Percorrer por autor "Medronho, Bruno"
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- Acacia wood fractionation using deep eutectic solvents: extraction, recovery, and characterization of the different fractionsPublication . Magalhães, Solange; Moreira, Adriana; Almeida, Ricardo; Cruz, Pedro Fernandes; Alves, Luís; Costa, Carolina; Mendes, Cátia; Medronho, Bruno; Romano, Anabela; Carvalho, Maria da Graça; Gamelas, José A. F.; Rasteiro, Maria da GraçaThe selective extraction and recovery of different lignocellulosic molecules of interest from forestry residues is increasing every day not only to satisfy the needs of driving a society toward more sustainable approaches and materials (rethinking waste as a valuable resource) but also because lignocellulosic molecules have several applications. For this purpose, the development of new sustainable and ecologically benign extraction approaches has grown significantly. Deep eutectic solvents (DESs) appear as a promising alternative for the processing and manipulation of biomass. In the present study, a DES formed using choline chloride and levulinic acid (ChCl:LA) was studied to fractionate lignocellulosic residues of acacia wood (Acacia dealbata Link), an invasive species in Portugal. Different parameters, such as temperature and extraction time, were optimized to enhance the yield and purity of recovered cellulose and lignin fractions. DESs containing LA were found to be promising solvent systems, as the hydrogen bond donor was considered relevant in relation to lignin extraction and cellulose concentration. On the other hand, the increase in temperature and extraction time increases the amount of extracted material from biomass but affects the purity of lignin. The most promising DES system, ChCELA in a ratio of 1:3, was found to not significantly depolymerize the extracted lignin, which presented a similar molecular weight to a la-aft lignin. Additionally, the P-31 NMR results revealed that the extracted lignin has a high content of phenolic OH groups, which favor its reactivity. A mixture of ChCl:LA may be considered a fully renewable solvent, and the formed DES presents good potential to fractionate wood residues.
- Adsorption of cationic lignin derivatives on negatively charged model surfaces and hair fibers: implications for hair conditioning performancePublication . Catarina Fernandes; Cabaça, Daniela; Guzmán, Eduardo; Serra, Ricardo; Eivazi, Alireza; Norgren, Magnus; Alves, Luís; Medronho, Bruno; Rasteiro, Maria da Graça; Varela, CarlaThe application of cosmetic ingredients into hair formulations relies on their extensive characterization and on understanding their mechanisms of action. Specifically, in the case of hair conditioning agents, their efficiency in treating hair must be proved before testing them on real complex formulations. In this work, we investigate the deposition of three cationic polymers onto model surfaces that mimic the negative surface potential of highly damaged hair. Two CHPTAC-cationized lignins (CL0.34 and CL0.61) were evaluated and compared with a commercial polyquaternium (PQ11). The two selected lignin derivatives exhibited different degrees of cationic substitution (DS) and ζ-potential (CL0.34: DS = 0.34 ± 0.01 and ζ-potential = 12.8 ± 0.4 mV; CL0.61: DS = 0.61 ± 0.03 and ζ-potential = 18.8 ± 0.3 mV). Atomic force microscopy (AFM) and quartz crystal microbalance with dissipation monitoring (QCM-D) were used to evaluate the adsorbed layers formed by the polymers and their mechanical properties. Among the tested lignin conditioning agents, CL0.61 exhibited conditioning behavior, forming layers whose properties closely resembled those of the benchmark polymer PQ11. CL0.61 and PQ11 were both efficient at reducing the frizz effect on real bleached hair, effectively overcompensating the hair surface potential, which shifted from negative to positive values, confirming their effective adsorption after conditioning and rinsing. By combining advanced interfacial characterization with structure–property–function relationships, this work provides fundamental insights into polymer adsorption and performance at biointerfaces, supporting the rational design of functional materials and highlighting the potential of cationic lignin derivatives as viable, biobased conditioning agents for future hair-care formulations.
- Advancements in detection and mitigation strategies for Petroleum-Derived contaminants in aquatic environments: a comprehensive reviewPublication . Duarte, Hugo; Aliaño González, María José; Medronho, BrunoThe exponential increase in the production and transportation of petroleum-derived products observed in recent years has been driven by the escalating demand for energy, textiles, plastic-based materials, and other goods derived from petroleum. Consequently, there has been a corresponding rise in spills of these petroleum derivatives, particularly in water sources utilized for transportation or, occasionally, illegally utilized for tank cleaning or industrial equipment maintenance. Numerous researchers have proposed highly effective techniques for detecting these products, aiming to facilitate their cleanup or containment and thereby minimize environmental pollution. However, many of these techniques rely on the identification of individual compounds, which presents significant drawbacks, including complexity of handling, subjectivity, lengthy analysis times, infeasibility for in situ analysis, and high costs. In response, there has been a notable surge in the utilization of sensors or generalized profiling techniques serving as sensors to generate characteristic fingerprints of these products, thereby circumventing the aforementioned disadvantages. This review comprehensively examines the evolution of techniques employed for detecting petroleum-derived products in water samples, along with their associated advantages and disadvantages. Furthermore, the review examines current perspectives on methods for the removal and/or containment of these products from water sources, to minimize their environmental impact and the associated health repercussions on living organisms and ecosystems.
- Brief overview on bio-based adhesives and sealantsPublication . Magalhães, Solange; Alves, Luís; Medronho, Bruno; Fonseca, Ana C.; Romano, Anabela; Coelho, Jorge F.J.; Norgren, MagnusAdhesives and sealants (AS) are materials with excellent properties, versatility, and simple curing mechanisms, being widely used in different areas ranging from the construction to the medical sectors. Due to the fast-growing demand for petroleum-based products and the consequent negative environmental impact, there is an increasing need to develop novel and more sustainable sources to obtain raw materials (monomers). This reality is particularly relevant for AS industries, which are generally dependent on non-sustainable fossil raw materials. In this respect, biopolymers, such as cellulose, starch, lignin, or proteins, emerge as important alternatives. Nevertheless, substantial improvements and developments are still required in order to simplify the synthetic routes, as well as to improve the biopolymer stability and performance of these new bio-based AS formulations. This environmentally friendly strategy will hopefully lead to the future partial or even total replacement of non-renewable petroleum-based feedstock. In this brief overview, the general features of typical AS are reviewed and critically discussed regarding their drawbacks and advantages. Moreover, the challenges faced by novel and more ecological alternatives, in particular lignocellulose-based solutions, are highlighted.
- Cationic lignin derivatives in hair conditioners: Formulation development and rheological modelingPublication . Fernandes, Catarina; Crespo, Catarina; Cabaça, Daniela; Pocinho, Ana; Alves, Luís; Medronho, Bruno; Rasteiro, Maria da Graça; Varela, CarlaReplacing petrochemical-based cationic conditioning polymers with renewable alternatives is a key challenge in the redesign of more sustainable hair care products. In this work, cationic lignin-derivatives, prepared via a single-step cationization process using 3-chloro-2-hydroxypropyltrimethylammonium chloride (CHPTAC) were explored as alternatives to petrochemical-based cationic conditioning agents in hair conditioning products. Formulations were prepared using either these derivatives or a widely used synthetic cationic polymer (polyquaternium-11, PQ11) and characterized in terms of their physicochemical and rheological properties, and stability. Replacing PQ11 with cationic lignin derivatives did not affect the stability or the physicochemical properties of the formulations. The effect of the formulation components on the viscosity was systematically studied using a design of experiments, resulting in a predictive model describing the relationship between composition and viscosity. In addition, the lignin-based conditioners exhibited higher UV absorption than a commercial conditioner reference, with a 15-fold relative UV absorption. A preliminary proof-of-concept application on hair demonstrated improved definition and reduced frizz, supporting the potential of cationic lignin derivatives as alternative biobased conditioning agents.
- Cellulose-based edible films for probiotic entrapmentPublication . Singh, Poonam; Magalhaes, Solange; Alves, Luis; Antunes, Filipe; Miguel, Maria; Lindman, Bjorn; Medronho, BrunoEncapsulation with edible films is a promising approach that may solve the disadvantages associated with the use of bioactive compounds as food additives. This is particularly relevant in the case of probiotics, since their stability in food matrices and in the gastrointestinal tract may be rather poor. Therefore, new cellulose-based edible films have been successfully developed and characterized. Sodium carboxymethyl cellulose (CMC) and hydroxyethyl cellulose (HEC) were used for the film preparation and cross-linked with citric acid (CA) under reasonably mild conditions. Model probiotic bacteria (Lactobacillus rhamnosus GG) were incorporated in the films either during the film formation and casting or after the film synthesis, via bacteria diffusion and adsorption. The later approach could efficiently entrap and preserve viable bacteria. The mechanical properties and swelling ability could be tuned by varying the HEC/CMC ratio and the amount of CA. Moreover, the surface area and total pore volume of the films considerably decreased after cross-linking. Overall, these novel films are regarded as promising inexpensive and friendly matrices for food protection and packaging applications.
- Cellulose-stabilized oil-in-water emulsions: structural features, microrheology, and stabilityPublication . Costa, Carolina; Rosa, Pedro; Filipe, Alexandra; Medronho, Bruno; Romano, Anabela; Liberman, Lucy; Talmon, Yeshayahu; Norgren, MagnusCellulose-based oil-in-water (O/W) emulsions were studied by diffusing wave spectroscopy (DWS) regarding the effect of the cellulose concentration and mixing rate on the average droplet size, microrheological features and stability. Furthermore, the microstructure of these emulsions was imaged by cryo-scanning electron microscopy (cryo-SEM). The micrographs showed that cellulose was effectively adsorbed at the oil-water interface, resembling a film-like shell that protected the oil droplets from coalescing. The non-adsorbed cellulose that was observed in the continuous aqueous medium, contributed to the enhancement of the viscosity of the medium, leading to an improvement in the stability of the overall system. Generally, the higher the cellulose concentration and mixing rate, the smaller the emulsion droplets formed, and the higher was their stability. The combination of both techniques, DWS and cryo-SEM, revealed a very appealing and robust methodology for the characterization and design of novel emulsion-based formulations.
- Chitosan-dextran sulfate hydrogels as a potential carrier for probioticsPublication . Falco, Cigdem Yucel; Falkman, Peter; Risbo, Jens; Cardenas, Marite; Medronho, BrunoPhysical and chemical (crosslinked with genipin) hydrogels based on chitosan and dextran sulfate were developed and characterized as novel bio-materials suitable for probiotic encapsulation. The swelling of the hydrogels was dependent on the composition and weakly influenced by the pH of the media. The morphology analysis supports the swelling data showing distinct changes in microstructure depending on the composition. The viability and culturability tests showed approx. 3.6 log CFLI/mL decrease of cells (L acidophilus as model) incorporated into chemical hydrogels when compared to the number of viable native cells. However, the live/dead viability assay evidenced that a considerable amount of viable cells were still entrapped in the hydrogel network and therefore the viability is most likely underestimated. Overall, the developed systems are robust and their structure, rheology and swelling properties can be tuned by changing the blend ratio, thus constituting appealing bio-matrices for cell encapsulation. (C) 2017 Elsevier Ltd. All rights reserved.
- Clouding of nonionic surfactantsPublication . Lindman, Bjorn; Medronho, Bruno; Karlstrom, GunnarNonionic surfactants have broad applications such as cleaning and dispersion stabilization, which frequently are hampered by strong temperature sensitivities. As manifested by clouding and decreased solubility with increasing temperature, the interaction between water and the oligo(oxyethylene) head-groups is becoming less favorable. Different aspects of surfactant self-assembly, like the critical micelle concentration, micelle size and shape, intermicellar interactions and phase separation phenomena are reviewed as well as suggested underlying causes of the temperature dependence. Furthermore, the effect of cosolutes on clouding and the behavior of related systems, non-aqueous solutions and nonionic polymers, are examined. (C) 2016 Elsevier Ltd. All rights reserved.
- Customising sustainable bio-based polyelectrolytes: introduction of charged and hydrophobic groups in cellulosePublication . Magalhães, Solange; Aliaño González, María José; Cruz, Pedro F.; Rosenberg, Rose; Haffke, Dirk; Norgren, Magnus; Alves, Luís; Medronho, Bruno; Rasteiro, Maria da GraçaAbstract: Cellulose has been widely explored as a sustainable alternative to synthetic polymers in industrial applications, thanks to its advantageous properties. The introduction of chemical modifications on cellulose structure, focusing on cationic and hydrophobic modifications, can enhance its functionality and expand the range of applications. In the present work, cationization was carried out through a two-step process involving sodium periodate oxidation followed by a reaction with the Girard T reagent, yielding a degree of substitution for cationic groups (DScationic) between 0.3 and 1.8. Hydrophobic modification was achieved via esterification with fatty acids derived from commercial plant oils, using an enzyme-assisted, environmentally friendly method. Lipase-catalysed hydrolysis, optimised at 0.25% enzyme concentration and with a 1 h reaction time, produced an 84% yield of fatty acids, confirmed by FTIR and NMR analyses. The degree of substitution for hydrophobic groups (DShydrophobic) ranged from 0.09 to 0.66. The molecular weight (MW) of the modified cellulose derivatives varied from 1.8 to 141 kDa. This dual modification strategy enables the creation of cellulose-based polymers with controlled electrostatic and hydrophobic characteristics, customisable for specific industrial applications. Our approach presents a sustainable and flexible solution for developing cellulose derivatives tailored to diverse industrial needs.
