Synthesis, Structural Determination, and Antifungal Activity of Novel Fluorinated Quinoline Analogs.

A series of new fluorinated quinoline analogs were synthesized using Tebufloquin as the lead compound, 2-fluoroaniline, ethyl 2-methylacetoacetate, and substituted benzoic acid as raw materials. Their structures were confirmed by 1H NMR, 13C NMR, and HRMS. The compound 8-fluoro-2,3-dimethylquinolin-4-yl 4-(tert-butyl)benzoate (2b) was further determined by X-ray single-crystal diffraction. The antifungal activity was tested at 50 µg/mL, and the bioassay results showed that these quinoline derivatives had good antifungal activity. Among them, compounds 2b, 2e, 2f, 2k, and 2n exhibited good activity (>80%) against S. sclerotiorum, and compound 2g displayed good activity (80.8%) against R. solani.

Synthesis, Herbicidal Activity, Mode of Action, and In Silico Analysis of Novel Pyrido[2,3-d]pyrimidine Compounds.

Natural products are a main source of new chemical entities for use in drug and pesticide discovery. In order to discover lead compounds with high herbicidal activity, a series of new pyrido[2,3-d] pyrimidine derivatives were designed and synthesized using 2-chloronicotinic acid as the starting material. Their structures were characterized with 1H NMR, 13C NMR and HRMS, and the herbicidal activities against dicotyledonous lettuce (Lactuca sativa), field mustard (Brassica campestris), monocotyledonous bentgrass (Agrostis stolonifera) and wheat (Triticum aestivum) were determined. The results indicated that most of the pyrido[2,3-d] pyrimidine derivatives had no marked inhibitory effect on lettuce at 1 mM. However, most of the pyrido[2,3-d] pyrimidine derivatives possessed good activity against bentgrass at 1 mM. Among them, the most active compound, 3-methyl-1-(2,3,4-trifluorophenyl)pyrido[2,3-d]pyrimidine-2,4(1H,3H)-dione (2o), was as active as the positive controls, the commercial herbicides clomazone and flumioxazin. Molecular simulation was performed with molecular docking and DFT calculations. The docking studies provided strong evidence that 2o acts as an herbicide by inhibition of protoporphyrinogen oxidase. However, the physiological results indicate that it does not act on this target in vivo, implying that it could be metabolically converted to a compound with a different molecular target.

Synthesis, crystal structure, herbicidal activity and mode of action of new cyclopropane-1,1-dicarboxylic acid analogues.

A new series of cyclopropane-1,1-dicarboxylic (CPD) acid analogues were designed and synthesized. CPD is an inhibitor of ketol-acid reductoisomerase (KARI), an enzyme of the branched chain amino acid pathway in plants. The structures of CPD analogues were characterized by 1H NMR and HRMS. The structure of N,N'-bis(4-(tert-butyl)phenyl)cyclopropane-1,1-dicarboxamide was further elucidated by X-ray diffraction. The herbicidal activities of these compounds were tested against lettuce (Lactuca sativa) and bentgrass (Agrostis stolonifera). Most of these compounds exhibited low herbicidal activity against both plant species. Among them, N,N'-bis(2-ethylphenyl)cyclopropane-1,1-dicarboxamide displayed moderate activity against bentgrass. Inhibition of KARI activity by the CPD analogues was also assessed experimentally and by molecular docking simulation with results supporting inhibition of KARI as their mode of action. These results provide the basis for design of more effective KARI inhibitors.

Synthesis and Pesticidal Activity of New Niacinamide Derivatives Containing a Flexible, Chiral Chain.

Natural products are a source for pesticide or drug discovery. In order to discover lead compounds with high fungicidal or herbicidal activity, new niacinamide derivatives derived from the natural product niacinamide, containing chiral flexible chains, were designed and synthesized. Their structures were confirmed by 1H NMR, 13C NMR and HRMS analysis. The fungicidal and herbicidal activities of these compounds were tested. The fungicidal activity results demonstrated that the compound (S)-2-(2-chloronicotinamido)propyl-2-methylbenzoate (3i) exhibited good fungicidal activity (92.3% inhibition) against the plant pathogen Botryosphaeria berengriana at 50 µg/mL and with an EC50 of 6.68 ± 0.72 µg/mL, which is the same as the positive control (fluxapyroxad). Compound 3i was not phytotoxic and could therefore be used as a fungicide on crops. Structure-activity relationships (SAR) were studied by molecular docking simulations with the succinate dehydrogenase of the fungal mitochondrial respiratory chain.

LDPE/M-TiO2 composite films for modified atmosphere packaging to realize comprehensive preservation of strawberry (Fragaria × ananassa Duch.).

BACKGROUND: A shelf-life that is too short is the main problem with strawberries. Nano-TiO2 can catalyze and oxidize ethylene under ultraviolet (UV) light irradiation to eliminate its ripening effect on fruits and prolong the freshness period. RESULTS: In this work, nano-TiO2 modified by methacryloxy propyl trimethoxyl silane (KH570) was blended with low-density polyethylene (LDPE) to prepare modified atmosphere packaging (MAP), and the influence of TiO2 content on films was analyzed before and after UV treatment. The results show that the modified nano-TiO2 (M-TiO2 ) can be uniformly distributed in LDPE, improving its mechanical strength, hydrophobicity, oxygen barrier and UV shielding properties. A modified atmosphere with low ethylene, low O2 and high CO2 can be created to inhibit the ripening and spoilage of strawberries. The weight loss rate of fruit can be effectively reduced. The tendency of fruit firmness decline and nutrient loss can be slowed and stabilized, contributing to controllable shelf-life. Excellent freshness preservation function can be realized without special UV treatment. CONCLUSION: Since UV treatment is rare in actual storage and transportation, LDPE/M-TiO2 composite film has practical value as MAP for strawberry and similar non-climacteric fruits. © 2022 Society of Chemical Industry.

1,2,4-Oxadiazole-Based Bio-Isosteres of Benzamides: Synthesis, Biological Activity and Toxicity to Zebrafish Embryo.

To discover new compounds with broad spectrum and high activity, we designed a series of novel benzamides containing 1,2,4-oxadiazole moiety by bioisosterism, and 28 benzamides derivatives with antifungal activity were synthesized. These compounds were evaluated against four fungi: Botrytis cinereal, FusaHum graminearum, Marssonina mali, and Thanatephorus cucumeris. The results indicated that most of the compounds displayed good fungicidal activities, especially against Botrytis cinereal. For example, 10a (84.4%), 10d (83.6%), 10e (83.3%), 10f (83.1%), 10i (83.3%), and 10l (83.6%) were better than pyraclostrobin (81.4%) at 100 mg/L. In addition, the acute toxicity of 10f to zebrafish embryo was 20.58 mg/L, which was classified as a low-toxicity compound.

Host-guest interaction-mediated fabrication of a hybrid microsphere-structured supramolecular hydrogel showing high mechanical strength.

The introduction of structured microsphere composites into hydrogels is found to improve their mechanical strength capability. Herein, chitosan microspheres were functionalized with poly(acrylamide-co-1-benzyl-3-vinylimidazolium bromide) (CS-P(AM-G)), which was synthesized through an in situ copolymerization of acrylamide and a guest functional monomer. Supramolecular hydrogels were fabricated by dynamic host-guest interactions between guest units and the host molecule cucurbit[8]uril (CB[8]). Investigations on the mechanical properties of the hydrogels show that the tensile stress and the compress stress of the hydrogels are five times higher than those of CB[8] hydrogels without CS, and the healing efficiency of the hydrogels at room temperature is 88% after 24 h. The results show that CS microspheres serve as both polyfunctional initiating and cross-linking centers, whereas the dynamic host-guest interactions endow the hydrogels with a higher self-healing property. The process provides a novel method for the production of tough and self-healing supramolecular hydrogels with various potential applications.

Design, synthesis and antifungal activity of threoninamide carbamate derivatives via pharmacophore model.

Thirty-six novel threoninamide carbamate derivatives were designed and synthesised using active fragment-based pharmacophore model. Antifungal activities of these compounds were tested against Oomycete fungi Phytophthora capsici in vitro and in vivo. Interestingly, compound I-1, I-2, I-3, I-6 and I-7 exhibited moderate control effect (>50%) against Pseudoperonospora cubensis in greenhouse at 6.25 µg/mL, which is better than that of control. Meanwhile most of these compounds exhibited significant inhibitory against P. capsici. The other nine fungi were also tested. More importantly, some compounds exhibited remarkably high activities against Sclerotinia sclerotiorum, P. piricola and R. solan in vitro with EC50 values of 3.74-9.76 µg/mL. It is possible that the model is reliabile and this method can be used to discover lead compounds for the development of fungicides.

Synthesis and Biological Activity of Benzamides Substituted with Pyridine-Linked 1,2,4-Oxadiazole.

To find pesticidal lead compounds with high activity, a series of novel benzamides substituted with pyridine-linked 1,2,4-oxadiazole were designed by bioisosterism, and synthesized easily via esterification, cyanation, cyclization and aminolysis reactions. The structures of the target compounds were confirmed by 1H-NMR, 13C-NMR and HRMS. The preliminary bioassay showed that most compounds had good larvicidal activities against mosquito larvae at 10 mg/L, especially compound 7a, with a larvicidal activity as high as 100%, and even at 1 mg/L was still 40%; at 50 mg/L, all the target compounds showed good fungicidal activities against the eight tested fungi. Moreover, compound 7h exhibited better inhibitory activity (90.5%) than fluxapyroxad (63.6%) against Botrytis cinereal. Therefore, this type of compound can be further studied.

Synthesis, biological activities and SAR studies of new 3-substitutedphenyl-4-substitutedbenzylideneamino-1,2,4-triazole Mannich bases and bis-Mannich bases as ketol-acid reductoisomerase inhibitors.

A series of new 3-substitutedphenyl-4-substitutedbenzylideneamino-1,2,4-triazole Mannich bases and bis-Mannich bases were synthesized through Mannich reaction with high yields. Their structures were confirmed by means of IR, 1H NMR, 13C NMR and elemental analysis. The preliminary bioassay indicated that compounds 7g, 7h and 7l exhibited potent in vitro inhibitory activities against ketol-acid reductoisomerase (KARI) with Ki value of (0.38 ±â€¯0.25), (6.59 ±â€¯2.75) and (8.46 ±â€¯3.99) µmol/L, respectively, and were comparable with IpOHA. They could be new KARI inhibitors for follow-up research. Some of the title compounds also exhibited obvious herbicidal activities against Echinochloa crusgalli and remarkable in vitro fungicidal activities against Physalospora piricola and Rhizoctonia cerealis. The SAR of the compounds were analyzed, in which the molecular docking revealed the binding mode of 7g with the KARI, and the 3D-QSAR results provided useful information for guiding further optimization of this kind of structures to discover new fungicidal agents towards Rhizoctonia cerealis.

Synthesis, nematocidal activity and docking study of novel chiral 1-(3-chloropyridin-2-yl)-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide derivatives.

A series of novel chiral fluorinated pyrazole carboxamides derivatives were designed and synthesized. All these title compounds were confirmed by NMR and MS. The primarily nematocidal activity results indicated that some of them exhibited good control efficacy against the tomato root-knot nematode disease caused by Meloidogyne incognita. The docking results indicated that compound 5n interact with amino acid residue Tyr 121, Trp 279 of AchE via hydrogen bond.

Synthesis and biological activities of novel 5-substituted-1,3,4-oxadiazole Mannich bases and bis-Mannich bases as ketol-acid reductoisomerase inhibitors.

A series of novel 5-substituted-1,3,4-oxadiazole Mannich bases and bis-Mannich bases have been conveniently synthesized in good yields. Their structures were characterized by IR, (1)H NMR, (13)C NMR and elemental analysis. The preliminary bioassay results indicated that some of the compounds showed promising in vitro fungicidal activities towards several test plant fungi; some of them exhibited significant herbicidal activities against Brassica campestris and excellent in vitro inhibitory activities against rice ketol-acid reductoisomerase (KARI). Among 14 novel compounds, 8c, 8d and 8m showed potent KARI inhibitory activities with Ki value of (0.96±0.42), (3.86±0.49) and (3.10±0.71) µmol/L, respectively, and were comparable with IpOHA. These compounds could be novel KARI inhibitors for further investigation. The density functional theory (DFT) calculations and molecular docking were carried out to study the structure-activity relationship (SAR) of the active inhibitors in this Letter.

Design, Synthesis, DFT Study and Antifungal Activity of Pyrazolecarboxamide Derivatives.

A series of novel pyrazole amide derivatives were designed and synthesized by multi-step reactions from phenylhydrazine and ethyl 3-oxobutanoate as starting materials, and their structures were characterized by NMR, MS and elemental analysis. The antifungal activity of the title compounds was determined. The results indicated that some of title compounds exhibited moderate antifungal activity. Furthermore, DFT calculations were used to study the structure-activity relationships (SAR).

Facile and efficient synthesis and herbicidal activity determination of novel 1,2,4-triazolo[4,3-a]pyridin-3(2H)-one derivatives via microwave irradiation.

A series of novel 1,2,4-triazolo[4,3-a]pyridin-3(2H)-one derivatives were synthesized and identified by (1)H NMR, single crystal X-ray diffraction, elemental analysis or HRMS, and their herbicidal activities were determined at different concentrations. It was found that some of the title compounds possess high herbicidal activity. Furthermore, DFT calculation was used to study the SAR.

Microwave assistant synthesis, antifungal activity and DFT theoretical study of some novel 1,2,4-triazole derivatives containing pyridine moiety.

In order to investigate the biological activity of novel 1,2,4-triazole compounds, seventeen novel 1,2,4-triazole derivatives containing pyridine moiety were synthesized under microwave assistant condition by multi-step reactions. The structures were characterized by 1H NMR, MS and elemental analyses. The target compounds were evaluated for their fungicidal activities against Stemphylium lycopersici (Enjoji) Yamamoto, Fusarium oxysporum. sp. cucumebrium, and Botrytis cinerea in vivo, and the results indicated that some of the title compounds displayed excellent fungicidal activities. Theoretical calculation of the title compound was carried out with B3LYP/6-31G (d,p). The full geometry optimization was carried out using 6-31G (d,p) basis set, and the frontier orbital energy, atomic net charges were discussed, and the structure-activity relationship was also studied.

Endocrine regulation of reproductive biology in echinoderms: An evolutionary perspective from closest marine invertebrate relatives to chordates.

Echinoderms are a phylum of invertebrate deuterostomes, which contain echinoids, asteroids, holothuroids, crinoids, and ophiuroids. Echinoderms have special evolutionary position and unique characteristics, including pentamerous radial body structure, elaborate calcareous endoskeletons, and versatile water vascular system. Echinoderms exhibit extraordinarily diverse reproductive modes: asexual reproduction, sexual reproduction, sexual reversal, etc. Endocrine regulation plays important well-known roles in sex differentiation, gonadal development and maturation, gametogenesis, and reproductive behavior in vertebrates. However, the entire picture of reproductive endocrinology in echinoderms as an evolutionary model of the closest marine invertebrate relatives to chordates has not been revealed. Here, we reviewed previous and recent research progress on reproductive endocrinology in echinoderms, mainly including two sections: Sex steroids in echinoderms and neuropeptide regulation in echinoderm reproduction. This review introduces a variety of endocrine regulatory mechanisms in reproductive biology of echinoderms. It discusses the vertebrate-like sex steroids, putative steroidogenic pathway and metabolism, and reproduction-related neuropeptides. The review will provide a deeper understanding about endocrine regulatory mechanisms of gonadal development in lower deuterostomes and the application of endocrine control in economic echinoderm species in aquaculture.

Magnetically separable Co0.6Fe2.4O4/MIL-101-NH2 adsorbent for Congo red efficient removal.

The development of effective and practical adsorbents for eliminating pollutants still remains a significant challenge. Herein, we synthesized a novel magnetically separable composite, Co0.6Fe2.4O4/MIL-101-NH2, through the in-situ growth of MIL-101-NH2 on magnetic nanoparticles, designed specifically for the removal of Congo red (CR) from aqueous solutions. MIL-101-NH2 possessed high BET surface area (240.485 m2•g-1) and facile magnetic separation function and can be swiftly separated (within 30 s) through an external magnetic field post-adsorption. The investigation systematically explored the influence of crucial parameters, including adsorbent dosage, pH, adsorption duration, temperature, and the presence of interfering ions, on CR adsorption performance. Findings indicate that CR adsorption adheres to the pseudo-second-order (PSO) kinetic model and the Langmuir isotherm model. Thermodynamic analysis reveals the spontaneity, endothermic nature, and orderly progression of the adsorption process. Remarkably, the adsorbent with 0.1 g•L-1 boasts an impressive maximum adsorption capacity of 1756.19 mg•g-1 for CR at 298.15 K, establishing its competitive advantage. The reuse of the adsorbent over 5 cycles remains 78% of the initial adsorption. The CR adsorption mechanisms were elucidated, emphasizing the roles of π-π interactions, electrostatic forces, hydrogen bonding, and metal coordination. Comparison with other dyes, such as methylene blue (MB) and methyl orange (MO), and exploration of adsorption performance in binary dye systems, demonstrates the superior capacity and selectivity of this adsorbent for CR. In conclusion, our magnetically separable metal-organic framework (MOF)based composite presents a versatile and effective solution for CR removal, with promising applications in water treatment and environmental remediation.

High-performance VO2/CNT@PANI with core-shell construction enable printable in-planar symmetric supercapacitors.

As a progressive electronic energy storage device, the flexible supercapacitor holds tremendous promise for powering wearable/portable electronic products. Of various pseudocapacitor materials, vanadium dioxide (VO2) has garnered extensive attention due to its impressive theoretical capacitance. However, the challenges of inferior cycling life and lower energy density to be addressed. Herein, we prepare VO2 nanorods with winding carbon nanotubes (CNT) via a facile solvothermal route, followed by in situ polymerization of polyaniline (PANI) shell. Taking full advantage of the synergistic effect, the VO2/CNT@PANI composite delivers a high specific capacitance of 354.2F/g at 0.5 A/g and a long cycling life of âˆ¼ 88.2 % over 5000 cycles resulting from the enhanced conductivity of CNT and stabilization of PANI shell. By screen printing the formulated inks with outstanding rheological behaviours, we manufacture an in-planar VO2/CNT@PANI symmetric supercapacitor (VO2/CNT@PANI SSC) device featuring an orderly arrangement structure. This device yields a remarkable areal energy density of 99.57 µWh/cm2 at a power density of 387.5 µW/cm2 while retaining approximately âˆ¼ 87.6 % of its initial capacitance after prolonged use. Furthermore, we successfully powered a portable game machine for more than 2 min using two SSCs connected in series with ease. Therefore, this work presents a universal strategy that utilises combination and coating to boost electrochemical performance for flexible high-performance supercapacitors.

The Impact of the Fresh Pork Display Lamps on the Sensory Response of Consumers to Fresh Pork.

Two studies were conducted to investigate the impact of fresh pork display lamps on consumers' sensory responses to pork products. In the first experiment, 63 participants were asked to evaluate pork products with different degrees of freshness under four fresh pork display lights and two LED lights. In the other experiment, 30 subjects participated in the Farnsworth-Munsell 100 hue test under the same lamps, with the aim of showing whether the fresh pork display lamps impaired color discrimination. The results showed that the light source had a significant effect on the color appearance evaluation of the pork products. The ratings for perceived freshness under the fresh pork display lamps were significantly higher than those of ordinary LED lamps, while the color discrimination performance of the subjects under those lamps was poor. It was demonstrated that improper component proportions of the light spectrum could influence observers' assessment of meat quality and weaken the observers' ability to distinguish the freshness level. Through this study, the authors would like to remind lamp users and manufacturers to not only be concerned about the improvement in the color appearance of pork, but also the need for consumers to be aware of the authentic freshness of the pork products.

Ratiometric fluorescence sensor based on deep learning for rapid and user-friendly detection of tetracycline antibiotics.

The detection of tetracycline antibiotics (TCs) in food holds great significance in minimizing their absorption within the human body. Hence, this study aims to develop a rapid, convenient, real-time, and accurate detection method for detecting antibiotics in an authentic market setting. A colorimetric fluorescence sensor was devised for tetracycline detection utilizing PVA aerogels as the substrate. Its operating principle is based on the IFE effect and antenna effect. A detection device is designed to capture fluorescence images while deep learning was employed to aid in the detection process. The sensor exhibits high responsiveness with a mere 60-s requirement for detection and demonstrates substantial color changes(blue to red), achieving 99% accuracy within the range of 10-100 µM with the assistance of deep learning (Resnet18). Real sample simulation tests yielded recovery rates between 95% and 130%. Overall, the proposed strategy proved to be a simple, portable, reliable, and responsive solution for rapid real-time TCs detection in food samples.