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.

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.

Temporal patterns of organ dysfunction in COVID-19 patients hospitalized in the intensive care unit: A group-based multitrajectory modeling analysis.

BACKGROUND: The course of organ dysfunction (OD) in Corona Virus Disease 2019 (COVID-19) patients is unknown. Herein, we analyze the temporal patterns of OD in intensive care unit-admitted COVID-19 patients. METHODS: Sequential organ failure assessment scores were evaluated daily within 2 weeks of admission to determine the temporal trajectory of OD using group-based multitrajectory modeling (GBMTM). RESULTS: A total of 392 patients were enrolled with a 28-day mortality rate of 53.6%. GBMTM identified four distinct trajectories. Group 1 (mild OD, n = 64), with a median APACHE II score of 13 (IQR 9-21), had an early resolution of OD and a low mortality rate. Group 2 (moderate OD, n = 140), with a median APACHE II score of 18 (IQR 13-22), had a 28-day mortality rate of 30.0%. Group 3 (severe OD, n = 117), with a median APACHR II score of 20 (IQR 13-27), had a deterioration trend of respiratory dysfunction and a 28-day mortality rate of 69.2%. Group 4 (extremely severe OD, n = 71), with a median APACHE II score of 20 (IQR 17-27), had a significant and sustained OD affecting all organ systems and a 28-day mortality rate of 97.2%. CONCLUSIONS: Four distinct trajectories of OD were identified, and respiratory dysfunction trajectory could predict nonpulmonary OD trajectories and patient prognosis.

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.

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.

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.

Carbon footprint analysis and carbon neutrality potential of desalination by electrodialysis for different applications.

Low-carbon water production technologies are indispensable for achieving sustainable development goals and mitigating global climate change. However, at present, many advanced water treatment processes lack a systematic assessment of related greenhouse gas (GHG) emissions. Thus, quantifying their life-cycle GHG emissions and proposing strategies toward carbon neutrality is urgently needed. This case study focuses on electrodialysis (ED), an electricity-driven desalination technology. To analyze the carbon footprint of ED desalination in various applications, a life cycle assessment model was developed based on industrial-scale ED processes. For seawater desalination, the carbon footprint is 59.74 kg CO2-eq/metric ton removed salt, which is one order of magnitude lower than that of high-salinity wastewater treatment and organic solvent desalination. Meanwhile, the power consumption during operation is the main hotspot of GHG emissions. Power grid decarbonization and improved waste recycling in China are projected to reduce the carbon footprint up to 92%. Meanwhile, the contribution of operation power consumption is expected to reduce from 95.83% to 77.84% for organic solvent desalination. Through sensitivity analysis, significant non-linear impacts of process variables on the carbon footprint were determined. Therefore, it is recommended to optimize the process design and operation to reduce power consumption based on the current fossil-based grid. GHG reduction for module production and disposal should also be emphasized. This method can be extended to general water treatment or other industrial technologies for carbon footprint assessment and reducing GHG emission.

The effect of lipid metabolism regulator anthocyanins from Aronia melanocarpa on 3T3-L1 preadipocytes and C57BL/6 mice via activating AMPK signaling and gut microbiota.

This study investigated lipid metabolism regulation by anthocyanins from Aronia melanocarpa (AAM) in 3T3-L1 preadipocytes and high fat diet (HFD) mice. Ultra-performance liquid chromatography/ion mobility quadrupole time-of-flight mass spectrometry analysis identified the constituents of AAM, which decreased lipid content and inflammation in 3T3-L1 cells without cytotoxicity. Meanwhile, taking normal diet and orlistat mice as references, AAM supplementation improved blood lipid levels and adipocyte degeneration, promoted beneficial gut microbial growth, and maintained lipid metabolism in HFD mice. Furthermore, AAM activated the AMP-activated protein kinase (AMPK) signaling pathway, accompanied by the regulation of adipogenic transcription factors and their target genes in vitro and in vivo. Collectively, our data demonstrated that AAM exhibits anti-adipogenic activities that were partially mediated by the AMPK pathway and gut microbiota regulation. This study provides new insight into the regulation of lipid metabolism by AAM and suggests that AAM has potential therapeutic effects on hyperlipidemia.

Optimization of Enzyme-Assisted Extraction and Purification of Flavonoids from Pinus koraiensis Nut-Coated Film and Antioxidant Activity Evaluation.

Pinus koraiensis nut-coated film is a kind of by-product of nut processing, which has been shown to contain flavonoids, polyphenols, and other substances that can be used to produce natural antioxidant extracts. In this study, response surface methodology (RSM) was used to optimize the extraction process of flavonoids of P. koraiensis nut-coated film (PNF), and macroporous resin HPD600 was used to purify PNF (P-PNF). Its antioxidant activity was examined by DPPH (1,1-diphenyl-2-picrylhydrazyl) radical scavenging capacity, oxygen free radical absorption capacity (ORAC), total oxygen radical capture (TRAP), and iron ion reduction capacity. Under the ideal extraction conditions comprising a cellulase dosage of 90 U/g, a material/liquid ratio of 1:20 (g/mL), and an extraction time of 2 h, the PNF yield was 3.37%. Purification conditions were sample concentration of 2.0 mg/mL, pH of 5, water washing volume of 3 bed volume (BV), eluent ethanol concentration of 50%, and volume of 2 BV. The P-PNF recovery was 84.32%, and purity increased from 33.80% to 61.70%. Additionally, P-PNF showed increased antioxidant activity compared to PNF. Cumulatively, this study obtained the optimal values for the process parameters in order to achieve the maximum rates of extraction of PNF for economically optimal production at an industrial scale.