Tunable Light-Responsive Polyurethane-urea Elastomer Driven by Photochemical and Photothermal Coupling Mechanism.

Light-driven soft actuators based on photoresponsive materials can be used to mimic biological motion, such as hand movements, without involving rigid or bulky electromechanical actuations. However, to our knowledge, no robust photoresponsive material with desireable mechanical and biological properties and relatively simple manufacture exists for robotics and biomedical applications. Herein, we report a new visible-light-responsive thermoplastic elastomer synthesized by introducing photoswitchable moieties (i.e., azobenzene derivatives) into the main chain of poly(ε-caprolactone) based polyurethane urea (PAzo). A PAzo elastomer exhibits controllable light-driven stiffness softening due to its unique nanophase structure in response to light, while possessing excellent hyperelasticity (stretchability of 575.2%, elastic modulus of 17.6 MPa, and strength of 44.0 MPa). A bilayer actuator consisting of PAzo and polyimide films is developed, demonstrating tunable bending modes by varying incident light intensities. Actuation mechanism via photothermal and photochemical coupling effects of a soft-hard nanophase is demonstrated through both experimental and theoretical analyses. We demonstrate an exemplar application of visible-light-controlled soft "fingers" playing a piano on a smartphone. The robustness of the PAzo elastomer and its scalability, in addition to its excellent biocompatibility, opens the door to the development of reproducible light-driven wearable/implantable actuators and lightweight soft robots for clinical applications.

Biodegradable poly(ethylene glycol-glycerol-itaconate-sebacate) copolyester elastomer with significantly reinforced mechanical properties by in-situ construction of bacterial cellulose interpenetrating network.

To address the concern that biodegradable elastomers are environmental-friendly but usually associated with poor properties for practical utilization, we report a star-crosslinked poly(ethylene glycol-glycerol-itaconate-sebacate) (PEGIS) elastomer synthesized by esterification, polycondensation and UV curing, and reinforced by bacterial cellulose (BC). The interpenetrating network of primary BC backbone and vulcanized elastomer is achieved by the "in-situ secondary network construction" strategy. With the well dispersion of BC without agglomeration, the mechanical properties of PEGIS are significantly enhanced in tensile strength, Young's modulus and elongation at break. The reinforcement strategy is demonstrated to be efficient and offers a route to the development of biodegradable elastomers for a variety of applications in the future.

Development and Analysis of an Origami-Based Elastomeric Actuator and Soft Gripper Control with Machine Learning and EMG Sensors.

This study investigates the characteristics of a novel origami-based, elastomeric actuator and a soft gripper, which are controlled by hand gestures that are recognized through machine learning algorithms. The lightweight paper-elastomer structure employed in this research exhibits distinct actuation features in four key areas: (1) It requires approximately 20% less pressure for the same bending amplitude compared to pneumatic network actuators (Pneu-Net) of equivalent weight, and even less pressure compared to other actuators with non-linear bending behavior; (2) The control of the device is examined by validating the relationship between pressure and the bending angle, as well as the interaction force and pressure at a fixed bending angle; (3) A soft robotic gripper comprising three actuators is designed. Enveloping and pinch grasping experiments are conducted on various shapes, which demonstrate the gripper's potential in handling a wide range of objects for numerous applications; and (4) A gesture recognition algorithm is developed to control the gripper using electromyogram (EMG) signals from the user's muscles.

Synthesis of shape-programmable elastomer for a bioresorbable, wireless nerve stimulator.

Materials that have the ability to manipulate shapes in response to stimuli such as heat, light, humidity and magnetism offer a means for versatile, sophisticated functions in soft robotics or biomedical implants, while such a reactive transformation has certain drawbacks including high operating temperatures, inherent rigidity and biological hazard. Herein, we introduce biodegradable, self-adhesive, shape-transformable poly (L-lactide-co-ε-caprolactone) (BSS-PLCL) that can be triggered via thermal stimulation near physiological temperature (∼38 °C). Chemical inspections confirm the fundamental properties of the synthetic materials in diverse aspects, and study on mechanical and biochemical characteristics validates exceptional stretchability up to 800 % and tunable dissolution behaviors under biological conditions. The integration of the functional polymer with a bioresorbable electronic system highlights potential for a wide range of biomedical applications.

Polymerizable deep eutectic solvent treated lignocellulose: Green strategy for synergetic production of tough strain sensing elastomers and nanocellulose.

Liquid free ion-conductive elastomers (ICEs) have demonstrated promising potential in various advanced application scenarios including sensor, artificial skin, and human-machine interface. However, ICEs that synchronously possess toughness, adhesiveness, stability, and anti-bacterial capability are still difficult to achieve yet highly demanded. Here, a one-pot green and sustainable strategy was proposed to fabricate multifunctional ICEs by extracting non-cellulose components (mainly lignin and hemicellulose) from lignocellulose with polymerizable deep eutectic solvents (PDES) and the subsequent in-situ photo-polymerization process. Ascribing to the uniform dispersion of non-cellulose components in PDES, the resultant ICEs demonstrated promising mechanical strength (a tensile strength of ~1200 kPa), high toughness (~9.1 MJ m-3), favorable adhesion (a lap-shear strength up to ~61.5 kPa toward metal), conducive stabilities, and anti-bacterial capabilities. With the help of such advantages, the ICEs exhibited sensitive (a gauge factor of ~23.5) and stable (~4000 cycles) performances in human motion and physiological signal detection even under sub-zero temperatures (e.g., -20 °C). Besides, the residue cellulose can be mechanically isolated into nanoscale fibers, which matched the idea of green chemistry.

Environmental risks of breakdown nanoplastics from synthetic football fields.

The widespread use of synthetic turf in sports has raised health concerns due to potential risks from nanoplastic inhalation or ingestion. Our research focused on detecting nanoplastics in drainage water from a synthetic football field and evaluating the toxicity of these materials after mechanical fragmentation. We collected and analysed drainage water samples for polymer content and subjected high-density polyethylene (HDPE) straws and ethylene propylene diene monomer (EPDM) granules used on synthetic football fields, to mechanical breakdown to create nanoplastics. The results indicated the presence of trace amounts of EPDM in the water samples. Furthermore, the toxicological assessment revealed that the broken-down nanoplastics and leachate from the surface of EPDM rubber granules exhibited high toxicity to Daphnia magna, while nanoplastics from the inner material exhibited no significant toxicity. The findings highlight the urgent need for future research to identify these specific toxic agents from the surface of EPDM granules.

Soft octopus-inspired suction cups using dielectric elastomer actuators with sensing capabilities.

Bioinspired and biomimetic soft grippers are rapidly growing fields. They represent an advancement in soft robotics as they emulate the adaptability and flexibility of biological end effectors. A prominent example of a gripping mechanism found in nature is the octopus tentacle, enabling the animal to attach to rough and irregular surfaces. Inspired by the structure and morphology of the tentacles, this study introduces a novel design, fabrication, and characterization method of dielectric elastomer suction cups. To grasp objects, the developed suction cups perform out-of-plane deflections as the suction mechanism. Their attachment mechanism resembles that of their biological counterparts, as they do not require a pre-stretch over a rigid frame or any external hydraulic or pneumatic support to form and hold the dome structure of the suction cups. The realized artificial suction cups demonstrate the capability of generating a negative pressure up to 1.3 kPa in air and grasping and lifting objects with a maximum 58 g weight under an actuation voltage of 6 kV. They also have sensing capabilities to determine whether the grasping was successful without the need of lifting the objects.

Study of sequential abiotic and biotic degradation of styrene butadiene rubber.

Styrene butadiene rubber is one of the main constituents of tire tread. During tire life, the tread material undergoes different stresses that impact its structure and chemical composition. Wear particles are then released into the environment as weathered material. To understand their fate, it is important to start with a better characterization of abiotic and biotic degradation of the elastomer material. A multi-disciplinary approach was implemented to study the photo- and thermo- degradation of non-vulcanized SBR films containing 15 w% styrene as well as their potential biodegradation by Rhodoccocus ruber and Gordonia polyisoprenivorans bacterial strains. Each ageing process leads to crosslinking reactions, much surface oxidation of the films and the production of hundreds of short chain compounds. These degradation products present a high level of unsaturation and oxidation and can be released into water to become potential substrates for microorganisms. Both strains were able to degrade from 0.2 to 1.2 % (% ThOD) of the aged SBR film after 30-day incubation while no biodegradation was observed on the pristine material. A 25-75 % decrease in the signal intensity of water extractable compounds was observed, suggesting that biomass production was linked to the consumption of low-molecular-weight degradation products. These results evidence the positive impact of abiotic degradation on the biodegradation process of styrene butadiene rubber.

Nuclear deformation and cell division of single cell on elongated micropatterned substrates fabricated by DMD lithography.

Cells sense mechanical signals from the surrounding environment and transmit them to the nucleus through mechanotransduction to regulate cellular behavior. Microcontact printing, which utilizes elastomer stamps, is an effective method for simulating the cellular microenvironment and manipulating cell morphology. However, the conventional fabrication process of silicon masters and elastomer stamps requires complex procedures and specialized equipment, which restricts the widespread application of micropatterning in cell biology and hinders the investigation of the role of cell geometry in regulating cell behavior. In this study, we present an innovative method for convenient resin stamp microfabrication based on digital micromirror device planar lithography. Using this method, we generated a series of patterns ranging from millimeter to micrometer scales and validated their effectiveness in controlling adhesion at both collective and individual cell levels. Additionally, we investigated mechanotransduction and cell behavior on elongated micropatterned substrates. We then examined the effects of cell elongation on cytoskeleton organization, nuclear deformation, focal adhesion formation, traction force generation, nuclear mechanics, and the growth of HeLa cells. Our findings reveal a positive correlation between cell length and mechanotransduction. Interestingly, HeLa cells with moderate length exhibit the highest cell division and proliferation rates. These results highlight the regulatory role of cell elongation in mechanotransduction and its significant impact on cancer cell growth. Furthermore, our methodology for controlling cell adhesion holds the potential for addressing fundamental questions in both cell biology and biomedical engineering.

Customisable Silicone Vessels and Tissue Phantoms for In Vitro Photoplethysmography Investigations into Cardiovascular Disease.

Age-related vessel deterioration leads to changes in the structure and function of the heart and blood vessels, notably stiffening of vessel walls, increasing the risk of developing cardiovascular disease (CVD), which accounts for 17.9 million global deaths annually. This study describes the fabrication of custom-made silicon vessels with varying mechanical properties (arterial stiffness). The primary objective of this study was to explore how changes in silicone formulations influenced vessel properties and their correlation with features extracted from signals obtained from photoplethysmography (PPG) reflectance sensors in an in vitro setting. Through alterations in the silicone formulations, it was found that it is possible to create elastomers exhibiting an elasticity range of 0.2 MPa to 1.22 MPa. It was observed that altering vessel elasticity significantly impacted PPG signal morphology, particularly reducing amplitude with increasing vessel stiffness (p < 0.001). A p-value of 5.176 × 10-15 and 1.831 × 10-14 was reported in the red and infrared signals, respectively. It has been concluded in this study that a femoral artery can be recreated using the silicone material, with the addition of a softener to achieve the required mechanical properties. This research lays the foundation for future studies to replicate healthy and unhealthy vascular systems. Additional pathologies can be introduced by carefully adjusting the elastomer materials or incorporating geometrical features consistent with various CVDs.

3D Printing Self-Healing and Self-Adhesive Elastomers for Wearable Electronics in Amphibious Environments.

To meet the demands of challenging usage scenarios, there is an increasing need for flexible electronic skins that can operate properly not only in terrestrial environments but also extend to complex aquatic conditions. In this study, we develop an elastomer by incorporating dynamic urea bonds and hydrogen bonds into the polydimethylsiloxane backbone, which exhibits excellent autonomous self-healing and reversible adhesive performance in both dry and wet environments. A multifunctional flexible sensor with excellent sensing stability, amphibious self-healing capacity, and amphibious self-adhesive performance is fabricated through solvent-free 3D printing. The sensor has a high sensing sensitivity (GF = 45.1) and a low strain response threshold (0.25%) and can be used to detect small human movements and physiological activities, such as muscle movement, joint movement, respiration, and heartbeat. The wireless wearable sensing system assembled by coupling this device with a bluetooth transmission system is suitable for monitoring strenuous human movement in amphibious environments, such as playing basketball, cycling, running (terrestrial environments), and swimming (aquatic environments). The design strategy provides insights into enhancing the self-healing and self-adhesive properties of soft materials and promises a prospective avenue for fabricating flexible electronic skin that can work properly in amphibious environments.

Highly Stretchable, Self-Healing, and Sensitive E-Skins at -78 °C for Polar Exploration.

Ultralow temperature-tolerant electronic skins (e-skins) can endow polar robots with tactile feedback for exploring in extremely cold polar environments. However, it remains a challenge to develop e-skins that enable sensitive touch sensation and self-healing at ultralow temperatures. Herein, we describe the development of a sensitive robotic hand e-skin that can stretch, self-heal, and sense at temperatures as low as -78 °C. The elastomeric substrate of this e-skin is based on poly(dimethylsiloxane) supramolecular polymers and multistrength dynamic H-bonds, in particular with quadruple H-bonding motifs (UPy). The structure-performance relationship of the elastomer at ultralow temperatures is investigated. The results show that elastomers with side-chain UPy units exhibit higher stretchability (∼3257%) and self-healing efficiency compared to those with main-chain UPy units. This is attributed to the lower binding energy variation and lower potential well. Based on the elastomer with side-chain UPy and man-made electric ink, a sensitive robotic hand e-skin for usage at -78 °C is constructed to precisely sense the shape of objects and specific symbols, and its sensation can completely self-recover after being damaged. The findings of this study contribute to the concept of using robotic hands with e-skins in polar environments that make human involvement limited, dangerous, or impossible.

Degradable biomedical elastomers: paving the future of tissue repair and regenerative medicine.

Degradable biomedical elastomers (DBE), characterized by controlled biodegradability, excellent biocompatibility, tailored elasticity, and favorable network design and processability, have become indispensable in tissue repair. This review critically examines the recent advances of biodegradable elastomers for tissue repair, focusing mainly on degradation mechanisms and evaluation, synthesis and crosslinking methods, microstructure design, processing techniques, and tissue repair applications. The review explores the material composition and cross-linking methods of elastomers used in tissue repair, addressing chemistry-related challenges and structural design considerations. In addition, this review focuses on the processing methods of two- and three-dimensional structures of elastomers, and systematically discusses the contribution of processing methods such as solvent casting, electrostatic spinning, and three-/four-dimensional printing of DBE. Furthermore, we describe recent advances in tissue repair using DBE, and include advances achieved in regenerating different tissues, including nerves, tendons, muscle, cardiac, and bone, highlighting their efficacy and versatility. The review concludes by discussing the current challenges in material selection, biodegradation, bioactivation, and manufacturing in tissue repair, and suggests future research directions. This concise yet comprehensive analysis aims to provide valuable insights and technical guidance for advances in DBE for tissue engineering.

4D printing for biomedical applications.

While three-dimensional (3D) printing excels at fabricating static constructs, it fails to emulate the dynamic behavior of native tissues or the temporal programmability desired for medical devices. Four-dimensional (4D) printing is an advanced additive manufacturing technology capable of fabricating constructs that can undergo pre-programmed changes in shape, property, or functionality when exposed to specific stimuli. In this Perspective, we summarize the advances in materials chemistry, 3D printing strategies, and post-printing methodologies that collectively facilitate the realization of temporal dynamics within 4D-printed soft materials (hydrogels, shape-memory polymers, liquid crystalline elastomers), ceramics, and metals. We also discuss and present insights about the diverse biomedical applications of 4D printing, including tissue engineering and regenerative medicine, drug delivery, in vitro models, and medical devices. Finally, we discuss the current challenges and emphasize the importance of an application-driven design approach to enable the clinical translation and widespread adoption of 4D printing.

Digital light 4D printing of bioresorbable shape memory elastomers for personalized biomedical implantation.

Four-dimensional (4D) printing unlocks new potentials for personalized biomedical implantation, but still with hurdles of lacking suitable materials. Herein, we demonstrate a bioresorbable shape memory elastomer (SME) with high elasticity at both below and above its phase transition temperature (Ttrans). This SME can be digital light 3D printed by co-polymerizing glycerol dodecanoate acrylate prepolymer (pre-PGDA) with acrylic acid monomer to form crosslinked Poly(glycerol dodecanoate acrylate) (PGDA)-Polyacrylic acid (PAA), or PGDA-PAA network. The printed complex, free-standing 3D structures with high-resolution features exhibit shape programming properties at a physiological temperature. By tuning the pre-PGDA weight ratios between 55 wt% and 70 wt%, Ttrans varies between 39.2 and 47.2 ℃ while Young's moduli (E) range 40-170 MPa below Ttrans with fractural strain (εf) of 170 %-200 %. Above Ttrans, E drops to 1-1.82 MPa which is close to those of soft tissue. Strikingly, εf of 130-180 % is still maintained. In vitro biocompatibility test on the material shows > 90 % cell proliferation and great cell attachment. In vivo vascular grafting trials underline the geometrical and mechanical adaptability of these 4D printed constructs in regenerating the aorta tissue. Biodegradation of the implants shows the possibility of their full replacement by natural tissue over time. To highlight its potential for personalized medicine, a patient-specific left atrial appendage (LAA) occluder was printed and implanted endovascularly into an in vitro heart model. STATEMENT OF SIGNIFICANCE: 4D printed shape-memory elastomer (SME) implants particularly designed and manufactured for a patient are greatly sought-after in minimally invasive surgery (MIS). Traditional shape-memory polymers used in these implants often suffer from issues like unsuitable transition temperatures, poor biocompatibility, limited 3D design complexity, and low toughness, making them unsuitable for MIS. Our new SME, with an adjustable transition temperature and enhanced toughness, is both biocompatible and naturally degradable, particularly in cardiovascular contexts. This allows implants, like biomedical scaffolds, to be programmed at room temperature and then adapt to the body's physiological conditions post-implantation. Our studies, including in vivo vascular grafts and in vitro device implantation, highlight the SME's effectiveness in aortic tissue regeneration and its promising applications in MIS.

Sustained antibacterial activity of orthodontic elastomeric ligature ties coated with a novel kombucha-derived bacterial nanocellulose: An in-vitro study.

Incipient carious lesions, the most common complication in orthodontic patients with fixed appliances, call for the development of novel preventive dental materials that do not rely on patient adherence. The present study aimed to assess the ability of elastomeric ligatures coated with bacterial nanocellulose (BNC) to deliver sustained antibacterial activity, during the standard 28-day interval between orthodontic appointments, without compromising their mechanical properties. Kombucha membrane was used to produce cellulose as a secondary product from the fermentation of tea broth with symbiotic bacteria and yeast culture. Characterization of BNC-coated elastomeric ligatures was performed using Fourier Transform Infrared Spectroscopy and Energy Dispersive Spectroscopy analysis. The samples were pre-treated by immersion first in isopropyl alcohol, then in 8 mL nanocellulose solution for 7 days. Tensile strain and strength of the BNC-coated and conventional ligatures were evaluated using a tensile testing machine. Direct contact and agar diffusion tests were performed to assess the antibacterial activity of nanocellulose. In addition, the release profile of BNC was evaluated. Data analysis was performed by one-way analysis of variance (ANOVA) followed by post-hoc Tukey's test and Wilcoxon signed-rank test. P values less than 0.05 was regarded as significant. There was no statistically significant difference in tensile strain and strength between the BNC-coated and conventional ligatures. The coated ligatures provided sustained antibacterial activity during the required 28 days. The use of BNC-coated elastomeric ligatures in patients with fixed orthodontic appliances might be a promising solution to plaque formation and subsequent enamel decalcification.

Instant tough adhesion of polymer networks.

Generating strong rapid adhesion between hydrogels has the potential to advance the capabilities of modern medicine and surgery. Current hydrogel adhesion technologies rely primarily on liquid-based diffusion mechanisms and the formation of covalent bonds, requiring prolonged time to generate adhesion. Here, we present a simple and versatile strategy using dry chitosan polymer films to generate instant adhesion between hydrogel-hydrogel and hydrogel-elastomer surfaces. Using this approach we can achieve extremely high adhesive energies (>3,000 J/m2), which are governed by pH change and non-covalent interactions including H-bonding, Van der Waals forces, and bridging polymer entanglement. Potential examples of biomedical applications are presented, including local tissue cooling, vascular sealing, prevention of surgical adhesions, and prevention of hydrogel dehydration. We expect these findings and the simplicity of this approach to have broad implications for adhesion strategies and hydrogel design.

High Signal to Noise Ratio Piezoelectric Thin Film Sensor Based on Elastomer Amplification for Ambulatory Blood Pressure Monitoring.

Continuous pulse wave detection can be used for monitoring and diagnosing cardiovascular diseases, and research on pulse sensing based on piezoelectric thin films is one of the hot spots. Usually, piezoelectric thin films do not come into direct contact with the skin and need to be connected through a layer of an elastic medium. Most views think that the main function of this layer of elastic medium is to increase the adhesion between the sensor component and the skin, but there is little discussion about the impact of the elastic medium on pulse vibration transmission. Here, we conducted a detailed study on the effects of Young's modulus and the thickness of elastic media on pulse sensing signals. The results show that the waveform amplitude of the piezoelectric sensing signal decreases with the increase of Young's modulus and thickness of the elastic medium. Then, we constructed a theoretical model of the influence of elastic media on pulse wave propagation. The amplitude of the pulse wave signal detected by the optimized sensor was increased to 480%. Our research shows that by regulating Young's modulus and thickness of elastic media, pulse wave signals can undergo a similar amplification effect, which has an important theoretical reference value for achieving ambulatory blood pressure monitoring based on high-quality pulse waves.

Thermo-growing ion clusters enabled healing strengthening and tough adhesion for highly reliable skin electronics.

Self-healing and self-adhesion capacities are essential for many modern applications such as skin-interfaced electronics for improving longevity and reliability. However, the self-healing efficiency and adhesive toughness of most synthetic polymers are limited to their original network, making reliability under dynamic deformation still challenging. Herein, inspired by the growth of living organisms, a highly stretchable supramolecular elastomer based on thermo-responsive ion clusters and a dynamic polysulfide backbone was developed. Attributed to the synergic growth of ion clusters and dynamic exchange of disulfide bonds, the elastomer exhibited unique healing strengthening (healing efficiency >200%) and thermo-enhanced tough adhesion (interfacial toughness >500 J m-2) performances. To prove its practical application in highly reliable skin electronics, we further composited the elastomer with a zwitterion to prepare a highly conductive ionic elastomer and applied it in wearable strain sensing and long-term electrophysiological detection. This work provides a new avenue to realize high reliability in skin interfaced electronics.

Design of 3D-Photoprintable, Bio-, and Hemocompatible Nonisocyanate Polyurethane Elastomers for Biomedical Implants.

Polyurethanes (PUs) have adjustable mechanical properties, making them suitable for a wide range of applications, including in the biomedical field. Historically, these PUs have been synthesized from isocyanates, which are toxic compounds to handle. This has encouraged the search for safer and more environmentally friendly synthetic routes, leading today to the production of nonisocyanate polyurethanes (NIPUs). Among these NIPUs, polyhydroxyurethanes (PHUs) bear additional hydroxyl groups, which are particularly attractive for derivatizing and adjusting their physicochemical properties. In this paper, polyether-based NIPU elastomers with variable stiffness are designed by functionalizing the hydroxyl groups of a poly(propylene glycol)-PHU by a cyclic carbonate carrying a pendant unsaturation, enabling them to be post-photo-cross-linked with polythiols (thiol-ene). Elastomers with remarkable mechanical properties whose stiffness can be adjusted are obtained. Thanks to the unique viscous properties of these PHU derivatives and their short gel times observed by rheology experiments, formulations for light-based three-dimensional (3D) printing have been developed. Objects were 3D-printed by digital light processing with a resolution down to the micrometer scale, demonstrating their ability to target various designs of prime importance for personalized medicine. In vitro biocompatibility tests have confirmed the noncytotoxicity of these materials for human fibroblasts. In vitro hemocompatibility tests have revealed that they do not induce hemolytic effects, they do not increase platelet adhesion, nor activate coagulation, demonstrating their potential for future applications in the cardiovascular field.