Sulfonamide modified chitosan oligosaccharide with high nematicidal activity against Meloidogyne incognita.

Chitosan oligosaccharide (COS) modification is a feasible way to develop novel green nematicides. This study involved the synthesis of various COS sulfonamide derivatives via hydroxylated protection and deprotection, which were then characterized using NMR, FTIR, MS, elemental analysis, XRD, and TG/DTG. In vitro experiments found that COS-alkyl sulfonamide derivatives (S6 and S11-S13) exhibited high mortality (>98 % at 1 mg/mL) against Meloidogyne incognita second-instar larvaes (J2s) among the derivatives. S6 can cause vacuole-like structures in the middle and tail regions of the nematode body and effectively inhibit egg hatching. In vivo tests have found that S6 has well control effects and low plant toxicity. Additionally, the structure-activity studies revealed that S6 with a high degree of substitution, a low molecular weight, and a sulfonyl bond on the amino group of the COS backbone exhibited increased nematicidal activity. The sulfonamide group is a potential active group for developing COS-based nematicides.

In vivo immunological activity of chitosan-derived nanoparticles.

Chitosan has been studied as an immunomodulator, but few studies have used chitosan derivatives as adjuvants alone. After a preliminary study, we found that nanoparticles prepared from chitosan derivatives had better cellular immune activity when used as an adjuvant. Therefore, animal experiments were conducted to further investigate the performance and mechanism of these nanoparticles as immune adjuvants. We injected mice with the chitosan nanoparticle vaccine and measured the expression levels of immunoglobulins, immune factors, and immune genes in tissues and tissue sections. The results showed that C236-HACC-OVA (C2,3,6-chitosan sulfate-chitosan quaternary ammonium salt-ovalbumin) and NO-HACC-OVA (NO-carboxymethyl chitosan-chitosan quaternary ammonium salt-ovalbumin) nanoparticles can significantly improve the secretion of the immune factors IL-6, TNF, and IL-1ß. The level of IgG1 was highly significant after administering both nanoparticles, but IgG2 was not significant in mice. Three immune factors (IL-4, IL-6, and IL-17) were secreted at high levels in mouse serum at a nanoparticle dose of 0.3 mg/mouse. These nanoparticles also have high safety in the liver, kidney, and spleen of mice. This study proves the possibility of using chitosan derivative nanoparticles as vaccine adjuvants. These data further indicate that chitosan derivative nanoparticles have potential for use as vaccine adjuvants and demonstrate that polysaccharides have a unique position in green vaccine research.

Synthesis and Characterization of Slow-Release Chitosan Oligosaccharide Pyridine Schiff Base Copper Complexes with Antifungal Activity.

Herein, a series of chitosan oligosaccharide copper complexes modified with pyridine groups (CPSx-Cu complexes) were successfully prepared via the Schiff base reaction and ion complexation reaction for slow-release fungicide. The structures of the synthesized derivatives were characterized via Fourier transform infrared spectroscopy and 1H and 13C nuclear magnetic resonance spectroscopy, and the unit configuration of the complexes was calculated using Gaussian software. The slow-release performance experiment demonstrated that the cumulative copper ion release rate of CPSx-Cu complexes was dependent on the type of substituents on the pyridine ring. Furthermore, the in vitro and in vivo antifungal activities of the CPSx-Cu complexes were investigated. At a concentration of 0.4 mg/mL, CPSx-Cu complexes completely inhibited the growth of Pythium vexans and Phytophthora capsici. Results indicated that CPSx-Cu complexes with slow-release ability exhibited better antifungal activity than thiodiazole-copper and copper sulfate basic. This study confirmed that combining chitosan oligosaccharide with bioactive pyridine groups and copper ions is an effective approach to further developing slow-release copper fungicides, providing new possibilities for the application of copper fungicides in green agriculture. This study lays the foundation for further studies on biogreen copper fungicides.

Elucidating the impact of oxygen functional groups on the catalytic activity of M-N4-C catalysts for the oxygen reduction reaction: a density functional theory and machine learning approach.

Efforts to enhance the efficiency of electrocatalysts for the oxygen reduction reaction (ORR) in energy conversion and storage devices present formidable challenges. In this endeavor, M-N4-C single-atom catalysts (MN4) have emerged as promising candidates due to their precise atomic structure and adaptable electronic properties. However, MN4 catalysts inherently introduce oxygen functional groups (OGs), intricately influencing the catalytic process and complicating the identification of active sites. This study employs advanced density functional theory (DFT) calculations to investigate the profound influence of OGs on ORR catalysis within MN4 catalysts (referred to as OGs@MN4, where M represents Fe or Co). We established the following activity order for the 2eORR: for OGs@CoN4: OH@CoN4 > CoN4 > CHO@CoN4 > C-O-C@CoN4 > COC@CoN4 > COOH@CoN4 > CO@CoN4; for OGs@FeN4: COC@FeN4 > CO@FeN4 > OH@FeN4 > FeN4 > COOH@FeN4 > CHO@FeN4 > C-O-C@FeN4. Multiple oxygen combinations were constructed and found to be the true origin of MN4 activity (for instance, the overpotential of 2OH@CoN4 as low as 0.07 V). Furthermore, we explored the performance of the OGs@MN4 system through charge and d-band center analysis, revealing the limitations of previous electron-withdrawing/donating strategies. Machine learning analysis, including GBR, GPR, and LINER models, effectively guides the prediction of catalyst performance (with an R2 value of 0.93 for predicting ΔG*OOH_vac in the GBR model). The Eg descriptor was identified as the primary factor characterizing ΔG*OOH_vac (accounting for 62.8%; OGs@CoN4: R2 = 0.9077, OGs@FeN4: R2 = 0.7781). This study unveils the significant impact of OGs on MN4 catalysts and pioneers design and synthesis criteria rooted in Eg. These innovative findings provide valuable insights into understanding the origins of catalytic activity and guiding the design of carbon-based single-atom catalysts, appealing to a broad audience interested in energy conversion technologies and materials science.

Mechanical Force-Induced Color-Variable Luminescence of Carbon Dots in Boric Acid Matrix.

Mechano-luminescent materials that exhibit distinct luminescence responses to force stimuli are urgently anticipated in view of application needs in the fields of sensing, anti-counterfeiting, optoelectronic devices, etc. However, most of the reported materials normally exhibit force-induced changes in luminescent intensity, whereas materials that possess force-induced color-variable luminescence remain rarely reported. Herein, for the first time, a novel mechanical force-induced color-variable luminescence material from carbon dots (CDs) in boric acid (CD@BA) is reported. At low CDs concentration, the luminescence of CD@BA exhibits a grinding-induced color variable from white to blue. This grinding-induced color variable can be switched to yellow-to-white changing by increasing the CDs concentration in BA. The grinding-induced color-variable luminescence originates from dynamic variation in emission ratio of fluorescence and room temperature phosphorescence, due to the influence of oxygen and water vapor in the air. At high CDs concentration, short-wavelength fluorescence undergoes more severe reabsorption compared to room temperature phosphorescence, leading to grinding-induced color-variable switching from white-to-blue to yellow-to-white. Based on the unique properties of CD@BA powder, the applications of recognizing and visualizing fingerprints on the surfaces of various of materials are demonstrated.

Activity of chitin/chitosan/chitosan oligosaccharide against plant pathogenic nematodes and potential modes of application in agriculture: A review.

Chemical nematicide is the most common method of controlling plant-parasitic nematodes (PPN). Given the negative impact of chemical nematicides on the environment and ecosystem, it is necessary to seek their alternatives and novel modes of application. Chitin oligo/polysaccharide (COPS), including chitosan and chitosan oligosaccharide, has unique biological properties. By producing ammonia, encouraging the growth of antagonistic bacteria, and enhancing crop tolerance, COPSs help suppress PPN growth during soil remediation. COPS is also an effective sustained-release carrier that can be used to overcome the shortcomings of nematicidal substances. This review summarizes the advancements of COPS research in nematode control from three perspectives of action mechanism as well as in slow-release carrier-loaded nematicides. Further, it discusses potential agricultural applications for nematode disease management.

The synthesis, characterization and immunological activity of mucopolysaccharide-quaternized chitosan nanoparticles.

In this study, nanoparticles were prepared by using positively charged quaternized chitosan and negatively charged mucopolysaccharide such as chondroitin sulfate, heparin and hyaluronic acid. The nanoparticles have a stable nanostructure with particle size in 336.2-424.5 nm, potential in 18.5-31.1 mV and polydispersity index PDI of 0.172-0.335. Moreover, their encapsulation efficiency was 68.77 % and 64.89 %, and they have low endotoxin and good stability. It can significantly promote the expression of IL-6, TNF-α, and IL-1ß of DCS cells. Moreover, the in vivo immune activity of heparin-quaternized chitosan-OVA nanoparticles against BALB/C mice was showed that, the nanoparticles could significantly promote the secretion of immunoglobulins in mice including IgG1 and IgG2. And nanoparticle also can promote the production of immune factors. Meanwhile, the expression of immune factor genes was also elevated. Furthermore, the results of tissue section experiments showed that the nanoparticles are safety of the body.

Design, Synthesis, and Antifungal Activities of Hymexazol Glycosides Based on a Biomimetic Strategy.

Hymexazol (HYM) is irreplaceable for treating soil-borne diseases due to its high efficiency and low cost, as a broad-spectrum fungicide. However, when HYM is absorbed by plants, it is rapidly converted into two glycoside metabolites, and the antifungal activities of these glycosides are inferior to that of HYM. Therefore, in this study, to maintain strong antifungal activity in vitro and in vivo, HYM was glycosylated with amino sugars that have diverse biological activities to simulate plant glycosylation. The antifungal experiment proved that glycoside 15 has the highest antifungal activity, and N-acetyl glucosamine and HYM had obvious synergistic effects. According to the structure-activity relationship studies, glycoside 15 had greater numbers of active electron-rich regions and front-line orbital electrons due to the introduction of N-acetyl glucosamine. Moreover, glycoside 15 can significantly promote plant growth and induce an increase in plant defense enzyme activity. Additionally, compared to HYM, the results of electron microscopy and proteomics revealed that glycoside 15 has a unique antifungal mechanism. The promising antifungal activity and interactions with plants mean that glycoside 15 is a potential green fungicide candidate. Furthermore, this research conducted an interesting exploration of the agricultural applications of amino sugars.

Synthesis and antifungal activity of slow-release pyridinylcarbonyl chitooligosaccharide copper complexes.

Copper fungicides are fungicides have a wide application, but their toxicity to plant growth and the damage they cause to the environment cannot be ignored. As such, the novel, low toxicity biogenic copper fungicide has strong industrial application prospects. Herein, pyridinylcarbonyl chitooligosaccharide ligands (pCOSx) and their copper complexes (pCOSx-Cu) were synthesized. The results showed that a p-π-π conjugated system was formed in pCOSx, resulting in the formation of a slowly dissociated coordination bond between the nitrogen atom of pyridyl and Cu2+ in pCOSx-Cu. The cumulative release rate of Cu2+ is positively correlated with the electron donating ability of pyridyl. Compared with the commercial copper fungicide thiodiazole­copper, pCOSx-Cu exhibited better antifungal activity, lower phytotoxicity and better biocompatibility. This work demonstrated that it was feasible to construct a conjugated system in a chitooligosaccharide copper complex to improve slow-release performance, which laid a foundation for the in-depth study of green copper fungicides. CHEMICAL COMPOUNDS: Chitooligosaccharide (PubChem CID: 3086191); Nicotinoyl chloride hydrochloride (PubChem CID: 88438); Isonicotinoyl chloride hydrochloride (PubChem CID: 12262826); 2-chloronicotinoyl chloride (PubChem CID: 2774541); Trimethylchlorosilane (PubChem CID: 6397); Tetrabutylammonium fluoride (PubChem CID: 2724141); Copper (II) acetate monohydrate (PubChem CID: 165397).

Novel Lead Compound Discovery from Aspergillus fumigatus 1T-2 against Meloidogyne incognita Based on a Chemical Ecology Study.

To replace biohazardous nematicides, there is an ever-increasing need to identify natural product-based agents to contain root-knot nematodes (RKNs) in agriculture. In this chemical ecology study, an antagonistic fungus Aspergillus fumigatus 1T-2, which could cause the formation of withering of the gut and vacuole-like structures in the nematode body, was isolated based on the gradually increased antagonistic interactions between the soil fungi and RKNs. Based on these typical morphological characteristics, a potent nematode-antagonistic compound 2-furoic acid, which had a simple structure, was successfully identified from 1T-2 fermentation broth by liquid chromatography-mass spectrometry (LC-MS). 2-Furoic acid showed effective mortality activity in vitro, of which the LC50 value to Megalaima incognita at 24 h was 37.75 µg/mL. 2-Furoic acid had similar mortality activity to the positive control fosthiazate at 30 µg/mL. Continuous 2-furoic acid exposure had obvious negative influences on both nematode vitality and egg hatchability. Notably, significant variations were observed in nematodes and eggs with 2-furoic acid treatment, which might be induced by novel nematocidal mechanisms. Furthermore, the 1T-2 fermentation broth and 2-furoic acid had significant control efficacy on M. incognita under the greenhouse test-tube assay. Overall, these findings provide valuable insights into the use of 2-furoic acid with biocontrol potential as a preferable lead structure for the development of innovative nematicides.

Fruits-Based Critical Nitrogen Dilution Curve for Diagnosing Nitrogen Status in Cotton.

Estimating the precise nutritional status of crop nitrogen (N) after flowering period is not only important to predict deficiency but the excess that could be revised by fertilization in future crops. Critical N dilution curves describing the critical N concentration ([N]c) in plant tissues during crop growth have been used to estimate the N status of whole plants in cotton. Little is known, however, about the critical N dilution curve for specific plant organs such as cotton fruits. The objective of this study was to verify the feasibility of fruits-based critical N dilution curve as a useful diagnostic tool for diagnosing the N status of cotton crops. A 3-year field experiment was conducted with seven N application rates (0-360 kg N ha-1) using the high-yielding cultivars Jimian 228 and Lumian 28, which differ in maturity. The relationship between fruits dry mass (DM) and N concentration ([N]) was analyzed, and a model of [N]c for cotton fruits was constructed and validated. The results showed that fruits [N]c decreased with increasing fruits DM. The critical N dilution curve based on cotton fruits was described by the equation [N]c = 2.49 × DM-0.12 (R 2 = 0.649, P < 0.0001) across cultivar-years. The N nutrition index (NNI) of the fruits (NNIf) with the N dilution curve was significantly related to the NNI of shoot DM, relative yield (RY), and boll density at most sampling dates. For an NNIf of approximately 1, the RY was nearly 95%, while it decreased with a decreasing NNIf below 1. The petiole nitrate-N (NO3-N) concentration was also linearly related to the NNIf, suggesting that the NO3-N concentration in the petiole was a good predictor of the NNIf. Therefore, fruits-based critical N dilution curve and the derived NNIf values will serve as a useful diagnostic tool for diagnosing N status in cotton crops.

Fluoroalkenyl-Grafted Chitosan Oligosaccharide Derivative: An Exploration for Control Nematode Meloidogyne Incognita.

The exploration of novel, environmentally friendly, and efficient nematicides is essential, and modifying natural biomacromolecules is one feasible approach. In this study, 6-O-(trifluorobutenyl-oxadiazol)-chitosan oligosaccharide derivative was synthesized and characterized by FTIR, NMR, and TG/DTG. Its bioactivity and action mode against root-knot nematode M. incognita were estimated. The results show that the derivative shows high nematicidal activity against J2s, and egg hatching inhibitory activity at 1 mg/mL. The derivative may affect nematode ROS metabolism and further damage intestinal tissue to kill nematode. Meanwhile, by synergism with improving crop resistance, the derivative performed a high control effect on the nematode with low phytotoxicity. These findings suggested that chitosan oligosaccharide derivatives bearing fluoroalkenyl groups are promising green nematicides.

Understanding the activity origin of oxygen-doped carbon materials in catalyzing the two-electron oxygen reduction reaction towards hydrogen peroxide generation.

Oxygen-doped carbon materials (OCM) have received a lot of attention for catalyzing the two-electron oxygen reduction reaction (2eORR) towards hydrogen peroxide generation, but the origin of their activity is not well understood. Based on density functional theory calculations, we introduce the Fukui function (f0), a more comprehensive and accurate method for identifying active sites and systematically investigating the activity of carbon materials doped with typical oxygen functional groups (OGs). According to the results, only ether or carbonyl has the potential to become the activity origin. The 2eORR activities of carbon materials co-doped by different OGs were then investigated, and a significant synergistic effect was discovered between different OGs (particularly between epoxy and other OGs), which might be the real active centers in OCM. To further understand the cause of the activity, the Fundamental Gap (Eg) was introduced to investigate the ability of various OCM to gain and lose electrons. The results show that the decrease in overpotential after oxygen co-doping can be attributed to the decrease in Eg. This work introduces descriptors (f0 and Eg) that can aid in the efficient design of catalysts and adds to our understanding of the 2eORR activity origin of OCM.

Loading Effect of Chitosan Derivative Nanoparticles on Different Antigens and Their Immunomodulatory Activity on Dendritic Cells.

Drug carrier nanoparticles (NPs) were prepared by the polyelectrolyte method, with chitosan sulfate, with different substituents and quaternary ammonium chitosan, including C236-HACC NPs, C36-HACC NPs, and C6-HACC NPs. To evaluate whether the NPs are suitable for loading different antigens, we chose bovine serum albumin (BSA), ovalbumin (OVA), and myoglobin (Mb) as model antigens to investigate the encapsulation effect of the NPs. The characteristics (size, potential, and encapsulation efficiency) of the NPs were measured. Moreover, the NPs with higher encapsulation efficiency were selected for the immunological activity research. The results showed that chitosan derivative NPs with different substitution sites had different loading effects on the three antigens, and the encapsulation rate of BSA and OVA was significantly better than that of Mb. Moreover, the NPs encapsulated with different antigens have different immune stimulating abilities to DCS cells, the immune effect of OVA-coated NPs was significantly better than that of BSA-coated NPs and blank NPs, especially C236-HACC-OVA NPs. Furthermore, we found that C236-HACC-OVA NPs could increase the phosphorylation level of intracellular proteins to activate cell pathways. Therefore, C236-HACC NPs are more suitable for the loading of antigens similar to the OVA structure.

Metabonomics analysis of drought resistance of wheat seedlings induced by ß-aminobutyric acid-modified chitooligosaccharide derivative.

Chitooligosaccharide grafted with ß-aminobutyric acid based on the idea of bioactive molecular splicing was prepared, and the differences in drought resistance activity before and after grafting were compared. The mechanism was investigated by comparing the differences of the derivative with the Control and Drought about metabolomes. The results showed that the expected derivative was successfully synthesized, named COS-BABA, and had better drought resistance-inducing activity than the raw materials. We suggest that COS-BABA induced drought resistance through second messenger-induced activation of signaling pathways related to traumatic acid and indol-3-lactic acid, which enhanced nucleic acid metabolism to accumulate nucleotides and decreased some amino acids to facilitate protein synthesis. These proteins are regulated to strengthen photosynthesis, resulting in the promotion of carbohydrate metabolism. The accumulation of unsaturated fatty acids stabilized the cell membrane structure and prevented nonstomatal water dissipation. This study provides ideas for the development of more effective drought resistance inducers.

Efficacy of a Chitin-Based Water-Soluble Derivative in Inducing Purpureocillium lilacinum against Nematode Disease (Meloidogyne incognita).

Plant-parasitic nematodes cause severe economic losses annually which has been a persistent problem worldwide. As current nematicides are highly toxic, prone to drug resistance, and have poor stability, there is an urgent need to develop safe, efficient, and green strategies. Natural active polysaccharides such as chitin and chitosan with good biocompatibility and biodegradability and inducing plant disease resistance have attracted much attention, but their application is limited due to their poor solubility. Here, we prepared 6-oxychitin with good water solubility by introducing carboxylic acid groups based on retaining the original skeleton of chitin and evaluated its potential for nematode control. The results showed that 6-oxychitin is a better promoter of the nematicidal potential of Purpureocillium lilacinum than other water-soluble chitin derivatives. After treatment, the movement of J2s and egg hatching were obviously inhibited. Further plant experiments found that it can destroy the accumulation and invasion of nematodes, and has a growth-promoting effect. Therefore, 6-oxychitin has great application potential in the nematode control area.

Design of Chitosan Sterilization Agents by a Structure Combination Strategy and Their Potential Application in Crop Protection.

Chitosan is the only cationic polysaccharide in nature. It is a type of renewable resource and is abundant. It has good biocompatibility, biodegradability and biological activity. The amino and hydroxyl groups in its molecules can be modified, which enables chitosan to contain a variety of functional groups, giving it a variety of properties. In recent years, researchers have used different strategies to synthesize a variety of chitosan derivatives with novel structure and unique activity. Structure combination is one of the main strategies. Therefore, we will evaluate the synthesis and agricultural antimicrobial applications of the active chitosan derivatives structure combinations, which have not been well-summarized. In addition, the advantages, challenges and developmental prospects of agricultural antimicrobial chitosan derivatives will be discussed.

Preparation of New Sargassum fusiforme Polysaccharide Long-Chain Alkyl Group Nanomicelles and Their Antiviral Properties against ALV-J.

Avian leukosis virus subgroup J (ALV-J) is an immunosuppressive virus which has caused heavy losses to the poultry breeding industry. Currently, there is no effective medicine to treat this virus. In our previous experiments, the low-molecular-weight Sargassum fusiforme polysaccharide (SFP) was proven to possess antiviral activity against ALV-J, but its function was limited to the virus adsorption stage. In order to improve the antiviral activity of the SFP, in this study, three new SFP long-chain alkyl group nanomicelles (SFP-C12M, SFP-C14M and SFP-C16M) were prepared. The nanomicelles were characterized according to their physical and chemical properties. The nanomicelles were characterized by particle size, zeta potential, polydispersity index, critical micelle concentration and morphology. The results showed the particle sizes of the three nanomicelles were all approximately 200 nm and SFP-C14M and SFP-C16M were more stable than SFP-C12M. The newly prepared nanomicelles exhibited a better anti-ALV-J activity than the SFP, with SFP-C16M exhibiting the best antiviral effects in both the virus adsorption stage and the replication stage. The results of the giant unilamellar vesicle exposure experiment demonstrated that the new virucidal effect of the nanomicelles might be caused by damage to the phospholipid membrane of ALV-J. This study provides a potential idea for ALV-J prevention and development of other antiviral drugs.

Synthesis and effects of the selective oxidation of chitosan in induced disease resistance against Botrytis cinerea.

Plant fungal diseases can lead to yield reduction and quality degradation in crops, which usually cause serious economic losses. Additionally, chemical fungicides used in the prevention and control of plant diseases are increasingly restricted due to resistance development and high toxicity. Therefore, biogenic fungicides such as chitosan with low toxicity and good biocompatibility are receiving increasing attention. This study found that the acid swelling chitosan pretreatment method can accelerate the rate of the specific oxidation of chitosan catalyzed by the TEMPO-NaBr-NaOCl system. This study proved that OCTS induces plant disease resistance, and the control efficiencies achieved in protection and treatment experiments against Botrytis cinerea were 80.6 % and 83.4 %, respectively, at 400 µg/mL OCTS. In addition, OCTS can promote plant growth and enhance plant defense enzyme activities. This research has realized a forward-looking exploration of the application of OCTS in the agricultural field.

Characterization of Different Salt Forms of Chitooligosaccharides and Their Effects on Nitric Oxide Secretion by Macrophages.

In this paper, chitooligosaccharides in different salt forms, such as chitooligosaccharide lactate, citrate, adipate, etc., were prepared by the microwave method. They were characterized by SEM, FTIR, NMR, etc., and the nitric oxide (NO) expression was determined in RAW 264.7 cells. The results showed that pure chitooligosaccharide was an irregular spherical shape with rough surface, and its different salt type products are amorphous solid with different honeycomb sizes. In addition to the characteristic absorption peaks of chitooligosaccharides, in FTIR, the characteristic absorption of carboxyl group, methylene group, and aromatic group in corresponding acid appeared. The characteristic absorption peaks of carbon in carboxyl group, hydrogen and carbon in methyl, methylene group, and aromatic group in corresponding acid also appeared in NMR. Therefore, the sugar ring structure and linking mode of chitooligosaccharides did not change after salt formation of chitooligosaccharides. Different salt chitooligosaccharides are completely different in promoting NO secretion by macrophages, and pure chitooligosaccharides are the best.