Plant Oil-Derived Epoxy Polymers toward Sustainable Biobased Thermosets.

Epoxy polymers (EPs) derived from soybean oil with varied chemical structures are synthesized. These polymers are then cured with anhydrides to yield soybean-oil-derived epoxy thermosets. The curing kinetic, thermal, and mechanical properties are well characterized. Due to the high epoxide functionality per epoxy polymer chain, these thermosets exhibit tensile strength over an order of magnitude higher than a control formulation with epoxidized soybean oil. More importantly, thermosetting materials ranging from soft elastomers to tough thermosets can be obtained simply by using different EPs and/or by controlling feed ratios of EPs to anhydrides.

UV-absorbent lignin-based multi-arm star thermoplastic elastomers.

Lignin-grafted copolymers, namely lignin-graft-poly(methyl methacrylate-co-butyl acrylate) (lignin-g-P(MMA-co-BA)), are synthesized via "grafting from" atom transfer radical polymerization (ATRP) with the aid of lignin-based macroinitiators. By manipulating the monomer feed ratios of MMA/BA, grafted copolymers with tunable glass transition temperatures (-10-40 °C) are obtained. These copolymers are evaluated as sustainable thermoplastic elastomers (TPEs). The results suggest that the mechanical properties of these TPEs lignin-g-P(MMA-co-BA) copolymers are improved significantly by comparing with those of linear P(MMA-co-BA) copolymer counterparts, and the elastic strain recovery is nearly 70%. Lignin-g-P(MMA-co-BA) copolymers exhibit high absorption in the range of the UV spectrum, which might allow for applications in UV-blocking coatings.

Advanced treatment of refractory organic pollutants in petrochemical industrial wastewater by bioactive enhanced ponds and wetland system.

A large-scale combined ponds-wetland system was applied for advanced treatment of refractory pollutants in petrochemical industrial wastewater. The system was designed to enhance bioactivity and biological diversity, which consisted of anaerobic ponds (APs), facultative ponds (FPs), aerobic pond and wetland. The refractory pollutants in the petrochemical wastewater to be treated were identified as alkanes, chloroalkanes, aromatic hydrocarbons, and olefins, which were significantly degraded and transformed along with the influent flowing through the enhanced bioactive ponds-wetland system. 8 years of recent operational data revealed that the average removal rate of stable chemical oxygen demand (COD) was 42.7 % and that influent COD varied from 92.3 to 195.6 mg/L. Final effluent COD could reach 65.8 mg/L (average). COD removal rates were high in the APs and FPs and accounted for 75 % of the total amount removed. This result indicated that the APs and FPs degraded refractory pollutants through the facilitation of bacteria growth. The changes in the community structures of major microbes were assessed by 16SrDNA-denaturing gradient gel electrophoresis. The same analysis was used to identify the main bacterial function for the removal of refractory pollutants in the APs and FPs. The APs and FPs displayed similar microbial diversities, and some of the identified bacteria degraded and removed refractory pollutants. The overall results proved the applicability, stability, and high efficiency of the ponds-wetland system with enhanced bioactivity in the advanced removal of refractory pollutants from petrochemical industrial wastewater.

Performance of the subsurface flow constructed wetlands for pretreatment of slightly polluted source water.

The slightly polluted source water of Yellow River was pretreated in a horizontal subsurface flow constructed wetland (HSFCW) and a lateral subsurface flow constructed wetland (LSFCW) in the Ji'nan city Reservoir, Shandong, China. During almost one years run, the results showed that at the hydraulic loading rate of 1 m/day, the removal efficiencies of chemical oxygen demand (COD), total nitrogen (TN), ammonium nitrogen (NH4 (+)-N) and total phosphorus (TP) in the HSFCW were 48.9, 51.4, 48.7 and 48.9 %, respectively, and the corresponding removal efficiencies in the LSFCW were 50.51, 53.12, 50.44 and 50.83 %, respectively. The HSFCW and LSFCW had a similar high potential for nutrients removal and LSFCW was slightly better. According to the China standard for surface water resources (GB3838-2002), mean effluent COD can reach the Class I (≤ 15 mg/L), and NH4 (+)-N and TP and TN can reach nearly the Class I (≤ 0.015 mg/L), the Class III (≤ 0.05 mg/L) and the Class IV (≤ 1.5 mg/L), respectively. It can be concluded that the slightly polluted source water from Reservoir was pretreated well by the constructed wetland.

[Synthesis and characterization of dihydroeugenol acrylate].

Dihydroeugenol acrylate was synthesized by the reaction of acryloyl chloride (AC) with lignin mode compound dihydroeugenol (DH) in the presence of TEA and characterized by using FTIR, GC/MS, 1H-NMR and GPC. FTIR spectra showed that, after the esterification with acryloyl chloride, the intensity of stretching vibration peak of O-H (centered at 3 495 cm(-1)) of DH was disappeared. At the same time, a new peak appeared at 1 762 cm(-1) which was assigned to ester group. Additionally, the appearance of 1 631 and 981 cm(-1) were attributed to the carbon - carbon double bond confirmed the success in the synthesis of DH-AC. 1H-NMR spectra showed that, after the esterification with acryloyl chloride, the proton signal of O-H at 5.5 ppm was disappeared. Meanwhile, the appearance of three new proton signals at 6.0 ppm, 6.4 and 6.7 ppm, attributed to the vinylic protons, indicated that acryloyl chloride was successfully grafted onto DH. The results further confirmed the structures of the DH-AC. GC-MS results showed the DH-AC had a high purity of 98.63%. GPC results showed that dihydroeugenol acrylate could polymerize in the 1,4-dioxane using a thermal initiator of AIBN (2.0 Wt% of total monomers). The weight average molecular mass (Mw) of the homopolymer is 37 400 g x mol(-1), and the number average molecular mass is 23 400 g x mol(-1)' with a polydispersity index Mw/Mn of 1.60, indicating that the dihydroeugenol acrylate has high polymerization activity. This strategy provides a novel approach for extending the comprehensive utilization of lignin.

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.

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.

[Chemical structure of bioethanol lignin by low-temperature alkaline catalytic hydrothermal treatment].

In order to improve the reaction activity of bioethanol lignin, we investigated the activation of bioethanol lignin by a hydrothermal treatment method. Catalytic hydrothermal treatment of bioethanol lignin was performed at 180 degrees C for 3 h in the presence of alkaline solutions (NaOH, Na2 CO3, KOH and K2 CO3), the change in bioethanol lignin structures was studied comparatively by FTIR, 1H NMR,GPC and elemental analysis. FTIR spectra showed that after alkali hydrothermal treatment, the band at 1 375 cm(-1) attributed to the phenolic hydroxyl groups increased, and the band intensity at 1 116 cm(-1) attributed to the ether bond decreased. On the other hand, the band at 1 597 and 1 511 cm(-1) attributed to aromatic skeletal vibration remained almost unchanged. 1H NMR spectra showed that after alkali hydrothermal treatment, the number of aromatic methoxyl is increased, and based on the increment of the content of phenolic hydroxyl, the catalytic activity can be ranked as follows: KOH > NaOH > K2 CO3 > Na2 CO3. Especially for KOH, the increment of the content of phenolic hydroxyl was 170%, because the ion radius of potassium cation is bigger than sodium cation, so the potassium cations more easily formed cation adducts with lignin. GPC results showed that the molecular weight of alkali hydrothermal treatment lignin decreased and the molecular distribution got wider. Elemental analysis showed that hydrothermal treatment could break the interlinkage between lignin and protein, which can reduce the protein content and increase the purity of lignin, meanwhile, the content of O and H both decreased,while C fell, indicating that the bioethanol lignin had suffered a decarbonylation reaction. This is the most benefit of the lignin as a substitute for phenol.

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.

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.

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.

Degradable rosin-ester-caprolactone graft copolymers.

We have carried out the synthesis of side-chain rosin-ester-structured poly(ε-caprolactone) (PCL) through a combination of ring-opening polymerization and click chemistry. Rosin structures are shown to be effectively incorporated into each repeat unit of caprolactone. This simple and versatile methodology does not require sophisticated purification of raw renewable biomass from nature. The rosin properties have been successfully imparted to the PCL polymers. The bulky hydrophenanthrene group of rosin increases the glass-transition temperature of PCL by >100 °C, whereas the hydrocarbon nature of rosin structures provides PCL excellent hydrophobicity with contact angle very similar to polystyrene and very low water uptake. The rosin-containing PCL graft copolymers exhibit full degradability and good biocompatibility. This study illustrates a general strategy to prepare a new class of renewable hydrocarbon-rich degradable biopolymers.

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.

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.

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.

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.

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.

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.

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.