Strain-Induced Phase Separation and Mechanomodulation of Ionic Conduction in Anisotropic Nanocomposite Ionogels.

Ionogels have great potential for the development of tissue-like, soft, and stretchable ionotronics. However, conventional isotropic ionogels suffer from poor mechanical properties, low efficient force transmission, and tardy mechanoelectric response, hindering their practical utility. Here, we propose a simple one-step method to fabricate bioinspired anisotropic nanocomposite ionogels based on a combination of strain-induced phase separation and mechanomodulation of ionic conduction in the presence of attapulgite nanorods. These ionogels show high stretchability (747.1% strain), tensile strength (6.42 MPa), Young's modulus (83.49 MPa), and toughness (18.08 MJ/m3). Importantly, the liquid crystalline domain alignment-induced microphase separation and ionic conductivity enhancement during stretching endow these ionogels with an unusual mechanoelectric response and dual-programmable shape-memory properties. Moreover, the anisotropic structure, good elasticity, and unique resistance-strain responsiveness give the ionogel-based strain sensors high sensitivity, rapid response time, excellent fatigue resistance, and unique waveform-discernible strain sensing, which can be applied to real-time monitoring of human motions. The findings offer a promising way to develop bioinspired anisotropic ionogels to modulate the microstructure and properties for practical applications in advanced ionotronics.

Stretchable and recyclable gelatin Ionogel based ionic skin with extensive temperature tolerant, self-healing, UV-shielding, and sensing capabilities.

Fabricating sustainable ionic skin with multi-functional outstanding performances using biocompatible natural polymer-based ionogel is highly desired but remains a great challenge up to now. Herein, a green and recyclable ionogel has been fabricated by in-situ cross-linking of gelatin with a green bio-based multifunctional cross-linker of Triglycidyl Naringenin in ionic liquid. Benefiting from the unique multifunctional chemical crosslinking networks along with multiple reversible non-covalent interactions, the as-prepared ionogels exhibit high stretchability (>1000 %), excellent elasticity, fast room-temperature self-healability (>98 % healing efficiency at 6 min), and good recyclability. These ionogels are also highly conductive (up to 30.7 mS/cm at 150 °C), and exhibit extensive temperature tolerance (-23 to 252 °C) and outstanding UV-shielding ability. As a result, the as-prepared ionogel can easily be applied as stretchable ionic skin for wearable sensors, which exhibits high sensitivity, fast response time (102 ms), excellent temperature tolerance, and stability over 5000 stretching-relaxing cycles. More importantly, the gelatin-based sensor can be used in signal monitor system for various human motion real-time detection. This sustainable and multifunctional ionogel provides a new idea for easy and green preparation of advanced ionic skins.

Highly Tough, Stretchable, and Recyclable Ionogels with Crosslink-Enhanced Emission Characteristics for Anti-Counterfeiting and Motion Detection.

Traditional luminescent ionogels often suffer from poor mechanical properties and a lack of recyclability and regeneration, which limits their further application and sustainable development. Herein, a luminescent ionogel with strong mechanical properties and good recyclability has been designed and fabricated by introducing dynamic coordination bonds via in situ one-step crosslinking of acrylic acid in ionic liquid of 1-ethyl-3-methylimidazolium diethylphosphate by zinc dimethacrylate. Due to the special crosslinking of dynamic coordination bonds along with the hydrogen bond interaction, the as-prepared ionogel displays excellent stretchability and toughness, good self-adhesiveness, fast self-healability, and recyclability. Interestingly, the obtained ionogels exhibit tunable photoluminescence caused by the crosslink-enhanced emission (CEE) effect from the coordination bonds. Importantly, ionogels can be applied in information storage, information encryption, anti-counterfeiting due to their simple and in situ preparation method, and their special fluorescence performances. Moreover, an ionogel-based wearable sensor has rapid response time and a high gauge factor of 3.22 within a wide strain range from 1 to 700%, which can monitor various human movements accurately from subtle to large-scale motions. This paper offers a promising way to fabricate sustainable functional ionic liquid-based composites with CEE characteristics via an in situ one-step polymerization method.

Self-healing pectin/cellulose hydrogel loaded with limonin as TMEM16A inhibitor for lung adenocarcinoma treatment.

Lung cancer as one of the highest incident malignant tumors did not receive satisfactory chemotherapy due to lack of specific drug targets and targeted drugs. This study screened a new effective lung tumor inhibitor limonin from herbal medicine, which inhibited proliferation and promoted apoptosis of lung adenocarcinoma cells by targeting specific high expressed TMEM16A ion channel. Moreover, a novel biodegradable self-healing hydrogel was prepared from acylhydrazide functionalized carboxymethyl cellulose (CMC-AH) and oxidized pectin (pec-CHO) to reduce the side effects of the limonin to the body. The hydrogels showed fast gelation, good biocompatibility and sustained limonin release property. The limonin-loaded hydrogel significantly inhibited the growth of lung adenocarcinoma in xenografts mice because the limonin inhibited the proliferation, migration and promoted apoptosis of LA795 cells, and eliminated the acute toxicity through sustained release from the hydrogel. Combined the antitumor performance of the limonin and sustained release of pec-CHO/CMC-AH hydrogel, this limonin/hydrogel system achieved satisfactory antitumor effect and eliminated side effects in vivo. Therefore, this system has great potential application for enhanced lung adenocarcinoma therapy.

Muscle-Mimetic Highly Tough, Conductive, and Stretchable Poly(ionic liquid) Liquid Crystalline Ionogels with Ultrafast Self-Healing, Super Adhesive, and Remarkable Shape Memory Properties.

Here, we report a simple method for preparing muscle-mimetic highly tough, conductive, and stretchable liquid crystalline ionogels which contains only one poly(ionic liquid) (PIL) in an ionic liquid via in situ free radical photohomopolymerization by using nitrogen gas instead of air atmosphere. Due to eliminating the inhibition caused by dissolved oxygen, the polymerization under nitrogen gas has much higher molecular weight, lower critical sol-gel concentration, and stronger mechanical properties. More importantly, benefiting from the unique loofah-like microstructures along with the strong internal ionic interactions, entanglements of long PIL chains and liquid crystalline domains, the ionogels show special optical anisotropic, superstretchability (>8000%), high fracture strength (up to 16.52 MPa), high toughness (up to 39.22 MJ/m3), and have ultrafast self-healing, ultrastrong adhesive, and excellent shape memory properties. Due to its excellent stretchability and good conductive-strain responsiveness, the as-prepared ionogel can be easily applied for high-performance flexible and wearable sensors for motion detecting. Therefore, this paper provides an effective route and developed method to generate highly stretchable conductive liquid crystalline ionogels/elastomers that can be used in widespread flexible and wearable electronics.

Dual Thermo-Responsive and Strain-Responsive Ionogels for Smart Windows and Temperature/Motion Monitoring.

In this work, a stretchable, dual thermo-responsive and strain-responsive ionogel has been synthesized by one-step photopolymerization. The obtained ionogel shows an ultrahigh stretchability (∼3000%), a high ionic conductivity (up to 3.1 mS/cm), and a good temperature tolerance (-40 to 300 °C). Importantly, these ionogels show an upper critical solution temperature-type phase transition with a wide tunable phase-transition temperature (17.5-42.5 °C) and reversible color/transparency switching. In particular, the as-prepared ionogel-based flexible/wearable temperature monitors and smart windows show an excellent designability and programmability, temperature modulation ability, and thermal responsiveness. Moreover, the ionogels-based strain sensors have temperature- and strain-dual responsibility and a broad strain-sensing range (1-700%), which can effectively monitor various motions. This strategy of fabricating dual thermo- and strain-responsive ionogels by using a one-step method and only one polymer holds great promise for the next generation of multifunctional stimuli-responsive materials.

Poly(aspartic acid) based self-healing hydrogel with blood coagulation characteristic for rapid hemostasis and wound healing applications.

External hemorrhage, caused by insufficient hemostasis or surgical failure, could leads to shock or even tissue necrosis as the results of excessive blood loss. Furthermore, delayed coagulation, chronic inflammation, bacterial infection and slow cell proliferation are also major challenges to effective wound repairing. In this study, a novel hemostatic hydrogel was prepared by cross-linking inorganic polyphosphate (PolyP) conjugated poly(aspartic acid) hydrazide (PAHP) and PEO90 dialdehyde (PEO90 DA). Based on the dynamic characteristics of the acylhydrazone bond, the hydrogel could repair its cracks when broken under external forces. At the same time, the hydrogel showed outstanding biocompatibility and tissue adhesion with remarkable hemostatic performance. The New Zealand rabbit ear artery used as a in vivo hemostasis model and the results showed the PAHP hydrogel could stop bleeding of traumatic wound and reduce blood loss significantly. Meanwhile, the PAHP hydrogel presented intrinsic antibacterial activity, thus could inhibit the bacterial infection. In addition, the hydrogel loaded with mouse epidermal growth factor (mEGF) accelerated the wound repair rate and promoted the regeneration of fresh tissue in the mouse full thickness skin defect model. Altogether, the PAHP hydrogels exhibits great potential in the biomedical application, especially in wound dressing materials and tissue repairing.

Highly Stretchable and Self-Adhesive Elastomers Based on Polymer Chain Rearrangement for High-Performance Strain Sensors.

Polydimethylsiloxane (PDMS) has been widely used in many fields. However, the polymerization process of the siloxane chain is highly complex, and it is challenging to enhance the mechanical properties of PDMS elastomers significantly. We found that adding a small amount of polyoxyethylene lauryl ether (Brij-35) into siloxane polymers can result in B-PDMS elastomers with high tensile properties and strong adhesion. It is worth noting that this is the first study to improve the mechanical properties of PDMS using Brij-35. Here, we intensely studied a variety of process conditions that influence the cross-linking of PDMS, emphasizing the modification mechanism of the polymer chain. The hydroxyl groups in Brij-35 and the platinum catalyst in PDMS form a complex, which inhibits the cross-linking process of PDMS, not only forming a heterogeneous cross-linking network in the B-PDMS but also disentangling the strongly wound siloxane polymer chain, thereby rearranging the PDMS polymer chains. Furthermore, in order to prepare a strain sensor based on the B-PDMS elastomer under safe and convenient conditions, we prepared laser-scribed graphene powder (LSGP) by laser-scribing of graphene oxide (GO) films, and the LSGP and carbon nanotubes (CNTs) endowed the B-PDMS elastomers with excellent electrical properties. The sensor could firmly adhere to the skin and generate a high-quality response to a variety of human motions, and it could drive the robotic hand to grasp and lift objects accurately. The high-performance strain sensors based on B-PDMS have broad applications in medical sensing and biopotential measurement.

Ultrastretchable, Adhesive, Fast Self-Healable, and Three-Dimensional Printable Photoluminescent Ionic Skin Based on Hybrid Network Ionogels.

Developing multifunctional stretchable ionic skin (I-Skin) to mimic the sensations of the human skin is of great interest and shows promising potential in wearable sensors and human-machine interfaces (HMIs). However, common ionogels prepared with small-molecule cross-linkers and single networks can hardly satisfy the requirements of adjustable mechanical properties, strong adhesion, fast self-healability, and good stability in extreme environments. Herein, an ultrastretchable (>10,000%), ultrastrong adhesive (>6.8 MPa), ultrafast self-healable (10 s), high thermally stable (-60 to 250 °C), and three-dimensional (3D)-printable photoluminescent ionogel with shape memory properties has been designed. The ionogel consists of hyperbranched polymer covalent-cross-linked poly(zwitterionic ionic liquid)-co-poly(acrylic acid) and multiple dynamic bonding cross-linked networks. The excellent performance of the ionogel-based high-stretchable strain sensor and the triboelectric nanogenerator (TENG)-based self-powered touch sensor is further demonstrated over a wide temperature range (-40 to 150 °C). More importantly, ionogel-based I-Skin can work as an HMI for human gesture recognition and real-time wireless control of robots under extreme vacuum conditions and can also self-heal immediately along with function recovery after mechanical damage.

3D Printable, Highly Stretchable, Superior Stable Ionogels Based on Poly(ionic liquid) with Hyperbranched Polymers as Macro-cross-linkers for High-Performance Strain Sensors.

Stretchable ionogels have recently emerged as promising soft and safe ionic conductive materials for use in wearable and stretchable electrochemical devices. However, the complex preparation process and insufficient thermomechanical stability greatly limit the precise rapid fabrication and application of stretchable ionogels. Here, we report an in situ 3D printing method for fabricating high-performance single network chemical ionogels as advanced strain sensors. The ionogels consist of a special cross-linking network constructed by poly(ionic liquid) and hyperbranched polymer (macro-cross-linkers) that exhibits high stretchability (>1000%), superior room-temperature ionic conductivity (up to 5.8 mS/cm), and excellent thermomechanical stability (-75 to 250 °C). The strain sensors based on ionogels have a low response time (200 ms), high sensitivity with temperature independence, long-term durability (2000 cycles), and excellent temperature tolerance (-60 to 250 °C) and can be used as human motion sensors. This work provides a new strategy to design highly stretchable and superior stable electronic devices.

Gelation, Liquid Crystalline Behavior, and Ionic Conductivity of Nanocomposite Ionogel Electrolytes Based On Attapulgite Nanorods.

Anisotropic nanoparticles and their dispersions have attracted much attention because of their distinguished characteristics and promising applications. In this study, the novel liquid crystalline nanocomposite ionogel electrolyte materials based on anisotropic nanoparticles of attapulgite (ATP) have been prepared. The gelation, liquid crystalline (LC) behavior, thermal stability, and ionic conductivity were systematically investigated. Rheological, polarized optical microscopy (POM), and small-angle X-ray scattering (SAXS) measurements demonstrated that these liquid crystalline ionogels showed a two-step mechanism consisting of gelation and subsequent reorganization of the gel. Interestingly, the obtained ionogel electrolytes were very stable and LC gel structures were not destroyed even though the temperature was as high as 200 °C. Furthermore, these ionogels possessed outstanding thermal stability and the decomposition temperature exceeded 400 °C. Remarkably, the LC nanocomposite ionogel electrolytes exhibited high room temperature ionic conductivity and the value still exceeded 1.0 × 10-3 S/cm even when the ATP concentration up to 30 wt %. These novel findings are very useful for the fabrication of high temperature resistant electrochemical devices and liquid crystalline nanocomposite materials.

Novel Chemical Cross-Linked Ionogel Based on Acrylate Terminated Hyperbranched Polymer with Superior Ionic Conductivity for High Performance Lithium-Ion Batteries.

A new family of chemical cross-linked ionogel is successfully synthesized by photopolymerization of hyperbranched aliphatic polyester with acrylate terminal groups in an ionic liquid of 1-butyl-3-methylimidazolium tetrafluoroborate (BMIMBF4). The microstructure, viscoelastic behavior, mechanical property thermal stability, and ionic conductivities of the ionogels are investigated systematically. The ionogels exhibit high mechanical strength (up to 1.6 MPa) and high mechanical stability even at temperatures up to 200 °C. It is found to be thermally stable up to 371.3 °C and electrochemically stable above 4.3 V. The obtained ionogels show superior ionic conductivity over a wide temperature range (from 1.2 × 10-3 S cm-1 at 20 °C up to 5.0 × 10-2 S cm-1 at 120 °C). Moreover, the Li/LiFePO4 batteries based on ionogel electrolyte with LiBF4 show a higher specific capacity of 153.1 mAhg-1 and retain 98.1% after 100 cycles, exhibiting very stable charge/discharge behavior with good cycle performance. This work provides a new method for fabrication of novel advanced gel polymer electrolytes for applications in lithium-ion batteries.

Chemically crosslinked liquid crystalline poly(ionic liquid)s/halloysite nanotubes nanocomposite ionogels with superior ionic conductivity, high anisotropic conductivity and a high modulus.

A novel type of chemically crosslinked liquid crystalline nanocomposite ionogel electrolyte based on poly(ionic liquid) (PIL) with superior ionic conductivity and high anisotropic conductivity was designed and synthesized using the in situ photopolymerization of sheared soft ionogels containing charged halloysite nanotubes (HNTs) and ionic liquid monomers. The oriented structure was investigated using scanning electron microscopy (SEM) and small-angle X-ray scattering (SAXS). The chemically crosslinked backbone of the PIL and the addition of HNTs endowed the flexible ionogels with a combined very high modulus (up to 26.7 MPa) and mechanical strength (up to 4.4 MPa). Crucially, the obtained ionogels exhibited high mechanical stability even at temperatures up to 200 °C. Remarkably, in terms of the conductivities, the resulting pre-sheared ionogels displayed superior room temperature ionic conductivity (up to 6 mS cm-1) and a very high conductivity anisotropy ratio (up to 1600), owing to the alignment of the HNTs with oppositely charged surfaces and the high ionic conductivity of the polyelectrolyte PILs. Furthermore, flexible solid-state supercapacitor devices based on the high ion-conductive nanocomposite ionogels were fabricated, which demonstrated high and temperature-dependent specific capacitance, and remarkable cycling stability and flexible performance.

A facile one-step grafting of polyphosphonium onto halloysite nanotubes initiated by Ce(iv).

Polyphosphonium was facilely grafted onto HNTs in an aqueous phase by a one-step method initiated by Ce(iv) at a mild temperature. The modified HNTs were immersed in a sodium alginate solution to achieve a uniform hydrogel that shows desirable antibacterial activity.

In Situ Synthesis of Imidazolium-Crosslinked Ionogels via Debus-Radziszewski Reaction Based on PAMAM Dendrimers in Imidazolium Ionic liquid.

This study reports a remarkably facile method to synthesize novel ionogels with imidazolium cycle crosslinks based on polyamidoamine (PAMAM) dendrimers via one-pot, modified Debus-Radziszewski reaction in ionic liquid 1-ethyl-3-methylimidazolium acetate ([EMIM][OAc]). High room temperature ionic conductivity (up to 6.8 mS cm-1 ) is achieved, and more remarkably, it can still exceed 1 mS cm-1 when the dendrimer content reached 70% because PAMAM dendrimers are completely amorphous with many cavities and the newly formed imidazolium crosslinks contains ions. The elastic modulus of these ionogels can exceed 106 Pa due to the newly-formed rigid imidazolium crosslinks. Crucially, these ionogels are robust gels even at temperatures up to 160 °C. Such novel ionogels with high ionic conductivity, tunable modulus, and flexibility are desirable for use in high-temperature flexible electrochemical devices.

Smart H2O2-Responsive Drug Delivery System Made by Halloysite Nanotubes and Carbohydrate Polymers.

A novel chemical hydrogel was facilely achieved by coupling 1,4-phenylenebisdiboronic acid modified halloysite nanotubes (HNTs-BO) with compressible starch. The modified halloysite nanotubes (HNTs) and prepared hydrogel were characterized by solid-state nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and transmission electron microscope (TEM). The linkage of B-C in the hydrogel can be degraded into B-OH and C-OH units in the presence of H2O2 and result in the degradation of the chemical hydrogel. Pentoxifylline was loaded into the lumen of the HNTs-BO, and then gave the pentoxifylline-loaded hydrogel. The drug release profile shows that it was no more than 7% dissolved when using phosphate buffer solution (PBS) as the release medium. Notably, a complete release (near 90%) can be achieved with the addition of H2O2 ([H2O2] = 1 × 10-4 M), suggesting a high H2O2 responsiveness of the as-formed hydrogel. The drug release results also show that the "initial burst release" can be effectively suppressed by loading pentoxifylline inside the lumen of the HNTs rather than embedding the drug in the hydrogel network. The drug-loaded hydrogel with H2O2-responsive release behavior may open up a broader application in the field of biomedicine.

Dependences of Rheological and Compression Mechanical Properties on Cellular Structures for Impact-Protective Materials.

In this study, three typical impact-protective materials, D3O, PORON XRD, and DEFLEXION were chosen to explore the dependences of rheological and compression mechanical properties on the internal cellular structures with polymer matrix characteristics, which were examined using Fourier transform infrared spectroscopy, thermogravimetric analyses, and scanning electron microscopy with energy dispersive spectroscopy. The rheological property of these three foaming materials were examined using a rheometer, and the mechanical property in a compression mode was further examined using an Instron universal tensile testing machine. The dependences of rheological parameters, such as dynamic moduli, normalized moduli, and loss tangent, on angular frequency, and the dependences of mechanical properties in compression, such as the degree of strain-hardening, hysteresis, and elastic recovery, on the strain rate for D3O, PORON XRD, and DEFLEXION can be well-correlated with their internal cellular structural parameters, revealing, for example, that D3O and PORON XRD exhibit simultaneously high strength and great energy loss in a high-frequency impact, making them suitable for use as soft, close-fitting materials; however, DEFLEXION dissipates much energy whether it suffers a large strain rate or not, making it suitable for use as a high-risk impact-protective material. The rheometry and compression tests used in this study can provide the basic references for selecting and characterizing certain impact-protective materials for applications.

Liquid crystal self-assembly of halloysite nanotubes in ionic liquids: a novel soft nanocomposite ionogel electrolyte with high anisotropic ionic conductivity and thermal stability.

We report a novel class of liquid crystalline (LC) nanohybrid ionogels fabricated via self-assembly of natural halloysite nanotubes (HNTs) in ionic liquids (ILs). The obtained ionogels are very stable and nonvolatile and show LC phases over a wide temperature range. Remarkably, the nanocomposite ionogels exhibit high anisotropic ionic conductivity after shear, and their room temperature ionic conductivity can reach 3.8 × 10(-3) S cm(-1) for aligned nanotubes perpendicular to the electrode even when the HNTs content increases to 40 wt%, which is 380 times higher than that obtained for aligned nanotubes parallel to the electrode, which is 1.0 × 10(-5) S cm(-1). Crucially, the obtained LC nanocomposite ionogels have very high thermal stability, which can sustain 400 °C thermal treatment. The findings will promote the development of novel nanocomposite ionogel electrolytes with faster ion transport and larger anisotropic conductivity.

Selective Modification of Halloysite Nanotubes with 1-Pyrenylboronic Acid: A Novel Fluorescence Probe with Highly Selective and Sensitive Response to Hyperoxide.

A novel fluorescence probe based on modified halloysite nanotubes (HNTs) by using 1-pyrenylboronic acid selectively grafted onto the inner surface of lumen was successfully achieved. The solid-state nuclear magnetic resonance ((13)C and (11)B), X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) confirmed that the boronic acid group only binds to alumina at the tube lumen and does not bind the tube's outer siloxane surface. The modified HNTs (HNTs-PY) inherit the spectroscopic properties relating to the pyrene units. Interestingly, the established Al-O-B linkage gives the H2O2-sensitivity to pyrene grafted tubes. HNTs-PY exhibits a highly specific "turn-off" response for hyperoxide over other reactive oxygen species (ROS) and oxidative ions owing to their chemoselective boronate-to-phenol switch. The "turn-off" response can even be tracked when the additional amount of H2O2 was limited to 1 × 10(-6) mol. Thus, the selective modification method under mild conditions for the design of novel organic-inorganic hybrid fluorescence probe may open up a broader application as well as for identification and diagnosis.

Liquid crystalline phase behavior and sol-gel transition in aqueous halloysite nanotube dispersions.

The liquid crystalline phase behavior and sol-gel transition in halloysite nanotubes (HNTs) aqueous dispersions have been investigated by applying polarized optical microscopy (POM), macroscopic observation, rheometer, small-angle X-ray scattering, scanning electron microscopy, and transmission electron microscopy. The liquid crystalline phase starts to form at the HNT concentration of 1 wt %, and a full liquid crystalline phase forms at the HNT concentration of 25 wt % as observed by POM and macroscopic observation. Rheological measurements indicate a typical shear flow behavior for the HNT aqueous dispersions with concentrations above 20 wt % and further confirm that the sol-gel transition occurs at the HNT concentration of 37 wt %. Furthermore, the HNT aqueous dispersions exhibit pH-induced gelation with more intense birefringence when hydrochloric acid (HCl) is added. The above findings shed light on the phase behaviors of diversely topological HNTs and lay the foundation for fabrication of the long-range ordered nano-objects.