Fabrication of fully bio-based malleable thermoset derived from cellulose, furfural and plant oil for advanced capacitive sensor.

Fabrication of sustainable bio-based malleable thermosets (BMTs) with excellent mechanical properties and reprocessing ability for applications in electronic devices has attracted more and more attention but remains significant challenges. Herein, the BMTs with excellent mechanical robustness and reprocessing ability were fabricated via integrating with radical polymerization and Schiff-base chemistry, and employed as the flexible substrate to prepare the capacitive sensor. To prepare the BMTs, an elastic bio-copolymer derived from plant oil and 5-hydroxymethylfurfural was first synthesized, and then used to fabricate the dynamic crosslinked BMTs through Schiff-base chemistry with the amino-modified cellulose and polyether amine. The synergistic effect of rigid cellulose backbone and the construction of dynamic covalent crosslinking network not only achieved high tensile strength (8.61 MPa) and toughness (3.77 MJ/m3) but also endowed the BMTs with excellent reprocessing ability with high mechanical toughness recovery efficiency of 104.8 %. More importantly, the BMTs were used as substrates to fabricate the capacitive sensor through the CO2-laser irradiation technique. The resultant capacitive sensor displayed excellent and sensitive humidity sensing performance, which allowed it to be successfully applied in human health monitoring. This work paved a promising way for the preparation of mechanical robustness malleable bio-thermosets for electronic devices.

Recyclable and mechanically tough nanocellulose reinforced natural rubber composite conductive elastomers for flexible multifunctional sensor.

The development of flexible wearable multifunctional electronics has gained great attention in the field of human motion monitoring. However, developing mechanically tough, highly stretchable, and recyclable composite conductive materials for application in multifunctional sensors remained great challenges. In this work, a mechanically tough, highly stretchable, and recyclable composite conductive elastomer with the dynamic physical-chemical dual-crosslinking network was fabricated by the combination of multiple hydrogen bonds and dynamic ester bonds. To prepare the proposed composite elastomers, the polyaniline-modified carboxylate cellulose nanocrystals (C-CNC@PANI) were used as both conductive filler to yield high conductivity of 15.08 mS/m, and mechanical reinforcement to construct the dynamic dual-crosslinking network with epoxidized natural rubber latex to realize the high mechanical strength (8.65 MPa) and toughness (29.57 MJ/m3). Meanwhile, the construction of dynamic dual-crosslinking network endowed the elastomer with satisfactory recyclability. Based on these features, the composite conductive elastomers were used as strain sensors, and electrode material for assembling flexible and recyclable self-powered sensors for monitoring human motions. Importantly, the composite conductive elastomers maintained reliable sensing and energy harvesting performance even after multiple recycling process. This study provides a new strategy for the preparation of recyclable, mechanically tough composite conductive materials for wearable sensors.

Self-strengthening and conductive cellulose composite hydrogel for high sensitivity strain sensor and flexible triboelectric nanogenerator.

Triboelectric nanogenerators (TENGs) as promising energy harvesting devices have gained increasing attention. However, the fabrication of TENG simultaneously meets the requirements of green start feedstock, flexible, stretchable, and environmentally friendly remains challenging. Herein, the hydroxyethyl cellulose macromonomer (HECM) simultaneously bearing acrylate and hydroxyl groups was first synthesized and used as a crosslinker to prepare the chemically and physically dual-crosslinked cellulose composite hydrogel for an electrode material of stretchable TENG. Meanwhile, the in-situ polymerization of pyrrole endowed the hydrogel with satisfactory conductivity of 0.40 S/m. More impressively, the synergies of the cellulose rigid skeleton and the construction of the dual-crosslinking network significantly improved the mechanical toughness, and the hydrogel exhibited excellent self-strengthening through cyclic compression mechanical training, the self-strengthening efficiency reached 124.7 % after 10 compression cycles. Given these features, the hydrogel was used as wearable strain sensors with extremely high sensitivity (GF = 3.95) for real-time monitoring human motions. Additionally, the hydrogel showed practical applications in stretchable H-TENG for converting mechanical energy into electric energy to light LEDs and power a digital watch, and in self-powered wearable sensors to distinguish human motions and English letters. This work provided a promising strategy for fabricating sustainable, eco-friendly energy harvesting and self-powered electronic devices.

Effect of Acute Psychological Stress on Speed Perception: An Event-Related Potential Study.

The present study tested the intrinsic ERP features of the effects of acute psychological stress on speed perception. A mental arithmetic task was used to induce acute psychological stress, and the light spot task was used to evaluate speed perception. Compared with judgments in the constant speed and uniform acceleration motion, judgments in the uniform deceleration motion were made more quickly and with higher accuracy; attention control was higher and peaked later; and there was longer N2 peak latency, larger N2 peak amplitude, and lower mean amplitude of the late negative slow wave (SW). Under stress, the reaction time was significantly shorter. The N2 peak amplitude and SW mean amplitude were significantly higher, attention control was higher and appeared earlier, and there was a greater investment of cognitive resources. The type of movement and evoked stress also interacted to predict behavioral and ERP measures. Under acute stress, judgments made in the uniform deceleration motion condition elicited lower N2 peak latency, higher attention control, and later peak attention. The results suggest that judgments of the speed of decelerating motion require a lower investment of cognitive resources than judgments of other kinds of motion, especially under acute stress. These findings are best interpreted in terms of the interaction of arousal and attention.

Biomimetic ultra-strong, ultra-tough, degradable cellulose-based composites for multi-stimuli responsive shape memory.

Fabrication of ultra-strong, ultra-tough, sustainable, and degradable bio-based composites is urgently needed but remains challenging. Here, a biomimetic sustainable, degradable, and multi-stimuli responsive cellulose/PCL/Fe3O4 composite with ultra-strong mechanical strength and ultra-high toughness was developed. To prepare the proposed composites, the soft poly(ε-caprolactone) (PCL) side chain was grafted onto the rigid cellulose backbone, then the cellulose graft copolymer (EC-g-PCL) reacted with rigid hexamethylenediamine modified Fe3O4 nanoparticle (Fe3O4-NH2) to construct the crosslinking network using MDI-50 as a crosslinker. Given by the construction of crosslinking network and the "hard" and "soft" interactive structure, the composites showed ultra-strong mechanical strength (25.7 MPa) and ultra-high toughness (107.0 MJ/m3), and the composite specimen could lift a weight of approximately 21,200 times its mass. The composites also exhibited rapid degradation ability with high degradation efficiency. In addition, the composites showed excellent thermal responsive shape memory property with a shape recovery ratio above 96 %. Most importantly, the Fe3O4 nanoparticles endowed the composites with photothermal conversion property, the composites exhibited superior NIR light-triggered shape memory capability. The EC-g-PCL/Fe3O4 composites with ultra-strong mechanical strength and ultra-high toughness have promising applications in heavy-lift, object transportation, and self-tightening knots.

A skin-inspired biomimetic strategy to fabricate cellulose enhanced antibacterial hydrogels as strain sensors.

With the development of wearable devices, the fabrication of strong, tough, antibacterial, and conductive hydrogels for sensor applications is necessary but remains challenging. Here, a skin-inspired biomimetic strategy integrated with in-situ reduction has been proposed. The self-assembly of cellulose to generate a cellulose skeleton was essential to realize the biomimetic structural design. Furthermore, in-situ generation of silver nanoparticles on the skeleton was easily achieved by a heating process. This process not only offered the excellent antibacterial property to hydrogels, but also improved the mechanical properties of hydrogels due to the elimination of negative effect of silver nanoparticles aggregation. The highest tensile strength and toughness could reach 2.0 MPa and 11.95 MJ/m3, respectively. Moreover, a high detection range (up to 1300%) and sensitivity (gauge factor = 4.4) was observed as the strain sensors. This study provides a new horizon to fabricate strong, tough and functional hydrogels for various applications in the future.

Synthesis of pH-Sensitive and Self-Fluorescent Polymeric Micelles Derived From Rosin and Vegetable Oils via ATRP.

Preparation and application of sustainable polymers derived from renewable resources are of great significance. The aim of this study is to synthesize a kind of sustainable polymeric micelles from rosin and vegetable oils via atom transfer radical polymerization (ATRP) and to investigate the doxorubicin delivery properties of these micelles. Dehydroabietic acid-based poly lauryl methacrylate (DA-PLMA) with narrow PDI of 1.13 was prepared in a well-controlled process using rosin as an ATRP initiator. Thereafter, carboxylic groups were introduced to form poly methacrylic acid (PMAA) moieties in DA-PLMA polymer via acid hydrolysis. The resulted DA-PLMA-PMAA could self-assemble in water to form pH-dependent polymeric micelles with a diameter of ∼65 nm and PDI as low as 0.105. Owing to the existence of rosin, DA-PLMA-PMAA micelles also showed self-fluorescence properties. In addition, Dox-loaded micelles were prepared in aqueous solution with the drug-loading capacity as high as 16.0% and showed sustained-release characteristics. These results demonstrate great promise for designing polymeric micellar from rosin and vegetable oils.

Ultra-strong hydroxypropyl cellulose/polyvinyl alcohol composite hydrogel by combination of triple-network and mechanical training.

To develop the hydrogels with high mechanical strength and excellent conductivity is always a challenging topic. In this study, the ultra-strong hydroxypropyl cellulose (HPC)/polyvinyl alcohol (PVA) composite hydrogels were prepared by combination of the triple-network and mechanical training. The proposed composite hydrogels were achieved by physically crosslinking HPC with PVA to form the first crosslinking network, in which the HPC fibers could decrease the crosslinking density of PVA matrix and generate a lot of water-rich porous area. Then, 2-hydroxyethyl acrylate (HEA), acrylamide (AM) and aluminium chloride diffused into the first network to fabricate the chemical crosslinking network and ionically cross-linked domains. The formation of triple-network enhanced the mechanical strength and toughness to 1.87 MPa and 339.09 kJ/m3, respectively. Especially, the crystalline domains of PVA chains could improve the hydrogel's fatigue resistance, and the orderly arrangement of the crystalline domains achieved through mechanical training process could further enhance the mechanical strength. The mechanical strength of pre-stretched composite hydrogel was increased up to 2.8 MPa. The composite hydrogels exhibit great applications in sensors, human-machine interactions, and wearable devices.

Wood-Derived Functional Polymeric Materials.

In recent years, tremendous efforts have been dedicated to developing wood-derived functional polymeric materials due to their distinctive properties, including environmental friendliness, renewability, and biodegradability. Thus, the uniqueness of the main components in wood (cellulose and lignin) has attracted enormous interest for both fundamental research and practical applications. Herein, the emerging field of wood-derived functional polymeric materials fabricated by means of macromolecular engineering is reviewed, covering the basic structures and properties of the main components, the design principle to utilize these main components, and the resulting wood-derived functional polymeric materials in terms of elastomers, hydrogels, aerogels, and nanoparticles. In detail, the natural features of wood components and their significant roles in the fabrication of materials are emphasized. Furthermore, the utilization of controlled/living polymerization, click chemistry, dynamic bonds chemistry, etc., for the modification is specifically discussed from the perspective of molecular design, together with their sequential assembly into different morphologies. The functionalities of wood-derived polymeric materials are mainly focused on self-healing and shape-memory abilities, adsorption, conduction, etc. Finally, the main challenges of wood-derived functional polymeric materials fabricated by macromolecular engineering are presented, as well as the potential solutions or directions to develop green and scalable wood-derived functional polymeric materials.

Ethyl cellulose based self-healing adhesives synthesized via RAFT and aromatic schiff-base chemistry.

In this work, reversible addition-fragmentation chain transfer (RAFT) polymerization and Schiff base chemistry was combined to fabricate self-healing adhesives. An esterification reaction was first performed to prepare ethyl cellulose based macroinitiators. Then, a "grafting from" RAFT of vanillin methacrylate and lauryl methacrylate was used to obtain graft copolymers. DSC result showed that the glass transition temperature was manipulated via changing the ratio of vanillin and fatty acids moieties. NMR spectrum analysis demonstrated the presence of aldehyde groups, which were available for the dynamic crosslinking to generate a network as self-healing adhesives. The adhesive test showed that the shear strength could reach 0.81 MPa with a self-healing efficiency of 98.7 %. The bottlebrush structures of copolymers and reversibility of Schiff base chemistry might collaboratively contribute to the high self-healing efficiency. This study provides a facile way to fabricate high-performance self-healing adhesives from ethyl cellulose and renewable resources.

Unexpected role of amphiphilic lignosulfonate to improve the storage stability of urea formaldehyde resin and its application as adhesives.

As the second-largest natural polymer, the utilization of lignin for practical applications has attracted increasing attention. In this study, lignosulfonate was employed to enhance the storage stability of urea formaldehyde (UF) resins. Cryo-scanning electron microscopy was firstly used to observe the influence of lignosulfonate addition on the colloidal morphology of UF resin. Moreover, adding lignosulfonate at different stages during the UF resins synthesis was also investigated to reveal its effect on storage stability. The potential interaction between lignosulfonate and UF resins was then analyzed via FT-IR, 13C CPMAS NMR, and zeta potential. It has been observed that lignosulfonate could increase the electrostatic repulsion of UF resins to avoid aging. No chemical reaction between UF resins and lignosulfonate was observed. After the elucidation of potential interaction, the effect of lignosulfonate on the curing process, thermal stability and adhesive performance of UF resins was systematically evaluated. Finally, as adhesives to fabricate eucalyptus plywood, the shear strength and formaldehyde release of UF resins with 20% addition of lignosulfonate could reach 0.88 MPa and 0.12 mg/L, respectively. Due to the excellent performance, low cost and wide availability of lignosulfonate, it might be industrially used as a stabilizer in the UF resins production.

Integration of metal-free ATRP and Diels-Alder reaction toward sustainable and recyclable cellulose-based thermoset elastomers.

Well-defined sustainable and recyclable thermoset elastomers derived from cellulose, fatty acid and furfural were successfully prepared via photoinduced metal-free ATRP and Diels-Alder (DA) reaction. Firstly, metal free ATRP was applied to prepare a range of thermoplastic cellulose graft copolymers with furfural groups. Then, a modified epoxidized soybean oil bearing 6-maleimidohexanoic group (ESOM) as a crosslinker was employed to perform DA reaction with furfural groups in these cellulose graft copolymers, by which the copolymer formed the dynamic crosslinked network and achieved the thermoset elastomers. The dynamic crosslinked network formed by DA reaction not only could increase the chain entanglement that was associated with the improved flexibility and could contribute to enhancing the mechanical strength up to 166 %, but also endowed these thermoset elastomers with recyclability, excellent shape memory and self-healing property. These thermoset elastomers can be used as self-healing strain sensor and wearable sensing devices after compounding them with carbon nanotubes.

Two-Step 3 D-Printing Approach toward Sustainable, Repairable, Fluorescent Shape-Memory Thermosets Derived from Cellulose and Rosin.

Invited for this month's cover is the group of Jifu Wang at Biomass-derived Photopolymer Materials, Institute of Chemical Industry of Forest Products, CAF. The image shows the application of cellulose and rosin to fabricate a class of renewable, repairable, fluorescent, and shape-memory thermosets by a two-step 3 D-printing approach. The Full Paper itself is available at 10.1002/cssc.201902191.

Combination of acid treatment and dual network fabrication to stretchable cellulose based hydrogels with tunable properties.

Cellulose based hydrogels with a relatively high stretchability were fabricated in the NaOH/urea system via sequential chemical crosslinking and dual network fabrication. The first step involved crosslinking of cellulose using epichlorohydrin as a crosslinker. Cryo-electron microscopy analysis revealed the utilization of diluted acid to treat hydrogels significantly affected the morphology of the first network and improved the mechanical properties. After diffusion of precursors into the first network, the dual network hydrogels were generated after the UV light-initiated polymerization. Raman spectroscopy demonstrated a spatial distribution of second networks within the first network. The compression strength of hydrogels synthesized under the optimized conditions was effectively enhanced from 0.04 MPa to 10.9 MPa. In addition, the tensile properties of hydrogels were easily adjusted via copolymerization of acrylic acid with acrylamide. The highest strain could reach 219.5% with a tensile strength of 1.4 MPa. This work provides a promising and simple strategy to develop a cellulose based hydrogel with enhanced and tunable mechanical properties for wide applications.

Effect of Acute Psychological Stress on Motion-in-Depth Perception: An Event-Related Potential Study.

The present study explored the intrinsic event-related potential (ERP) features of the effects of acute psychological stress on the processing of motion-in-depth perception using a dual-task paradigm. After a mental arithmetic task was used to induce acute psychological stress, a collision task was used to evaluate motion-in-depth perception. The error value and average amplitude of late slow waves (SW) were significantly larger for the earlier colliding spheres' than for the later colliding spheres. The P1 peak latency in the left occipital region was significantly shorter than that of the right occipital region in the motion-in-depth perception task. Compared to the control condition, the estimated value of residual time-to-collision and error value were significantly reduced, and the N1 peak amplitude and the SW averaged amplitude were significantly increased in the stress condition. Longer motion-in-depth time improved discrimination accuracy and decreased the investment of cognitive resources. Acute psychological stress increased behavioral performance and enhanced attention resources on the motion-in-depth perception task together with greater investment of cognitive resources.

Two-Step 3 D-Printing Approach toward Sustainable, Repairable, Fluorescent Shape-Memory Thermosets Derived from Cellulose and Rosin.

Efficiently converting biomass into multifunctional polymerized materials is a challenge to effect high-valued utilization of biomass resources. A two-step 3 D-printing approach has been developed to fabricate a class of robust, fluorescent shape-memory thermosets from cellulose and rosin-based photosensitive 3 D-printing resin solution. The stereolithography 3 D printing was first performed to form the first crosslinked network by UV-induced chain-growth polymerization, which fixed the shape of thermoset. Subsequently, isocyanate was applied to react with hydroxy in the monomer to form the second crosslinked network by thermally induced step-growth polymerization. The formation of a dual-cure network, leading to phase separation and increased crosslinking density, could greatly improve the mechanical and thermal properties of 3 D-printed thermosets and endow them with thermally triggered shape-memory properties and excellent repairability. The 3 D-printed thermosets are found to have strong luminescence resulting from aggregation-induced emission originating from rosin. In addition, these 3 D-printed thermosets could degrade in the presence of NaOH aqueous solution and in situ achieved a range of flexible conductive hydrogels that have important potential application in the flexible electronic materials and smart photoelectric materials.

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.

Fabrication of UV-absorbent cellulose-rosin based thermoplastic elastomer via "graft from" ATRP.

Cellulose-rosin based thermoplastic elastomers with UV absorption properties were fabricated by a combination of rosin, poly(butyl acrylate) (PBA) and ethyl cellulose (EC) via "graft from" ATRP with the aid of EC-rosin macroinitiator (EC-g-(DA)-Br) prepared by a simple esterification reaction between EC, dehydroabietic acid (DA, one of rosin's resin acids) and 2-bromoisobutylryl bromide. The introduction of rosin affords these elastomers with UV absorption property. And the glass transition temperature of these EC-rosin grafted copolymers could be tuned by changing the content of PBA. Moreover, the introduction of PBA to EC endowed EC-g-(DA)-g-PBA with a good film-forming property and excellent thermoplastic elastomer behavior. All of these EC-rosin grafted copolymers showed an excellent UV absorption performance, and maintained outstanding UV absorption capability after continuous UV-irradiation or being heated to 115 °C for 1 h. As a result, these EC-rosin grafted copolymers have a potential application in coating materials with UV absorption property.

miR-143-3p regulates cell proliferation and apoptosis by targeting IGF1R and IGFBP5 and regulating the Ras/p38 MAPK signaling pathway in rheumatoid arthritis.

It has been demonstrated that the deregulation of microRNAs (miRNAs) affects the development of rheumatoid arthritis (RA). The primary objective of the current study was to determine the role of miR-143-3p in the progression of RA. The expression of miR-143-3p in synovium taken from patients with RA was assessed by reverse transcription-quantitative polymerase chain reaction. The expression of miR-143-3p was higher in synovium tissues of RA than that of osteoarthritis (OA). The decreased expression of miR-143-3p suppressed cell proliferation and promoted apoptosis in vitro. In addition, inhibition of miR-143-3p decreased levels of inflammatory cytokines, as determined by an enzyme-linked immunosorbent assay. IGF1R and IGFBP5 were found to be the target genes of miR-143-3p, and it was demonstrated that miR-143-3p regulated the proliferation and apoptosis of MH7A cells by targeting IGF1R and IGFBP5. Furthermore, TNF-α treatment stimulated the Ras/p38 mitogen activated protein kinase (MAPK) signaling pathway, whereas miR-143-3p inhibition suppressed it. The results of the current study indicate that miR-143-3p may regulate cell proliferation and apoptosis by targeting IGF1R and IGFBP5 expression and regulating the Ras/p38 MAPK signaling pathways. Therefore, miR-143-3p may be a novel therapeutic target in RA.

Sustainable thermoplastic elastomers derived from cellulose, fatty acid and furfural via ATRP and click chemistry.

Cellulose-based thermoplastic elastomers (TPEs) have attracted considerable attention because of their rigid backbone, good mechanical properties, renewable nature and abundance. In the present study, sustainable TPEs based on ethyl cellulose (EC), fatty acid and furfural were generated by the combination of ATRP and "click chemistry". To fabricate sustainable TPEs with higher toughness, a range of polymers, including mono random-copolymer poly(tetrahydrofurfuryl methacrylate-co-lauryl methacrylate) (P(THFMA-co-LMA), dual polymer side chains PTHFMA and PLMA, and mono-block copolymer PTHFMA-b-PLMA, were designed as side chains to fabricate EC brush copolymers with random, dual or block side chain architectures using the "grafting from" and "grafting onto" methods. The multi-armed structures, chemical compositions and phase separation of these EC brush copolymers were confirmed by FT-IR, 1H NMR, GPC, DSC, TEM and SEM. Overall, three types of EC brush copolymers all exhibited the desired mechanical properties of TPEs. In addition, the EC brush copolymers with dual/block side chain architectures showed higher tensile strength than that of the random polymers with similar compositions.