Green Formation of Robust Supraparticles for Cargo Protection and Hazards Control in Natural Environments.

In parallel with important technological advances, nanoparticles have brought numerous environmental and toxicological challenges due to their high mobility and nonspecific surface activity. The hazards associated with nanoparticles can be significantly reduced while simultaneously keeping their inherent benefits by superstructuring. In this study, a low-temperature and versatile methodology is employed to structure nanoparticles into controlled morphologies from biogenic silica, used as a main building block, together with cellulose nanofibrils, which promote cohesion. The resultant superstructures are evaluated for cargo loading/unloading of a model, green biomolecule (thymol), and for photo-accessibility and mobility in soil. The bio-based superstructures resist extremely high mechanical loading without catastrophic failure, even after severe chemical and heat treatments. Additionally, the process allows pre and in situ loading, and reutilization, achieving remarkable dynamic payloads as high as 90 mg g-1 . The proposed new and facile methodology is expected to offer a wide range of opportunities for the application of superstructures in sensitive and natural environments

Controlled biocide release from hierarchically-structured biogenic silica: surface chemistry to tune release rate and responsiveness.

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

Functional lignocellulosic materials prepared by ATRP from a wood scaffold

Wood, a natural and abundant source of organic polymers, has been used as a scaffold to develop novel wood-polymer hybrid materials. Through a two-step surface-initiated Atom Transfer Radical Polymerization (ATRP), the porous wood structure can be effectively modified with polymer chains of various nature. In the present study, polystyrene and poly(N-isopropylacrylamide) were used. As shown with various characterization techniques including confocal Raman microscopy, FTIR, and SEM/EDX, the native wood ultrastructure and features are retained and the polymer chains can be introduced deep within the wood, i.e. inside the wood cell walls. The physical properties of the new materials have been studied, and results indicate that the insertion of polymer chains inside the wood cell wall alters the intrinsic properties of wood to yield a hybrid composite material with new functionalities. This approach to the functionalization of wood could lead to the fabrication of a new class of interesting functional materials and promote innovative utilizations of the renewable resource wood