During the resorbable-polymer-boom of the 1970s and 1980s, polycaprolactone (PCL) was used in the biomaterials field and a number of drug-delivery devices. Its popularity was soon superseded by faster resorbable polymers which had fewer perceived disadvantages associated with long term degradation (up to 3-4 years) and intracellular resorption pathways; consequently, PCL was almost forgotten for most of two decades. Recently, a resurgence of interest has propelled PCL back into the biomaterials-arena. The superior rheological and viscoelastic properties over many of its aliphatic polyester counterparts renders PCL easy to manufacture and manipulate into a large range of implants and devices. Coupled with relatively inexpensive production routes and FDA approval, this provides a promising platform for the production of longer-term degradable implants which may be manipulated physically, chemically and biologically to possess tailorable degradation kinetics to suit a specific anatomical site. This review will discuss the application of PCL as a biomaterial over the last two decades focusing on the advantages which have propagated its return into the spotlight with a particular focus on medical devices, drug delivery and tissue engineering.

The return of a forgotten polymer : Polycaprolactone in the 21st century

Nanotechnology in agriculture: Current status, challenges and future opportunities

Recent scientific data indicate that nanotechnology has the potential to positively impact the agrifood sector, minimizing adverse problems of agricultural practices on environment and human health, improving food security and productivity (as required by the predicted rise in global population), while promoting social and economic equity. In this context, we select and report on recent trends in nanomaterial-based systems and nanodevices that could provide benefits on the food supply chain specifically on sustainable intensification, and management of soil and waste. Among others, nanomaterials for controlled-release of nutrients, pesticides and fertilizers in crops are described as well as nanosensors for agricultural practices, food quality and safety.

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Nanotechnology in Agriculture: Which Innovation Potential Does It Have?

Achieving sustainable agricultural productivity and global food security are two of the biggest challenges of the new millennium. Addressing these challenges requires innovative technologies that can uplift global food production, while minimizing collateral environmental damage and preserving the resilience of agroecosystems against a rapidly changing climate. Nanomaterials with the ability to encapsulate and deliver pesticidal active ingredients (AIs) in a responsive (for example, controlled, targeted and synchronized) manner offer new opportunities to increase pesticidal efficacy and efficiency when compared with conventional pesticides. Here, we provide a comprehensive analysis of the key properties of nanopesticides in controlling agricultural pests for crop enhancement compared with their non-nanoscale analogues. Our analysis shows that when compared with non-nanoscale pesticides, the overall efficacy of nanopesticides against target organisms is 31.5% higher, including an 18.9% increased efficacy in field trials. Notably, the toxicity of nanopesticides toward non-target organisms is 43.1% lower, highlighting a decrease in collateral damage to the environment. The premature loss of AIs prior to reaching target organisms is reduced by 41.4%, paired with a 22.1% lower leaching potential of AIs in soils. Nanopesticides also render other benefits, including enhanced foliar adhesion, improved crop yield and quality, and a responsive nanoscale delivery platform of AIs to mitigate various pressing biotic and abiotic stresses (for example, heat, drought and salinity). Nonetheless, the uncertainties associated with the adverse effects of some nanopesticides are not well-understood, requiring further investigations. Overall, our findings show that nanopesticides are potentially more efficient, sustainable and resilient with lower adverse environmental impacts than their conventional analogues. These benefits, if harnessed appropriately, can promote higher crop yields and thus contribute towards sustainable agriculture and global food security. 

Nano-enabled pesticides for sustainable agriculture and global food security

An overview of the potential impacts of atrazine in aquatic environments: Perspectives for tailored solutions based on nanotechnology

Poly(ɛ-caprolactone) (PCL) nanocapsules have been previously developed as a carrier system for atrazine. However, the efficacy of this nanoformulation against weeds commonly found in crop cultures has not been tested yet. Here, we evaluated the post-emergence herbicidal activity of PCL nanocapsules containing atrazine against Amaranthus viridis (slender amaranth) and Bidens pilosa (hairy beggarticks), in comparison with a commercial formulation of atrazine. For both species, treatment with atrazine-loaded nanocapsules (at 2000 g ha-1) led to a greater decrease in the photosystem II activity (above 50% inhibition relative to the control) than the commercial atrazine formulation at the same concentration (around 40% inhibition). The growth of A. viridis plants was equally reduced by nanoatrazine and commercial formulation (above 64% for root and 75% for shoot). In the case of B. pilosa, atrazine-loaded nanocapsules decreased more effectively the root and shoot growth than the commercial formulation, leading to a loss of plant biomass. Moreover, for both species, the use of ten-fold diluted atrazine-loaded PCL nanocapsules (200 g ha-1) resulted in the same inhibitory effect in root and shoot growth as the commercial formulation at the standard atrazine dose. These results suggest that the utilization of atrazine-containing PCL nanocapsules potentiated the post-emergence control of A. viridis and B. pilosa by the herbicide. Thus, this nanoformulation emerges as an efficient alternative for weed control.

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Post-Emergence Herbicidal Activity of Nanoatrazine Against Susceptible Weeds

Poly(epsilon-caprolactone) (PCL) nanocapsules have been used as a carrier system for the herbicide atrazine, which is commonly applied to maize. We demonstrated previously that these atrazine containing polymeric nanocapsules were 10-fold more effective in the control of mustard plants (a target species), as compared to a commercial atrazine formulation. Since atrazine can have adverse effects on non-target crops, here we analyzed the effect of encapsulated atrazine on growth, physiological and oxidative stress parameters of soil-grown maize plants (Zea mays L.). One day after the post-emergence treatment with PCL nanocapsules containing atrazine (1 mg mL(-1)), maize plants presented 15 and 21% decreases in maximum quantum yield of photosystem II (PSII) and in net CO2 assimilation rate, respectively, as compared to water-sprayed plants. The same treatment led to a 1.8-fold increase in leaf lipid peroxidation in comparison with control plants. However, all of these parameters were unaffected 4 and 8 days after the application of encapsulated atrazine. These results suggested that the negative effects of atrazine were transient, probably due to the ability of maize plants to detoxify the herbicide. When encapsulated atrazine was applied at a 10-fold lower concentration (0.1 mg mL(-1)), a dosage that is still effective for weed control, no effects were detected even shortly after application. Regardless of the herbicide concentration, neither pre- nor post-emergence treatment with the PCL nanocapsules carrying atrazine resulted in the development of any macroscopic symptoms in maize leaves, and there were no impacts on shoot growth. Additionally, no effects were observed when plants were sprayed with PCL nanocapsules without atrazine. Overall, these results suggested that the use of PCL nanocapsules containing atrazine did not lead to persistent side effects in maize plants, and that the technique could offer a safe tool for weed control without affecting crop growth.

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Evaluation of the side effects of poly(epsilon-caprolactone) nanocapsules containing atrazine toward maize plants.

The quest for an ideal biomaterial perfectly matching the microenvironment of the surrounding tissues and cells is an endless challenge within biomedical research, in addition to integrating this with a facile and sustainable technology for its preparation. Engineering hydrogels through click chemistry would promote the sustainable invention of tailor-made hydrogels. Herein, we disclose a versatile and facile catalyst-free click chemistry for the generation of an innovative hydrogel by combining chondroitin sulfate (CS) and polyethylene glycol (PEG). Various multi-armed PEG-Norbornene (A-PEG-N) with different molecular sizes were investigated to generate crosslinked copolymers with tunable rheological and mechanical properties. The crosslinked and mechanically stable porous hydrogels could be generated by simply mixing the two clickable Tetrazine-CS (TCS) and A-PEG-N components, generating a self-standing hydrogel within minutes. The leading candidate (TCS-8A-PEG-N (40 kD)), based on the mechanical and biocompatibility results, was further employed as a scaffold to improve wound closure and blood flow in vivo. The hydrogel demonstrated not only enhanced blood perfusion and an increased number of blood vessels, but also desirable fibrous matrix orientation and normal collagen deposition. Taken together, these results demonstrate the potential of the hydrogel to improve wound repair and hold promise for in situ skin tissue engineering applications.

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Gustavo F. M. Sousa

Papers

Post-Emergence Herbicidal Activity of Nanoatrazine Against Susceptible Weeds

Evaluation of the side effects of poly(epsilon-caprolactone) nanocapsules containing atrazine toward maize plants.

Catalyst-Free Click Chemistry for Engineering Chondroitin Sulfate-Multiarmed PEG Hydrogels for Skin Tissue Engineering