g., medical dressing and suturing) in accelerating skin regeneration, while avoiding scar and keloid generation.

[1]  Zhuang Liu,et al.  Mechanically active adhesive and immune regulative dressings for wound closure , 2021 .

[2]  Z. Suo,et al.  Hydrogel–mesh composite for wound closure , 2021, Proceedings of the National Academy of Sciences.

[3]  Hong Yang,et al.  Healable and Rearrangeable Networks of Liquid Crystal Elastomers Enabled by Diselenide Bonds. , 2021, Angewandte Chemie.

[4]  A. Torbati,et al.  Body‐temperature s hape‐shifting liquid crystal elastomers , 2021 .

[5]  Steven A. Redford,et al.  Spatiotemporal control of liquid crystal structure and dynamics through activity patterning , 2021, Nature Materials.

[6]  Yonggang Huang,et al.  Designing Mechanical Metamaterials with Kirigami‐Inspired, Hierarchical Constructions for Giant Positive and Negative Thermal Expansion , 2020, Advanced materials.

[7]  Liang Feng,et al.  Repeatable and Reprogrammable Shape Morphing from Photoresponsive Gold Nanorod/Liquid Crystal Elastomers , 2020, Advanced materials.

[8]  Cedric P. Ambulo,et al.  Processing advances in liquid crystal elastomers provide a path to biomedical applications. , 2020, Journal of applied physics.

[9]  Z. Suo,et al.  Functional hydrogel coatings , 2020, National science review.

[10]  S. Cai,et al.  Three-dimensional printing of functionally graded liquid crystal elastomer , 2020, Science Advances.

[11]  Huajian Gao,et al.  Lipid coating and end functionalization govern the formation and stability of transmembrane carbon nanotube porins , 2020 .

[12]  S. Hollister,et al.  Designing Biodegradable Shape Memory Polymers for Tissue Repair , 2020, Advanced Functional Materials.

[13]  J. Hernandez-Ortiz,et al.  Prolate and oblate chiral liquid crystal spheroids. , 2020, Science Advances.

[14]  Xuanhe Zhao,et al.  Instant tough bioadhesive with triggerable benign detachment , 2020, Proceedings of the National Academy of Sciences.

[15]  S. Van Vlierberghe,et al.  Shape‐Memory Polymers for Biomedical Applications , 2020, Advanced Functional Materials.

[16]  M. Kaltenbrunner,et al.  Resilient yet entirely degradable gelatin-based biogels for soft robots and electronics , 2020, Nature Materials.

[17]  Qi Ge,et al.  Liquid‐Crystal‐Elastomer‐Based Dissipative Structures by Digital Light Processing 3D Printing , 2020, Advanced materials.

[18]  B. Audoly,et al.  A nonlinear beam model of photomotile structures , 2020, Proceedings of the National Academy of Sciences.

[19]  Yihui Zhang,et al.  Soft three-dimensional network materials with rational bio-mimetic designs , 2020, Nature Communications.

[20]  Min Ah Kim,et al.  Evaluation of anisotropic properties of striae distensae with regard to skin surface texture and viscoelasticity , 2020, Skin research and technology : official journal of International Society for Bioengineering and the Skin (ISBS) [and] International Society for Digital Imaging of Skin (ISDIS) [and] International Society for Skin Imaging.

[21]  Ravi R. Patel,et al.  Dynamically Crystalizing Liquid‐Crystal Elastomers for an Expandable Endplate‐Conforming Interbody Fusion Cage , 2019, Advanced healthcare materials.

[22]  Z. Suo,et al.  Fundamental limits to the electrochemical impedance stability of dielectric elastomers in bioelectronics. , 2019, Nano letters.

[23]  Yonggang Huang,et al.  Remotely Triggered Assembly of 3D Mesostructures Through Shape‐Memory Effects , 2019, Advanced materials.

[24]  J. Y. Sim,et al.  Mechanically transformative electronics, sensors, and implantable devices , 2019, Science Advances.

[25]  Xuanhe Zhao,et al.  Dry double-sided tape for adhesion of wet tissues and devices , 2019, Nature.

[26]  Yonggang Huang,et al.  2D Mechanical Metamaterials with Widely Tunable Unusual Modes of Thermal Expansion , 2019, Advanced materials.

[27]  Yang Wang,et al.  Electrically controlled liquid crystal elastomer–based soft tubular actuator with multimodal actuation , 2019, Science Advances.

[28]  Z. Suo,et al.  Hydrogel Paint , 2019, Advanced materials.

[29]  D. Mooney,et al.  Bioinspired mechanically active adhesive dressings to accelerate wound closure , 2019, Science Advances.

[30]  Zhigang Suo,et al.  Design molecular topology for wet-dry adhesion. , 2019, ACS applied materials & interfaces.

[31]  E. Terentjev,et al.  Enhanced Dynamic Adhesion in Nematic Liquid Crystal Elastomers , 2019, Advanced materials.

[32]  H. Qi,et al.  Long Liquid Crystal Elastomer Fibers with Large Reversible Actuation Strains for Smart Textiles and Artificial Muscles. , 2019, ACS applied materials & interfaces.

[33]  Huajian Gao,et al.  A viscoelastic adhesive epicardial patch for treating myocardial infarction , 2019, Nature Biomedical Engineering.

[34]  C. Chuong,et al.  The tension biology of wound healing , 2019, Experimental dermatology.

[35]  Kai Qu,et al.  Pure PEDOT:PSS hydrogels , 2019, Nature Communications.

[36]  Huajian Gao,et al.  Temperature- and rigidity-mediated rapid transport of lipid nanovesicles in hydrogels , 2019, Proceedings of the National Academy of Sciences.

[37]  Baolin Guo,et al.  Adhesive Hemostatic Conducting Injectable Composite Hydrogels with Sustained Drug Release and Photothermal Antibacterial Activity to Promote Full-Thickness Skin Regeneration During Wound Healing. , 2019, Small.

[38]  Yonggang Huang,et al.  Three-dimensional piezoelectric polymer microsystems for vibrational energy harvesting, robotic interfaces and biomedical implants , 2019, Nature Electronics.

[39]  S. Cai,et al.  A Light‐Powered Ultralight Tensegrity Robot with High Deformability and Load Capacity , 2018, Advanced materials.

[40]  J. Aizenberg,et al.  Multiresponsive polymeric microstructures with encoded predetermined and self-regulated deformability , 2018, Proceedings of the National Academy of Sciences.

[41]  X. Pei,et al.  Double-layer sandwich annulus with ultra-low thermal expansion , 2018, Composite Structures.

[42]  Huajian Gao,et al.  Rapid transport of deformation-tuned nanoparticles across biological hydrogels and cellular barriers , 2018, Nature Communications.

[43]  J. Lewis,et al.  3D Printing of Liquid Crystal Elastomeric Actuators with Spatially Programed Nematic Order , 2018, Advanced materials.

[44]  Albert P H J Schenning,et al.  Liquid crystal elastomer coatings with programmed response of surface profile , 2018, Nature Communications.

[45]  Akihiro Takezawa,et al.  Design methodology for porous composites with tunable thermal expansion produced by multi-material topology optimization and additive manufacturing , 2017 .

[46]  Shu Yang,et al.  Universal inverse design of surfaces with thin nematic elastomer sheets , 2017, Proceedings of the National Academy of Sciences.

[47]  Ali Khademhosseini,et al.  Advances in engineering hydrogels , 2017, Science.

[48]  Baolin Guo,et al.  Antibacterial anti-oxidant electroactive injectable hydrogel as self-healing wound dressing with hemostasis and adhesiveness for cutaneous wound healing. , 2017, Biomaterials.

[49]  Yonggang Huang,et al.  Printing, folding and assembly methods for forming 3D mesostructures in advanced materials , 2017 .

[50]  John A. Rogers,et al.  Recent progress in flexible and stretchable piezoelectric devices for mechanical energy harvesting, sensing and actuation , 2016 .

[51]  Yanlei Yu,et al.  Photocontrol of fluid slugs in liquid crystal polymer microactuators , 2016, Nature.

[52]  D. Wiersma,et al.  Structured light enables biomimetic swimming and versatile locomotion of photoresponsive soft microrobots. , 2016, Nature materials.

[53]  A. Javey,et al.  Printed Carbon Nanotube Electronics and Sensor Systems , 2016, Advanced materials.

[54]  Huanyu Cheng,et al.  A nonlinear mechanics model of bio-inspired hierarchical lattice materials consisting of horseshoe microstructures. , 2016, Journal of the mechanics and physics of solids.

[55]  F. B. Madsen,et al.  The Current State of Silicone-Based Dielectric Elastomer Transducers. , 2016, Macromolecular rapid communications.

[56]  Taylor H. Ware,et al.  Localized soft elasticity in liquid crystal elastomers , 2016, Nature Communications.

[57]  T. White,et al.  Programmable and adaptive mechanics with liquid crystal polymer networks and elastomers. , 2015, Nature materials.

[58]  Bo Li,et al.  Isotropic Negative Thermal Expansion Metamaterials. , 2015, ACS applied materials & interfaces.

[59]  Mitsuru Kitamura,et al.  Porous composite with negative thermal expansion obtained by photopolymer additive manufacturing , 2015, 1504.07724.

[60]  T. White,et al.  Voxelated liquid crystal elastomers , 2015, Science.

[61]  Paul Martin,et al.  Wound repair and regeneration: Mechanisms, signaling, and translation , 2014, Science Translational Medicine.

[62]  Eleftherios E. Gdoutos,et al.  Thin Films with Ultra‐low Thermal Expansion , 2014, Advanced materials.

[63]  Martin Leary,et al.  A review of shape memory alloy research, applications and opportunities , 2014 .

[64]  Yong Zhu,et al.  Recent advances in shape–memory polymers: Structure, mechanism, functionality, modeling and applications , 2012 .

[65]  Carter S. Haines,et al.  Electrically, Chemically, and Photonically Powered Torsional and Tensile Actuation of Hybrid Carbon Nanotube Yarn Muscles , 2012, Science.

[66]  C. Ohm,et al.  Liquid Crystalline Elastomers as Actuators and Sensors , 2010, Advanced materials.

[67]  H. Finkelmann,et al.  Main-Chain Liquid Crystalline Elastomers : Monomer and Cross-Linker Molecular Control of the Thermotropic and Elastic Properties , 2008 .

[68]  P. Keller,et al.  An Artificial Muscle with Lamellar Structure Based on a Nematic Triblock Copolymer , 2004 .

[69]  M. Shelley,et al.  Fast liquid-crystal elastomer swims into the dark , 2004, Nature materials.

[70]  F Patat,et al.  Sex‐ and site‐dependent variations in the thickness and mechanical properties of human skin in vivo , 2000, International journal of cosmetic science.

[71]  H. Finkelmann,et al.  Investigations on liquid crystalline polysiloxanes 3. Liquid crystalline elastomers — a new type of liquid crystalline material , 1981 .

[72]  Jianxing Liu,et al.  Mechanics of unusual soft network materials with rotatable structural nodes , 2021 .

[73]  R. Langer,et al.  Flexible piezoelectric devices for gastrointestinal motility sensing , 2017, Nature Biomedical Engineering.

[74]  Yen Wei,et al.  Mouldable liquid-crystalline elastomer actuators with exchangeable covalent bonds. , 2014, Nature materials.

[75]  H. Finkelmann,et al.  Nematic main-chain elastomers: Coupling and orientational behavior , 2009 .