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Rhododendron ponticum (R. ponticum), a rapidly spreading invasive species in Ireland, was investigated for its potential use in creating sustainable bioproducts. This study explored the utilization of R. ponticum biomass as a source of microfibrillated cellulose (MFC) for fungal cultivation. The production of MFC was evaluated employing a novel cryocrushing treatment combined with a twin-screw extruder (TSE). The results demonstrated a significant increase in film strength, up to 332.3 MPa, with increasing TSE steps compared to 72.5 MPa in untreated samples. X-ray diffraction (XRD) analysis revealed a decrease in crystallinity from 68.93 % to 59.2 %, following cryocrushing and TSE treatment. Additionally, MFC subjected to the highest TSE treatment (12 steps) was successfully used as a substrate for cultivating Agaricus blazei mushrooms using 0.2 wt%, 0.5 wt%, and 1 wt% MFC over a period of 7 days. Fourier-transform infrared spectroscopy (FTIR) confirmed the presence of chitin/chitin glucan within the fungal fibers. This research highlights the potential for transforming the invasive R. ponticum into valuable biocomposite materials. These MFC-fungus composites hold promise for various applications, including sustainable packaging, biodegradable plastics, and eco-friendly textiles., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

Background: Cachaça (Brazilian spirit) is an alcoholic beverage of cultural and economic importance in Brazil. Its artisanal production is usually conducted in copper alembics, which results in contamination. The development of effective biosorbents from cheap matrices is an alternative to minimize both solid waste generation and copper levels in cachaça. The present work evaluates the obtention of nanocellulose-based materials from the major residue generated during the processing of palm heart from the Brazilian peach palm, through different processing techniques. Materials were characterized by physicochemical composition and their sorbent capacities for copper removal from aqueous solutions, and a simulation was conducted to evaluate potential application in the adequacy of cachaça to meet Brazilian legislation requirements., Results: The different processing methods resulted in different cellulose concentrations, with the highest concentration in the bleached material (B3, 694 g kg -1 of cellulose), and different specific surface areas (1.02-12.4 m 2  g -1 ). Copper adsorption onto nanocellulose obtained from peach palm external sheath is fast, with a predominance of a chemisorption mechanism. Isotherms were best represented by Langmuir's model, suggesting a monolayer adsorption. Simulations indicate that B3 is a suitable material for the removal of copper from cachaça, and small amounts of biosorbent (733.5 g) are required for the reduction of copper concentrations (10 to 3 mg L -1 ) in 1000 L of cachaça., Conclusion: This study demonstrated that the obtention of biosorbents from peach palm solid residues is promising and this nanocellulose-based material can be used for copper removal from contaminated cachaça. © 2024 Society of Chemical Industry., (© 2024 Society of Chemical Industry.)

New routes for biomass valorization have been developing by the scientific community. The aim of this work was developing a novel OrganoCat-based protocol and deeply understand the structure of the obtained lignins. Microwave-assisted OrganoCat-based process was performed using a biphasic system (ethyl acetate and oxalic acid or HCl) at mild conditions. OrganoCat-based lignins (OCLs) were characterized by compositional analysis, FTIR, 1 H, 13 C, 1 H 13 C HSQC, 31 P NMR, TGA and GPC. The solubility of OCLs in different organic solvents and their antioxidant capacity against DPPH were investigated. The spectroscopic analyses showed that OCLs have high residual extractives and the lignin motifs were preserved. OCLs have presented lower thermal stability than MWL, but showed great antioxidant activities and high solubility in a wide range of organic solvents. A novel biorefinery protocol yielded coconut shell lignins with peculiar structural and compositional features and several technological applications through an eco-friendly, sustainable and relatively low-cost biphasic pulping process., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Defibrillating cellulose through various grinding steps and incorporating it into hydrogels introduces unique properties that warrant thorough exploration. This study investigates cellulose defibrillation at different steps (15-120) using an ultra-fine friction grinder, blended with high-molecular-weight polyvinyl alcohol (PVA), and crosslinked via freeze-thawing. A critical discovery is the influence of defibrillation on the hydrogel structure, as evidenced by reduced crystallinity, thermal degradation, and the enhanced swelling of PVA chains. Despite an increased elastic modulus of up to 120 steps, the synthesized material maintains remarkable strength under hydrated conditions, holding significant promise in biomaterial applications.

Rhododendron ponticum is an invasive species that spreads rapidly and is described as one of the biggest threats to peatlands in Ireland. This study offers an innovative approach to utilizing Rhododendron waste. Initially, sawdust was submitted to a bleaching treatment and the nanofibrillated cellulose (NFC) was obtained using two different methods: ultra-fine friction grinding and twin-screw extrusion with the assistance of TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy) pre-treatment. The samples processed through twin-screw extrusion exhibited the presence of NFC at five intervals, as confirmed by TEM analysis. However, these samples displayed a higher diameter deviation compared to those processed through grinding alone. Notably, after 20 extrusion steps, the NFC diameter became more uniform, reaching approximately 35 nm. Sedimentation tests showed that extrusion produced more homogeneous cellulose size than the grinder method. However, FTIR characterization for the samples showed a unique band related to C-O-C glycosidic linkage. The results showed that grinding breaks these groups resulting in crystallinity values lower than extrusion, 50 % compared 60 %. Therefore, NFC with 20 steps by grinding was blended with polycaprolactone to produce a 3D scaffold using a 3D printer at different ratios of 1-5 % addition. The effect of 1 % of NFC was unique showing significant enhanced mechanical properties compared to pure polycaprolactone (PCL), additionally, the NFC does not exhibit toxicity so these materials show promise for biomedical applications., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

Slow-release urea fertilisers have been shown to present acceptable values for plant yield and mitigate the harmful effect of soil emission gases. This study synthesises a slow-release fertiliser containing fumed-nanosilica, nanofibrillated cellulose as well as sodium alginate as a urea carrier to analyse the growth parameters of Eucalyptus urograndis seedlings and potential emission of soil gases, N 2 O, CH 4 , CO 2 and ammonia volatilisation. The developed supraparticles, arranged layered nanoparticle structure, presented a decrease in the normal nitrogen content of urea of 19%, which is attributed to the binding of this element. A good electrostatic interaction between the elements was confirmed by the FTIR with 20% of nitrogen content from its chemical composition and an increase in thermal degradation of the main components when synthesised. The profile of urea release presented to be as first-order with 85% of this compound was released only after 60 days. These characteristics led to statistically increased growth of Eucalyptus seedlings compared to the controls, which improves with higher dosages of urea. Values of biomass and characteristics of the plant were used for principal component analysis which resulted in good cluster formation based on the upward concentration of urea added to the plant. Nevertheless, flux gases were statistically higher for certain time periods on lower urea particle concentration, while increased concentration presented N 2 O emissions within standard rates with no significant variation in the other measured gases, which was attributed to the soil microbial targeted consumption. Therefore, this material can be beneficial in the agriculture industry., (© 2022. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

This study evaluated the inclusion of nanofibers from soybean hulls and pupunha peach palm heart sheaths in the diet of growing rabbits. Twenty-four New Zealand White rabbits (male and female) were allocated in three experimental groups: control, fed a basal diet; Nanosoy, fed a diet containing 7% soybean-hull nanofibers; and Nanopupunha, fed a diet containing 7% pupunha palm heart-sheath nanofibers. The Nanosoy-group rabbits showed poorer final weight, daily feed intake, and daily weight gain than those in other groups. In the duodenum, villus height, total mucosal thickness, and villus width were higher in rabbits that received nanofiber-supplemented diets than in the controls. Higher villus density and wall thickness were observed in Nanopupunha-fed rabbits than in the controls. In the jejunum, although the crypt depth was higher in Nanosoy-fed rabbits, the villus height:crypt depth ratio was higher in the Nanopupunha-fed group. Nanosoy-fed animals exhibited increased count Enterobacteriaceae populations. Rabbits in both nanofiber-fed groups exhibited higher lactic-acid bacterial counts than those in the control-diet group. Therefore, although the inclusion of 7% Nanopupunha in the diet of rabbits did not alter the performance, it improved intestinal health and increased the lactic-acid bacterial count in the cecum of growing rabbits.

The cosmetics market has recently undergone changes as consumers increasingly seek sustainable products. In this context, agro-derived lignins have the potential for cosmetics applications. Thus, this study investigated the photoprotective activity and skin irritation potential (OECD TG 439 with SkinVitro-RHE, an in-house reconstructed human epidermis (RHE) model) of a kraft lignin (LE) and two LE-derived lignins modified by enzymatic reactions to achieve higher molecular weight (Mw) (R1: intermediate Mw and E60: highest Mw). Results showed that LE and R1 lignins present adequate photoprotective activity with averages Sun Protection Factor (SPF) of 33.8 ± 0.02 and 22.7 ± 0.04, respectively. The E60 also present adequate SPF (22.4 ± 0.2); however, due to its poor solubility, this lignin has potential application as a physical filter. In terms of safety, these lignins did not cause skin irritation or cellular and structural damage to the epidermis. Additionally, using an analysis based on the autofluorescence feature of lignin, no sign of the tested lignins was found in exposed RHE models, indicating that these three lignins did not penetrate the skin. Altogether, the results indicate a promising application of kraft lignins for sunscreen products regarding safer alternatives and product sustainability. Also, the SkinVitro-RHE showed to be a good model for evaluating the skin irritation potential of substances, including natural cosmetic ingredients., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

The control of pests in agricultural systems is currently based on the widespread use of pesticides that efficiently control pests but have negative effects on the environment and humans. Thus, several studies have been conducted to develop alternative sustainable ways to control pests in agriculture. The use of semiochemicals presents a good alternative to develop a sustainable tool monitoring and control insect pests in crops areas. The dispensing carriers of semiochemicals are typically made of non-degradable material, often petroleum derivatives such as butyl rubber, that become polluting waste after application. To develop a biodegradable and low-cost dispenser for semiochemicals, particles of CaCO 3 and a CaCO 3 /Kraft lignin composite were synthesized using CO 2 bubbling, characterized and evaluated for 30 days as a dispenser of the limonene molecule, which is a common semiochemical in plants and also pheromone component is some insect species, such as the lesser mealworm Alphitobius diaperinus. Furthermore, limonene is volatile molecule that is easy to acquire and low-cost, which makes it an ideal semiochemical to evaluate the potential of the CaCO 3 particles and CaCO 3 /Kraft lignin composite as a semiochemical dispenser for use in agriculture. The pure calcium carbonate I, pure calcium carbonate II, and composite I synthesized particles presented a larger specific surface area than the other composites. All the particles evaluated showed a slow limonene release rate between the 5th and 30th days evaluated, indicating the potential of these materials as pheromone dispensers. The composites with higher specific surface area, calcium carbonate II (19.5 m 2 /g) and composite I (23.1 m 2 /g), released a higher level of limonene during the 30 days evaluated., (© 2022. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

The effect of harvest location on cooked pinhão seeds (Araucaria angustifolia) was investigated with regard to its centesimal composition, minerals, and color, and later correlated with environmental and soil variables. Significant differences between cooked pinhão from various harvesting locations were seen; also, principal component analysis was performed for the minerals, protein, moisture, total starch, and color parameters. The geographic location was one of the most important factors. Caçador presented greater differences: lower values for moisture, minerals, geographic parameter, and color characteristics. However, nearby localities, such as Cruz Machado with Bituruna and Lapa with São João do Triunfo, presented similar overall values for minerals and geographic parameters. Each regional geographic location was able to present unique characteristics so that the principal component analysis categorized it in specific quadrants, which is also in agreement with the CIELAB color space. However, hierarchical tree exhibited that CAÇ was the most distinct, due to the most distant municipality, presenting a unique microbiome. The pinhão is a source of various nutrients, which contributes to healthy dietetic daily values. It provides from 20% to 30% of dietary fiber, Cu (42.2%), P (31.1%), K (23.5%), and Zn (22.1%), while also providing quantities of Mg (12.9%), Mn (12.4%), Fe (11.5%), and Ca (6.4%). Therefore, it is possible to obtain food products based on cooked pinhão that contain many nutritional components associated with human health benefits. PRACTICAL APPLICATION: The pinheiro-do-paraná is a conifer that is currently endangered. However, the commercial use of its seeds may be key to guaranteeing its preservation, in addition to strengthening the economies of households and small producers. The pinhão collected from a large area of Araucária forests, after subsequent boiling, removal of the almond, grinding, and freezing provides large amounts of carbohydrates, higher dietary fiber content, resistant starch, and large quantities of Cu, P, K, and Z, in addition to significant amounts of Mg, Mn, Fe, and Ca. All of these are desirable characteristics that increase the value of pinhão., (© 2022 Institute of Food Technologists®.)

Biomaterials come from natural sources such as animals, plants, fungi, algae, and bacteria, composed mainly of protein, lipid, and carbohydrate molecules. The great diversity of biomaterials makes these compounds promising for developing new products for technological applications. In this sense, antioxidant biomaterials have been developed to exert biological and active functions in the human body and industrial formulations. Furthermore, antioxidant biomaterials come from natural sources, whose components can inhibit reactive oxygen species (ROS). Thus, these materials incorporated with antioxidants, mainly from plant sources, have important effects, such as anti-inflammatory, wound healing, antitumor, and anti-aging, in addition to increasing the shelf-life of products. Aiming at the importance of antioxidant biomaterials in different technological segments as biodegradable, economic, and promising sources, this review presents the main available biomaterials, antioxidant sources, and assigned biological activities. In addition, potential applications in the biomedical and industrial fields are described with a focus on innovative publications found in the literature in the last five years.

The reuse of agro-industrial waste assumes great importance today. Pinhão is the seed of Araucaria angustifolia , which is native to the mountains of southern Brazil, Paraguay, and Argentina. The coat is a by-product of this seed and is rich in phenolic compounds. The present study aimed to use the residue as a precursor material for the production of nanocellulose through the mechanical defibrillation process and perform the characterization of the films and the gel to investigate the effect on the physical and regenerative properties when incorporated with polyvinyl alcohol (PVA). The modulus of elasticity was higher when the MFC of pinhão was added to the PVA. Film and gel had their cytotoxicity tested by MTT assay using 3T3 fibroblast and Schwann cancer cells, and a migration assay was also performed using the scratch test on HaCat keratinocyte cells. For the scratch test, film and gel samples with low concentration presented a complete scratch closure in 72 h. Molecular docking was performed and quercetin had the ideal interaction score values, so it was used with the PACAP protein which presented a slightly moderate interaction with the protein synthesis of Schwann cells, presenting compactness of the compound after 14 ns.

This work investigates peripheral nerve regeneration using membranes consisting of pure chitosan (CHI), which was further blended with nanofibrillated cellulose, with citric acid as crosslinker, with posterior addition of polyvinyl alcohol, with subsequent freeze thawing. Nanocellulose improves the mechanical and thermal resistance, as well as flexibility of the film, which is ideal for the surgical procedure. The hydrogel presented a slow rate of swelling, which is adequate for cell and drug delivery. A series of in vitro tests revealed to be non-toxic for neuronal Schwann cell from the peripheral nervous system of Rattus norvegicus, while there was a slight increase in toxicity if crosslink is performed-freeze-thaw. The in vivo results, using rabbits with a 5 mm gap nerve defect, revealed that even though pure CHI was able to regenerate the nerve, it did not present functional recovery with only the deep pain attribute being regenerated. When autologous implant was used jointly with the biomaterial membrane, as a covering agent, it revealed a functional recovery within 15 d when cellulose and the hydrogel were introduced, which was attributed to the film charge interaction that may help influence the neuronal axons growth into correct locations. Thus, indicating that this system presents ideal regeneration as nerve conduits., (© 2021 IOP Publishing Ltd.)

Lignin is a complex phenolic biopolymer present in plant cell walls and a by-product of the cellulose pulping industry. Lignin has functional properties, such as antioxidant activity, that make it a potential natural active ingredient for health-care products. However, not all safety aspects of lignin fractions have been adequately investigated. Herein, we evaluated the antioxidant and genotoxic potential of two hardwood kraft lignins (F3 and F5). The chemical characterization of F3 and F5 demonstrated their thermal stability and the presence of different phenolic units, while the DPPH assay confirmed the antioxidant activity of these lignin fractions. Despite being antioxidants in the DPPH assay, F3 and F5 were capable of generating intracellular reactive oxygen species (ROS) and subsequently causing oxidative DNA damage (Comet assay) in HepG2 cells. The biological relevance of the DPPH assay might be uncertain in some cases; therefore, we suggest combining in chemico tests with biological system-based tests to determine efficacy and safety levels of lignins and define appropriate applications of lignins for consumer products. Moreover, kraft lignins obtained by acid precipitation may pose risks to human health; however, as genotoxicity is not the sole endpoint of toxicity required in hazard assessments, additional toxicological evaluations are needed., (Copyright © 2021 Elsevier B.V. All rights reserved.)

The effectiveness of tannic acid as antimicrobial and wound healing for burns have been shown for a century; however, uncontrolled target dosage may result in undesirable side-effects. Remarkably, tannic acid polyphenols compounds crosslinked with polymeric materials produce a strong composite containing the beneficial properties of this tannin. However, investigation of the crosslink structure and its antibacterial and regenerative properties are still unknown when using nanocellulose by mechanical defibrillation; additionally, due to the potential crosslink structure with chitosan, its structure can be complex. Therefore, this work uses bleach kraft nanocellulose in order to investigate the effect on the physical and regenerative properties when incorporated with chitosan and tannic acid. This film results in increased rigidity with a lamellar structure when incorporated with tannic acid due to its strong hydrogen bonding. The release of tannic acid varied depending on the structure it was synthesised with, whereas with chitosan it presented good release model compared to pure cellulose. In addition, exhibiting similar thermal stability as pure cellulose films with antibacterial properties tested against S. aureus and E. coli with good metabolic cellular viability while also inhibiting NF-κB activity, a characteristic of tannic acid.

Thymol, a monoterpene phenol, is used as a natural biocide. To circumvent its chemical instability, we propose use of thymol-loaded biogenic silica nanoparticles (BSiO 2 #THY NPs); however, the toxicity of this system for aquatic organisms is unknown. Thus, the present study aimed to evaluate the toxicogenetic effects induced by thymol, BSiO 2 NP, and BSiO 2 #THY on Artemia salina and zebrafish (Danio rerio) early life stages. We also investigated the impact of BSiO 2 aggregation in different exposure media (saline and freshwater). Based on the median lethal concentration at 48 h (LC50 48h ), BSiO 2 #THY (LC50 48h  = 1.06 mg/L) presented similar toxic potential as thymol (LC50 48h  = 1.03 mg/L) for A. salina, showing that BSiO 2 had no influence on BSiO 2 #THY toxicity. Because BSiO 2 aggregated and sedimented faster in A. salina aqueous medium than in the other medium, this NP had lower interaction with this microcrustacean. Thus, BSiO 2 #THY toxicity for A. salina is probably due to the intrinsic toxicity of thymol. For zebrafish early life stages, BSiO 2 #THY (LC50 96h  = 13.13 mg/L) was more toxic than free thymol (LC50 96h  = 25.60 mg/L); however, BSiO 2 NP has no toxicity for zebrafish early life stages. The lower aggregation of BSiO 2 in the freshwater medium compared to the saline medium may have enhanced thymol's availability for this aquatic organism. Also, BSiO 2 #THY significantly induced sublethal effects as thymol, and both were genotoxic for zebrafish. In conclusion, although BSiO 2 #THY still needs improvements to ensure its safety for freshwater ecosystems, BSiO 2 NP seems to be a safe nanocarrier for agriculture. Environ Toxicol Chem 2021;40:333-341. © 2020 SETAC., (© 2020 SETAC.)

Kraft lignin, so far useful for energy generation, has been gathering considerable attention as an alternative material to replace fossil-based resources mainly due to its high phenolic content. However, the wide molecular weight distribution and chemical composition heterogeneity led to the development of fractionation methods. Herein, to narrow such characteristics we used eucalypt kraft lignin fractionated at pH's 9, 7, 5 and 3 by sequential acid precipitation. These lignin fractions were first characterised by simultaneous pyrolysis and trimethylsilylation (SPyT) with N-Methyl-N-(trimethylsilyl) trifluoroacetamide with posterior tests of antioxidant, antibacterial, and antitumour activities. We observed higher ratio of syringyl/guaiacyl groups and increase in antioxidant activity in those fractions with lower molecular weight (precipitated at lower pH's). Fractions precipitated at pH's 9 and 7 have shown an outstanding antibacterial activity against five bacteria. Moreover, fractions 7 and 5 presented at cytotoxicity tests higher ability to inhibit the growth of U87MG and T98G glioma cells, while only a slight inhibition of adult human fibroblasts (non-tumour cells) was detected., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Microfibrillated cellulose films have been gathering considerable attention due to their high mechanical properties and cheap cost. Additionally, it is possible to include compounds within the fibrillated structure in order to confer desirable properties. Ilex paraguariensis A. St.-Hil, yerba mate leaf extract has been reported to possess a high quantity of caffeoylquinic acids that may be beneficial for other applications instead of its conventional use as a hot beverage. Therefore, we investigate the effect of blending yerba mate extract during and after defibrillation of Eucalyptus sp. bleached kraft paper by ultrafine grinding. Blending the extract during defibrillation increased the mechanical and thermal properties, besides being able to use the whole extract. Afterwards, this material was also investigated with high content loadings of starch and glycerine. The results present that yerba mate extract increases film resistance, and the defibrillated cellulose is able to protect the bioactive compounds from the extract. Additionally, the films present antibacterial activity against two known pathogens S. aureus and E. coli , with high antioxidant activity and increased cell proliferation. This was attributed to the bioactive compounds that presented faster in vitro wound healing, suggesting that microfibrillated cellulose (MFC) films containing extract of yerba mate can be a potential alternative as wound healing bandages.

Background: Crusts in 7th follow-up day: G1 yes; G2 no; G3 no (left to right). Bespite all the advances in medicine and the wide variety of dressings available, the treatment of burn wounds still represents an important medical challenge. The pinus cellulose membrane dressing is a biomaterial with characteristics similar to those of bacterial cellulose, but with lower cost., Aim: To evaluate the efficacy of pinus nanocellulose membrane on healing of deep second degree burns in rats and compare with Membracel®., Method: Thirty male Wistar rats were submitted to deep second degree burn in dorse, with boiling water at 97o C for 20 s, generating a 314 mm² area wound. The animals were distributed in three dressing groups (n=10): group 1 - simple gauze; group 2 - bacterial cellulose membrane (Membracel®); and group 3 - pinus cellulose membrane. They were evaluated for 20 days to verify clinical condition, macro and microscopic appearance and wound contraction., Results: All of them remained clinically well with no differences in weight. Crusts were observed in group 1, and none in groups 2 and 3. Regarding to scar contraction, groups 2 and 3 were similar, better than group 1. Microscopic analysis showed predominance of advanced healing degree in groups 1 and 3, and initial in group 2. Mature collagen was predominant in all groups., Conclusion: The pinus nanocellulose membrane is effective in the treatment of experimental second degree burn in rats and its effectiveness is similar to that of the bacterial nanocellular membrane.

Microfibrillated cellulose as a reinforcement agent has been investigated extensively due to their unique characteristics, which can reorder the structure of polymers and hydrogels leading to improved mechanical properties with minimal disadvantages in terms of the targeted original applications. However, effect of using a macro- to a micro-fibrillated cellulose onto polyvinyl alcohol hydrogels is still unknown, because of the unique ability for both to be produced as hydrogels from freeze-thawing mechanisms - hydrogen bonding - there is a potential synergism. Therefore, macro and microfibrillated kraft bleached paper was synthesised at various concentrations on polyvinyl alcohol hydrogels. The overall effect presented a strong interaction between both compounds but it was increased with macrofibrillated cellulose. Increase in crystallinity was also observed with a macro-sized fibre without variation on tensile elastic modulus but an overall improvement was perceived on thermal properties and a slower swelling rate with a microfibrillated cellulose., Competing Interests: Declaration of Competing Interest The authors declare that there are no conflicts of interest regarding the publication of this manuscript., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Superstructured colloidal materials exploit the synergies between components to develop new or enhanced functions. Cohesion is a primary requirement for scaling up these assemblies into bulk materials, and it has only been fulfilled in case-specific bases. Here, we demonstrate that the topology of nanonetworks formed from cellulose nanofibrils (CNFs) enables robust superstructuring with virtually any particle. An intermixed network of fibrils with particles increases the toughness of the assemblies by up to three orders of magnitude compared, for instance, to sintering. Supramolecular cohesion is transferred from the fibrils to the constructs following a power law, with a constant decay factor for particle sizes from 230 nm to 40 μm. Our findings are applicable to other nanofiber dimensions via a rationalization of the morphological aspects of both particles and nanofibers. CNF-based cohesion will move developments of functional colloids from laboratory-scale toward their implementation in large-scale nanomanufacturing of bulk materials., (Copyright © 2020 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).)

Cassava bagasse, a high-fiber coproduct of cassava starch processing, was used to produce lignocellulose nanofibers (LCNF) to apply as reinforcement in cassava starch films. LCNF-reinforced cast starch films were evaluated for changes in structural, thermal and mechanical properties and compared with control films reinforced with commercial grade nanoclay (Nclay). Five different types of cassava starch cast-films were produced: no-reinforcement control, two LCNF-reinforced, and two Nclay-reinforced, each at 0.65 and 1.3% w w -1 . The LCNF morphology showed the characteristic microscopic structure of lignocellulose nanofibers, with an aspect ratio > 85 and average diameter of 4.5 nm. All reinforced films were transparent and had a good distribution of the nanoparticles within. The opacity values reduced for the films with all nanoreinforcements, compared to control. The permeability to water vapor reduced with reinforcements, with lower values for the films tested with LCNF 0.65 and Nclay 1.3. Thermal stability improved with 1.3% of LCNF and both concentrations of Nclay. Tensile stress for films increased and elongation at break value decreased with both types of nanoreinforcements., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Pyroligneous acid (PA) is a by-product of bio-oil, which is obtained by pyrolysis of the wood. This product has been tested for use in several areas, such as agriculture, as a promising green herbicide; however, there are few scientific data regarding its environmental impacts. For this study, an ecotoxicity testing battery, composed of Daphnia magna acute toxicity test, Allium cepa test and in vitro Comet assay with the rainbow trout gonad-2 cell fish line (RTG-2) were used to evaluate the acute toxicity and genotoxicity of PA obtained from fast pyrolysis of eucalyptus wood fines. The PA presented acute toxicity to D. magna (microcrustacea) with EC 50 of 26.12 mg/L, and inhibited the seed germination (EC 50 5.556 g/L) and root development (EC 50 3.436 g/L) of A. cepa (higher plant). No signs of genotoxicity (chromosomal aberrations and micronuclei in A. cepa and primary DNA lesions in RTG-2 cells) were detected to this product. The acute toxicity and absence of genotoxicity may relate to the molecules found in the PA, being the phenolic fraction the key chemical candidate responsible for the toxicity observed. In addition, daphnids seem to be more sensitivity to the toxicity of PA than higher plants based on their EC 50 values. This first ecotoxicological evaluation of PA from fast pyrolysis pointed out the need of determining environmental exposure limits to promote the safer agriculture use of this product, avoiding impacts to living organisms., (Copyright © 2019. Published by Elsevier Inc.)

Understanding of how hemicellulose acts on the rheology of microfibrillated cellulose in suspension or after drying is insufficient. In this study, different concentrations of hemicellulose in the cellulose pulp of Eucalyptus sp. were obtained by alkaline treatment with potassium hydroxide. The treated pulps and the suspension of microfibrils obtained were characterized by thermogravimetric analysis, zeta potential, scanning electron microscopy, rheological analysis, X-ray diffraction and dynamic mechanical analysis. The lowest hemicellulose content obtained was approximately 2% wt. Treatments with KOH above 10% did not cause a significant reduction in hemicellulose content and caused a change in the type of cellulose crystallinity. The rheological analysis showed that the apparent viscosity of the suspensions was strongly influenced by the presence of hemicellulose. The morphology of the MFC films of the treated pulps presented the appearance of voids with the reduction of hemicellulose content, generating a decrease in its mechanical properties., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

In this work, a novel dual-response hydrogel for enhanced bone repair following multiple fractures was investigated. The conventional treatment of multiple bone fracture consists on removing smaller bone fragments from the body in a surgery, followed by the fixation of the bone using screws and plates. This work proposes an alternative for this treatment via in situ UV-initiated radical polymerization of a novel IPN hydrogel composed of PAA/P(NiPAAM-co-PEGDMA) incorporated with ceramic additives. The influence of different additives on mechanical properties and sensitivity of the polymer, as well as the prepolymer mixture, were investigated in order to analyse the suitability of the composites for bone healing applications. This material exhibited an interpenetrating network, confirmed by FTIR, with ceramics particles dispersed in between the polymer network. These structures presented high strength by tensile tests, sensitivity to pH and temperature and a decrease on Tg values of NiPAAm depending on the amount of PEGDMA and ceramics added; although, the addition of ceramics to these composites did not decrease their stability drastically. Finally, cytotoxicity tests revealed variations on the toxicity, whereas the addition of TCP presented to be non-toxic and that the cell viability increased when ceramics additives were incorporated into the polymeric matrix with an increased reporter activity of NF-κB, associated with aiding fibroblast adhesion. Hence, it was possible to optimise feedstock ratios to increase the applicability of the prepolymer mixture as a potential treatment of multiple fractures.

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.)

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., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

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.)