Tailoring Hydrogel Structures: Investigating the Effects of Multistep Cellulose Defibrillation on Polyvinyl Alcohol Composites.

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.

Nanofibrillated cellulose originated from Rhododendron ponticum to produce scaffolds using 3D printing for biomedical 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.

Supraparticles as slow-release fertiliser in seedling potential growth of Eucalyptus urograndis and greenhouse gas flux impacts.

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, N2O, CH4, CO2 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 N2O 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.

Linking geographical origin with nutritional, mineral, and visual proprieties of pinhão (Araucaria angustifolia seed) from the south of Brazil.

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.

Characterization of Gels and Films Produced from Pinhão Seed Coat Nanocellulose as a Potential Use for Wound Healing Dressings and Screening of Its Compounds towards Antitumour Effects.

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.

In Vivo Evaluation and Nutritional Quality of By-Products Subjected to Solid-State Fermentation Using Shiitake Culinary-Medicinal Mushroom, Lentinula edodes (Agaricomycetes).

This study evaluates the nutritional quality and in vivo biological activity of a peach palm by-product food ingredient processed via solid-state fermentation by shiitake culinary-medicinal mushroom, Lentinula edodes. The group of Wistar rats that consumed this diet had higher total dietary fiber content, digestibility, rate of protein quality, and protein efficiency. They also presented a late and softer insulinemic peak with an increase in the glycemic index, demonstrating amino acid limitation but with a feasible matrix as a complement protein. Discrete variation on total cholesterol and triglycerides was observed with a reduction in lipid profile, attributed to its high dietary fiber content. Lipids from within the liver and stool revealed that the fermented diet contained the lowest rates of fat in the liver and, consequently, the highest elimination compared to the other control diets. The serum lipid profile suggests a positive modulation of this diet, and that it has good nutritional quality with the potential to positively influence glycemic and lipid profiles.

Self-Photopolymerizable Hydrogel-Ceramic Composites with Scavenger Properties.

The photocatalytic behaviours of semiconductive ceramic nanoparticles such as TiO2, ZnO, Fe2O3, and Fe3O4, have been extensively studied in photocatalysis and photopolymerization, due to their ability to produce radical species under ultraviolet-visible light, and even in dark conditions. In addition, in the form of microparticles, TiO2 and its Magnéli phases are capable of neutralizing radical species, and a heterogeneous catalytic process has been suggested to explain this property, as it is well known as scavenging activity. Thus, in this study, we demonstrate that these ceramic powders, in the form of microparticles, could be used as photoinitiators in UV polymerization in order to synthesize a hydrogel matrix. Them, embedded ceramic powders could be able to neutralize radical species of physiological media once implanted. The hydrogel matrix would regulate the exchange of free radicals in any media, while the ceramic particles would neutralize the reactive species. Therefore, in this work, the scavenger activities of TiO2, ZnO, Fe2O3, and Fe3O4 microparticles, along with their photoinitiation yield, were evaluated. After photopolymerization, the gel fraction and swelling behaviour were evaluated for each hydrogel produced with different ceramic initiators. Gel fractions were higher than 60%, exhibiting variation in their scavenging activity. Therefore, we demonstrate that ceramic photoinitiators of TiO2, ZnO, Fe2O3, and Fe3O4 can be used to fabricate implantable devices with scavenger properties in order to neutralize radical species involved in inflammatory processes and degenerative diseases.

Brushite bone cement containing polyethylene glycol for bone regeneration.

BACKGROUND: Bone cements aid in bone regeneration; however, if the handling time is not well established for the material to harden, complications may arise. OBJECTIVE: This work investigates the effect of using polyethylene glycol (PEG) and characterize it in brushite bone cement in order to obtain desirable handling times as well as its regeneration in vivo to analyse if addition of this polymer may significantly modify its properties. METHODS: PEG 4000 was synthesised with wollastonite by phosphorization reaction in order to form brushite which was further cured by oven drying. They were further characterised and tested in vivo as tibial bone defect model using rabbits. RESULTS: Addition of PEG exhibited handling times of 60 min with a low increase in temperature when curing. Brushite phase of ∼71% was obtained after cement hardening with good compressive strength (25 MPa) and decent values of porosity (33%). In vivo presented that, at 40 days postoperatively, accelerated bone neoformation with partial consolidation at 30 days and total after 60 days when using bone cement. CONCLUSIONS: Addition of PEG does not disrupt the beneficial properties of the bone cement and can be a potential alternative to control the time-temperature profile of hardening these materials.

Development, Characterization and Cell Viability Inhibition of PVA Spheres Loaded with Doxorubicin and 4'-Amino-1-Naphthyl-Chalcone (D14) for Osteosarcoma.

Chalcones (1,3-diaryl-2-propen-1-ones) are naturally occurring polyphenols with known anticancer activity against a variety of tumor cell lines, including osteosarcoma (OS). In this paper, we present the preparation and characterization of spheres (~2 mm) from polyvinyl alcohol (PVA) containing a combination of 4'-Amino-1-Naphthyl-Chalcone (D14) and doxorubicin, to act as a new polymeric dual-drug anticancer delivery. D14 is a potent inhibitor of osteosarcoma progression and, when combined with doxorubicin, presents a synergetic effect; hence, physically crosslinked PVA spheres loaded with D14 and doxorubicin were prepared using liquid nitrogen and six freeze-thawing cycles. Physical-chemical characterization using a scanning electron microscope (SEM), differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD) presented that the drugs were incorporated into the spheres via weak interactions between the drugs and the polymeric chains, resulting in overall good drug stability. The cytotoxicity activity of the PVA spheres co-encapsulating both drugs was tested against the U2OS human osteosarcoma cell line by 3- (4,5-dimethylthiazol-2-yl) -2,5-diphenyltetrazolium bromide (MTT) assay, and compared to the spheres carrying either D14 or doxorubicin alone. The co-delivery showed a cytotoxic effect 2.6-fold greater than doxorubicin alone, revealing a significant synergistic effect with a coefficient of drug interaction (CDI) of 0.49. The obtained results suggest this developed PVA sphere as a potential dual-drug delivery system that could be used for the prominent synergistic anticancer activity of co-delivering D14 and doxorubicin, providing a new potential strategy for improved osteosarcoma treatment.

Microfibrillated cellulose films containing chitosan and tannic acid for wound healing applications.

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.

Yerba Mate Extract in Microfibrillated Cellulose and Corn Starch Films as a Potential Wound Healing Bandage.

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.

Characterisation and in vivo evaluation of Araucaria angustifolia pinhão seed coat nanosuspension as a functional food source.

Araucaria angustifolia seeds from South America are culturally important; however, the seed coat is generally discarded and it has yet to find a beneficial commercial impact. Herein, we propose a new formulation for the use of the seed coat for the production of a food source. A nanosuspension was developed under two conditions, bleached and unbleached treatment. Initial characterisation of the seed coat, as well as the nanosuspension, was conducted, in which nanofibrils with antioxidant activity and high values of phenol and sterol classes with health-promoting ability were detected by GC-MS; however, after bleaching, the compounds were removed. The nanosuspension induced a decrease in cholesterol, triglycerides, glucose levels and weight gain when added to the daily rat diet. No significant differences were determined when bleach treatment was used, suggesting that dietary fibre plays a more significant role. Histology analysis and biochemical markers reported no toxicity from the rat ingestion of the nanoformulation.

Development of alginate beads with encapsulated jabuticaba peel and propolis extracts to achieve a new natural colorant antioxidant additive.

This work aims to encapsulate anthocyanins and phenolic compounds extracted from a native Brazilian fruit peel - jabuticaba (Plinia cauliflora (Mart.) Kausel) and propolis from Tubuna (Scaptotrigona bipunctata) stingless bees, with great potential benefits for human health. The alginate encapsulation was conducted by the ionotropic gelation through the dripping into the CaCl2 solution. Both raw extracts were characterized by TPC - total phenolic content (Folin-Ciocalteu), AA -antioxidant activity (DPPH and ABTS assays), and TMAC - total monomeric anthocyanin concentration (pH differential method); as well as their resultant mixture (2:1 jabuticaba/propolis). The obtained beads presented highly efficient encapsulation of total polyphenols (~98%) and monomeric anthocyanins (~89%), with spherical morphology and smooth surface obtaining a mean diameter between 200 and 250 µm. In vitro release study showed that JPE/alginate beads were completely disintegrated at pH 7.4 (intestinal pH), but they were resistant to gastric pH (1.2) presenting a slow release of about 40% in 240 min. This is the first report that encapsulates the mixture of jabuticaba and propolis extracts and may contribute to the utilization of a great source of bioactive compounds besides the potential pigment of anthocyanins, an alternative to natural and healthy food/beverage colorants.

Injectable bone substitute based on chitosan with polyethylene glycol polymeric solution and biphasic calcium phosphate microspheres.

We described a method to produce an injectable bone substitute consisting of a solid and liquid phase, this solid was formed using the coacervation method consisting of a mixture of Hydroxyapatite (HAp) and beta-Tricalcium Phosphate (ß-TCP) which the sodium alginate - precursor - was removed during sinterization. The biphasic calcium phosphate microspheres had varying size distributions depending on the flow rate and these microspheres were mixed with a polymeric solution, chitosan and polyethylene glycol, and depending on the ratio of these phases, the injectability results varied. Nonetheless, the force required for complete removal will not disrupt the accuracy of injection into the bone defect while the biomaterial exhibited no cytotoxicity with promising results from in vivo using tibia bone defect in rabbits at 30 and 60 days whereas bone repair was more intense and accentuated with the usage of the biomaterial, and was gradually absorbed during the evaluated periods.

Effect of cellulose size-concentration on the structure of polyvinyl alcohol hydrogels.

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.

A tough and novel dual-response PAA/P(NiPAAM-co-PEGDMA) IPN hydrogels with ceramics by photopolymerization for consolidation of bone fragments following fracture.

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.

The evaluation of the potential ecotoxicity of pyroligneous acid obtained from fast pyrolysis.

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 EC50 of 26.12 mg/L, and inhibited the seed germination (EC50 5.556 g/L) and root development (EC50 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 EC50 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.

Platelet-Rich Plasma, Hydroxyapatite, and Chitosan in the Bone and Cartilaginous Regeneration of Femoral Trochlea in Rabbits: Clinical, Radiographic, and Histomorphometric Evaluations.

The aim of this study was to evaluate the trochlear bone and cartilaginous regeneration of rabbits using the association of PRP, chitosan, and hydroxyapatite. Hole was made in rabbit troches, one hole in each animal remained empty (group C), and one was filled by a combination of PRP, chitosan, and hydroxyapatite (group T). Clinical-orthopedic, radiographic, and histomorphometric evaluations were performed. Clinical-orthopedic evaluation showed lameness of two members of the T group and one member of group C. The radiographic evaluation showed that the T group showed absence of subchondral bone reaction (33%). The presence of moderate subchondral bone reaction was more frequently reported in group C with 67%. Microscopic evaluation revealed a presence of tissue neoformation, composed of connective tissue. Microscopic findings were similar in both groups, with a difference in the amount of neoformed tissue being perceptible, which was confirmed after the morphometric analysis, which revealed a significant difference in the quantity of newly formed tissue at the bone/cartilage/implant interface. The composite base of the association of chitosan, hydroxyapatite, and platelet-rich plasma favored bone and cartilage healing.