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Nano-engineered delivery systems have emerged as possible solutions for more efficient pest management in agriculture. Likewise for nanostructured drug delivery systems (DDS) in medicine, the use of biocide delivery systems (BDS) brought concerns on their toxicology on non-targeted organisms. Plants, for instance, are the foundation of the ecosystem, acting as primary actor in the food chain and is associated with the whole biodiversity, being strictly related to human health. This is a very important consideration to fully understand the benefits of using delivery systems for crop protection and production. Herein, a biocide delivery system was prepared by loading nanostructured, microscaled, biogenic silica particles with thymol, a known phytotoxicant. The resulting system contains 120 mg of thymol per gram of silica and displays slow release features. The Allium cepa bioassay was chosen to demonstrate how the toxicity and cellular damages induced by thymol can be significantly reduced through a slow, controlled, release strategy. The lower mobility of the reference particles associated with slow-delivery features reduced the toxicity and cellular damages caused by thymol in the plant genetic model., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Biocides are essential for crop protection, packaging and several other biosystem applications. Therein, properties such as tailored and controlled release are paramount in the development of sustainable biocide delivery systems. We explore the self-similar nano-organized architecture of biogenic silica particles to achieve high biocide payload. The high surface area accessibility of the carrier allowed us to develop an efficient, low energy loading strategy, reaching significant dynamic loadings of up to 100 mg·g -1 . The release rate and responsiveness were tuned by manipulating the interfaces, using either the native hydroxyl surfaces of the carrier or systems modified with amines or carboxylic acids in high density. We thoroughly evaluated the impact of the carrier-biocide interactions on the release rate as a function of pH, ionic strength and temperature. The amine and carboxyl functionalization strategy led to three-fold decrease in the release rate, while higher responsiveness against important agro-industrial variables. Key to our discoveries, nanostructuring thymol in the biogenic silica endowed systems with controlled, responsive release promoting remarkable, high and localized biocidal activity. The interfacial factors affecting related delivery were elucidated for an increased and localized biocidal activity, bringing a new light for the development of controlled release systems from porous materials.

We review biocide delivery systems (BDS), which are designed to deter or control harmful organisms that damage agricultural crops, forests and forest products. This is a timely topic, given the growing socio-economical concerns that have motivated major developments in sustainable BDS. Associated designs aim at improving or replacing traditional systems, which often consist of biocides with extreme behavior as far as their solubility in water. This includes those that compromise or pollute soil and water (highly soluble or volatile biocides) or those that present low bioavailability (poorly soluble biocides). Major breakthroughs are sought to mitigate or eliminate consequential environmental and health impacts in agriculture and silviculture. Here, we consider the most important BDS vehicles or carriers, their synthesis, the environmental impact of their constituents and interactions with the active components together with the factors that affect their rates of release such as environmental factors and interaction of BDS with the crops or forest products. We put in perspective the state-of-the-art nanostructured carriers for controlled release, which need to address many of the challenges that exist in the application of BDS., (Copyright © 2017 Elsevier B.V. All rights reserved.)