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Research Project
REviving AgroFLOrestal RESidues: From Intermolecular Interactions in Natural Polyphenols to Novel Biomaterials of Added Value.
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Poly(butylene succinate)-based composites with technical and extracted lignins from wood residues
Publication . Melro, Elodie; Duarte, Hugo; Eivazi, Alireza; Costa, Carolina; Faleiro, Maria Leonor; Rosa Da Costa, Ana; Antunes, Filipe E.; Valente, Artur J. M.; Romano, Anabela; Norgren, Magnus; Medronho, Bruno
Poly(butylene succinate) (PBS) has been drawing attention as a reliable biodegradable and sustainable alternative to synthetic petroleum-based polymers. In this study, PBS-lignin composites were developed using a recently extracted lignin (LA-lignin) from pine wood residues employing an innovative sustainable approach. These composites were systematically compared with PBS-based composites formed with commonly used technical lignins. The molecular weight of the lignins was evaluated, along with various structural and performance-related properties. The LA-lignin/PBS composites display a remarkably low water solubility (ca. < 2%), water uptake (ca. 100 degrees). Moreover, the rigidity and thermal stability of the LA-lignin-PBS composites were higher than those of the systems formed with technical lignins. Although all composites studied present remarkable antioxidant features, the novel LA-lignin-PBS systems stand out in terms of antiadhesion activity against both Gram-positive and Gram-negative bacteria. Overall, the systematic analysis performed in this work regarding the impact of various lignins on the formed PBS composites enables a better understanding of the essential structural and compositional lignin features for achieving biobased materials with superior properties.
Sustainable extraction of polyphenols from vine shoots using deep eutectic solvents: influence of the solvent, vitis sp., and extraction technique
Publication . Duarte, Hugo; Aliaño-González, María José; Cantos-Villar, Emma; Faleiro, Leonor; Romano, Anabela; Medronho, Bruno
Vine shoots are the main by-products of grapevine pruning with no added value. In the present study, deep
eutectic solvents (DESs) were used as alternatives to traditional chemical solvents, for the extraction of phyto chemicals from grapevine shoots. Three levulinic acid-based DESs were tested for the first time, and their per formance was compared to methanol (a standard chemical solvent) regarding the extraction of phenolic
compounds from thirteen Vitis sp. shoots. Two extraction methods have been applied: ultrasound-assisted
extraction and solid-liquid extraction. A total of eleven polyphenols which belongs to four families (proantho cyanins, stilbenes, hydroxycinnamic acids, and flavonols) have been identified and quantified in the extracts.
The statistical analysis shows that the levulinic acid-based DES systems are novel and important alternatives to
chemical solvents due to favourable eco-friendly properties and remarkable extraction performance of poly phenols. On the other hand, the ultrasound-assisted extraction technique has significantly increased the
extraction rate in comparison to the solid-liquid extraction method with p-values lower than 0.05 for most
compounds. The genetic factor has been shown to play an important role in the content of extracted polyphenols,
being V. riparia pubescente the one that presented the highest concentrations of extracted polyphenols. Finally,
the polyphenol-enriched extracts have proven important properties such as antioxidant activity and significant
delay in bacteria growth against both gram-positive and gram-negative bacteria. It is important to note that, to
the best of our knowledge, this is the first time that deep eutectic solvents have been used for the extraction of
bioactive compounds from vine shoot residues.
Ultrasound-assisted extraction of Polyphenols from maritime pine residues with deep eutectic solvents
Publication . Duarte, Hugo; Gomes, Valentim; Aliaño-González, María José; Faleiro, Maria Leonor; Romano, Anabela; Medronho, Bruno
Deep eutectic solvents represent an important alternative in the field of green solvents
due to their low volatility, non-toxicity, and low synthesis cost. In the present investigation, we
propose the production of enriched polyphenolic extracts from maritime pine forest residues via
an ultrasound-assisted approach. A Box–Behnken experimental design with a response surface
methodology was used with six variables to be optimized: solid-to-solvent ratio, water percentage,
temperature and time of extraction, amplitude, and catalyst concentration. The mixture of levulinic
and formic acids achieved the highest extraction yield of polyphenols from pine needle and bark
biomass. In addition, the solid-to-solvent ratio was found to be the only influential variable in the
extraction (p-value: 0.0000). The optimal conditions were established as: 0.1 g of sample in 10 mL of
LA:FA (70:30%, v/v) with 0% water and 0 M H2SO4 heated to 30 ◦C and extracted during 40 min
with an ultrasound amplitude of 80% at 37 kHz. The bioactive properties of polyphenol-enriched
extracts have been proven with significant antioxidant (45.90 ± 2.10 and 66.96 ± 2.75 mg Trolox
equivalents/g dw) and antimicrobial activities. The possibility to recycle and reuse the solvent was
also demonstrated; levulinic acid was successfully recovered from the extracts and reused in novel
extractions on pine residues. This research shows an important alternative to obtaining polyphenolenriched extracts from forest residues that are commonly discarded without any clear application,
thus opening an important window toward the valorization of such residues.
Lignin-furanic rigid foams: Enhanced methylene blue removal capacity, recyclability, and flame retardancy
Publication . Duarte, Hugo; Brás, João; Saoudi Hassani, El Mokhtar; Aliaño González, María José; Magalhães, Solange; Alves, Luís; Valente, Artur J. M.; Eivazi, Alireza; Norgren, Magnus; Romano, Anabela; Medronho, Bruno
Worldwide, populations face issues related to water and energy consumption. Water scarcity has intensified globally, particularly in arid and semiarid regions. Projections indicate that by 2030, global water demand will rise by 50%, leading to critical shortages, further intensified by the impacts of climate change. Moreover, wastewater treatment needs further development, given the presence of persistent organic pollutants, such as dyes and pharmaceuticals. In addition, the continuous increase in energy demand and rising prices directly impact households and businesses, highlighting the importance of energy savings through effective building insulation. In this regard, tannin-furanic foams are recognized as promising sustainable foams due to their fire resistance, low thermal conductivity, and high water and chemical stability. In this study, tannin and lignin rigid foams were explored not only for their traditional applications but also as versatile materials suitable for wastewater treatment. Furthermore, a systematic approach demonstrates the complete replacement of the tannin-furan foam phenol source with two lignins that mainly differ in molecular weight and pH, as well as how these parameters affect the rigid foam structure and methylene blue (MB) removal capacity. Alkali-lignin-based foams exhibited notable MB adsorption capacity (220 mg g−1), with kinetic and equilibrium data analysis suggesting a multilayer adsorption process. The prepared foams demonstrated the ability to be recycled for at least five adsorption-desorption cycles and exhibited effective flame retardant properties. When exposed to a butane flame for 5 min, the foams did not release smoke or ignite, nor did they contribute to flame propagation, with the red glow dissipating only 20 s after flame exposure.
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Funding agency
Fundação para a Ciência e a Tecnologia
Funding programme
Concurso para Financiamento de Projetos de Investigação Científica e Desenvolvimento Tecnológico em Todos os Domínios Científicos - 2017
Funding Award Number
PTDC/ASP-SIL/30619/2017