Environmentally friendly COpper-engineered nanoparticles: innovative FUNgicide to reduce copper accumulation.

Información del proyecto

ECOFUN

Identificador del acuerdo de subvención: 101150434

DOI

10.3030/101150434

Proyecto cerrado

Fecha de la firma de la CE 14 Marzo 2024

Fecha de inicio 1 Mayo 2024

Fecha de finalización 30 Abril 2026

Financiado con arreglo a

• Marie Skłodowska-Curie Actions (MSCA)

Coste total

Sin datos

Aportación de la UE

€ 165 312,96

Coordinado por

UNIVERSIDAD DE GRANADA
Spain

Periodic Reporting for period 1 - ECOFUN (Environmentally friendly COpper-engineered nanoparticles: innovative FUNgicide to reduce copper accumulation.)

Período documentado: 2024-05-01 hasta 2026-04-30

Resumen del contexto y de los objetivos generales del proyecto

Plant protection products have been used in agriculture for over a century, and among them copper-based fungicides remain essential tools for disease control, particularly for crops like tomatoes, cucumbers, and grapevines. However, their repeated application leads to the accumulation of copper in agricultural soils, where it is toxic to soil organisms and disrupts microbial communities. Regulatory actions promoted by various governments and the European Union are increasing pressure to reduce copper inputs to minimise its impact, making it urgent to develop new plant protection products that maintain efficacy while reducing environmental burden.
The ECOFUN project aimed to address this challenge through nanotechnology, developing smart copper-based nanomaterials as more efficient plant protection products, allowing a significant reduction of copper input in the environment. This new formulation was designed through the engineering of non-toxic, bone-inspired calcium phosphate nanoparticles (ACP), which are simultaneously capable of supplying plants with essential nutrients (phosphorus and calcium). The project was also specifically designed to validate the efficiency of the resulting nanomaterials against important plant-pathogenic fungi through in vitro tests and, ultimately, in vivo experiments. ECOFUN aimed for a reduction of at least 50% of the copper input compared to conventional products.
The project was structured around three main scientific work packages: synthesis, scale-up, and characterisation of the nanomaterial (WP1), in vitro biological evaluation against fungal and bacterial pathogens (WP2), and in vivo validation in greenhouse and field conditions (WP3), complemented by training, dissemination, and networking activities.

Trabajo realizado desde el comienzo del proyecto hasta el final del período abarcado por el informe y los principales resultados hasta la fecha

The synthesis of CuACP nanoparticles was optimised through a rapid (5-minute), room-temperature precipitation reaction using aqueous solutions and green chemistry procedures. The final formulation incorporates approximately 8,4% copper by weight and produces nanoparticles with a core size of 10–20 nm and a hydrodynamic diameter in suspension of around 250 nm. Scale-up to 2-litre batches yielding approximately 500 g of material was successfully demonstrated, with full retention of physicochemical properties and a production cost competitive with conventional copper fungicides.
A key scientific contribution was the resolution of an apparent inconsistency in X-ray Photoelectron Spectroscopy (XPS) data, which initially suggested the unexpected presence of Cu⁺ ions in the material. Through a dedicated investigation published in Applied Surface Science (doi: 10.1016/j.apsusc.2026.167000) it was demonstrated that copper exists exclusively as Cu²⁺ within the nanomaterial bulk, and that the Cu⁺ signal was an artefact of beam-induced reduction during analysis. This finding has methodological implications beyond ECOFUN, clarifying how XPS data on copper containing nanomaterials should be interpreted.
Copper release kinetics were characterised in multiple media, revealing that release is strongly modulated by the chemical environment: slow and minimal in neutral water, but rapid and complete in acidic media or media containing chelating agents.
A core achievement was the foliar adhesion performance: CuACP retained 60% of the applied copper after simulated rainfall, compared to only around 30% for conventional copper sulphate and a commercial copper hydroxide product.
In vitro antifungal assays showed that CuACP achieves enhanced efficacy against Botrytis cinerea (IC₅₀ of 40,2 ppm compared to 67,5 ppm for copper sulphate) and improved inhibition by 30% of Alternaria solani compared to ionic copper. This increased efficacy may be related to acidification of the environment in the presence of fungi due to secretion of acidic molecules, which promotes copper release from the carrier. Antibacterial assays against Pseudomonas syringae demonstrated that after simulated rainfall, CuACP completely prevented bacterial growth on leaf surfaces, whereas copper sulphate failed due to poor rainfastness. Cytotoxicity evaluation on human cell lines showed a safety profile comparable to conventional copper compounds.
Greenhouse trials on tomato plants infected with Alternaria solani showed that CuACP at 50% of the conventional copper dose achieved effective disease control comparable to or better than the commercial counterpart throughout the experimental period, reaching thus the overarching goal of the ECOFUN action. Field trials on cucumber crops targeting Podosphaera xanthii (powdery mildew) were conducted in collaboration with an industrial partner; data are currently under final analysis.
Finally, a comprehensive ecotoxicological assessment conducted in collaboration with the University of Aveiro (Portugal), following OECD guidelines, demonstrated that CuACP results in significantly lower copper mobility in soil pore waters and a safer profile for soil invertebrates (Folsomia candida, Enchytraeus crypticus) compared to ionic copper sulphate at equivalent concentrations.

Avances que van más allá del estado de la técnica e impacto potencial esperado (incluida la repercusión socioeconómica y las implicaciones sociales más amplias del proyecto hasta la fecha)

ECOFUN advances the state of the art in several aspects. The CuACP nanomaterial combines multiple improvements: a one-step scalable formulation involving low-cost reagents and water-based solutions; superior foliar adhesion, which is particularly advantageous in rainy scenarios; copper release that can be triggered by acidic molecules released by fungal pathogens, enabling on-demand delivery and increased efficiency against specific fungal strains; under controlled conditions with simulated rainfall, the nanomaterial retained twice as much copper on leaf surfaces compared to commercial counterparts, successfully addressing the initial ECOFUN copper-reduction objective; finally, being bioinspired, the nanomaterial is a strong candidate for low environmental impact, which was confirmed by a favourable ecotoxicological profile. These advancements represent significant progress compared to the state of the art in copper nanomaterials and an improved efficiency profile relative to commercial copper-based products.

The demonstration of scaled-up synthesis at a competitive production cost is a critical step towards market translation. Production and commercialisation are key future aspects to fully realise the impact of this action. Moreover, to further support the exploitation pathway, a patent was filed during the project with the Spanish Intellectual Property Office (reference P27614ES00), covering a related calcium phosphate-based nanocarrier system for herbicide delivery. This output confirms the broader technological potential of the carrier.

Key needs for further uptake include: additional field efficacy trials on different plant/pathogen systems to expand the application range of the new nanoformulation, along with the related maximum residue level (MRL) validation studies; optimisation of operational protocols for different crops and pathogens; studies on integrated pest management protocols in combination with other fungicides; and regulatory engagement with EFSA and national authorities for product authorisation under EU pesticide regulation.