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Title: Effect of variations in manufacturing and material properties on the self-folding behaviors of hydrogel and elastomer bilayer structures
The stimuli-responsive self-folding structure is ubiquitous in nature, for instance, the mimosa folds its leaves in response to external touch or heat, and the Venus flytrap snaps shut to trap the insect inside. Thus, modeling self-folding structures has been of great interest to predict the final configuration and understand the folding mechanism. Here, we apply a simple yet effective method to predict the folding angle of the temperature-responsive nanocomposite hydrogel/elastomer bilayer structure manufactured by 3D printing, which facilitates the study of the effect of the inevitable variations in manufacturing and material properties on folding angles by comparing the simulation results with the experimentally measured folding angles. The defining feature of our method is to use thermal expansion to model the temperature-responsive nanocomposite hydrogel rather than the nonlinear field theory of diffusion model that was previously applied. The resulted difference between the simulation and experimentally measured folding angle ( i.e. , error) is around 5%. We anticipate that our method could provide insight into the design, control, and prediction of 3D printing of stimuli-responsive shape morphing ( i.e. , 4D printing) that have potential applications in soft actuators, robots, and biomedical devices.  more » « less
Award ID(s):
Author(s) / Creator(s):
; ; ;
Date Published:
Journal Name:
Soft Matter
Page Range / eLocation ID:
8771 to 8778
Medium: X
Sponsoring Org:
National Science Foundation
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  1. Abstract

    Untethered stimuli‐responsive soft materials with programmed sequential self‐folding are of great interest due to their ability to achieve task‐specific shape transformation with complex final configuration. Here, reversible and sequential self‐folding soft actuators are demonstrated by utilizing a temperature‐responsive nanocomposite hydrogel with different folding speeds but the same chemical composition. By varying the UV light intensity during the photo‐crosslinking of the nanocomposite hydrogel, different types of microstructures can be realized via phase separation mechanisms, which allow to control the folding speeds. The self‐folding structures are fabricated by integrating two dissimilar materials (i.e., a nanocomposite hydrogel and an elastomer) into hinge‐based bilayer structures via extrusion‐based 3D printing. It has been demonstrated that the folding kinetics can be accelerated by more than one order of magnitude due to the phase‐separated microstructure formed by the relatively weaker UV intensity (≈10 mW cm‐2) compared to the one formed by stronger UV intensity (≈100 mW cm‐2). 3D structures with sequential self‐folding capabilities are realized by prescribing actuation speeds and folding angles to specific hinges of the nanocomposite hydrogel. Sequential folding box and self‐locking latch structures are fabricated to demonstrate the ability to capture and hold objects underwater.

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  2. Abstract

    Self‐folding is a powerful approach to fabricate materials with complex 3D forms and advanced properties using planar patterning steps, but suffers from intrinsic limitations in robustness due to the highly bifurcated nature of configuration space around the flat state. Here, a simple mechanism is introduced to achieve robust self‐folding of microscale origami by separating actuation into two discrete steps using different thermally responsive hydrogels. First, the vertices are pre‐biased to move in the desired direction from the flat state by selectively swelling one of the two hydrogels at high temperature. Subsequently, the creases are folded toward their target angles by activating swelling of the second hydrogel upon cooling to room temperature. Since each vertex can be individually programmed to move upward or downward, it is possible to robustly select the desired branch even in multi‐vertex structures with reasonably high complexity. This strategy provides key new principles for designing shaping‐morphing materials that avoid undesired distractor states, expanding their potential applications in areas such as soft robotics, sensors, mechanical metamaterials, and deployable devices.

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  3. This data set for the manuscript entitled "Design of Peptides that Fold and Self-Assemble on Graphite" includes all files needed to run and analyze the simulations described in the this manuscript in the molecular dynamics software NAMD, as well as the output of the simulations. The files are organized into directories corresponding to the figures of the main text and supporting information. They include molecular model structure files (NAMD psf or Amber prmtop format), force field parameter files (in CHARMM format), initial atomic coordinates (pdb format), NAMD configuration files, Colvars configuration files, NAMD log files, and NAMD output including restart files (in binary NAMD format) and trajectories in dcd format (downsampled to 10 ns per frame). Analysis is controlled by shell scripts (Bash-compatible) that call VMD Tcl scripts or python scripts. These scripts and their output are also included.

    Version: 2.0

    Changes versus version 1.0 are the addition of the free energy of folding, adsorption, and pairing calculations (Sim_Figure-7) and shifting of the figure numbers to accommodate this addition.

    Conventions Used in These Files

    Structure Files
    - graph_*.psf or sol_*.psf (original NAMD (XPLOR?) format psf file including atom details (type, charge, mass), as well as definitions of bonds, angles, dihedrals, and impropers for each dipeptide.)

    - graph_*.pdb or sol_*.pdb (initial coordinates before equilibration)
    - repart_*.psf (same as the above psf files, but the masses of non-water hydrogen atoms have been repartitioned by VMD script repartitionMass.tcl)
    - freeTop_*.pdb (same as the above pdb files, but the carbons of the lower graphene layer have been placed at a single z value and marked for restraints in NAMD)
    - amber_*.prmtop (combined topology and parameter files for Amber force field simulations)
    - repart_amber_*.prmtop (same as the above prmtop files, but the masses of non-water hydrogen atoms have been repartitioned by ParmEd)

    Force Field Parameters
    CHARMM format parameter files:
    - par_all36m_prot.prm (CHARMM36m FF for proteins)
    - par_all36_cgenff_no_nbfix.prm (CGenFF v4.4 for graphene) The NBFIX parameters are commented out since they are only needed for aromatic halogens and we use only the CG2R61 type for graphene.
    - toppar_water_ions_prot_cgenff.str (CHARMM water and ions with NBFIX parameters needed for protein and CGenFF included and others commented out)

    Template NAMD Configuration Files
    These contain the most commonly used simulation parameters. They are called by the other NAMD configuration files (which are in the namd/ subdirectory):
    - template_min.namd (minimization)
    - template_eq.namd (NPT equilibration with lower graphene fixed)
    - template_abf.namd (for adaptive biasing force)

    - namd/min_*.0.namd

    - namd/eq_*.0.namd

    Adaptive biasing force calculations
    - namd/eabfZRest7_graph_chp1404.0.namd
    - namd/eabfZRest7_graph_chp1404.1.namd (continuation of eabfZRest7_graph_chp1404.0.namd)

    Log Files
    For each NAMD configuration file given in the last two sections, there is a log file with the same prefix, which gives the text output of NAMD. For instance, the output of namd/eabfZRest7_graph_chp1404.0.namd is eabfZRest7_graph_chp1404.0.log.

    Simulation Output
    The simulation output files (which match the names of the NAMD configuration files) are in the output/ directory. Files with the extensions .coor, .vel, and .xsc are coordinates in NAMD binary format, velocities in NAMD binary format, and extended system information (including cell size) in text format. Files with the extension .dcd give the trajectory of the atomic coorinates over time (and also include system cell information). Due to storage limitations, large DCD files have been omitted or replaced with new DCD files having the prefix stride50_ including only every 50 frames. The time between frames in these files is 50 * 50000 steps/frame * 4 fs/step = 10 ns. The system cell trajectory is also included for the NPT runs are output/eq_*.xst.

    Files with the .sh extension can be found throughout. These usually provide the highest level control for submission of simulations and analysis. Look to these as a guide to what is happening. If there are scripts with step1_*.sh and step2_*.sh, they are intended to be run in order, with step1_*.sh first.


    The directory contents are as follows. The directories Sim_Figure-1 and Sim_Figure-8 include README.txt files that describe the files and naming conventions used throughout this data set.

    Sim_Figure-1: Simulations of N-acetylated C-amidated amino acids (Ac-X-NHMe) at the graphite–water interface.

    Sim_Figure-2: Simulations of different peptide designs (including acyclic, disulfide cyclized, and N-to-C cyclized) at the graphite–water interface.

    Sim_Figure-3: MM-GBSA calculations of different peptide sequences for a folded conformation and 5 misfolded/unfolded conformations.

    Sim_Figure-4: Simulation of four peptide molecules with the sequence cyc(GTGSGTG-GPGG-GCGTGTG-SGPG) at the graphite–water interface at 370 K.

    Sim_Figure-5: Simulation of four peptide molecules with the sequence cyc(GTGSGTG-GPGG-GCGTGTG-SGPG) at the graphite–water interface at 295 K.

    Sim_Figure-5_replica: Temperature replica exchange molecular dynamics simulations for the peptide cyc(GTGSGTG-GPGG-GCGTGTG-SGPG) with 20 replicas for temperatures from 295 to 454 K.

    Sim_Figure-6: Simulation of the peptide molecule cyc(GTGSGTG-GPGG-GCGTGTG-SGPG) in free solution (no graphite).

    Sim_Figure-7: Free energy calculations for folding, adsorption, and pairing for the peptide CHP1404 (sequence: cyc(GTGSGTG-GPGG-GCGTGTG-SGPG)). For folding, we calculate the PMF as function of RMSD by replica-exchange umbrella sampling (in the subdirectory Folding_CHP1404_Graphene/). We make the same calculation in solution, which required 3 seperate replica-exchange umbrella sampling calculations (in the subdirectory Folding_CHP1404_Solution/). Both PMF of RMSD calculations for the scrambled peptide are in Folding_scram1404/. For adsorption, calculation of the PMF for the orientational restraints and the calculation of the PMF along z (the distance between the graphene sheet and the center of mass of the peptide) are in Adsorption_CHP1404/ and Adsorption_scram1404/. The actual calculation of the free energy is done by a shell script ("") in the 1_free_energy/ subsubdirectory. Processing of the PMFs must be done first in the 0_pmf/ subsubdirectory. Finally, files for free energy calculations of pair formation for CHP1404 are found in the Pair/ subdirectory.

    Sim_Figure-8: Simulation of four peptide molecules with the sequence cyc(GTGSGTG-GPGG-GCGTGTG-SGPG) where the peptides are far above the graphene–water interface in the initial configuration.

    Sim_Figure-9: Two replicates of a simulation of nine peptide molecules with the sequence cyc(GTGSGTG-GPGG-GCGTGTG-SGPG) at the graphite–water interface at 370 K.

    Sim_Figure-9_scrambled: Two replicates of a simulation of nine peptide molecules with the control sequence cyc(GGTPTTGGGGGGSGGPSGTGGC) at the graphite–water interface at 370 K.

    Sim_Figure-10: Adaptive biasing for calculation of the free energy of the folded peptide as a function of the angle between its long axis and the zigzag directions of the underlying graphene sheet.


    This material is based upon work supported by the US National Science Foundation under grant no. DMR-1945589. A majority of the computing for this project was performed on the Beocat Research Cluster at Kansas State University, which is funded in part by NSF grants CHE-1726332, CNS-1006860, EPS-1006860, and EPS-0919443. This work used the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by National Science Foundation grant number ACI-1548562, through allocation BIO200030. 
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  4. Abstract

    Stimuli‐responsive hydrogels with programmable shapes produced by defined patterns of particles are of great interest for the fabrication of small‐scale soft actuators and robots. Patterning the particles in the hydrogels during fabrication generally requires external magnetic or electric fields, thus limiting the material choice for the particles. Acoustically driven particle manipulation, however, solely depends on the acoustic impedance difference between the particles and the surrounding fluid, making it a more versatile method to spatially control particles. Here, an approach is reported by combining direct acoustic force to align photothermal particles and photolithography to spatially immobilize these alignments within a temperature‐responsive poly(N‐isopropylacrylamide) hydrogel to trigger shape deformation under temperature change and light exposure. The spatial distribution of particles can be tuned by the power and frequency of the acoustic waves. Specifically, changing the spacing between the particle patterns and position alters the bending curvature and direction of this composite hydrogel sheet, respectively. Moreover, the orientation (i.e., relative angle) of the particle alignments with respect to the long axis of laser‐cut hydrogel strips governs the bending behaviors and the subsequent shape deformation by external stimuli. This acousto‐photolithography provides a means of spatiotemporal programming of the internal heterogeneity of composite polymeric systems.

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  5. Inspired by nature, we herein demonstrate a family of multi-responsive hydrogel-based actuators that are encoded with anisotropic swelling behavior to provide rapid and controllable motion. Fabrication of the proposed anisotropy-encoded hydrogel actuators relies on the high resolution stereolithography 3D printing of functionally graded structures made of discrete layers having different volume expansion properties. Three separate synthetic strategies based on (i) asymmetrical distribution of a layer's surface area to volume ratio via mechanical design, (ii) crosslinking density via UV photo-exposure, or (iii) chemical composition via resin vat exchange have been accordingly demonstrated for developing very smooth gradients within the printed hydrogel-based actuator. Our chemomechanical programming enables fast, reversible, repeatable and multimodal bending actuation in response to any immediate environmental change ( i.e. based on osmotic pressure, temperature and pH) from a single printed structure. 
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