Highly Stretchable Conductive Covalent Coacervate Gels for Electronic Skin

Highly stretchable electrically conductive hydrogels have been extensively researched in recent years, especially for applications in strain and pressure sensing, electronic skin, and implantable bioelectronic devices. Herein, we present a new cross-linked complex coacervate approach to prepare conductive hydrogels that are both highly stretchable and compressive. The gels involve a complex coacervate between carboxylated nanogels and branched poly(ethylene imine), whereby the latter is covalently cross-linked by poly(ethylene glycol) diglycidyl ether (PEGDGE). Inclusion of graphene nanoplatelets (Gnp) provides electrical conductivity as well as tensile and compressive strain-sensing capability to the hydrogels. We demonstrate that judicious selection of the molecular weight of the PEGDGE cross-linker enables the mechanical properties of these hydrogels to be tuned. Indeed, the gels prepared with a PEGDGE molecular weight of 6000 g/mol defy the general rule that toughness decreases as strength increases. The conductive hydrogels achieve a compressive strength of 25 MPa and a stretchability of up to 1500%. These new gels are both adhesive and conformal. They provide a self-healable electronic circuit, respond rapidly to human motion, and can act as strain-dependent sensors while exhibiting low cytotoxicity. Our new approach to conductive gel preparation is efficient, involves only preformed components, and is scalable

Highly Stretchable Conductive Covalent Coacervate Gels for Electronic Skin.

Highly stretchable electrically conductive hydrogels have been extensively researched in recent years, especially for applications in strain and pressure sensing, electronic skin, and implantable bioelectronic devices. Herein, we present a new cross-linked complex coacervate approach to prepare conductive hydrogels that are both highly stretchable and compressive. The gels involve a complex coacervate between carboxylated nanogels and branched poly(ethylene imine), whereby the latter is covalently cross-linked by poly(ethylene glycol) diglycidyl ether (PEGDGE). Inclusion of graphene nanoplatelets (Gnp) provides electrical conductivity as well as tensile and compressive strain-sensing capability to the hydrogels. We demonstrate that judicious selection of the molecular weight of the PEGDGE cross-linker enables the mechanical properties of these hydrogels to be tuned. Indeed, the gels prepared with a PEGDGE molecular weight of 6000 g/mol defy the general rule that toughness decreases as strength increases. The conductive hydrogels achieve a compressive strength of 25 MPa and a stretchability of up to 1500%. These new gels are both adhesive and conformal. They provide a self-healable electronic circuit, respond rapidly to human motion, and can act as strain-dependent sensors while exhibiting low cytotoxicity. Our new approach to conductive gel preparation is efficient, involves only preformed components, and is scalable

Study on conductive hydrogels in flexible and wearable triboelectric devices towards energy-harvesting and sensing applications (エネルギーハーベスティングおよびセンシングに向けたフレキシブルでウェアラブルな摩擦発電デバイスにおける導電性ハイドロゲルに関する研究)

信州大学(Shinshu university)博士（工学）この博士論文は、次の学術雑誌論文を一部に使用しています。 / ACS Applied Materials Interfaces 14(7) :9126-9137(2022); doi:10.1021/acsami.1c23176 / Advanced Fiber Materials 4(6) :1486-1499(2022); doi:10.1007/s42765-022-00181-4 / Chemical Engineering Journal 457 :141276(2023); doi:10.1016/j.cej.2023.141276ThesisDONG, LI. Study on conductive hydrogels in flexible and wearable triboelectric devices towards energy-harvesting and sensing applications (エネルギーハーベスティングおよびセンシングに向けたフレキシブルでウェアラブルな摩擦発電デバイスにおける導電性ハイドロゲルに関する研究). 信州大学, 2023, 博士論文. 博士（工学）, 甲第802号, 令和05年03月20日授与.doctoral thesi

Rosettes & Ribbons: Some Recent Accomplishments of Note at the School

Developing a simple produces for efficient derivation of motor neurons (MNs) is essential for neural tissue engineering studies. Stem cells with high capacity for neural differentiation and scaffolds with the potential to promote motor neurons differentiation are promising candidates for neural tissue engineering. Recently, human olfactory ecto-mesenchymal stem cells (OE-MSCs), which are isolated easily from the olfactory mucosa, are considered a new hope for neuronal replacement due to their neural crest origin. Herein, we synthesized conducting hydrogels using different concentration of chitosan-g-aniline pentamer, gelatin, and agarose. The chemical structures, swelling and deswelling ratio, ionic conductivity and thermal properties of the hydrogel were characterized. Scaffolds with 10 chitosan-g-aniline pentamer/gelatin (S10) were chosen for further investigation and the potential of OE-MSCs as a new source for programming to motor neuron-like cells investigated on tissue culture plate (TCP) and conductive hydrogels. Cell differentiation was evaluated at the level of mRNA and protein synthesis and indicated that conductive hydrogels significantly increased the markers related to motor neurons including Hb-9, Islet-1 and ChAT compared to TCP. Taken together, the results suggest that OE-MSCs would be successfully differentiated into motor neuron-like cells on conductive hydrogels and would have a promising potential for treating motor neuron-related diseases. © 201

Microengineered Hollow Graphene Tube Systems Generate Conductive Hydrogels with Extremely Low Filler Concentration

The fabrication of electrically conductive hydrogels is challenging as the introduction of an electrically conductive filler often changes mechanical hydrogel matrix properties. Here, we present an approach for the preparation of hydrogel composites with outstanding electrical conductivity at extremely low filler loadings (0.34 S m-1, 0.16 vol %). Exfoliated graphene and polyacrylamide are microengineered to 3D composites such that conductive graphene pathways pervade the hydrogel matrix similar to an artificial nervous system. This makes it possible to combine both the exceptional conductivity of exfoliated graphene and the adaptable mechanical properties of polyacrylamide. The demonstrated approach is highly versatile regarding porosity, filler material, as well as hydrogel system. The important difference to other approaches is that we keep the original properties of the matrix, while ensuring conductivity through graphene-coated microchannels. This novel approach of generating conductive hydrogels is very promising, with particular applications in the fields of bioelectronics and biohybrid robotics

Polyvinyl Alcohol/Graphene Oxide Conductive Hydrogels via the Synergy of Freezing and Salting Out for Strain Sensors

Hydrogels of flexibility, strength, and conductivity have demonstrated broad applications in wearable electronics and soft robotics. However, it is still a challenge to fabricate conductive hydrogels with high strength massively and economically. Herein, a simple strategy is proposed to design a strong ionically conductive hydrogel. This ion-conducting hydrogel was obtained under the synergistic action by salting out the frozen mixture of polyvinyl alcohol (PVA) and graphene oxide (GO) using a high concentration of sodium chloride solution. The developed hydrogel containing only 5 wt% PVA manifests good tensile stress (65 kPa) and elongation (180%). Meanwhile, the PVA matrix doped with a small amount of GO formed uniformly porous ion channels after salting out, endowed the PVA/GO hydrogel with excellent ionic conductivity (up to 3.38 S m; -1; ). Therefore, the fabricated PVA/GO hydrogel, anticipated for a strain sensor, exhibits good sensitivity (Gauge factor = 2.05 at 100% strain), satisfying working stability (stably cycled for 10 min), and excellent recognition ability. This facile method to prepare conductive hydrogels displays translational potential in flexible electronics for engineering applications

Anti-freezing conductive zwitterionic composite hydrogels for stable multifunctional sensors

Zwitterionic conductive hydrogels have shown potential application in wearable strain and pressure sensors. However, there are still fundamental challenges to achieve zwitterionic hydrogels with excellent mechanical properties, able to keep flexibility at sub-zero temperatures. To overcome these limitations, a zwitterionic conductive hydrogel was fabricated in this work by in-situ polymerization of aniline (ANI) monomer in a copolymer of sulfobetaine methacrylate (SBMA) and acrylic acid (AA) matrix. The obtained hydrogel possesses outstanding anti-freezing performance (without obvious loss of stretchability at −18 °C) and water-retaining properties, due to the introduction of LiCl on the zwitterionic polymer matrix. The synergy of chemical and physical crosslinking between poly (SBMA-co-AA) and polyaniline (PANI) networks enhance the mechanical performance of the zwitterionic hydrogel, that exhibits a fracture tensile strength of 470 kPa, and a fracture strain up to 600 %. Additionally, the integration of PANI confers stable conductivity (2.23 S m−1, maintained at 1.89 S m−1 even at −18 °C), high sensitivity (GF = 1.74), and short response and recovery times (223 ms and 191 ms, respectively). The hydrogel can be applied as a flexible sensor to accurately detect various human motions. This work provides a feasible strategy for developing wearable multifunctional sensors in a wide working temperature range.</p

Highly sensitive, stretchable and durable strain sensors based on conductive double-network polymer hydrogels

Hydrogel-based strain sensors have been attracting immense attention for wearable electronic devices owing to their intrinsic soft characteristics and flexibility. However, developing hydrogel sensors with hightensile strength, stretchability, and strain sensitivity remains a great challenge. Herein, we report a technique to synthesize highly sensitive hydrogel-based strain sensors by integrating carbon nanofibers (CNFs) with a double-network (DN) polymer hydrogel matrix comprising of a physically cross-linked agar network and a covalently cross-linked polyacrylamide (PAAm) network. The resultant nanocomposite sensors display superior piezoresistive sensitivity with a hightrue gauge factor (GFT = 1.78) at an ultrahigh strain of 1,000%, a fast response time and linear correlation of ln(R/R0) and ln(L/L0) up to 1,000% strain. Most significantly, these sensors possess highmechanical strength (~0.6 MPa) and superb durability (>1,000 cycles at strain of 100%), stemming from the effective energy dissipation mechanism of the first agar network acting as sacrificial bonds and the CNFs serving as dynamic nanofillers. The combination of highstrain sensitivity and ultrahigh stretchability of hydrogel sensors makes it possible to sense both small mechanical deformations induced by human motions and large strain up to 1,000%

Highly Conductive, Stretchable, and Cell-Adhesive Hydrogel by Nanoclay Doping

Electrically conductive materials that mimic physical and biological properties of tissues are urgently required for seamless brain-machine interfaces. Here, a multinetwork hydrogel combining electrical conductivity of 26 S m-1 , stretchability of 800%, and tissue-like elastic modulus of 15 kPa with mimicry of the extracellular matrix is reported. Engineering this unique set of properties is enabled by a novel in-scaffold polymerization approach. Colloidal hydrogels of the nanoclay Laponite are employed as supports for the assembly of secondary polymer networks. Laponite dramatically increases the conductivity of in-scaffold polymerized poly(ethylene-3,4-diethoxy thiophene) in the absence of other dopants, while preserving excellent stretchability. The scaffold is coated with a layer containing adhesive peptide and polysaccharide dextran sulfate supporting the attachment, proliferation, and neuronal differentiation of human induced pluripotent stem cells directly on the surface of conductive hydrogels. Due to its compatibility with simple extrusion printing, this material promises to enable tissue-mimetic neurostimulating electrodes

Organic electrode coatings for next-generation neural interfaces

Traditional neuronal interfaces utilize metallic electrodes which in recent years have reached a plateau in terms of the ability to provide safe stimulation at high resolution or rather with high densities of microelectrodes with improved spatial selectivity. To achieve higher resolution it has become clear that reducing the size of electrodes is required to enable higher electrode counts from the implant device. The limitations of interfacing electrodes including low charge injection limits, mechanical mismatch and foreign body response can be addressed through the use of organic electrode coatings which typically provide a softer, more roughened surface to enable both improved charge transfer and lower mechanical mismatch with neural tissue. Coating electrodes with conductive polymers or carbon nanotubes offers a substantial increase in charge transfer area compared to conventional platinum electrodes. These organic conductors provide safe electrical stimulation of tissue while avoiding undesirable chemical reactions and cell damage. However, the mechanical properties of conductive polymers are not ideal, as they are quite brittle. Hydrogel polymers present a versatile coating option for electrodes as they can be chemically modified to provide a soft and conductive scaffold. However, the in vivo chronic inflammatory response of these conductive hydrogels remains unknown. A more recent approach proposes tissue engineering the electrode interface through the use of encapsulated neurons within hydrogel coatings. This approach may provide a method for activating tissue at the cellular scale, however, several technological challenges must be addressed to demonstrate feasibility of this innovative idea. The review focuses on the various organic coatings which have been investigated to improve neural interface electrodes