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.

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.

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.

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.

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.

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.

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, self-adhesive, and stretchable conductive hydrogel for multifunctional sensor prepared by catechol modified nanocellulose stabilized poly(α-thioctic acid).

Self-healing, self-adhesive, and stretchable bio-based conductive hydrogels exhibit properties similar to those of biological tissues, making them an urgent requirement for emerging wearable devices. The primary challenge lies in devising straightforward strategies to accomplish all the aforementioned performances and achieve equilibrium among them. This study used the natural compound thioctic acid (TA) and modified cellulose to prepare conductive hydrogels with stretchability, healing, and self-adhesion through a simple one-step strategy. Metastable poly(TA) was obtained through ring-opening polymerization of lithiated TA, followed by the introduction of dopamine-grafted cellulose nanofibers (DCNF) to stabilize poly(TA) and prepare PTALi/DCNF hydrogels with the aforementioned properties. The hydrogels demonstrated remarkable conductivity, attributed to the existence of Li + ions, with a maximum conductivity of 17.36 mS/cm. The self-healing capacity of the hydrogels was achieved owing to the presence of disulfide bond in TA. The introduction of DCNF can effectively stabilize poly(TA), endow the hydrogel with self-adhesion ability, improve the mechanical properties, and further enhance the formability of hydrogels. Generally, bio-based PTALi/DCNF hydrogels with stretchability, self-healing, self-adhesion, and conductivity are obtained through a simple strategy and used as a sensor with a wide response range and high sensitivity. Hydrogels have significant potential for application in wearable electronic devices, electronic skins, and soft robots.

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.

Preparation of Eu(III) Complexes Containing Maleopimaric Acid Anhydride with Ultra-narrow and Efficient Fluorescence Emission for High Determination on Gallic Acid in Acetonitrile Solution.

Two novel Eu(III) complexes constructed by maleopimaric acid anhydride (MPA) and 2,2'-bipyridyl (Bpy) / 1, 10-phenanthroline (Phen), named as MPA-Bpy-Eu / MPA-Phen-Eu, have been synthesized by a one-step precipitation method. FTIR, UV, TG, elemental analysis, XPS, and ESI-MS revealed the successful coordination of Eu(III) ions with MPA and Bpy / Phen through Eu-O and Eu-N bonds, respectively. Introducing MPA into coordinate structure increased the electron cloud density in 3d5/2 orbit of Eu(III) ions, enhanced the absolute quantum yields of MPA-Bpy-Eu (89.27%) and MPA-Phen-Eu (94.41%), and decreased the full width at half maxima of 5D0 → 7F2 transitions of MPA-Bpy-Eu (2.23 nm) and MPA-Phen-Eu (2.93 nm), respectively. The fluorescence quenching experiments showed that there was a good linear relationship between the relative fluorescence intensity of MPA-Bpy-Eu and gallic acid (GA) concentration in acetonitrile solution in the range of 0 to 8.41 × 10-2 mM. The results of UV-vis spectra, the fluorescence lifetimes, and the quantum yields demonstrated that the dynamic quenching model played a major role in the quenching process of GA on MPA-Bpy-Eu. The quenching process of GA on MPA-Phen-Eu involved dual fluorescence quenching mechanistic pathways, including static and dynamic models.

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.

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.

Facile Strategy for Preparing a Rosin-Based Low-k Material: Molecular Design of Free Volume.

Low-k dielectrics are urgently needed in modern integrated circuits. The introduction of free volume instead of porous structures has become a powerful strategy to reduce the k value. According to this strategy, the biomass resource rosin-containing hydrogenated phenanthrene ring was introduced into benzocyclobutene (BCB) resin to reduce the k value; then a rosin-based BCB monomer was successfully synthesized. Meanwhile, the BCB monomer without a rosin skeleton was prepared. After converting the monomers into thermo-crosslinked materials, notably that the rosin skeleton has a great influence on the free volume and k value of the material. The fractional free volume and k value of the former are 26% and 2.44, respectively, and those of the latter are 14% and 2.84, respectively. In addition, the distances between molecular chains and the density of the former are 0.60 nm and 1.06 g cm-3, respectively; those of the latter are 0.56 nm and 1.28 g cm-3, respectively. These data show that introducing hydrogenated phenanthrene rings occupies part of the space and hinders the packing of molecular chains, which increases the distance between molecular chains and reduces the density of the polymer, resulting in an increasing free volume and a reducing k value. Notably that introducing hydrogenated phenanthrene rings cannot affect other properties of the material. Therefore, this research indicates that introducing rosin skeletons can prepare high-performance materials, which provide some promising low-k materials for the development of electronics and microelectronics.