Flexible and ultrasensitive piezoresistive electronic skin based on chitin/sulfonated carbon nanotube films.

Wearable electronic skin has gained increasing popularity due to its remarkable properties of high flexibility, sensitivity, and lightweight, making it an ideal choice for detecting human physiological activity. In this study, we successfully prepared e-skin using regenerated chitin (RCH) and sulfonated carbon nanotubes (SCNTs). The e-skin demonstrated brilliant mechanical and sensing properties, exhibiting a sensitivity of 1.75 kPa-1 within the 0-5 kPa range and a fast response-recovery time of <10 ms. Furthermore, it displayed an ultra-low detection limit of 1.39 Pa (5 mg), exceptional stability (up to 11,000 cycles), and a remarkable mechanical strength, reaching up to 50 MPa. Moreover, the e-skin was fabricated through a simple and economical approach. With the popularity of micro sensing devices, the e-skin holds tremendous potential for various applications, including wearable electronic devices, health and sports monitoring, artificial intelligence and other fields.

High-performance dielectric film capacitors based on cellulose/Al2O3 nanosheets/PVDF composites.

The design and preparation of novel renewable biomass-based dielectric composites have drawn great attention recently. Here, cellulose was dissolved in NaOH/urea aqueous solution, and Al2O3 nanosheets (AONS) synthesized by hydrothermal method were used as fillers. Then the regenerated cellulose (RC)-AONS dielectric composite films were prepared by regeneration, washing and drying. The two-dimensional AONS had a better effect on improving the dielectric constant and breakdown strength of the composites, so that the RC-AONS composite film with 5 wt% AONS content reached an energy density of 6.2 J/cm3 at 420 MV/m. Furthermore, in order to improve the dielectric energy storage properties of cellulose films in high humidity environment, the hydrophobic polyvinylidene fluoride (PVDF) was innovatively introduced to construct RC-AONS-PVDF composite films. The energy storage density of the prepared ternary composite films could reach 8.32 J/cm3 at 400 MV/m, which was 416 % improvement against that of the commercially biaxially oriented polypropylene (2 J/cm3), and could be cycled for >10,000 times under 200 MV/m. Concurrently, the water absorption of the composite film in humidity was effectively reduced. This work broadens the application prospect of biomass-based materials in the field of film dielectric capacitor.

Ho-Ion-Polymer/Graphene Heterojunctions Toward Room-Temperature Ferromagnets.

Organic ferromagnetic materials offer great promise for spintronic devices, carbon-based chips, and quantum communications, but remain as a challenging issue due to their low saturation magnetization and/or unsustainable ferromagnetic properties. To date, magnetic ion polymers have displayed paramagnetism without exception at room-temperature. In this study, it is reported for the first time that, owing to the structural restriction and charge exchange of Ho ion by polymer/graphene π-π stacking heterojunctions, holmium ion polymer composites exhibited typical hysteresis lines of ferromagnetic materials at room temperature. The room-temperature ferromagnetic ion polymer composite presented the highest saturation magnetization value of 3.36 emu g-1 and unprecedented sustainable ferromagnetism, compared to reported room-temperature organic ferromagnetic materials. Accordingly, prepared ferromagnetic composites also achieved impressive wave absorption properties, with a maximum reflection loss of as much as -57.32 dB and a broad absorption bandwidth of 5.05 GHz. These findings may promote the development of room-temperature organic ferromagnetic materials.

Alicyclic polyimides with large band gaps exhibit superior high-temperature capacitive energy storage.

Flexible polymer dielectrics for capacitive energy storage that can function well at elevated temperatures are increasingly in demand for continuously advancing and miniaturizing electrical devices. However, traditional high-resistance polymer dielectrics composed of aromatic backbones have a compromised band gap (Eg) and hence suffer from low breakdown strength and a huge loss at high temperatures. Here, based on the density functional theory (DFT) calculations, rigid and non-coplanar alicyclic segments are introduced into the polyimide backbone to overcome the incompatibility of a high glass transition temperature (Tg) and large Eg. Thanks to the large optical Eg (∼4.6 eV) and high Tg (∼277 °C), the all-alicyclic polyimide at 200 °C delivers a maximum discharge energy density (Ue) of 5.01 J cm-3 with a charge-discharge efficiency (η) of 78.1% at 600 MV m-1, and a record Ue of 2.55 J cm-3 at η = 90%, which is 10-fold larger than that of the state-of-art commercial polyetherimides (PEIs). In addition, compared with aromatic polyimides, the all-alicyclic polyimide possesses a better self-clearing characteristic due to a smaller ratio of carbon to hydrogen and oxygen, which facilitates its long-term reliability in practical applications.

TOCN/copper calcium titanate composite aerogel films as high-performance triboelectric materials for energy harvesting.

The development of high-performance cellulose-based triboelectric nanogenerators (TENG) has been a subject widely concerned by researchers. Here, we prepared a composite aerogel film based on TEMPO-oxidized cellulose nanofiber (TOCN) and copper calcium titanate (CaCu3Ti4O12, CCTO) nanoparticles. Under their comprehensive effects of the enhanced dielectric performance, the TOCN/CCTO-20 composite film with 20 % CCTO content based TENG device showed the best output performance of an open circuit voltage of 152 V, a short circuit current of 33.8 µA and a power density of 483 mW/m2, which were 3.37, 4.07 and 3.71 times higher than that of the pure TOCN based TENG device, respectively. In addition, effects of external force conditions, aerogel film size parameters and the agglomeration state of high filler content on the output performance were also studied. These results indicated that the TOCN/CCTO composite aerogel films can be used as efficient and low-cost cellulose-based triboelectric positive materials for energy harvesting.

Hydrangea-like nanocellulose microspheres with high dye adsorption and drug encapsulation prepared by emulsion method.

Currently, microspheres with high adsorption capacity play a crucial role in dye adsorption and drug loading. In this study, 2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPO)-oxidized cellulose nanofibrils (TOCN) could be used to form nanocellulose microspheres by the emulsion method. The prepared hydrangea-like nanocellulose microspheres presented a stable three-dimensional network porous structure and exhibited excellent adsorption properties. The TOCN microspheres had a high adsorption capacity for methylene blue (MB) and methyl orange (MO) with the optimal adsorption capacity of 412.1 mg g-1 and 286.5 mg g-1 under neutral conditions, respectively. The TOCN microspheres displayed excellent adsorption selectivity on MB/MO mixed dyes, which could be used to selectively adsorb MB. Besides, the encapsulation rate of the positively charged drug doxorubicin hydrochloride (DOX) was as high as 93 %, and the drug loading capacity was as high as 34.5 %. Overall, our prepared nanocellulose microspheres had great potential for application in dye adsorption and drug delivery systems.

Corona-Poled Porous Electrospun Films of Gram-Scale Y-Doped ZnO and PVDF Composites for Piezoelectric Nanogenerators.

For digging out eco-friendly and well-performed energy harvesters, piezoelectric nanogenerators are preferred owing to their effortless assembly. Corona-poling promotes output performance of either aligned or porous PVDF electrospun films and higher piezoelectric output was achieved by corona-poled porous PVDF electrospun films due to more poled electret dipoles in pores. Increasing the duration of electrospinning rendered more electret dipoles in PVDF porous electrospun films, resulting in higher piezoelectric output. Moreover, corona-poled PVDF/Y-ZnO porous electrospun films performed better than corona-poled PVDF/ZnO porous electrospun films because of the larger polar crystal face of Y-ZnO. Flexible piezoelectric polymer PVDF and high-piezoelectric Y-ZnO complement each other in electrospun films. With 15 wt% of Y-ZnO, corona-poled PVDF/Y-ZnO porous electrospun films generated maximum power density of 3.6 µW/cm2, which is 18 times that of PVDF/BiCl3 electrospun films.

Fine mapping of powdery mildew and stripe rust resistance genes Pm5V/Yr5V transferred from Dasypyrum villosum into wheat without yield penalty.

KEY MESSAGE: The novel wheat powdery mildew and stripe rust resistance genes Pm5V/Yr5V are introgressed from Dasypyrum villosum and fine mapped to a narrowed region in 5VS, and their effects on yield-related traits were characterized. The powdery mildew and stripe rust seriously threaten wheat production worldwide. Dasypyrum villosum (2n = 2x = 14, VV), a relative of wheat, is a valuable resource of resistance genes for wheat improvement. Here, we describe a platform for rapid introgression of the resistance genes from D. villosum into the wheat D genome. A complete set of new wheat-D. villosum V (D) disomic substitution lines and 11 D/V Robertsonian translocation lines are developed and characterized by molecular cytogenetic method. A new T5DL·5V#5S line NAU1908 shows resistance to both powdery mildew and stripe rust, and the resistances associated with 5VS are confirmed to be conferred by seedling resistance gene Pm5V and adult-plant resistance gene Yr5V, respectively. We flow-sort chromosome arm 5VS and sequence it using the Illumina NovaSeq 6000 system that allows us to generate 5VS-specific markers for genetic mapping of Pm5V/Yr5V. Fine mapping shows that Pm5V and Yr5V are closely linked and the location is narrowed to an approximately 0.9 Mb region referencing the sequence of Chinese Spring 5DS. In this region, a NLR gene in scaffold 24,874 of 5VS orthologous to TraesCS5D02G044300 is the most likely candidate gene for Pm5V. Soft- and hard-grained T5DL·5V#5S introgressions confer resistance to both powdery mildew and stripe rust in diverse wheat genetic backgrounds without yield penalty. Meanwhile, significant decrease in plant height and increase in yield were observed in NIL-5DL·5V#5S compared with that in NIL-5DL·5DS. These results indicate that Pm5V/Yr5V lines might have the potential value to facilitate wheat breeding for disease resistance.

Polyimide Nanodielectrics Doped with Ultralow Content of MgO Nanoparticles for High-Temperature Energy Storage.

Advanced polymer dielectrics with high energy density at elevated temperatures are highly desired to meet the requirements of modern electronic and electrical systems under harsh conditions. Herein, we report a novel polyimide/magnesium oxide (PI/MgO) nanodielectric that exhibits high energy storage density (Ue) and charge-discharge efficiency (η) along with excellent cycling stability at elevated temperatures. Benefiting from the large bandgap of MgO and the extended interchain spacing of PI, the composite films can simultaneously achieve high dielectric constant and high breakdown strength, leading to enhanced energy storage density. The nanocomposite film doped with 0.1 vol% MgO can achieve a maximum Ue of 2.6 J cm-3 and a η of 89% at 450 MV m-1 and 150 °C, which is three times that of the PI film under the same conditions. In addition, embedding ultralow content of inorganic fillers can avoid aggregation and facilitate its large-scale production. This work may provide a new paradigm for exploring polymer nanocomposites with excellent energy storage performance at high temperatures and under a high electric field.

Porous cellulose composite aerogel films with super piezoelectric properties for energy harvesting.

The piezoelectric effect is one of the most promising electromechanical coupling processes for mechanical energy conversion and energy harvesting. However, natural polymer based piezoelectric materials are of poor piezoelectric performance. we developed flexible porous piezoelectric aerogel films based on TEMPO-oxidized cellulose nanofibrils (TOCN) and MoS2 nanosheets. Those aerogel films possessed large specific surface areas and abundant mesopores. Moreover, they exhibited very good piezoelectric properties when a field strength of 20 MV/m was used to polarize MoS2 nanosheets and air in the mesopores. When assembled to piezoelectric nanogenerators (PENGs), a TOCN/MoS2 aerogel film PENG containing 6 wt% of MoS2 exhibited the best output performance. It generated an open circuit voltage of 42 V and a short-circuit current of 1.1 µA, a maximum area power density of 1.29 µW/cm2 and a maximum volume power density of 0.143 µW/cm3. These features enable them to be promising piezoelectric materials for energy harvesting.

Solid-state cooling by elastocaloric polymer with uniform chain-lengths.

Although the elastocaloric effect was found in natural rubber as early as 160 years ago, commercial elastocaloric refrigeration based on polymer elastomers has stagnated owing to their deficient elastocaloric effects and large extension ratios. Herein, we demonstrate that polymer elastomers with uniform molecular chain-lengths exhibit enormous elastocaloric effects through reversible conformational changes. An adiabatic temperature change of -15.3 K and an isothermal entropy change of 145 J kg-1 K-1, obtained from poly(styrene-b-ethylene-co-butylene-b-styrene) near room temperature, exceed those of previously reported elastocaloric polymers. A rotary-motion cooling device is tailored to high-strains characteristics of rubbers, which effectively discharges the cooling energy of polymer elastomers. Our work provides a strategy for the enhancement of elastocaloric effects and could promote the commercialization of solid-state cooling devices based on polymer elastomers.

Highly Sensitive Multifunctional Electronic Skin Based on Nanocellulose/MXene Composite Films with Good Electromagnetic Shielding Biocompatible Antibacterial Properties.

Electronic skin has aroused extensive research interest due to high similarity with human skin. Realizing a multifunctional electronic skin that is highly consistent with skin functions and endowed with more other functions is now a more urgent need and important challenge. Here, we use 2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPO)-oxidized cellulose nanofibril (TOCN) dispersion and highly conductive Ti3C2TX dispersion to prepare TOCN/Ti3C2TX composite film through vacuum-assisted filtration. The obtained composite film imitating the nacre-like lamellar structure of natural shells has good mechanical properties (124.6 MPa of tensile strength). Meanwhile, the composite film also showed excellent electromagnetic shielding performance (36 dB), biocompatibility, and antibacterial properties. In addition, the piezoresistive sensor assembled from the composite film exhibited a high sensitivity (11.6 kPa-1), fast response and recovery time (≤10 ms), ultralow monitoring limit (0.2 Pa), and long-term stability (>10 000 cycles). It also could detect human daily activities such as finger bent, chewing, and so on.

Synchronously Strengthen and Toughen Polypropylene Using Tartaric Acid-Modified Nano-CaCO3.

In order to overcome the challenge of synchronously strengthening and toughening polypropylene (PP) with a low-cost and environmental technology, CaCO3 (CC) nanoparticles are modified by tartaric acid (TA), a kind of food-grade complexing agent, and used as nanofillers for the first time. The evaluation of mechanical performance showed that, with 20 wt.% TA-modified CC (TAMCC), the impact toughness and tensile strength of TAMCC/PP were 120% and 14% more than those of neat PP, respectively. Even with 50 wt.% TAMCC, the impact toughness and tensile strength of TAMCC/PP were still superior to those of neat PP, which is attributable to the improved compatibility and dispersion of TAMCC in a PP matrix, and the better fluidity of TAMCC/PP nanocomposite. The strengthening and toughening mechanism of TAMCC for PP involves interfacial debonding between nanofillers and PP, and the decreased crystallinity of PP, but without the formation of ß-PP. This article presents a new applicable method to modify CC inorganic fillers with a green modifier and promote their dispersion in PP. The obtained PP nanocomposite simultaneously achieved enhanced mechanical strength and impact toughness even with high content of nanofillers, highlighting bright perspective in high-performance, economical, and eco-friendly polymer-inorganic nanocomposites.

Significant Improvements in Dielectric Constant and Energy Density of Ferroelectric Polymer Nanocomposites Enabled by Ultralow Contents of Nanofillers.

Polymer dielectrics with excellent processability and high breakdown strength (Eb ) enable the development of high-energy-density capacitors. Although the improvement of dielectric constant (K) of polymer dielectric has been realized by adding high-K inorganic fillers with high contents (>10 vol%), this approach faces significant challenges in scalable film processing. Here, the incorporation of ultralow ratios (<1 vol%) of low-K Cd1- x Znx Se1- y Sy nanodots into a ferroelectric polymer is reported. The polymer composites exhibit substantial and concurrent increase in both K and Eb , yielding a discharged energy density of 26.0 J cm-3 , outperforming the current dielectric polymers and nanocomposites measured at ≤600 MV m-1 . The observed unconventional dielectric enhancement is attributed to the structural changes induced by the nanodot fillers, including transformation of polymer chain conformation and induced interfacial dipoles, which have been confirmed by density function theory calculations. The dielectric model established in this work addresses the limitations of the current volume-average models on the polymer composites with low filler contents and gives excellent agreement to the experimental results. This work provides a new experimental route to scalable high-energy-density polymer dielectrics and also advances the fundamental understanding of the dielectric behavior of polymer nanocomposites at atomistic scales.

Effect of Stretching on Crystalline Structure, Ferroelectric and Piezoelectric Properties of Solution-Cast Nylon-11 Films.

Compared to polyvinylidene fluoride (PVDF) and its copolymers, castor-oil-derived nylon-11 has been less explored over the past decades, despite its excellent piezoelectric properties at elevated temperatures. To utilize nylon-11 for future sensor or vibrational energy harvesting devices, it is important to control the formation of the electroactive δ' crystal phase. In this work, nylon-11 films were first fabricated by solution-casting and were then uniaxially stretched at different stretching ratios (SR) and temperatures (Ts) to obtain a series of stretched films. The combination of two-dimensional wide-angle X-ray diffraction (2D-WAXD) and differential scanning calorimetry (DSC) techniques showed that the fraction of the δ' crystal phase increased with the stretching ratio and acquired a maximum at a Ts of 80 °C. Further, it was found that the ferroelectric and piezoelectric properties of the fabricated nylon-11 films could be correlated well with their crystalline structure. Consequently, the stretched nylon-11 film stretched at an SR of 300% and a Ts of 80 °C showed maximum remanent polarization and a remarkable piezoelectric coefficient of 7.2 pC/N. A simple piezoelectric device with such a nylon-11 film was made into a simple piezoelectric device, which could generate an output voltage of 1.5 V and a current of 11 nA, respectively.

Combination of retinoids and narrow-band ultraviolet B inhibits matrix metalloproteinase 13 expression in HaCaT keratinocytes and a mouse model of psoriasis.

Matrix metalloproteinase13 (MMP13) can be released by keratinocytes and fibroblasts and involved in the pathogenesis of skin disorders. Retinoic acid derivative drugs include tazarotene and acitretin. Tazarotene/acitretin and narrow-band ultraviolet B (NB-UVB) irradiation are common treatment options for psoriasis. However, their impact on MMP13 expression in the context of psoriasis has yet to be determined. The expression of MMP13 was analyzed in patients with psoriasis. The effects of tazarotene/acitretin and NB-UVB on MMP13 expression were also investigated in a mouse model of psoriasis. Human HaCaT keratinocytes were exposed to acitretin or NB-UVB and then assayed for cell proliferation and MMP13 expression levels. We showed that patients with psoriasis had increased levels of MMP13 protein in skin lesions and serum samples. Exposure to acitretin and NB-UVB irradiation alone or in combination led to reduction of cell proliferation and MMP13 expression in HaCaT cells. Consistently, tazarotene treatment or NB-UVB irradiation attenuated imiquimod-induced psoriasis-like dermatitis and decreased MMP13 expression in a mouse model. Based on these from HaCaT keratinocytes cells and animal experiments, we suggest that tazarotene/acitretin and NB-UVB irradiation can inhibit the expression of MMP13 in HaCaT keratinocytes and psoriasis mouse models. Blockade of MMP13 activity may have therapeutic potential in improving symptoms of psoriasis.

High Performance Supercapacitors Based on Mesopore Structured Multiwalled Carbon Nanotubes.

A 3D CNT/few layered graphene construct (CNT-FLG) with mesopore structure was fabricated and applied in supercapacitors. The structure was acquired through a two-step method. Firstly, commercial multiwalled carbon nanotubes (MCNTs) were oxidized in a mixed solution of concentrated acid and modified with a couple of long-chain organic ions. Second, the above resultant product was carbonized at a high temperature. The achieved structure offers a 3D interconnected electrically conductive network as well as mesopore structure. It also significantly improves the specific surface area of MCNTs. Result of BET tests showed that the specific surface area of CNT-FLG reached to 2235 m2 /g. When acted as electrode materials in a supercapacitor structure, specific capacitance was approximately 531.2 F/g at a current density of 0.8 A/g. At current density of 50 A/g, specific capacitance remained 204.4 F/g. Besides, the capacitance retention was as high as 96.18 % after 10000 cycles at the current density of 5 A/g.

Magnetoelectric effect in flexible nanocomposite films based on size-matching.

Flexible magnetoelectric (ME) nanocomposites with a strong coupling between ferromagnetism and ferroelectricity are of significant importance from the point of view of next-generation flexible electronic devices. However, a high loading of magnetic nanomaterials is needed to achieve preferable ME response due to the size mismatch of the magnetostrictive phase and piezoelectric phase. In this work, ultra-small CoFe2O4 nanoparticles were prepared to match the size of the polar crystal in poly(vinylidene fluoride-trifluoroethylene) (P(VDF-TrFE)), and 1H,1H,2H,2H-perfluorooctyltriethoxysilane (POTS) is introduced to enhance the interplay between P(VDF-TrFE) and CoFe2O4. The above multiple effects promote a good connection between the magnetostrictive phase and the piezoelectric phase. Therefore, an effective transference of stress from CoFe2O4 to P(VDF-TrFE) can be achieved. The as-prepared P(VDF-TrFE)/CoFe2O4@POTS exhibits a high ME coupling coefficient of 34 mV cm-1 Oe-1 when the content of CoFe2O4@POTS is 20 wt%. The low loading of fillers ensures the flexibility of ME nanocomposite films.

Cellulose/BaTiO3 nanofiber dielectric films with enhanced energy density by interface modification with poly(dopamine).

Flexible electrostatic capacitors have many potential applications in modern electric power systems. In this study, flexible cellulose-based dielectric films were prepared by compositing regenerated cellulose (RC) and one-dimensional BaTiO3 nanofiber (BTNF) via a simple and environmentally friendly process. To improve compatibility and distributional homogeneity of the fillers/matrix, BTNF was surface modified by dopamine to prepare the poly(dopamine) modified BTNF (PDA@BTNF). The obtained RC/PDA@BTNF composite films (RC-PDA@BTNF) possessed higher dielectric constant and breakdown strength than those of the RC and RC/BTNF composite films. In particular, RC/PDA@BTNF composite films with 2 vol% PDA@BTNF (RC-2PDA@BTNF) exhibited a high discharged energy density of 17.1 J/cm3 at 520 MV/m, which exceeded 40 % compared with that of RC-2BTNF at 460 MV/m. Meanwhile, RC-2PDA@BTNF could continuously work for more than 10,000 times with a high efficiency of 91 %. Furthermore, the composite films could maintain good dielectric properties for a long time when stored in vacuum condition (under 0.3 atm). Therefore, these flexible cellulose-based dielectric materials are promising in the field of novel high-performance film dielectric capacitors.

Necklace-like ferroferric oxide (Fe3O4) nanoparticle/carbon nanofibril aerogels with enhanced lithium storage by carbonization of ferric alginate.

Theoretically, transition metal oxide/carbon nanofibril aerogels are promising candidates for lithium-ion battery anode materials as they combine the high stability and electrical conductivity of the carbon matrix and the high theoretical specific capacity of transition metal oxide (TMO). However, challenges still exist to embed TMO nanoparticles into thin carbon nanofibril absolutely and tightly, limiting further improvements in electrochemical performances of the composites. Herein, necklace-like Fe3O4/carbon nanofibril aerogel (Fe3O4/CNF) was constructed by crosslinking alginate with Fe3+, followed by carbonization of the obtained ferric alginate aerogel. Based on an "egg-box" helical structure resulting from strong coordination between the Fe3+ and the carboxylate groups of alginate, three-dimensional interconnected carbon aerogel was facilely fabricated with Fe3O4 nanoparticles (~11 nm in diameter) firmly embedded in ultrafine carbon nanofibrils (~18 nm in diameter), exhibiting a special necklace-like structure. Consequently, the composite exhibits a high reversible capacity and stability of 1176 mAh g-1 over 200 cycles at 1 A g-1 and a high rate performance of 615 mAh g-1 at 4 A g-1. These Fe3O4/CNF aerogels may have potential applications for enhanced lithium storage of electrochemical devices.