Ecofriendly Controlled-Release Insecticide Carrier: pH-/Temperature-Responsive Rosin-Derived Hydrogels for Avermectin Delivery against Mythimna separata (Walker).

The exploration of environmentally friendly, less toxic, sustained-release insecticide is increasing with the growing demand for food to meet the requirements of the expanding population. As a sustained-release carrier, the unique, environmentally friendly intelligent responsive hydrogel system is an important factor in improving the efficiency of insecticide utilization and accurate release. In this study, we developed a facile approach for incorporating the natural compound rosin (dehydroabietic acid, DA) and zinc ions (Zn2+) into a poly(N-isopropylacrylamide) (PNIPAM) hydrogel network to construct a controlled-release hydrogel carrier (DA-PNIPAM-Zn2+). Then, the model insecticide avermectin (AVM) was encapsulated in the carrier at a drug loading rate of 36.32% to form AVM@DA-PNIPAM-Zn2+. Surprisingly, the smart controlled carrier exhibited environmental responsiveness, strongly enhanced mechanical properties, self-healing ability, hydrophobicity, and photostability to ensure a balance between environmental friendliness and the precision of the drug release. The release experiments showed that the carboxyl and amide groups in the polymer chains alter the intermolecular forces within the hydrogel meshes and ingredient diffusion by changing temperatures (25 and 40 °C) and pH values (5.8, 7.4, and 8.5), leading to different release behaviors. The insecticidal activity of the AVM@DA-PNIPAM-Zn2+ against oriental armyworms was good, with an effective minimum toxicity toward aquatic animals. Therefore, AVM@DA-PNIPAM-Zn2+ is an effective drug delivery system against oriental armyworms. We anticipate that this ecofriendly, sustainable, smart-response carrier may broaden the utilization rosin and its possible applications in the agricultural sector.

Red Fluorescent Molecule with Aggregation-Induced Emission Based on Dehydroabietic Acid Diarylamine for Bioimaging.

In this paper, molecules with AIE red light properties were designed by coupling dehydroabietic acid diarylamine and 2,3-diphenylfumaronitrile, which were designated 2DTPA-CN and 2TPA-CN. The emission wavelengths were 683 nm and 701 nm, respectively. The 2DTPA-CN and 2TPA-CN showed typical AIE characteristics with large Stokes shifts of 7.4 × 104 cm-1 and 6.7 × 104 cm-1, respectively. The obvious solvatochromism and electron cloud distributions of HOMO/LUMO in the ground and excited states both reveal the intramolecular charge transfer (ICT) effect. The 2DTPA-CN, boasting exceptional biocompatibility, was successfully prepared into nanoparticles (NPs), which were applied to tumor cell imaging, showing good bioimaging effects both in vitro imaging in live cells and in vivo imaging in live mice. The results demonstrated that it possesses significant potential as an effective bioimaging reagent for the detection of tumor cells. Furthermore, the incorporation of 2,3-diphenylfumaronitrile moieties to dehydroabietic acid diarylamine emerged as a proficient approach to broaden the emission wavelengths of rosin-based fluorescent materials.

Efficient Control of Rhizoctonia solani Using Environmentally Friendly pH-Responsive Tannic Acid-Rosin Nano-Microcapsules.

A nanomicrocapsule system was constructed through the polymerization of tannic acid (TA) and emulsifier OP-10 (OP-10), followed by the chelation of iron ions, to develop a safe and effective method for controlling Rhizoctonia solani in agriculture. The encapsulated active component is a rosin-based triazole derivative (RTD) previously synthesized by our research group (RTD@OP10-TA-Fe). The encapsulation efficiency of the nanomicrocapsules is 82.39%, with an effective compound loading capacity of 96.49%. Through the encapsulation of the RTD via nanomicrocapsules, we improved its water solubility, optimized its stability, and increased its adhesion to the leaf surface. Under acidic conditions (pH = 5.0), the release rate of nanomicrocapsules at 96 h is 96.31 ± 0.8%, which is 2.04 times higher than the release rate under normal conditions (pH = 7.0). Additionally, the results of in vitro and in vivo antifungal assays indicate that compared with the original compound, the nanomicrocapsules exhibit superior antifungal activity (EC50 values of RTD and RTD@OP10-TA-Fe are 1.237 and 0.860 mg/L, respectively). The results of field efficacy trials indicate that compared with RTD, RTD@OP10-TA-Fe exhibits a more prolonged period of effectiveness. Even after 3 weeks, the antifungal rate of RTD@OP10-TA-Fe remains at 40%, whereas RTD, owing to degradation, shows an antifungal rate of 11.11% during the same period. Furthermore, safety assessment results indicate that compared with the control, RTD@OP10-TA-Fe has almost no impact on the growth of rice seedlings and exhibits low toxicity to zebrafish. This study provides valuable insights into controlling R. solani and enhancing the compound performance.

Degradable, anti-swelling, high-strength cellulosic hydrogels via salting-out and ionic coordination.

Cellulosic hydrogels are widely used in various applications, as they are natural raw materials and have excellent degradability. However, their poor mechanical properties restrict their practical application. This study presents a facile approach for fabricating cellulosic hydrogels with high strength by synergistically utilizing salting-out and ionic coordination, thereby inducing the collapse and aggregation of cellulose chains to form a cross-linked network structure. Cellulosic hydrogels are prepared by soaking cellulose in an Al2(SO4)3 solution, which is both strong (compressive strength of up to 16.99 MPa) and tough (compressive toughness of up to 2.86 MJ/m3). The prepared cellulosic hydrogels exhibit resistance to swelling in different solutions and good biodegradability in soil. The cellulosic hydrogels are incorporated into strain sensors for human-motion monitoring by introducing AgNWs. Thus, the study offers a promising, simple, and scalable approach for preparing strong, degradable, and anti-swelling hydrogels using common biomass resources with considerable potential for various applications.

Discovery of novel acrylopimaric acid triazole derivatives as promising antifungal agents.

BACKGROUND: To further develop potential natural fungicides, two series of new acrylopimaric acid triazole derivatives were synthesized, and their antifungal activities were tested and evaluated. RESULTS: In vitro antifungal activity results indicated that compound 5m exhibited significant inhibitory activity against Rhizoctonia solani with an half maximal effective concentration (EC50) value of 1.528 mg/L. Its antifungal effect was comparable to that of the commercially available fungicide fluconazole, epoxiconazole and propiconazole (EC50 values of 1.441, 0.815 and 1.173 mg/L). Subsequently, in vivo studies were conducted on compound 5m, which revealed its significant protective and curative effects against R. solani. In addition, physiological and biochemical studies showed that compound 5m could disrupt the morphology and ultrastructure of R. solani mycelium, increase cell membrane permeability, inhibit ergosterol synthesis, and enhance the activity of defense enzymes in rice plants. Three-dimensional quantitative structure-activity relationship (3D-QSAR) studies revealed that the molecular structure significantly influenced the binding of compound 5m to the receptor, thereby enhancing its antifungal activity. CONCLUSION: Compound 5m exhibits excellent antifungal activity against R. solani, making it a promising candidate fungicide for the prevention and control of R. solani. © 2024 Society of Chemical Industry.

Facile synthesis of lignin-based Fe-MOF for fast adsorption of methyl orange.

To rapidly remove dyes from wastewater, iron-based metal-organic frameworks modified with phenolated lignin (NH2-MIL@L) were prepared by a one-step hydrothermal method. Analyses of the chemical structure and adsorption mechanism of the NH2-MIL@L proved the successful introduction of lignin and the enhancement of its adsorption sites. Compared with NH2-MIL-101-Fe without phenolated lignin, the modification with lignin increased the methyl orange (MO) adsorption rate of NH2-MIL@L. For the best adsorbent, NH2-MIL@L4, the MO adsorption efficiency in MO solution reached 95.09% within 5 min. NH2-MIL@L4 reached adsorption equilibrium within 90 min, exhibiting an MO adsorption capacity of 195.31 mg/g. The process followed pseudo-second-order kinetics and the Dubinin-Radushkevich model. MO adsorption efficiency of NH2-MIL@L4 was maintained at 89.87% after six adsorption-desorption cycles. In mixed solutions of MO and methylene blue (MB), NH2-MIL@L4 achieved an MO adsorption of 94.02% at 5 min and reached MO adsorption equilibrium within 15 min with an MO adsorption capacity of 438.6 mg/g, while the MB adsorption equilibrium was established at 90 min with an MB adsorption rate and capacity of 95.60% and 481.34 mg/g, respectively. NH2-MIL@L4 sustained its excellent adsorption efficiency after six adsorption-desorption cycles (91.2% for MO and 93.4% for MB). The process of MO adsorption by NH2-MIL@L4 followed the Temkin model and pseudo-second-order kinetics, while MB adsorption followed the Dubinin-Radushkevich model and pseudo-second-order kinetics. Electrostatic interactions, π-π interactions, hydrogen bonding, and synergistic interactions affected the MO adsorption process of NH2-MIL@L4.

Discovery of Potential Rosin-Based Triazole Antifungal Candidates to Control Valsa mali for Sustainable Crop Protection.

To investigate the potential application value of dehydroabietic acid, 27 novel dehydroabietyl-1,2,4-triazole-5-thioether-based derivatives were designed and characterized by IR, 1H NMR, 13C NMR, and LC-MS. Their antifungal activities were evaluated against five plant fungi, namely, Valsa mali, Colletotrichum orbiculare, Fusarium graminearum, Sclerotinia sclerotiorum, and Gaeumannomyces graminis; the results showed that compound 5h-1 (Co. 5h-1) exhibited a considerable inhibitory effect against V. mali. Moreover, in vivo experiments indicated that Co. 5h-1 had a certain protective effect on apple branches. The preliminary structure-activity relationship analysis suggested that the electron-withdrawing group on the benzyl group was significantly better than that of other substituent derivatives. Through electron microscopy analysis, it was found that Co. 5h-1 hindered the growth of mycelia, damaged their cell structure, and caused the large accumulation of reactive oxygen species (ROS). Preliminary research on the mode of action indicated that Co. 5h-1 could affect the activity of CAT by increasing the α-helix (0.790%), decreasing the ß-sheet (0.170%), which led to the accumulation of ROS. In addition, Co. 5h-1 also affected the activity of CYP51, hindered the biosynthesis of ergosterol, and increased cell membrane permeability. Overall, this above research proposed that Co. 5h-1 can be a novel leading structure for development of a fungicide agent.

Synthesis of Acrylopimaric Acid Triazole Derivatives and Their Antioomycete Activity against Phytophthora capsici.

To develop new antioomycete agents against plant pathogens, two series of acrylopimaric acid triazole derivatives from rosin were synthesized. The in vitro antioomycete activity of these derivatives was evaluated and screened against Pseudoperonospora cubensisi, Plasmopara viticola, Phytophthora sojae, Phytophthora infestans, and Phytophthora capsici. Compound 5m showed the highest antioomycete activity against P. capsici, with a half-maximal effective concentration (EC50) value that was lower than that of the positive control metalaxyl (1.391 and 1.815 mg/L, respectively). Compound 5m demonstrated satisfactory protective and curative efficacy against P. capsici in pepper in in vivo antioomycete activity studies. Physiological and biochemical testing showed that the action mechanism of compound 5m on P. capsici involved altering the morphology and ultrastructure of the mycelium, increasing cell membrane permeability, inducing dysfunction of the nucleus and mitochondria, and ultimately causing cell necrosis. In addition, the analysis of three-dimensional quantitative structure-activity relationship (3D-QSAR) revealed the significance of the molecular structure and charge distribution in the interaction between compound 5m and its target. Collectively, these findings indicate that compound 5m has the potential as an antioomycete candidate.

Fully Biobased Degradable Vitrimer Foams: Mechanical Robust, Catalyst-Free Self-Healing, and Shape Memory Properties.

Thermosetting foams have limited capabilities for recycling, reprocessing, or reshaping. Moreover, most of the foaming agents currently employed in these foams are derived from organic compounds sourced from petrochemicals, thereby posing a significant environmental threat due to heightened pollution. To solve these problems, a fully biobased degradable vitrimer foam (EPC-X) was fabricated using an environmentally friendly all-in-one foaming strategy by cross-linking epoxidized malepimaric anhydride (EMPA), 1,5-diaminopentane (PDA), and 1,5-diaminopentane carbamate (PDAC) as a latent curing-blowing agent. To our delight, the vitrimer foams exhibit excellent mechanical properties (2.86 ± 0.11 MPa compressive strength) owing to their unique rigid rosin backbone and cross-linking networks. The presence of dynamic ß-hydroxy ester bonds and the self-catalytic behavior of tertiary amine groups facilitate network rearrangement without requiring additional catalysts, thereby resulting in the development of EPC-X with rapid self-healing and shape memory properties. The self-healing foam could support a weight of 500 g (approximately 562 times its own mass). Moreover, these high-performance vitrimer foams can also be easily degraded in an ethanolamine (EA) or NaOH solution under mild conditions. Such a design strategy offers an alternative approach for developing superior degradable and thermal stimuli-responsive thermosetting foams.

CO2-Responsive Rosin-Based Supramolecular Hydrogels: Diverse Chiral Nanostructures and Their Application in In Situ Synthesis of Chiral Gold Nanoparticles.

Natural small molecules have demonstrated tremendous potential for the construction of supramolecular chiral nanostructures owing to their unique molecular structures and chirality. In this study, novel CO2-responsive supramolecular hydrogels were constructed using a series of rosin-based surfactants (CnMPAN, n = 10, 12, and 14). The macroscopic properties, rheological properties, nanostructures, and intermolecular interactions of the hydrogels were investigated using differential scanning calorimetry, rotational rheometry, cryogenic transmission electron microscopy, and Fourier transform infrared spectroscopy. Interestingly, diverse nanostructures containing helical nanofibers, interwoven nanofibers, and twisted nanoribbons were formed in the hydrogels, which were rarely observed in reported supramolecular hydrogels, and the strength of the hydrogels was significantly enhanced by increasing the CnMPAN concentration and the alkyl chain length. The obtained hydrogels exhibited excellent CO2-responsiveness, with no obvious variation in the nanostructures and rheological properties after response to CO2/N2 for five cycles. Taking advantage of the chiral nanostructures of hydrogels, gold nanoparticles (GNPs) were further prepared. The average particle sizes of the resulting GNPs were as low as 2.5 nm, and the GNPs also had a chiral structure. It is worth noting that no additional reductants and UV-light irradiation were used during the reduction process of GNPs. This study emphasizes that the unique molecular structure and chirality of rosin are critical for the preparation of hydrogels with chiral nanostructures. In addition, this study enriches the applications of forest resources.

Adsorption of methyl orange from aqueous solution with lignin-modified metal-organic frameworks: Selective adsorption and high adsorption capacity.

The lignin-based metal-organic framework (UIO-g-NL) was prepared by a Schiff base reaction of aminated lignin and the zirconium cluster-based MOF (UIO-66-NH2) as an adsorbent of methyl orange (MO). The results showed that UIO-g-NL maintained the original crystal structure and aminated lignin was successfully introduced after functionalization. UIO-g-NL selectively adsorbed MO from a mixed solution 50 mg/L MO and 50 mg/L methylene blue (MB), with an adsorption efficiency of nearly 100%. In a mixed solution 250 mg/L MB and 250 mg/L MO, UIO-g-NL adsorbed both dyes with 1120.70 mg/g for MB and 961.54 mg/g for MO. Hydrogen bonding, π-π and NH-π interactions, and electrostatic attraction contribute to the MO adsorption by UIO-g-NL. In the MO/MB mixture, MO adsorption by UIO-g-NL follows the pseudo-second-order kinetic and Freundlich isotherm models, which is an endothermic, spontaneous, and feasible adsorption process. Furthermore, the MO adsorption efficiency of UIO-g-NL remained high (>90%) after six re-use cycles.

Lignin-modified metal-organic framework as an effective adsorbent for the removal of methyl orange.

Herein, lignin-modified metal-organic frameworks (NH2-UIO@L) are prepared using a one-step synthesis as sorbents for the removal of organic dyes from water. The introduction of lignin improved the adsorption sites. NH2-UIO@L2 adsorption of MO conforms to Langmuir model, and the adsorption capacity of NH2-UIO@L2 on MO was 214.13 mg·L-1 with an adsorption efficiency up to 99.28 %, which was significantly higher than values for other adsorbents. Due to hydrogen bonds, π-π interactions and electrostatic interactions, MO was effectively removed by NH2-UIO@L2 and its adsorption efficiency is maintained at 90.55 % after six cycles. The adsorption kinetics showed that the NH2-UIO@L2 adsorption of MO was chemical adsorption and controlled by intraparticle diffusion and external mass transfer. Further, the adsorption performance of NH2-UIO@L2 on MO and MB in mixed MO/MB solution was investigated. The adsorption capacity of NH2-UIO@L2 in mixed MO/MB solution was 207.04 mg·L-1 for MO and 243.31 mg·L-1 for MB; the adsorption of NH2-UIO@L2 on MO followed the Dubinin-Radushkevich and pseudo-second-order models, and the adsorption on MB followed the Temkin and pseudo-second-order models. Hydrogen bonds, π-π interactions, and pore filling are all implicated in the removal of MO and MB. In particular, the electrostatic attraction between MB and MO improves the adsorption efficiency of NH2-UIO@L2 on MB. NH2-UIO@L2 has good reusability, maintaining an adsorption efficiency of 97.66 % for MO and up to 99.15 % for MB after six cycles. Its simple preparation and superior adsorption suggest that NH2-UIO@L2 has considerable potential to remove organic dyes from wastewater.

Design and Synthesis of Antifungal Candidates Containing Triazole Scaffold from Natural Rosin against Valsa mali for Crop Protection.

Two series of dehydroabietyl-1,2,4-triazole-4-Schiff-based derivatives were synthesized from rosin to control plant fungal diseases. In vitro evaluation and screening of the antifungal activity were performed using Valsa mali, Colletotrichum orbiculare, Fusarium graminearum, Sclerotinia sclerotiorum, and Gaeumannomyces graminis. Compound 3f showed excellent fungicidal activity against V. mali (EC50 = 0.537 µg/mL), which was significantly more effective than the positive control fluconazole (EC50 = 4.707 µg/mL). Compound 3f also had a considerable protective effect against V. mali (61.57%-92.16%), which was slightly lower than that of fluconazole (85.17-100%) at 25-100 µg/mL. Through physiological and biochemical analyses, the preliminary mode of action of compound 3f against V. mali was explored. Ultrastructural observation of mycelia showed that compound 3f hindered the growth of the mycelium and destroyed the ultrastructure of V. mali seriously. Conductivity analysis and laser scanning confocal microscope staining showed that compound 3f changed cell-membrane permeability and caused accumulation of reactive oxygen species. The enzyme activity results showed that compound 3f significantly inhibited the activity of CYP51 (59.70%), SOD (76.9%), and CAT (67.86%). Molecular docking identified strong interaction energy between compound 3f and crystal structures of CYP51 (-11.18 kcal/mol), SOD (-9.25 kcal/mol), and CAT (-8.79 kcal/mol). These results provide guidance for the discovery of natural product-based antifungal pesticide candidates.

Self-healing, EMI shielding, and antibacterial properties of recyclable cellulose liquid metal hydrogel sensor.

Flexible hydrogels are promising materials for the preparation of artificial intelligence electronics and wearable devices. Introducing a rigid conductive material into the hydrogels can improve their electrical conductivities. However, it may have poor interfacial compatibility with the flexible hydrogel matrix. Therefore, we prepared a hydrogel containing flexible and highly ductile liquid metal (LM). The hydrogel can be used as a strain sensor to monitor human motion. The hydrogel showed many properties (i.e., recyclability, EMI shielding properties (33.14 dB), antibacterial (100 %), strain sensitivity (gauge factor = 2.92), and self-healing) that cannot be achieved simultaneously by a single hydrogel. Furthermore, the recycling of LM and their application to hydrogel-based EMI shielding materials have not been investigated previously. Due to its excellent properties, the prepared flexible hydrogel has great potential for applications in artificial intelligence, personal healthcare, and wearable devices.

Lignin/sodium alginate hydrogel for efficient removal of methylene blue.

In this work, a class of bio-based hydrogels (LN-NH-SA hydrogel) were prepared from aminated lignin and sodium alginate. The physical and chemical properties of the LN-NH-SA hydrogel were fully characterized using field emission scanning electron microscopy, thermogravimetric analysis, fourier transform infrared spectroscopy, N2 adsorption-desorption isotherms, and other techniques. LN-NH-SA hydrogels were tested for the adsorption of dyes (methyl orange and methylene blue). The LN-NH-SA@3 hydrogel showed better adsorption efficiency for MB with a maximum adsorption capacity of 388.81 mg·g-1, a bio-based adsorbent with a high adsorption capacity. The adsorption process followed the pseudo-second-order model and fitted to the Freundlich isotherm equation. More importantly, LN-NH-SA@3 hydrogel maintained 87.64 % adsorption efficiency after 5 cycles. Overall, the proposed hydrogel with environmentally friendly and low cost is promising for the absorption of dye contamination.

Chitosan/graphene oxide hybrid hydrogel electrode with porous network boosting ultrahigh energy density flexible supercapacitor.

To overcome the low energy density and poor conductivity of conventional electrode materials for building supercapacitor, herein, a hybrid hydrogel prepared from compositing bio-based chitosan with holey graphene oxide by microwave-assisted hydrothermal is proposed. This binary hydrogel is endowed with heteroatomic functional groups and conductive porous network by chemical pretreatments, where amides and carboxyl groups are introduced during the acylation modification of chitosan to enable it soluble in water for sufficient reaction, while the oxidation etching for graphene oxide in the defect area by H2O2 facilitates in-plane nanopores network to provide abundant active surface and short ion diffusion pathway. Benefited from the high conductivity and flexibility, this hydrogel present promising performance when used as additive-free electrode in a three-electrode, with a high specific capacitance of 377 F/g at 5 A/g. The rich nitrogen and oxygen groups on surface of the hydrogel contribute to high capacitance directly, while the in-plane nanopores and hierarchically porous network benefit to promote their wettability, accelerate the charge transfer and enhance their charge storage ability. When the hydrogel composite is adopted into a flexible solid-state supercapacitor employing lignin hydrogel electrolyte, it unfolds a specific capacitance of 210 F/g at 0.5 A/g, with an ultrahigh energy density of 31 Wh/kg at the power density of 150 W/kg. The solid-state supercapacitor exhibits promising potential in applications such as signal sensor and portable energy storage.

Discovery of rosin-based acylhydrazone derivatives as potential antifungal agents against rice Rhizoctonia solani for sustainable crop protection.

BACKGROUND: The use of fungicides to protect crops from diseases is an effective method, and novel environmentally friendly plant-derived fungicides with enhanced performance and low toxicity are urgent requirements for sustainable agriculture. RESULTS: Two kinds of rosin-based acylhydrazone compounds were designed and prepared. Based on the antifungal activity assessment against Rhizoctonia solani, Fusarium oxysporum, Phytophthora capsici, Sclerotinia sclerotiorum, and Botrytis cinerea, acylhydrazone derivatives containing a thiophene ring were screened and showed an inhibitory effect on rice R. solani. Among them, Compound 4n, with an electron-withdrawing group on the benzene ring structure attached to the thiophene ring, showed optimal activity, and the EC50 value was 0.981 mg L-1 , which was lower than that of carbendazim. Furthermore, it was indicated that 4n could affect the mycelial morphology, cell membrane permeability and microstructure, cause the generation of reactive oxygen species in fungal cells, and damage the nucleus and mitochondrial physiological function, resulting in the cell death of R. solani. Meanwhile, Compound 4n exhibited a better therapeutic effect on in vivo rice plants. However, the induction activity of 4n on the defense enzyme in rice leaf sheaths showed that 4n stimulates the initial resistance of rice plants by removing active oxygen, thereby protecting the cell membrane or enhancing the strength of the cell wall. Through the quantitative structure-activity relationship study, the quantitative chemical and electrostatic descriptors significantly affect the binding of 4n with the receptor, which improves its antifungal activity. CONCLUSION: This study provides a basis for exploiting potential rosin-based fungicides in promoting sustainable crop protection. © 2022 Society of Chemical Industry.

Scalable Production of Biodegradable, Recyclable, Sustainable Cellulose-Mineral Foams via Coordination Interaction Assisted Ambient Drying.

Heavy reliance on petrochemical-based plastic foams in both industry and society has led to severe plastic pollution (the so-called "white pollution"). In this work, we develop a biodegradable, recyclable, and sustainable cellulose/bentonite (Cel/BT) foam material directly from resource-abundant natural materials (i.e., lignocellulosic biomass and minerals) via ambient drying. The strong resistance to the capillary force-driven structural collapse of the preformed three-dimensional (3D) network during the ambient drying process can be ascribed to the purpose-designed cellulose-bentonite coordination interaction, which provides a practical way for the locally scalable production of foam materials with designed shapes without complex processing and intensive energy consumption. Benefiting from the strong cellulose-bentonite coordination interaction, the Cel/BT foam material demonstrates high mechanical strength and outstanding thermal stability, outperforming commercial plastic polystyrene foam. Furthermore, the Cel/BT foam presents environmental impacts much lower than those of petrochemical-based plastic foams as it can be 100% recycled in a closed-loop recycling process and easily biodegraded in the environment (natural cellulose goes back to the carbon cycle, and bentonite minerals return to the geological cycle). This study demonstrates an energy-efficient ambient drying approach for the local and scalable production of an all-natural cellulose/bentonite foam for sustainable packaging, buildings, and beyond, presenting great potential in response to "white pollution" and resource shortage.

Fast and Reversible Photoresponsive Self-Assembly Behavior of Rosin-Based Amphiphilic Polymers.

Designing stimulus-responsive amphiphilic polymers with a fast photoresponsive self-assembly behavior remains a challenge. Two series of rosin-terminated and azobenzene-terminated amphiphilic polymers (PAMn and PMAn) with fast and reversible photoresponsive properties were prepared using rosin-based azobenzene groups and polyethylene glycol, respectively. Under 5-10 s of UV irradiation, the polymers showed trans-to-cis isomerization and reached a photosteady state. For the PAMn polymer, the absorbance of the absorption peak at 325 nm recovered to more than 95% of the initial value under visible light for 5-10 s, whereas that of the PMAn polymer recovered completely. Notably, the PAMn and PMAn polymers initially self-assembled to vesicles or spherical micelles, and various morphological changes were achieved by manipulating UV irradiation time, with the initial morphology again recovered under dark conditions or visible-light irradiation. Remarkably, vesicles of the PAM34 and PMA34 polymers presented an intermediate open-vesicle state before being completely deformed under UV irradiation because of the existence of a π-π interaction. Finally, the ability of PAM34 and PMA34 polymer vesicles to perform the controlled release and reversible loading of a fluorescent probe was evaluated.

Strong, tough, ionic conductive, and freezing-tolerant all-natural hydrogel enabled by cellulose-bentonite coordination interactions.

Ionic conductive hydrogels prepared from naturally abundant cellulose are ideal candidates for constructing flexible electronics from the perspective of commercialization and environmental sustainability. However, cellulosic hydrogels featuring both high mechanical strength and ionic conductivity remain extremely challenging to achieve because the ionic charge carriers tend to destroy the hydrogen-bonding network among cellulose. Here we propose a supramolecular engineering strategy to boost the mechanical performance and ionic conductivity of cellulosic hydrogels by incorporating bentonite (BT) via the strong cellulose-BT coordination interaction and the ion regulation capability of the nanoconfined cellulose-BT intercalated nanostructure. A strong (compressive strength up to 3.2 MPa), tough (fracture energy up to 0.45 MJ m-3), yet highly ionic conductive and freezing tolerant (high ionic conductivities of 89.9 and 25.8 mS cm-1 at 25 and -20 °C, respectively) all-natural cellulose-BT hydrogel is successfully realized. These findings open up new perspectives for the design of cellulosic hydrogels and beyond.