In‐Gel Direct Laser Writing for 3D‐Designed Hydrogel Composites That Undergo Complex Self‐Shaping

Abstract Self‐shaping and actuating materials inspired by biological system have enormous potential for biosensor, microrobotics, and optics. However, the control of 3D‐complex microactuation is still challenging due to the difficulty in design of nonuniform internal stress of micro/nanostructures. Here, we develop in‐gel direct laser writing (in‐gel DLW) procedure offering a high resolution inscription whereby the two materials, resin and hydrogel, are interpenetrated on a scale smaller than the wavelength of the light. The 3D position and mechanical properties of the inscribed structures could be tailored to a resolution better than 100 nm over a wide density range. These provide an unparalleled means of inscribing a freely suspended microstructures of a second material like a skeleton into the hydrogel body and also to direct isotropic volume changes to bending and distortion motions. In the combination with a thermosensitive hydrogel rather small temperature variations could actuate large amplitude motions. This generates complex modes of motion through the rational engineering of the stresses present in the multicomponent material. More sophisticated folding design would realize a multiple, programmable actuation of soft materials. This method inspired by biological system may offer the possibility for functional soft materials capable of biomimetic actuation and photonic crystal application.

[1]  S. Minko,et al.  Multiresponsive, Hierarchically Structured Membranes: New, Challenging, Biomimetic Materials for Biosensors, Controlled Release, Biochemical Gates, and Nanoreactors , 2009 .

[2]  Satoru Shoji,et al.  Size dependent nanomechanics of coil spring shaped polymer nanowires , 2015, Scientific Reports.

[3]  J. Greener,et al.  Three-dimensional shape transformations of hydrogel sheets induced by small-scale modulation of internal stresses , 2013, Nature Communications.

[4]  Jason B. Shear,et al.  High‐Resolution Patterning of Hydrogels in Three Dimensions using Direct‐Write Photofabrication for Cell Guidance , 2009 .

[5]  L. Mahadevan,et al.  Hygromorphs: from pine cones to biomimetic bilayers , 2009, Journal of The Royal Society Interface.

[6]  Costas Fotakis,et al.  Shrinkage of microstructures produced by two-photon polymerization of Zr-based hybrid photosensitive materials. , 2009, Optics express.

[7]  Kristi S Anseth,et al.  Controlled two-photon photodegradation of PEG hydrogels to study and manipulate subcellular interactions on soft materials. , 2010, Soft matter.

[8]  Peter Fratzl,et al.  Origami-like unfolding of hydro-actuated ice plant seed capsules. , 2011, Nature communications.

[9]  Martin Wegener,et al.  Direct laser writing of three-dimensional submicron structures using a continuous-wave laser at 532 nm , 2010 .

[10]  Martin Wegener,et al.  Direct Laser Writing of Three‐ Dimensional Photonic Crystals with a Complete Photonic Bandgap in Chalcogenide Glasses , 2006 .

[11]  Frank Greer,et al.  Fabrication and deformation of three-dimensional hollow ceramic nanostructures. , 2013, Nature materials.

[12]  Yu Suk Choi,et al.  Digital Plasmonic Patterning for Localized Tuning of Hydrogel Stiffness , 2014, Advanced functional materials.

[13]  R. Gattass,et al.  Achieving λ/20 Resolution by One-Color Initiation and Deactivation of Polymerization , 2009, Science.

[14]  S. Kawata,et al.  Three-dimensional microfabrication with two-photon-absorbed photopolymerization. , 1997, Optics letters.

[15]  Hang Zhang,et al.  Soft Microrobots Employing Nonequilibrium Actuation via Plasmonic Heating , 2017, Advanced materials.

[16]  Ryo Yoshida,et al.  Self‐Oscillating Gels Driven by the Belousov–Zhabotinsky Reaction as Novel Smart Materials , 2010, Advanced materials.

[17]  Ximin He,et al.  Synthetic homeostatic materials with chemo-mechano-chemical self-regulation , 2012, Nature.

[18]  Martin Wegener,et al.  Tailored 3D Mechanical Metamaterials Made by Dip‐in Direct‐Laser‐Writing Optical Lithography , 2012, Advanced materials.

[19]  Xing Yi Ling,et al.  Shape-shifting 3D protein microstructures with programmable directionality via quantitative nanoscale stiffness modulation. , 2015, Small.

[20]  Joanna Aizenberg,et al.  Direct writing and actuation of three-dimensionally patterned hydrogel pads on micropillar supports. , 2011, Angewandte Chemie.

[21]  Y. Osada,et al.  A polymer gel with electrically driven motility , 1992, Nature.

[22]  Toyoichi Tanaka,et al.  Volume phase transition in a nonionic gel , 1984 .

[23]  M. Jamal,et al.  Differentially photo-crosslinked polymers enable self-assembling microfluidics. , 2011, Nature communications.

[24]  Salvador Pané,et al.  Soft micromachines with programmable motility and morphology , 2016, Nature Communications.

[25]  Leonid Ionov,et al.  Biomimetic 3D self-assembling biomicroconstructs by spontaneous deformation of thin polymer films , 2012 .

[26]  Hang Zhang,et al.  Dynamic Switching of Helical Microgel Ribbons , 2017, Nano letters.

[27]  Zhongze Gu,et al.  Bio-inspired variable structural color materials. , 2012, Chemical Society reviews.

[28]  Joseph M DeSimone,et al.  Direct fabrication and harvesting of monodisperse, shape-specific nanobiomaterials. , 2005, Journal of the American Chemical Society.

[29]  Nobufumi Atoda,et al.  Mechanism of Resist Pattern Collapse during Development Process , 1993 .

[30]  A. Studart,et al.  Multimaterial magnetically assisted 3D printing of composite materials , 2015, Nature Communications.

[31]  E. Sharon,et al.  Shaping of Elastic Sheets by Prescription of Non-Euclidean Metrics , 2007, Science.

[32]  L. Mahadevan,et al.  Physical Limits and Design Principles for Plant and Fungal Movements , 2005, Science.

[33]  R. Hayward,et al.  Designing Responsive Buckled Surfaces by Halftone Gel Lithography , 2012, Science.

[34]  T. Kurokawa,et al.  Control superstructure of rigid polyelectrolytes in oppositely charged hydrogels via programmed internal stress , 2014, Nature Communications.

[35]  Stephen Z. D. Cheng,et al.  Three-dimensional actuators transformed from the programmed two-dimensional structures via bending, twisting and folding mechanisms , 2011 .

[36]  E. Smela,et al.  Controlled Folding of Micrometer-Size Structures , 1995, Science.