Aligned wave-like elastomer fibers with robust conductive layers via electroless deposition for stretchable electrode applications.

Flexible wearable electronics play an important role in the healthcare industry due to their unique skin affinity, portability and breathability. Despite great progress, it still remains a big challenge to facilely fabricate stretchable electrodes with low resistance, excellent stability and a wide tensile range. Here, we propose a handy and time-saving strategy for the fabrication of elastomeric films consisting of wave-like fibers with a robust conductive layer of silver nanoparticles (AgNPs) immobilized using polydopamine (PDA) and silicone rubber (SR). To realize better stretchability, electrospun thermoplastic polyurethane (TPU) mats with oriented nanofibers were treated via ethanol to achieve a wavy structure, which also allowed for the decoration of AgNP precursors on the TPU surface via PDA assisted electroless deposition (ELD). Therefore, the electrodes achieved a stretchability of 120% with high electrical conductivity (486 S cm-1). The films with a reduction time of 30 min showed superior electrical conductivity indicated by a resistance increase of only 100% within 50% strain. The TPU/PDA/AgNP/SR composites with a shorter reduction time of silver precursors could monitor human motions as wearable strain sensors with a wide work strain range (0-98%) and a high sensitivity (with a gauge factor (GF) of up to 81.76) for a strain of 80-98%. Therefore, they are an excellent candidate for potential application in prospective stretchable electronics.

Dual-initiating and living frustrated Lewis pairs: expeditious synthesis of biobased thermoplastic elastomers.

Biobased poly(γ-methyl-α-methylene-γ-butyrolactone) (PMMBL), an acrylic polymer bearing a cyclic lactone ring, has attracted increasing interest because it not only is biorenewable but also exhibits superior properties to petroleum-based linear analog poly(methyl methacrylate) (PMMA). However, such property enhancement has been limited to resistance to heat and solvent, and mechanically both types of polymers are equally brittle. Here we report the expeditious synthesis of well-defined PMMBL-based ABA tri-block copolymers (tri-BCPs)-enabled by dual-initiating and living frustrated Lewis pairs (FLPs)-which are thermoplastic elastomers showing much superior mechanical properties, especially at high working temperatures (80-130 °C), to those of PMMA-based tri-BCPs. The FLPs consist of a bulky organoaluminum Lewis acid and a series of newly designed bis(imino)phosphine superbases bridged by an alkyl linker, which promote living polymerization of MMBL. Uniquely, such bisphosphine superbases initiate the chain growth from both P-sites concurrently, enabling the accelerated synthesis of tri-BCPs in a one-pot, two-step procedure. The results from mechanistic studies, including the single crystal structure of the dually initiated active species, detailed polymerizations, and kinetic studies confirm the livingness of the polymerization and support the proposed polymerization mechanism featuring the dual initiation and subsequent chain growth from both P-sites of the superbase di-initiator.

Biomimetic structure of chitosan reinforced epoxy natural rubber with self-healed, recyclable and antimicrobial ability.

Inspired by biomaterials with hard and soft structures, we reported a type of self-healed, recyclable and antimicrobial elastomers material (ECTS) which exhibited both strong mechanical strength and high toughness. ECTS was designed by furfuryl amine modified epoxy natural rubber (ENR-FA) and furaldehyde modified chitosan (CTS-FUR) through Diels-Alder (D-A) reaction. The dynamic loading capacity of the chitosan skeleton, the stress ductility of the matrix and the dynamic cross-linking between the hard and soft components gave the elastomer excellent mechanical strength, toughness and self-healing ability. The tensile strength and the elongation at break could reach up to 7.55 MPa and 487%, respectively. In addition, due to the reversibility of the covalent bond between chitosan framework and rubber matrix, the crosslinking network destroyed by external force could be reestablished under high temperature stimulation. The mechanical properties of the sample could be restored to more than 90% of the original sample, whether it was complete fracture, cyclic damage or recyclable. ECTS exhibited excellent antibacterial activity against both gram-positive bacteria (Staphylococcus aureus) and gram-negative bacteria (Pseudomonas aeruginosa), with antibacterial efficiency more than 99%. So, ECTS might has a promising application prospect in medical materials, intelligent devices, 4D-printing, etc.

Cyclodextrin-modified poly(octamethylene citrate) polymers towards enhanced sorption properties.

Herein, we describe the synthesis of poly(1,8-octamethylene citrate) materials modified in the bulk with 2-hydroxypropyl-ß-cyclodextrin (cPOCCD), biodegradable elastomers with intrinsic sorption properties for drug delivery. The chemical structure, physicochemical properties, in vitro drug loading and release profiles of cPOCCD were investigated. Thus, cPOCCD polyesters absorb the studied drugs more effective and release them for a longer period of time than poly(1,8-octamethylene citrate) materials not containing cyclodextrins.

Poly(ethylene glycol) Diacrylate Based Electro-Active Ionic Elastomer.

Preparation and low voltage induced bending (converse flexoelectricity) of crosslinked poly(ethylene glycol) diacrylate (PEGDA), modified with thiosiloxane (TS) and ionic liquid (1-hexyl-3-methylimidazolium hexafluorophosphate) (IL) are reported. In between 2µm PEDOT:PSS electrodes at 1 V, it provides durable (95% retention under 5000 cycles) and relatively fast (2 s switching time) actuation with the second largest strain observed so far in ionic electro-active polymers (iEAPs). In between 40 nm gold electrodes under 8 V DC voltage, the film can be completely curled up (270° bending angle) with 6% strain that, to the best of the knowledge, is unpreceded among iEAPs. These results render great potential for the TS/PEGDA/IL based electro-active actuators for soft robotic applications.

Study on miscibility, thermal properties, degradation behaviors, and toughening mechanism of poly(lactic acid)/poly (ethylene-butylacrylate-glycidyl methacrylate) blends.

In the work, the poly(lactic acid) (PLA)/poly (ethylene-butylacrylate-glycidyl methacrylate) (PTW) blends were prepared by melt compounding. PTW as a toughening agent for PLA, the PLA/PTW blends had good compatibility due to the chemical reaction between the epoxy groups of PTW and the end group of PLA during the blending process. With increasing PTW content from 0 to 20%, the impact strength of PLA/PTW blends was enhanced from 4.6 to 54.1 kJ/m2 and the elongation at break was increased from 5.6% to 270%. The scanning electron microscopy (SEM) images of the impact fracture surfaces showed a large amount of cavities and plastic deformation, which caused by the elastomer and the interfacial adhesion enhanced through the interaction of the terminal functional groups. That was the reason that the toughness of PLA was increased. Finally, proteinase K-catalyzed degradation tests shown that the addition of PTW was beneficial to the biodegradation of PLA and reduced environmental pollution.

Synthesis and characterization of stable and biological active chitin-based polyurethane elastomers.

In this work, the preparation of novel biocompatible polyurethane (PU) elastomers were carried out using curcumin and 1,4-butanediol (1,4-BDO) via step growth polymerization reaction of hydroxyl terminated polybutadiene (HTPB), toluene diisocyanate (TDI) and chitin to improve the biocompatibility, antibacterial and antioxidant properties of PU elastomers. Five samples were synthesized by varying moles ratio of curcumin and 1,4-BDO. The structural study of blends was done by FTIR spectroscopy which confirmed the incorporation of curcumin and 1,4-BDO into the polyurethane matrix. TGA analysis of polyurethane (PU) blends showed good thermal stability with 0.25 M curcumin and 1.75 M 1,4-BDO. Measurements of antibacterial properties were done via agar diffusion method which showed outstanding potential against selected strains of bacteria. The results revealed that biocompatibility, antibacterial and antioxidant potential of purposed polyurethanes elastomers were improved by the incorporation of curcumin which might be the precursor of biomedical applications. Collectively, this work is a footstep towards the synthesis of innovative biocompatible materials which made it suitable for biological applications.

Tough Ordered Mesoporous Elastomeric Biomaterials Formed at Ambient Conditions.

Synthetic dry elastomers are randomly cross-linked polymeric networks with isotropic and unordered higher-level structural features. However, their growing use as soft-tissue biomaterials has demanded the need for an ordered and anisotropic nano-micro (or) mesoarchitecture, which is crucial for imparting specific properties such as hierarchical toughening, anisotropic mechanics, sustained drug delivery, and directed tissue growth. High processing cost, poor control in 3D, and compromised mechanical properties have made it difficult to synthesize tough and dry macroscopic elastomers with well-organized nano-microstructures. Inspired from biological design principles, we report a tough ordered mesoporous elastomer formed via bottom-up lyotropic self-assembly of noncytotoxic, polymerizable amphiphilic triblock copolymers and hydrophobic polymers. The elastomer is cross-linked using covalent cross-links and physical hydrophobic entanglements that are organized in a periodic manner at the nanoscale. This transforms into a well-ordered hexagonal arrangement of nanofibrils that are highly oriented at the micron scale, further organized as 3D macroscale objects. The ordered nano-microstructure and molecular multinetwork endows the elastomer with hierarchical toughening while possessing excellent stiffness and elongation comparable to engineering elastomers like silicone and vulcanized rubber. Processing of the elastomer is performed at ambient conditions using 3D printing and photo-cross-linking, which is fast and energy efficient and enables production of complex 3D objects with tailorable sub-millimeter features such as macroporosity. Furthermore, the periodic and amphiphilic nanostructure permits functionalization of the elastomer with secondary components such as inorganic nanoparticles or drug molecules, enabling complementary mechanical properties such as high stiffness and functional capabilities such as in localized drug delivery applications.

Self-Healing Polyester Urethane Supramolecular Elastomers Reinforced with Cellulose Nanocrystals for Biomedical Applications.

Stretchable self-healing urethane-based biomaterials have always been crucial for biomedical applications; however, the strength is the main constraint of utilization of these healable materials. Here, a series of novel, healable, elastomeric, supramolecular polyester urethane nanocomposites of poly(1,8-octanediol citrate) and hexamethylene diisocyanate reinforced with cellulose nanocrystals (CNCs) are introduced. Nanocomposites with various amounts of CNCs from 10 to 50 wt% are prepared using solvent casting technique followed by the evaluation of their microstructural features, mechanical properties, healability, and biocompatibility. The synthesized nanocomposites indicate significantly higher tensile modulus (approximately 36-500-fold) in comparison to the supramolecular polymer alone. Upon exposure to heat, the materials can reheal, but nevertheless when the amount of CNC is greater than 10 wt%, the self-healing ability of nanocomposites is deteriorated. These materials are capable of rebonding ruptured parts and fully restoring their mechanical properties. In vitro cytotoxicity test of the nanocomposites using human dermal fibroblasts confirms their good cytocompatibility. The optimized structure, self-healing attributes, and noncytotoxicity make these nanocomposites highly promising for tissue engineering and other biomedical applications.

Aliphatic Polyester Thermoplastic Elastomers Containing Hydrogen-Bonding Ureidopyrimidinone Endgroups.

Polylactide- block-poly(γ-methyl-ε-caprolactone)- block-polylactide (LML) is a sustainable thermoplastic elastomer (TPE) candidate that exhibits competitive mechanical properties as compared to traditional styrenic TPEs. The relatively low glass transition temperature of the polylactide endblocks, however, results in stress relaxation and low levels of elastic recovery. We report the synthesis and characterization of poly(γ-methyl-ε-caprolactone) (PMCL) and LML end-functionalized with ureidopyrimidinone (UPy) hydrogen-bonding moieties to improve the elastic performance of these polymers. Although UPy-functionalized PMCL shows dynamical mechanical behavior that is distinct from the unfunctionalized homopolymer, it does not exhibit elastomeric behavior at room temperature. The addition of UPy endgroups to LML increases the ultimate tensile strength, elongation at break, and tensile toughness compared to unfunctionalized LML. Stress relaxation studies at a fixed strain show reduced levels of stress relaxation in LML with UPy endgroups. The stress relaxation was further reduced by including semicrystalline poly(( S, S)-lactide) as endblocks with UPy endgroups.

Renewable Terpene Derivative as a Biosourced Elastomeric Building Block in the Design of Functional Acrylic Copolymers.

In order to move away from traditional petrochemical-based polymer materials, it is imperative that new monomer systems be sought out based on renewable resources. In this work, the synthesis of a functional terpene-containing acrylate monomer (tetrahydrogeraniol acrylate, THGA) is reported. This monomer was polymerized in toluene and bulk via free-radical polymerizations, achieving high conversion and molecular weights up to 278 kg·mol-1. The synthesized poly(THGA) shows a relatively low Tg (-46 °C), making it useful as a replacement for low Tg acrylic monomers, such as the widely used n-butyl acrylate. RAFT polymerization in toluene ([M]0 = 3.6 mol·L-1) allowed for the well-controlled polymerization of THGA with degrees of polymerization (DP n) from 25 to 500, achieving narrow molecular weight distributions ( D̵ ≈ 1.2) even up to high conversions. At lower monomer concentrations ([M]0 = 1.8 mol·L-1), some evidence of intramolecular chain transfer to polymer was seen by the detection of branching (arising from propagation of midchain radicals) and terminal double bonds (arising from ß-scission of midchain radicals). Poly(THGA) was subsequently utilized for the synthesis of poly(THGA)- b-poly(styrene)- b-poly(THGA) and poly(styrene)- b-poly(THGA)- b-poly(styrene) triblock copolymers, demonstrating its potential as a component of thermoplastic elastomers. The phase separation and mechanical properties of the resulting triblock copolymer were studied by atomic force microscopy and rheology.

Sustainable elastomers derived from cellulose, rosin and fatty acid by a combination of "graft from" RAFT and isocyanate chemistry.

Utilization of natural sustainable feedstock to fabricate polymers has attracted remarkable attention. In this work, we reported a strategy to prepare a series of grafted copolymers from rosin, fatty acids and ethyl cellulose. The process involved the preparation of EC-based macro-RAFT agent through a simple esterification reaction, followed by a "grafting from" reversible addition-fragmentation chain transfer polymerization (RAFT) of DAGMA (derived from rosin) and LMA (derived from fatty acid) to achieve a class of EC-g-P(DAGMA-co-LMA) graft copolymers with a tunable Tg tuned by the DAGMA/LMA molar ratio. Then, hexamethylene diisocyanate (HDI) was used to crosslink these graft copolymers. The mechanical and dynamic thermo-mechanical properties of tests showed that elastic recovery values of copolymers were enhanced to 90%, as compared to the un-crosslinked samples. Additionally, all these polymers showed an excellent UV absorption performance. This study provides a facile way to fabricate biobased elastomeric materials with improved mechanical properties.

Preparation and Characterization of Isosorbide-Based Self-Healable Polyurethane Elastomers with Thermally Reversible Bonds.

Polyurethane (PU) is a versatile polymer used in a wide range of applications. Recently, imparting PU with self-healing properties has attracted much interest to improve the product durability. The self-healing mechanism conceivably occurs through the existence of dynamic reversible bonds over a specific temperature range. The present study investigates the self-healing properties of 1,4:3,6-dianhydrohexitol-based PUs prepared from a prepolymer of poly(tetra-methylene ether glycol) and 4,4'-methylenebis(phenyl isocyanate) with different chain extenders (isosorbide or isomannide). PU with the conventional chain extender 1,4-butanediol was prepared for comparison. The urethane bonds in 1,4:3,6-dianhydrohexitol-based PUs were thermally reversible (as confirmed by the generation of isocyanate peaks observed by Fourier transform infrared spectroscopy) at mildly elevated temperatures and the PUs showed good mechanical properties. Especially the isosorbide-based polyurethane showed potential self-healing ability under mild heat treatment, as observed in reprocessing tests. It is inferred that isosorbide, bio-based bicyclic diol, can be employed as an efficient chain extender of polyurethane prepolymers to improve self-healing properties of polyurethane elastomers via reversible features of the urethane bonds.

Synthesis, Characterization, and Bacterial Fouling-Resistance Properties of Polyethylene Glycol-Grafted Polyurethane Elastomers.

Despite advances in material sciences and clinical procedures for surgical hygiene, medical device implantation still exposes patients to the risk of developing local or systemic infections. The development of efficacious antimicrobial/antifouling materials may help with addressing such an issue. In this framework, polyethylene glycol (PEG)-grafted segmented polyurethanes were synthesized, physico-chemically characterized, and evaluated with respect to their bacterial fouling-resistance properties. PEG grafting significantly altered the polymer bulk and surface properties. Specifically, the PEG-grafted polyurethanes possessed a more pronounced hard/soft phase segregated microstructure, which contributed to improving the mechanical resistance of the polymers. The better flexibility of the soft phase in the PEG-functionalized polyurethanes compared to the pristine polyurethane (PU) was presumably also responsible for the higher ability of the polymer to uptake water. Additionally, dynamic contact angle measurements evidenced phenomena of surface reorganization of the PEG-functionalized polyurethanes, presumably involving the exposition of the polar PEG chains towards water. As a consequence, Staphylococcus epidermidis initial adhesion onto the surface of the PEG-functionalized PU was essentially inhibited. That was not true for the pristine PU. Biofilm formation was also strongly reduced.

Synthesis of Soft Polysiloxane-urea Elastomers for Intraocular Lens Application.

This study discusses a synthesis route for soft polysiloxane-based urea (PSU) elastomers for their applications as accommodating intraocular lenses (a-IOLs). Aminopropyl-terminated polydimethylsiloxanes (PDMS) were previously prepared via the ring-chain equilibration of the cyclic siloxane octamethylcyclotetrasiloxane (D4) and 1,3-bis(3-aminopropyl)-tetramethyldisiloxane (APTMDS). Phenyl groups were introduced into the siloxane backbone via the copolymerization of D4 and 2,4,6,8-tetramethyl-2,4,6,8-tetraphenyl-cyclotetrasiloxane (D4Me,Ph). These polydimethyl-methyl-phenyl-siloxane-block copolymers were synthesized for increasing the refractive indices of polysiloxanes. For applications as an a-IOL, the refractive index of the polysiloxanes must be equivalent to that of a young human eye lens. The polysiloxane molecular weight is controlled by the ratio of the cyclic siloxane to the endblocker APTMDS. The transparency of the PSU elastomers is examined by the transmittance measurement of films between 200 and 750 nm, using a UV-Vis spectrophotometer. Transmittance values at 750 nm (upper end of the visible spectrum) are plotted against the PDMS molecular weight, and > 90% of the transmittance is observed until a molecular weight of 18,000 g·mol-1. Mechanical properties of the PSU elastomers are investigated using stress-strain tests on die-cut dog-bone-shaped specimens. For evaluating mechanical stability, mechanical hysteresis is measured by repeatedly stretching (10x) the specimens to 5% and 100% elongation. Hysteresis considerably decreases with the increase in the PDMS molecular weight. In vitro cytotoxicity of some selected PSU elastomers is evaluated using an MTS cell viability assay. The methods described herein permit the synthesis of a soft, transparent, and noncytotoxic PSU elastomer with a refractive index approximately equal to that of a young human eye lens.

Development of Light-Responsive Liquid Crystalline Elastomers to Assist Cardiac Contraction.

RATIONALE: Despite major advances in cardiovascular medicine, heart disease remains a leading cause of death worldwide. However, the field of tissue engineering has been growing exponentially in the last decade and restoring heart functionality is now an affordable target; yet, new materials are still needed for effectively provide rapid and long-lasting interventions. Liquid crystalline elastomers (LCEs) are biocompatible polymers able to reversibly change shape in response to a given stimulus and generate movement. Once stimulated, LCEs can produce tension or movement like a muscle. However, so far their application in biology was limited by slow response times and a modest possibility to modulate tension levels during activation. OBJECTIVE: To develop suitable LCE-based materials to assist cardiac contraction. METHODS AND RESULTS: Thanks to a quick, simple, and versatile synthetic approach, a palette of biocompatible acrylate-based light-responsive LCEs with different molecular composition was prepared and mechanically characterized. Out of this, the more compliant one was selected. This material was able to contract for some weeks when activated with very low light intensity within a physiological environment. Its contraction was modulated in terms of light intensity, stimulation frequency, and ton/toff ratio to fit different contraction amplitude/time courses, including those of the human heart. Finally, LCE strips were mounted in parallel with cardiac trabeculae, and we demonstrated their ability to improve muscular systolic function, with no impact on diastolic properties. CONCLUSIONS: Our results indicated LCEs are promising in assisting cardiac mechanical function and developing a new generation of contraction assist devices.

Conductive elastomer composites for fully polymeric, flexible bioelectronics.

Flexible polymeric bioelectronics have the potential to address the limitations of metallic electrode arrays by minimizing the mechanical mismatch at the device-tissue interface for neuroprosthetic applications. This work demonstrates the straightforward fabrication of fully organic electrode arrays based on conductive elastomers (CEs) as a soft, flexible and stretchable electroactive composite material. CEs were designed as hybrids of polyurethane elastomers (PU) and poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS), with the aim of combining the electrical properties of PEDOT:PSS with the mechanical compliance of elastomers. CE composites were fabricated by solvent casting of PEDOT:PSS dispersed in dissolved PU at different conductive polymer (CP) loadings, from 5 wt% to 25 wt%. The formation of PEDOT:PSS networks within the PU matrix and the resultant composite material properties were examined as a function of CP loading. Increased PEDOT:PSS loading was found to result in a more connected network within the PU matrix, resulting in increased conductivity and charge storage capacity. Increased CP loading was also determined to increase the Young's modulus and reduce the strain at failure. Biological assessment of CE composites showed them to mediate ReNcell VM human neural precursor cell adhesion. The increased stiffness of CE films was also found to promote neurite outgrowth. CE sheets were directly laser micromachined into a functional array and shown to deliver biphasic waveforms with comparable voltage transients to Pt arrays in in vitro testing.

Simple Synthesis of Elastomeric Photomechanical Switches That Self-Heal.

This article introduces a simple two-stage method to synthesize and program a photomechanical elastomer (PME) for light-driven artificial muscle-like actuations in soft robotics. First, photochromic azobenzene molecules are covalently attached to a polyurethane backbone via a two-part step-growth polymerization. Next, mechanical alignment is applied to induce anisotropic deformations in the PME-actuating films. Cross-linked through dynamic hydrogen bonds, the PMEs also possess autonomic self-healing properties without external energy input. This self-healing allows for a single alignment step of the PME film and subsequent "cut and paste" assembly for multi-axis actuation of a self-folded soft-robotic gripper from a single degree of freedom optical input.

Molecular Bottlebrushes as Novel Materials.

Molecular bottlebrushes are building blocks for the design of unique polymeric materials whose physical properties are fundamentally governed by their densely grafted structures. Recent developments in the area of reversible deactivation radical polymerization enabled facile and effective control over multiple molecular parameters. Owing to large molecular size, anisotropic conformation, and reduced chain entanglement, molecular bottlebrushes have empowered various applications that are challenging to achieve with linear polymers. In this Review, we focus on determining correlations between brushlike architectures and materials properties.

A Self-Healing Dielectric Supramolecular Elastomer Functionalized with Aniline Tetramer.

A new design strategy to produce a supramolecular elastomer with self-healing and dielectric properties by synthesizing an aniline tetramer (AT)-functionalized supramolecular elastomer (SE-AT) is demonstrated. The termination of AT in the supramolecular system not only shortens linear amide molecular chain to decrease glass transition temperature but also destroys the crystallization to achieve amorphous structure. The SE-AT provides two kinds of noncovalent bonding including π-π stacking and the hydrogen bond, which makes the material more easily healed. The SE-AT20% can heal mechanical properties within 24 h at room temperature without any external stimulus. The dielectric constant shows a continuous increase overall with increasing AT content. The material exhibits good electro-mechanical properties, which is attributed to a simultaneous increase in dielectric constant and decrease in modulus. The maximum actuated strain significantly increases with the increasing AT content and the SE-AT20% reaches 10% at 1 V µm-1 . Moreover, SE-AT exhibits the ability to regain actuated strain on the location of the mechanical damage after self-healing.