Functional Soft Materials Research Articles

Electro-optically addressable and rewritable transparent liquid crystal bistable waveguide display devices

Soft functional materials are in high demand to develop novel devices with excellent dynamic performances because they respond to specific stimuli with distinct functions. Here, we have examined sodium dodecyl sulfonate (SDS) ions doped into negative cholesteric liquid crystals (CLCs), employing an optically sensitive poly(N-vinyl carbazole) (PVK) film on ITO substrates for demonstrating a bistable light waveguide display device. The coated PVK film has the potential to block direct current (DC) electric fields and transform an insulator into a conductor when exposed to suitable ultraviolet (UV) stimuli, thus achieving pattern-addressing through the utilization of dynamic scattering of liquid crystals (LCs). Hence, the sample exhibits text pattern scattering and remains transparent under patterned UV stimuli. Initially, an external stimulus DC field was applied to the CLC cell to switch the planar textures in the region shining with UV light to focal conic textures that remain prolonged even after stimulus removal. Then,we examine the novel concept of a voltage-free “remote writing display”usingtransparentbistable waveguides displays by edge-lit white LED stimuli. Such advanced transparent displays offer robust stability, manufacturability, and cost-effectiveness for various applications in different environments and industries, such as automotive, e-paper, and augmented reality devices.

Flexible and Self‐Healable Fluorescent Films with Tunable Emission via Solid‐Phase Molecular Self‐Assembly Design

AbstractFlexible luminescent materials are usually in the form of gels and films. Solid‐state films have advantages in practical applications due to their long‐term stability. However, the fabrication process by conventional methods remains laborious and unsustainable. Here, a facile and green route is reported for fabricating flexible luminescent films via an elegant solid‐phase molecular self‐assembly design. First, Eu3+/Tb3+‐based metallosupramolecular coordination polyelectrolytes (MEPEs) and tetraphenylethylene (TPE)‐based MEPEs are designed with an antenna bis‐ligands to get individual R, G, and B emission. Then, by repeatedly pressing the MEPEs‐cetyltrimethylammonium bromide (CTAB) precipitates, obtained from their mixing aqueous solutions, R, G, and B emission films are obtained at room temperature, respectively. The emission color can be simply tuned by adjusting molar ratio of Eu3+: Tb3+: TPE. Notably, humidity‐responsive white emission film is obtained when Eu3+: Tb3+: TPE = 3:1:2.5. Owing to the dynamic coordination and electrostatic interaction, which can be activated by hydrating water, these films can be facilely reprocessed and self‐healed with the aid of water at room temperature. It is hoped that this approach to fabricate flexible supramolecular luminescent films can be applied to design various advanced functional soft materials.

Bioinspired Mechanochromic Liquid Crystal Materials: From Fundamentals to Functionalities and Applications.

Inspired by intriguing color changeable ability of natural animals, the design and fabrication of artificial mechanochromic materials capable of changing colors upon stretching or pressing have attracted intense scientific interest. Liquid crystal (LC) is a self-organized soft matter with anisotropic molecular alignment. Due to the sensitivity to various external stimulations, LC has been considered as an emerging and appealing responsive building block to construct intelligent materials and advanced devices. Recently, mechanochromic LC materials have becoming a hot topic in multifields from flexible artificial skins to visualized sensors and smart biomimetic devices. In this review, the recent progress of mechanochromic LCs is comprehensively summarized. Firstly, the mechanism and functionalities of mechanochromic LC is introduced, followed by preparation of various functional materials based on mechanochromic LCs. Then the applications of mechanochromic LCs are provided. Finally, the conclusion and outlooks of this field is given. This overview is hoped to provide inspiration in fabrication of advanced functional soft materials for scientists and engineers from multidisciplines including materials science, elastomers, chemistry, and physical science.

Amino Acid-Derived Supramolecular Assembly and Soft Materials.

Amino acids (AAs), serving as the primary monomer of peptides and proteins, are widely present in nature. Benefiting from their inherent advantages, such as chemical diversity, low cost, ease of modification, chirality, biosafety, and bio-absorbability, AAs have been extensively exploited to create self-assembled nanostructures and supramolecular soft materials. In this review article, we systematically describe the recent progress regarding amino acid-derived assembly and functional soft materials. A brief background and several classified assemblies of AAs and their derivatives (chemically modified AAs) are summarized. The key non-covalent interactions to drive the assembly of AAs are emphasized based on the reported systems of self-assembled and co-assembled AAs. We discuss the molecular design of AAs and the general rules behind the hierarchical nanostructures. The resulting soft materials with interesting properties and potential applications are demonstrated. The conclusion and remarks on AA-based supramolecular assemblies are also presented from the viewpoint of chemistry, materials, and bio-applications.

Dual design strategy for carboxymethyl cellulose-polyaniline composite hydrogels as super-sensitive amphibious sensors

Conductive hydrogels as ideal candidate materials for flexible sensors have exhibited many promising applications. However, complex application environments, such as low temperatures or underwater conditions, have introduced new requirements for hydrogel sensors. Herein, a high-performance conductive hydrogel based on carboxymethyl cellulose-polyaniline (CMC-PANI) submicron spheres, poly (vinyl alcohol) (PVA) and phytic acid (PA) was designed and fabricated via a dual design strategy. CMC-PANI particles were introduced to not only empower the good electromechanical performance to the hydrogels, but also enhance the mechanical properties. The obtained hydrogel exhibited good mechanical property, anti-freezing, anti-swellable behavior and recyclable performance. Resistive-type strain sensors assembled by the prepared hydrogels exhibited high pressure sensitivity (34.17×10−2 kPa−1) and fast response time (100 ms), which can clearly detect the pulse beats. Moreover, the hydrogel sensors can achieve long-term stability, high sensitivity and fatigue resistance as an underwater sensor. Based on these favorable performances, the conductive polymer hydrogels may open up an enticing avenue for functional soft materials in health diagnostic and electronic components.

Nonequilibrium relaxation of soft responsive colloids.

Stimuli-responsive macromolecules display large conformational changes during their dynamics, sometimes switching between states. Such a multi-stability is useful for the development of soft functional materials. Here, we introduce a mean-field dynamical density functional theory for a model of responsive colloids to study the nonequilibrium dynamics of a colloidal dispersion in time-dependent external fields, with a focus on the coupling of translational and conformational dynamics during their relaxation. Specifically, we consider soft Gaussian particles with a bimodal size distribution between two confining walls with time-dependent (switching-on and off) external gravitational and osmotic fields. We find a rich relaxation behavior of the systems in excellent agreement with particle-based Brownian dynamics computer simulations. In particular, we find time-asymmetric relaxations of integrated observables (wall pressures, mean size, and liquid center-of-mass) for activation/deactivation of external potentials, respectively, which are tunable by the ratio of translational and conformational diffusion time scales. Our work thus paves the way for studying the nonequilibrium relaxation dynamics of complex soft matter with multiple degrees of freedom and hierarchical relaxations.

Advancing Flexible Sensors through On-Demand Regulation of Supramolecular Nanostructures.

The evolution of flexible sensors heavily relies on advances in soft-material design and sensing mechanisms. Supramolecular chemistry offers a powerful toolbox for manipulating nanoscale and molecular structures within soft materials, thus fostering recent advancements in flexible sensors and electronics. Supramolecular interactions have been utilized to nanoengineer functional sensing materials or construct chemical sensors with lower cost and broader targets. In this perspective, we will highlight the use of supramolecular interactions to regulate and optimize nanostructures within functional soft materials and illustrate their importance in expanding the nanocavities of bioreceptors for chemical sensing. Overall, a bridge between tissue-mimicking flexible sensors and cell-mimetic supramolecular chemistry has been built, which will further advance human healthcare innovation.

The determination of the curing induced, nonlinear elastic field of an inclusion in photo-cured materials

A wide variety of photo-cured materials have recently been developed with the rapid advancement of three-dimensional (3D) printing technology. However, most of these materials are designed as soft functional materials, and their failure mechanisms have received little attention. This work studies the mesoscale residual stress defects of photo-cured materials that are generated due to non-uniform curing and volume shrinkage during the manufacturing process. The defects are simplified as uncured inclusions embedded within a fully cured, infinite matrix which are then additionally cured. A large deformation model, validated against finite element analysis, is established to determine the nonlinear elastic field induced by the curing of inclusions with different Poisson’s ratio and shape (i.e., sphere and prolate spheroid), and is shown to outperform the infinitesimal strain model. This large deformation model, which includes a phase evolution constitutive model to describe the inclusion’s behavior and a compressible neo-Hookean model to describe the matrix’s behavior, is derived based on the same elastic field distribution as that in the infinitesimal strain solution and an ellipsoid-ellipsoid transformation kinematics assumption. The final solution is expressed in a discrete formulation and is exact for the spherical inclusion and approximate for the prolate spheroid inclusion. The prediction results of the theoretical model are compared with the finite element analysis, and reasonable agreement is obtained. This study may lay a foundation for investigating the effects of mesoscale residual stress defects on the mechanical behavior of 3D printing materials.

Supramolecular assembled macroscopic soft scaffolds of thioindigo amphiphiles as cell-material interfaces

Biocompatible synthetic supramolecular systems have been proven success in fabricating regenerative biomedical materials with intrinsic functionality, tunability, and stimuli-responsiveness. However, it remains highly challenging to develop a supramolecular soft scaffold that allows transferring intrinsic microscopic aligned structural properties to cell attachments. Herein, we report a thioindigo bola-amphiphile (TIA) that is equipped with long alkyl-linker to connect the carboxylic acid end-group on the opposite side. Though photoresponsiveness of TIA is hindered in aqueous medium, it can be slightly improved by utilizing a co-solvent system or doping TIA with other amphiphiles. Electron microscopies and X-ray diffraction analysis suggest that a large aspect ratio of TIA nanostructures assembled into macroscopic soft scaffold with high degree of unidirectional alignment. The fabricated TIA macroscopic soft scaffold is further incubated with hMSCs, in revealing unidirectional aligned cell attachments. This work could provide an alternative strategy towards development of next-generation biocompatible soft functional materials.

Liquid Metal Chameleon Tongues: Modulating Surface Tension and Phase Transition to Enable Bioinspired Soft Actuators

Leveraging the unique attributes of functional soft materials to generate force and deformation, significant advancements in soft actuators are driving the evolution of smart robotics. Liquid metals (LMs), known for their high deformability and tunable morphology, demonstrate remarkable actuating capabilities through controllable surface tension. Inspired by the predation method of chameleons, this work introduces a bioinspired LM actuator (BLMA) by modulating the morphology of LM. This BLMA enables high‐strain (up to 170%) actuation by precisely directing LM droplets toward an electrode. Various parameters affecting the BLMA's actuating performance are explored. Notably, the application of a reductive voltage induces rapid solidification of supercooled LM, facilitating phase transition at room temperature. The solidified LM enhances its holding force of BLMA by over 1000 times. To underscore the superior capabilities of the BLMA, diverse applications, such as a complex two‐dimensional plane actuator, a stepper motor with adjustable step intervals, a phase transition‐controlled relay, and a laser code lock actuation gate set, are presented. It is anticipated that the exceptional characteristics of the BLMA will propel advancements in the realms of soft robotics and mechatronics.

Self-Assembly of Ionic Superdiscs in Nanopores.

Discotic ionic liquid crystals (DILCs) consist of self-assembled superdiscs of cations and anions that spontaneously stack in linear columns with high one-dimensional ionic and electronic charge mobility, making them prominent model systems for functional soft matter. Compared to classical nonionic discotic liquid crystals, many liquid crystalline structures with a combination of electronic and ionic conductivity have been reported, which are of interest for separation membranes, artificial ion/proton conducting membranes, and optoelectronics. Unfortunately, a homogeneous alignment of the DILCs on the macroscale is often not achievable, which significantly limits the applicability of DILCs. Infiltration into nanoporous solid scaffolds can, in principle, overcome this drawback. However, due to the experimental challenges to scrutinize liquid crystalline order in extreme spatial confinement, little is known about the structures of DILCs in nanopores. Here, we present temperature-dependent high-resolution optical birefringence measurement and 3D reciprocal space mapping based on synchrotron X-ray scattering to investigate the thermotropic phase behavior of dopamine-based ionic liquid crystals confined in cylindrical channels of 180 nm diameter in macroscopic anodic aluminum oxide membranes. As a function of the membranes' hydrophilicity and thus the molecular anchoring to the pore walls (edge-on or face-on) and the variation of the hydrophilic-hydrophobic balance between the aromatic cores and the alkyl side chain motifs of the superdiscs by tailored chemical synthesis, we find a particularly rich phase behavior, which is not present in the bulk state. It is governed by a complex interplay of liquid crystalline elastic energies (bending and splay deformations), polar interactions, and pure geometric confinement and includes textural transitions between radial and axial alignment of the columns with respect to the long nanochannel axis. Furthermore, confinement-induced continuous order formation is observed in contrast to discontinuous first-order phase transitions, which can be quantitatively described by Landau-de Gennes free energy models for liquid crystalline order transitions in confinement. Our observations suggest that the infiltration of DILCs into nanoporous solids allows tailoring their nanoscale texture and ion channel formation and thus their electrical and optical functionalities over an even wider range than in the bulk state in a homogeneous manner on the centimeter scale as controlled by the monolithic nanoporous scaffolds.

Functional Soft Materials with Resistance to Liquid Leakage for Thermal Energy Storage

AbstractFunctional soft materials have great potential commercial applications in thermal energy storage, which are required to have a long life, good flexibility, and resistance to liquid leakage. Herein, a composite hydrogel with thermal storage properties is prepared through coupling molecular self‐assembly and in situ polymerization. Hydrophobic stearic acid (SA), as a thermal storage phase change material (PCM), is dispersed in polyacrylamide (PAM) hydrogel network in the form of oil–water emulsion (O/W). The PAM polymer network with good flexibility physically limits high‐frequency collision between SA PCM droplets. This unique design avoids demulsification in phase change emulsion so that the as‐prepared hydrogel composite can resist liquid leakage. The PAM hydrogel network plays the role of heterogeneous nucleation, resulting in the super‐cooling of SA emulsion at only 0.3 °C. On the other hand, SA PCM droplets in as‐prepared soft material do not directly contact with liquid water, so melting/crystallization process is independent of water. As a result, the soft material exhibits a thermal storage density of up to 99.3 J g−1. The present study is an important step toward designing soft energy storage materials.

Single-Material Solvent-Driven Polydimethylsiloxane Sponge Bending Actuators.

Soft robots mimic the agility of living organisms without rigid joints and muscles. Continuum bending (CB) is one type of motion living organisms can display. CB can be achieved using pneumatic, electroactive, or thermal actuators prepared by casting an active layer on a passive layer. The corresponding input actuates only the active layer in the assembly resulting in the bending of the structure. These two different layers must be laminated well during manufacturing. However, the formed bilayer can still delaminate later, and the detachment hampers the actuator's reversible, long-time use. An approach to creating a single material bending actuator was previously reported, for which spatial gradient swelling was used. This authentic approach allows a single material to be manufactured as a bending actuator, allowing easy access to such actuators without lamination. In this study, we show spatial porosity differences in the sponges of polydimethylsiloxane (PDMS) (a common material in soft robotics) can be used to create the required anisotropy for bending. The spongy polymers are manufactured through table sugar templates and actuated by (organic) solvent absorption/desorption. This enables some versatility in the mechanical properties, shape, actuation force, and actuation speed. The one-material system's straightforward production and seamless nature are advantageous for reversible and repetitive bending. This simple method can further be developed in hydrogels and polymers for soft robotics and functional materials.

Responsiveness of Charged Double Network Hydrogels to Ionic Environment

AbstractCharged double network (DN) hydrogels are widely studied for their desirable mechanical strength and tunable properties. In this work, the influence of polymer concentration on microstructure and properties of agarose/polyacrylic acid DN hydrogels is studied. Agarose, the first network, is a brittle biopolymer, while polyacrylic acid (PAAc) is a weak polyelectrolyte. The microstructure, visualized in liquid environment, displays an agarose scaffold coated and interconnected by PAAc, deviating from the common assumption of an entangled double network. Importantly, the charging of PAAc in the hydrogel is regulated not only by the pH and weak polyelectrolyte effects, but also by the restricted swelling of the double network, and hence, it is an inherent regulation mechanism of charged hydrogels. The interactions between the hydrogel and the ionic environment induce microstructural changes and charging of the double network, impacting surface properties such as topography, stiffness, and adhesion, which are spatially resolved by liquid‐environment atomic force microscopy. The responsiveness of the DN hydrogels significantly depends on both polymer concentrations and ion concentrations. These findings provide insights into the responsive behavior of double network hydrogels and reveal universal mechanisms for charged hydrogels, which can guide the future development of functional soft materials.

Soft Materials with Time-Programmed Changes in Physical Properties through Lyotropic Phase Transitions Induced by pH-Changing Reactions.

We present the development of time-programmable functional soft materials. The materials undergo reversible phase transitions between lyotropic phases with different topologies and symmetries, which in turn have very different physical properties: viscosity, diffusion, and optical transparency. Here, this behavior is achieved by combining pH-responsive lyotropic phases made from the lipid monoolein doped with 10% oleic acid, with chemical reactions that have well-defined controllable kinetics: autocatalytic urea-urease and methyl formate hydrolysis, which increase and decrease pH, respectively. In this case, we use small-angle X-ray scattering (SAXS) and optical imaging to show temporally controlled transitions between the cloudy hexagonal phase, which is a two-dimensional (2D) array of cylindrical inverse micelles, and the transparent, highly viscous three-dimensional (3D) bicontinuous cubic phases. By combining these into a single reaction mixture where the pH increases and then decreases again, we can induce a sequential transformation cycle from hexagonal to cubic and back to hexagonal over several hours. The sample therefore changes from cloudy to transparent and back again as a proof-of-concept demonstration for a wider range of soft materials with time-programmable changes in physical properties.

Exploring the Potentials of Chitin and Chitosan-Based Bioinks for 3D-Printing of Flexible Electronics: The Future of Sustainable Bioelectronics.

Chitin and chitosan-based bioink for 3D-printed flexible electronics have tremendous potential for innovation in healthcare, agriculture, the environment, and industry. This biomaterial is suitable for 3D printing because it is highly stretchable, super-flexible, affordable, ultrathin, and lightweight. Owing to its ease of use, on-demand manufacturing, accurate and regulated deposition, and versatility with flexible and soft functional materials, 3D printing has revolutionized free-form construction and end-user customization. This study examined the potential of employing chitin and chitosan-based bioinks to build 3D-printed flexible electronic devices and optimize bioink formulation, printing parameters, and postprocessing processes to improve mechanical and electrical properties. The exploration of 3D-printed chitin and chitosan-based flexible bioelectronics will open new avenues for new flexible materials for numerous industrial applications.

Multimodal Soft Robotic Actuation and Locomotion.

Diverse and adaptable modes of complex motion observed at different scales in living creatures are challenging to reproduce in robotic systems. Achieving dexterous movement in conventional robots can be difficult due to the many limitations of applying rigid materials. Robots based on soft materials are inherently deformable, compliant, adaptable, and adjustable, making soft robotics conducive to creating machines with complicated actuation and motion gaits. This review examines the mechanisms and modalities of actuation deformation in materials that respond to various stimuli. Then, strategies based on composite materials are considered to build toward actuators that combine multiple actuation modes for sophisticated movements. Examples across literature illustrate the development of soft actuators as free-moving, entirely soft-bodied robots with multiple locomotion gaits via careful manipulation of external stimuli. The review further highlights how the application of soft functional materials into robots with rigid components further enhances their locomotive abilities. Finally, taking advantage of the shape-morphing properties of soft materials, reconfigurable soft robots have shown the capacity for adaptive gaits that enable transition across environments with different locomotive modes for optimal efficiency. Overall, soft materials enable varied multimodal motion in actuators and robots, positioning soft robotics to make real-world applications for intricate and challenging tasks.

Oxidation‐Responsive Supramolecular Hydrogel Based on a Simple Fmoc‐Cysteine Derivative Capable of Showing Autonomous Gel–Sol–Gel Transitions

AbstractAqueous soft matter, including supramolecular hydrogels capable of exhibiting stimuli–responsive macroscopic phase transitions, has attracted increasing attention for the exploration of functional soft materials. However, the investigation of supramolecular hydrogels that undergo autonomous and multiple macroscopic phase transitions (e.g., gel–sol–gel, sol–gel–sol) in response to the surrounding environment without repeated additions of stimuli has remained largely unexplored. In this study, the oxidation‐responsive autonomous gel–sol–gel transitions of supramolecular hydrogels fabricated via the self‐assembly of a simple fluorenylmethyloxycarbonyl (Fmoc)‐protected, benzylated cysteine (Fmoc‐CBzl) is presented. During the evaluation of the oxidation process of Fmoc‐CBzl, it is revealed that the oxidized products, two diastereomeric sulfoxides (Fmoc‐CBzl‐(R)‐O and Fmoc‐CBzl‐(S)‐O), exhibit significantly different self‐assembly propensities under aqueous conditions. It may be noteworthy that the chirality of sulfoxide is largely overlooked and not effectively used to modulate supramolecular, self‐assembled nanostructures. The difference in the self‐assembly propensities and kinetics of self‐assembly/disassembly as well as co‐assembly will contribute to oxidation‐responsive autonomous gel–sol–gel transitions.

Red-light-controlled supramolecular assemblies of indigo amphiphiles at multiple length scales

Amphiphilic molecules functionalized with photoresponsive motifs have attractive prospects for applications in smart functional bio-material ranging from cell-material interfaces to drug delivery systems owing to the precisely controllable functionality of self-assembled hierarchical supramolecular structures in aqueous media by a non-invasive light stimulation with high temporal- and spatial-resolution. However, most of reported photoresponsive amphiphiles are triggered by bio-damaging UV-light, which greatly limits the potential in bio-related applications. Herein, we present newly designed red-light controlled N,N’-diaryl-substituted indigo amphiphiles (IA), exhibiting excellent photoswitchablity and photostability with dual red-/green-light in organic media. Meanwhile, aqueous solutions of IA assembled into supramolecular structures in both microscopic and macroscopic length-scale, though the photoresponsiveness of IA is slightly compromised in aqueous media. At macroscopic length-scale, morphological changes of IA macroscopic scaffold prepared by a shear-flow method can be fine adjusted upon red-light irradiation. Moreover, the preferential attachment of live h-MSCs to IA macroscopic scaffold surface also indicates a good biocompatibility of IA macroscopic scaffold. These results provide the potential for developing the next generation of red-light controlled soft functional materials with good biocompatibility.

Ultralight, Robust, Thermal Insulating Silica Nanolace Aerogels Derived from Pickering Emulsion Templates.

Synthesis of silica aerogel insulators with ultralight weight and strong mechanical properties using a simplified technique remains challenging for functional soft materials. This study introduces a promising method for the fabrication of mechanically reinforced ultralight silica aerogels by employing attractive silica nanolace (ASNLs)-armored Pickering emulsion templates. For this, silica nanolaces (SiNLs) are fabricated by surrounding a cellulose nanofiber with necklace-shaped silica nanospheres. In order to achieve amphiphilicity, which is crucial for the stabilization of oil-in-water Pickering emulsions, hydrophobic alkyl chains and hydrophilic amine groups are grafted onto the surface of SiNLs by silica coupling reactions. Freeze-drying of ASNLs-armored Pickering emulsions has established a new type of aerogel system. The ASNLs-supported mesoporous aerogel shows 3-fold greater compressive strength, 4-fold reduced heat transfer, and a swift heat dissipation profile compared to that of the bare ASNL aerogel. Additionally, the ASNL aerogel achieves an ultralow density of 8 mg cm-3, attributed to the pore architecture generated from closely jammed emulsion drops. These results show the potential of the ASNL aerogel system, which is ultralight, mechanically stable, and thermally insulating and could be used in building services, energy-saving technologies, and the aerospace industry.