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.

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.

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.

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.

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.