Multifunctional Nanocarriers Based on Chitosan Oligomers and Graphitic Carbon Nitride Assembly

In this study, a graphitic carbon nitride and chitosan oligomers (g-C3N4–COS) nanocarrier assembly, which was obtained by cross-linking with methacrylic anhydride (MA), was synthesized and characterized. Its characterization was carried out using infrared spectroscopy, elemental and thermal analyses, and transmission electron microscopy. The new nanocarriers (NCs), with an average particle size of 85 nm in diameter and a 0.25 dispersity index, showed photocatalytic activity (associated with the g-C3N4 moiety), susceptibility to enzymatic degradation (due to the presence of the COS moiety), and high encapsulation and moderate-high release efficiencies (>95% and >74%, respectively). As a proof of concept, the visible-light-driven photocatalytic activity of the NCs was tested for rhodamine B degradation and the reduction of uranium(VI) to uranium(IV). Regarding the potential of the nanocarriers for the encapsulation and delivery of bioactive products for crop protection, NCs loaded with Rubia tinctorum extracts were investigated in vitro against three Vitis vinifera phytopathogens (viz. Neofusicoccum parvum, Diplodia seriata, and Xylophilus ampelinus), obtaining minimum inhibitory concentration values of 750, 250, and 187.5 µg·mL−1, respectively. Their antifungal activity was further tested in vivo as a pruning wound protection product in young ‘Tempranillo’ grapevine plants that were artificially infected with the two aforementioned species of the family Botryosphaeriaceae, finding a significant reduction of the necrosis lengths in the inner woody tissues. Therefore, g-C3N4-MA-COS NCs may be put forward as a multifunctional platform for environmental and agrochemical delivery applications

Bark extract of Uncaria tomentosa L. for the control of strawberry phytopathogens

Gray mold (Botrytis cinerea Pers.), crown and fruit rot (Phytophthora cactorum (Lebert and Cohn) J.Schröt), and verticillium wilt (Verticillium dahliae Kleb.) are among the main diseases that affect the strawberry crop. In the study presented herein, the bark extract of Uncaria tomentosa (Willd. ex Schult.) DC, popularly known as “cat’s claw”, has been evaluated for its capability to act as a sustainable control method. The bioactive compounds present in the aqueous ammonia extract were characterized by gas chromatography–mass spectroscopy, and the antimicrobial activity of the extract—alone and in combination with chitosan oligomers (COS)—was assessed in vitro and as a coating for postharvest treatment during storage. Octyl isobutyrate (30.7%), 19α methyl-2-oxoformosanan-16-carboxylate (9.3%), tetrahydro-2-methyl-thiophene (4.7%), and α-methyl manofuranoside (4.4%) were identified as the main phytoconstituents. The results of in vitro growth inhibition tests showed that, upon conjugation of the bark extract with COS, complete inhibition was reached at concentrations in the 39–93.75 μg∙mL−1 range, depending on the pathogen. Concerning the effect of the treatment as a coating to prolong the storage life and control decay during post-harvest storage, high protection was observed at a concentration of 1000 μg∙mL−1. Because of this effectiveness, higher than that attained with conventional synthetic fungicides, the bark extracts of cat’s claw may hold promise for strawberry crop protection

Lignin–chitosan nanocarriers for the delivery of bioactive natural products against wood-decay phytopathogens

The use of nanocarriers (NCs), i.e., nanomaterials capable of encapsulating drugs and releasing them selectively, is an emerging field in agriculture. In this study, the synthesis, characterization, and in vitro and in vivo testing of biodegradable NCs loaded with natural bioactive products was investigated for the control of certain phytopathogens responsible for wood degradation. In particular, NCs based on methacrylated lignin and chitosan oligomers, loaded with extracts from Rubia tinctorum, Silybum marianum, Equisetum arvense, and Urtica dioica, were first assayed in vitro against Neofusicoccum parvum, an aggressive fungus that causes cankers and diebacks in numerous woody hosts around the world. The in vitro antimicrobial activity of the most effective treatment was further explored against another fungal pathogen and two bacteria related to trunk diseases: Diplodia seriata, Xylophilus ampelinus, and Pseudomonas syringae pv. syringae, respectively. Subsequently, it was evaluated in field conditions, in which it was applied by endotherapy for the control of grapevine trunk diseases. In the in vitro mycelial growth inhibition tests, the NCs loaded with R. tinctorum resulted in EC90 concentrations of 65.8 and 91.0 μg·mL−1 against N. parvum and D. seriata, respectively. Concerning their antibacterial activity, a minimum inhibitory concentration of 37.5 μg·mL−1 was obtained for this treatment against both phytopathogens. Upon application via endotherapy on 20-year-old grapevines with clear esca and Botryosphaeria decay symptoms, no phytotoxicity effects were observed (according to SPAD and chlorophyll fluorescence measurements) and the sugar content of the grape juice was not affected either. Nonetheless, the treatment led to a noticeable decrease in foliar symptoms as well as a higher yield in the treated arms as compared to the control arms (3177 vs. 1932 g/arm), suggestive of high efficacy. Given the advantages in terms of controlled release and antimicrobial product savings, these biodegradable NCs loaded with natural extracts may deserve further research in large-scale field tests

Characterization of Leptoglossus occidentalis eggs and egg glue

Producción CientíficaSimple Summary: This study explored the chemical components of the egg glue used by the Western Conifer Seed Bug (Leptoglossus occidentalis Heidemann, 1910) to agglutinate eggs and adhere to pine needles. Results showed that the adhesive secretion includes plasticizers and thermoplastic elastomer resins with semiochemical properties in an oily matrix containing proteins. This knowledge of the egg glue composition can be used to develop new control strategies for L. occidentalis, potentially limiting the economic impact caused by this pest insect that reduces the production of pine nuts by up to 25%.The western conifer seed bug (Leptoglossus occidentalis Heidemann, 1910, Heteroptera: Coreidae) has a significant economic impact due to the reduction in the quality and viability of conifer seed crops; it can feed on up to 40 different species of conifers, showing a clear predilection for Pinus pinea L. in Europe. Its incidence is especially relevant for the pine nut-producing industry, given that the action of this pest insect can reduce the production of pine nuts by up to 25%. As part of ongoing efforts aimed at the design of control strategies for this insect, this work focuses on the characterization (by scanning electron microscopy–energy-dispersive X-ray spectroscopy, Fourier-transform infrared spectroscopy, and gas chromatography–mass spectroscopy, GC–MS) of the compounds released by these insects during oviposition, with emphasis on the adhesive secretion that holds L. occidentalis eggs together. Elemental analysis pointed to the presence of significant amounts of compounds with high nitrogen content. Functional groups identified by infrared spectroscopy were compatible with the presence of chitin, scleroproteins, LNSP-like and gelatin proteins, shellac wax analogs, and policosanol. Regarding the chemical species identified by GC–MS, eggs and glue hydromethanolic extracts shared constituents such as butyl citrate, dibutyl itaconate, tributyl aconitate, oleic acid, oleamide, erucamide, and palmitic acid, while eggs also showed stearic and linoleic acid-related compounds. Knowledge of this composition may allow advances in new strategies to address the problem caused by L. occidentalis.Unión Europea, LIFE MycoRestore - (project LIFE18 CCA/ES/001110

Characterization of Leptoglossus occidentalis Eggs and Egg Glue

[EN] The western conifer seed bug (Leptoglossus occidentalis Heidemann, 1910, Heteroptera: Coreidae) has a significant economic impact due to the reduction in the quality and viability of conifer seed crops; it can feed on up to 40 different species of conifers, showing a clear predilection for Pinus pinea L. in Europe. Its incidence is especially relevant for the pine nut-producing industry, given that the action of this pest insect can reduce the production of pine nuts by up to 25%. As part of ongoing efforts aimed at the design of control strategies for this insect, this work focuses on the characterization (by scanning electron microscopy–energy-dispersive X-ray spectroscopy, Fourier-transform infrared spectroscopy, and gas chromatography–mass spectroscopy, GC–MS) of the compounds released by these insects during oviposition, with emphasis on the adhesive secretion that holds L. occidentalis eggs together. Elemental analysis pointed to the presence of significant amounts of compounds with high nitrogen content. Functional groups identified by infrared spectroscopy were compatible with the presence of chitin, scleroproteins, LNSP-like and gelatin proteins, shellac wax analogs, and policosanol. Regarding the chemical species identified by GC–MS, eggs and glue hydromethanolic extracts shared constituents such as butyl citrate, dibutyl itaconate, tributyl aconitate, oleic acid, oleamide, erucamide, and palmitic acid, while eggs also showed stearic and linoleic acid-related compounds. Knowledge of this composition may allow advances in new strategies to address the problem caused by L. occidentalis.SIThis research was funded by LIFE project MYCORESTORE, “Innovative use of mycological resources for resilient and productive Mediterranean forests threatened by climate change”, LIFE18 CCA/ES/001110

Encapsulación de extractos de Uncaria tomentosa en nanotransportadores para el control de Botrytis cinerea en fresa

Given the risks to health and the environment associated with synthetic fungicides, itis necessary to explore safe, effective, and sustainable alternatives. One viable approach is theutilization of bioactive natural products (BNPs). However, BNPs face problems of lability,solubility, and lack of specificity. These issues can be overcome through the implementation ofnanoencapsulation. This study focuses on the development of novel nanocarriers designed toencapsulate bioactive compounds, specifically a Uncaria tomentosa extract. Their applicability asa coating for postharvest protection of strawberry fruits against Botrytis cinerea Pers. wasinvestigated at a laboratory scale, both in vitro and ex-situ. In in vitro inhibition tests, thenanocarrier loaded with the U. tomentosa extract demonstrated remarkable efficacy, exhibitinga minimum inhibitory concentration of 22.5 μg·mL–1, better than that of the unencapsulatedextract, and resulted in a significant reduction in the quantity of active substance required. Asfor the impact on prolonging shelf life and controlling rot during postharvest fruit storage, thetreatment showed excellent protection of artificially inoculated strawberry fruits at aconcentration of 45 μg·mL–1. The findings suggest that nanocarriers containing extracts fromcat's claw bark hold promise as biorational agents and, notably, as an alternative to conventionalfungicides for managing strawberry phytopathogens.Dados los riesgos para la salud y el medio ambiente asociados a los fungicidas sintéticos, es necesario explorar alternativas seguras, eficaces y sostenibles. Un enfoque viable es la utilización de productos naturales bioactivos (BNP). Sin embargo, los BNP se enfrentan a problemas de labilidad, solubilidad y falta de especificidad. Estos problemas pueden superarse mediante la aplicación de la nanoencapsulación. Este estudio se centra en el desarrollo de nuevos nanotransportadores diseñados para encapsular compuestos bioactivos, concretamente un extracto de Uncaria tomentosa. Su aplicabilidad como recubrimiento para la protección postcosecha de frutos de fresa frente a Botrytis cinerea Pers. se investigó a escala de laboratorio, tanto in vitro como ex situ. En las pruebas de inhibición in vitro, el portador cargado con el extracto de U. tomentosa demostró una eficacia notable, presentando una concentración inhibitoria mínima de 22,5 μg-mL-1, mejor que la del extracto no encapsulado, y dio lugar a una reducción significativa de la cantidad de sustancia activa necesaria. En cuanto al impacto en la prolongación de la vida útil y el control de la podredumbre durante el almacenamiento de la fruta después de la cosecha, el tratamiento mostró una excelente protección de los frutos de fresa inoculados artificialmente a una concentración de 45 μg-mL-1. Los resultados sugieren que los nanotransportadores que contienen extractos de corteza de uña de gato son prometedores como agentes biológicos y, en particular, como alternativa a los fungicidas convencionales para el control de los fitopatógenos de la fresa.Creative Commons Attribution-NonCommercial-NoDerivs 3.0 Spai

<i>Uncaria tomentosa</i>-Loaded Chitosan Oligomers–Hydroxyapatite–Carbon Nitride Nanocarriers for Postharvest Fruit Protection

Given the risks associated with synthetic fungicides, it is crucial to explore safe and sustainable alternatives. One potential solution is using bioactive natural products (BNPs). However, BNPs face challenges like lability, solubility, and lack of specificity. These issues can be addressed through nanoencapsulation. This study focuses on the evaluation of novel chitosan oligomers–hydroxyapatite–carbon nitride (COS–HAp–g-C3N4) nanocarriers (NCs) for encapsulating BNPs, specifically an extract from Uncaria tomentosa bark. The NCs were characterized by transmission electron microscopy, energy-dispersive X-ray spectroscopy, and infrared spectroscopy. The NCs were monodisperse, with a mean diameter of 250 nm, and showed an encapsulation efficiency of 82%. The suitability of the loaded NCs (COS–HAp–g-C3N4–BNP, in a 2:1:0.5:1 weight ratio) for postharvest fruit protection was investigated in vitro and ex situ at a laboratory scale. Results regarding their efficacy against Botrytis cinerea on strawberries, Colletotrichum gloeosporioides on mangoes, Penicillium expansum on apples, Monilinia laxa on peaches, and Sclerotinia sclerotiorum on kiwifruit are presented. Minimum inhibitory concentrations of 250, 375, 375, 250, and 187.5 μg·mL−1 were found in vitro, respectively, while higher doses (500, 750, 750, 250, and 375 μg·mL−1, respectively) were needed to achieve effective control in postharvest tests on artificially inoculated fruit. These findings suggest that NCs containing extracts from U. tomentosa bark show promise as biorational agents and as alternatives to conventional fungicides for managing postharvest phytopathogens

Carvacrol Encapsulation in Chitosan&ndash;Carboxymethylcellulose&ndash;Alginate Nanocarriers for Postharvest Tomato Protection

Advancements in polymer science and nanotechnology hold significant potential for addressing the increasing demands of food security, by enhancing the shelf life, barrier properties, and nutritional quality of harvested fruits and vegetables. In this context, biopolymer-based delivery systems present themselves as a promising strategy for encapsulating bioactive compounds, improving their absorption, stability, and functionality. This study provides an exploration of the synthesis, characterization, and postharvest protection applications of nanocarriers formed through the complexation of chitosan oligomers, carboxymethylcellulose, and alginate in a 2:2:1 molar ratio. This complexation process was facilitated by methacrylic anhydride and sodium tripolyphosphate as cross-linking agents. Characterization techniques employed include transmission electron microscopy, energy-dispersive X-ray spectroscopy, infrared spectroscopy, thermal analysis, and X-ray powder diffraction. The resulting hollow nanospheres, characterized by a monodisperse distribution and a mean diameter of 114 nm, exhibited efficient encapsulation of carvacrol, with a loading capacity of approximately 20%. Their suitability for phytopathogen control was assessed in vitro against three phytopathogens&mdash;Botrytis cinerea, Penicillium expansum, and Colletotrichum coccodes&mdash;revealing minimum inhibitory concentrations ranging from 23.3 to 31.3 &mu;g&middot;mL&minus;1. This indicates a higher activity compared to non-encapsulated conventional fungicides. In ex situ tests for tomato (cv. &lsquo;Daniela&rsquo;) protection, higher doses (50&ndash;100 &mu;g&middot;mL&minus;1, depending on the pathogen) were necessary to achieve high protection. Nevertheless, these doses remained practical for real-world applicability. The advantages of safety, coupled with the potential for a multi-target mode of action, further enhance the appeal of these nanocarriers

F,O,S-Codoped Graphitic Carbon Nitride as an Efficient Photocatalyst for the Synthesis of Benzoxazoles and Benzimidazoles

Graphitic carbon nitride (g-C3N4) is a metal-free heterogeneous catalyst that has attracted attention because of its good chemical stability, cost-effectiveness, and environmental friendliness. In the work presented herein, F,O,S-codoped carbon nitride was synthesized by heating a mixture of melamine cyanurate and trifluoromethanesulfonic acid at 550 °C for 50 min. The obtained product was characterized by transmission electron microscopy, infrared spectroscopy, X-ray powder diffraction, CHNS elemental analysis, total combustion-ion chromatography, X-ray photoelectron spectroscopy, scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy, and UV-Vis spectroscopy. Results point to an F,O,S-codoped g-C3N4. The material was applied as a photocatalyst for the formation of benzoxazoles and benzimidazoles by condensation–aromatization of 2-aminophenol or 1,2-phenylenediamine with suitable aldehydes (viz. benzaldehyde, 4-chlorobenzaldehyde, 2-naphthaldehyde, 2-hydroxybenzaldehyde, and 2-methoxybenzaldehyde), obtaining yields of up to 90% in 15 min under visible light irradiation, with good selectivity and reusability. Thus, the reported findings suggest that this F,O,S-codoped g-C3N4 may hold promise as a metal-free photocatalyst for the rapid synthesis of 2-arylbenzoxazoles and 2-arylbenzimidazoles

Nanotransportadores basados en quitosano y nitruro de carbono para el control de enfermedades de la madera de la vid

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