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Publications (10 of 51) Show all publications
Duarte, T. A., Pereira, R. F., Medronho, B., Maltseva, E. S., Krivoshapkina, E. F., Varela-Dopico, A., . . . de Zea Bermudez, V. (2024). A Glance at Novel Ionanofluids Incorporating Silk-Derived Carbon Dots. Chemistry of Materials, 36(3), 1136-1152
Open this publication in new window or tab >>A Glance at Novel Ionanofluids Incorporating Silk-Derived Carbon Dots
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2024 (English)In: Chemistry of Materials, ISSN 0897-4756, E-ISSN 1520-5002, Vol. 36, no 3, p. 1136-1152Article in journal (Refereed) Published
Abstract [en]

One of the hallmarks of the current efforts in the field of thermal energy is heat transfer enhancement. Ionanofluids (INFs), a combination of nanomaterials and ionic liquids (ILs), are an appealing category of thermal fluids. In this work, we introduce sustainable INFs composed of carbon dots derived from Bombyx mori silk fibroin (SF) dispersed in a mixture of 1-butyl-3-methylimidazolium chloride (IL1) and 1-(4-sulfobutyl)-3-methylimidazolium triflate (IL2). The syntheses were performed at mild conditions, with reaction times of 3, 4, and 5 h, and without purification steps. The INFs display room-temperature emission in the visible spectral range with quantum yield values up to 0.09 and are essentially viscous fluids (G″ > G′). A marked shear thinning behavior is observed at high shear rates, particularly for the systems SFIL1IL2-3h and SFIL1IL2-4h. The INFs demonstrate relatively high heat capacity and thermal conductivity values in comparison to state-of-the-art INFs. Under suitable illumination conditions, the INFs can convert light into heat in an efficient manner, with photothermal conversion efficiencies of up to 28%, similar to other reported INFs. SFIL1IL2-5h exhibits remarkable stability over time within the range of working temperatures. This work paves the way for the development of new thermal fluids for enhanced heat transfer technologies using sustainable synthesis routes and natural raw precursor materials. 

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2024
Keywords
carbon dots, imidazolium ionic liquids, ionanofluids, silk fibroin, thermal fluids
National Category
Chemical Sciences
Identifiers
urn:nbn:se:miun:diva-50261 (URN)10.1021/acs.chemmater.3c01370 (DOI)001162248400001 ()2-s2.0-85181564510 (Scopus ID)
Available from: 2024-01-16 Created: 2024-01-16 Last updated: 2024-03-01Bibliographically approved
Magalhães, S., Aliaño-González, M. J., Cruz, P. F., Rosenberg, R., Haffke, D., Norgren, M., . . . da Graça Rasteiro, M. (2024). Customising Sustainable Bio-Based Polyelectrolytes: Introduction of Charged and Hydrophobic Groups in Cellulose. Polymers, 16(22), Article ID 3105.
Open this publication in new window or tab >>Customising Sustainable Bio-Based Polyelectrolytes: Introduction of Charged and Hydrophobic Groups in Cellulose
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2024 (English)In: Polymers, E-ISSN 2073-4360, Vol. 16, no 22, article id 3105Article in journal (Refereed) Published
Abstract [en]

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. 

Place, publisher, year, edition, pages
MDPI AG, 2024
Keywords
cationization, cellulose, functionalisation, hydrophobicity, vegetable fatty acids
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:miun:diva-53225 (URN)10.3390/polym16223105 (DOI)2-s2.0-85210151581 (Scopus ID)
Available from: 2024-12-03 Created: 2024-12-03 Last updated: 2024-12-03
Magalhaes, S., Aliano-Gonzalez, M. J., Rodrigues, M., Fernandes, C., Mendes, C. V. T., Carvalho, M. G. S., . . . Rasteiro, M. d. (2024). Enhancing Cellulose and Lignin Fractionation from Acacia Wood: Optimized Parameters Using a Deep Eutectic Solvent System and Solvent Recovery. Molecules, 29(15), Article ID 3495.
Open this publication in new window or tab >>Enhancing Cellulose and Lignin Fractionation from Acacia Wood: Optimized Parameters Using a Deep Eutectic Solvent System and Solvent Recovery
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2024 (English)In: Molecules, ISSN 1431-5157, E-ISSN 1420-3049, Vol. 29, no 15, article id 3495Article in journal (Refereed) Published
Abstract [en]

Cellulose and lignin, sourced from biomass, hold potential for innovative bioprocesses and biomaterials. However, traditional fractionation and purification methods often rely on harmful chemicals and high temperatures, making these processes both hazardous and costly. This study introduces a sustainable approach for fractionating acacia wood, focusing on both cellulose and lignin extraction using a deep eutectic solvent (DES) composed of choline chloride (ChCl) and levulinic acid (LA). A design of experiment was employed for the optimization of the most relevant fractionation parameters: time and temperature. In the case of the lignin, both parameters were found to be significant variables in the fractionation process (p-values of 0.0128 and 0.0319 for time and temperature, respectively), with a positive influence. Likewise, in the cellulose case, time and temperature also demonstrated a positive effect, with p-values of 0.0103 and 0.028, respectively. An optimization study was finally conducted to determine the maximum fractionation yield of lignin and cellulose. The optimized conditions were found to be 15% (w/v) of the wood sample in 1:3 ChCl:LA under a treatment temperature of 160 degrees C for 8 h. The developed method was validated through repeatability and intermediate precision studies, which yielded a coefficient of variation lower than 5%. The recovery and reuse of DES were successfully evaluated, revealing remarkable fractionation yields even after five cycles. This work demonstrates the feasibility of selectively extracting lignin and cellulose from woody biomass using a sustainable solvent, thus paving the way for valorization of invasive species biomass.

Place, publisher, year, edition, pages
MDPI AG, 2024
Keywords
biomass fractionation, deep eutectic solvents, Box-Behnken design, acacia wood, lignocellulose
National Category
Chemical Sciences
Identifiers
urn:nbn:se:miun:diva-52158 (URN)10.3390/molecules29153495 (DOI)001287196300001 ()39124900 (PubMedID)2-s2.0-85200757401 (Scopus ID)
Available from: 2024-08-19 Created: 2024-08-19 Last updated: 2024-08-19
Magalhaes, S., Paciencia, D., Rodrigues, J. M. M., Lindman, B., Alves, L., Medronho, B. & Rasteiro, M. d. (2024). Insights on Microplastic Contamination from Municipal and Textile Industry Effluents and Their Removal Using a Cellulose-Based Approach. Polymers, 16(19), Article ID 2803.
Open this publication in new window or tab >>Insights on Microplastic Contamination from Municipal and Textile Industry Effluents and Their Removal Using a Cellulose-Based Approach
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2024 (English)In: Polymers, E-ISSN 2073-4360, Vol. 16, no 19, article id 2803Article in journal (Refereed) Published
Abstract [en]

The rampant use of plastics, with the potential to degrade into insidious microplastics (MPs), poses a significant threat by contaminating aquatic environments. In the present study, we delved into the analysis of effluents from textile industries, a recognized major source of MPs contamination. Data were further discussed and compared with a municipal wastewater treatment plant (WWTP) effluent. All effluent samples were collected at the final stage of treatment in their respective WWTP. Laser diffraction spectroscopy was used to evaluate MP dimensions, while optical and fluorescence microscopies were used for morphology analysis and the identification of predominant plastic types, respectively. Electrophoresis was employed to unravel the prevalence of negative surface charge on these plastic microparticles. The analysis revealed that polyethylene terephthalate (PET) and polyamide were the dominant compounds in textile effluents, with PET being predominant in municipal WWTP effluents. Surprisingly, despite the municipal WWTP exhibiting higher efficiency in MP removal (ca. 71% compared to ca. 55% in textile industries), it contributed more to overall pollution. A novel bio-based flocculant, a cationic cellulose derivative derived from wood wastes, was developed as a proof-of-concept for MP flocculation. The novel derivatives were found to efficiently flocculate PET MPs, thus allowing their facile removal from aqueous media, and reducing the threat of MP contamination from effluents discharged from WWTPs.

Place, publisher, year, edition, pages
MDPI AG, 2024
Keywords
microplastics, textile and municipal effluents, wastewater treatment plant, polyethylene terephthalate (PET)
National Category
Water Treatment
Identifiers
urn:nbn:se:miun:diva-52991 (URN)10.3390/polym16192803 (DOI)001332622400001 ()39408517 (PubMedID)2-s2.0-85206497325 (Scopus ID)
Available from: 2024-11-01 Created: 2024-11-01 Last updated: 2024-11-01
Fernandes, C., Aliaño-González, M. J., Cid Gomes, L., Bernin, D., Gaspar, R., Fardim, P., . . . Varela, C. (2024). Lignin extraction from acacia wood: Crafting deep eutectic solvents with a systematic D-optimal mixture-process experimental design. International Journal of Biological Macromolecules, 280, Article ID 135936.
Open this publication in new window or tab >>Lignin extraction from acacia wood: Crafting deep eutectic solvents with a systematic D-optimal mixture-process experimental design
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2024 (English)In: International Journal of Biological Macromolecules, ISSN 0141-8130, E-ISSN 1879-0003, Vol. 280, article id 135936Article in journal (Refereed) Published
Abstract [en]

Lignin is a complex biopolymer whose efficient extraction from biomass is crucial for various applications. Deep eutectic solvents (DES), particularly natural-origin DES (NADES), have emerged as promising systems for lignin fractionation and separation from other biomass components. While ternary DES offer enhanced fractionation performance, the role of each component in these mixtures remains unclear. In this study, the effects of adding tartaric acid (Tart) or citric acid (Cit) to a common binary DES mixture composed of lactic acid (Lact) and choline chloride (ChCl) were investigated for lignin extraction from acacia wood. Ternary Cit-based DES showed superior performance compared to Tart-based DES. Using a combined mixture-process D-Optimal experimental design, the Lact:Cit:ChCl DES composition and extraction temperature were optimized targeting maximum lignin yield and purity. The optimal conditions (i.e., Lact:Cit:ChCl, 0.6:0.3:0.1 molar ratio, 140 °C) resulted in a lignin extraction yield of 99.63 ± 1.24 % and a lignin purity of 91.45 ± 1.03 %. Furthermore, this DES exhibited feasible recyclability and reusability without sacrificing efficiency. 

Place, publisher, year, edition, pages
Elsevier BV, 2024
Keywords
Biomass fractionation, DES recovery and reuse, Design of experiments, Lignin extraction, Lignin purity, Ternary deep eutectic solvents
National Category
Organic Chemistry
Identifiers
urn:nbn:se:miun:diva-52751 (URN)10.1016/j.ijbiomac.2024.135936 (DOI)001331073100001 ()39322130 (PubMedID)2-s2.0-85205394809 (Scopus ID)
Available from: 2024-10-08 Created: 2024-10-08 Last updated: 2024-11-01
Ribau Teixeira, M., Ismail, A., Medronho, B., Alves, L., Pedrosa, J. F., Ferreira, P. J., . . . Rosa da Costa, A. M. (2024). Nanofibrillated cationic cellulose derivatives as flocculants for domestic wastewater treatment. Journal of Water Process Engineering, 58, Article ID 104817.
Open this publication in new window or tab >>Nanofibrillated cationic cellulose derivatives as flocculants for domestic wastewater treatment
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2024 (English)In: Journal of Water Process Engineering, E-ISSN 2214-7144, Vol. 58, article id 104817Article in journal (Refereed) Published
Abstract [en]

Natural-based coagulants have emerged as a reliable option to implement more sustainable operations and management of wastewater treatment plants. This work aims at evaluating the use of cationic nanofibrillated celluloses (cNFC) as novel bio-based flocculants to treat domestic wastewaters by the most widely employed treatment process – coagulation/flocculation. Two cNFC samples were prepared with different charge densities and tested as coagulant/flocculants using different water characteristics. The effect of cNFCs was studied by measuring the residual turbidity and dissolved organic carbon. The aggregation mechanism and kinetics of flocculation were also evaluated. Results show that cNFC can be used as an efficient flocculant to treat medium and high DOC waters since they considerably reduce turbidity (turbidity removals varied between 66.0 % and 85.7 % for the waters and cNFCs tested) without increasing dissolved organic carbon. Instead, cNFC removed dissolved organic carbon from domestic wastewaters (between 22.1 % and 65.5 % of DOC removals for the waters and cNFCs tested), which is a novel remarkable finding and a step forward in this knowledge area. High density charged cNFC revealed superior removal capacity at lower doses than the commercial coagulant FeCl3.

Place, publisher, year, edition, pages
Elsevier BV, 2024
Keywords
Cationic derivatives, Coagulation, Flocculation, Nanocelluloses, Organic matter
National Category
Water Treatment
Identifiers
urn:nbn:se:miun:diva-50356 (URN)10.1016/j.jwpe.2024.104817 (DOI)001168206800001 ()2-s2.0-85182870267 (Scopus ID)
Available from: 2024-01-31 Created: 2024-01-31 Last updated: 2024-03-08Bibliographically approved
Saoudi Hassani, E. M., Duarte, H., Brás, J., Taleb, A., Taleb, M., Rais, Z., . . . Medronho, B. (2024). On the Valorization of Olive Oil Pomace: A Sustainable Approach for Methylene Blue Removal from Aqueous Media. Polymers, 16(21), Article ID 3055.
Open this publication in new window or tab >>On the Valorization of Olive Oil Pomace: A Sustainable Approach for Methylene Blue Removal from Aqueous Media
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2024 (English)In: Polymers, E-ISSN 2073-4360, Vol. 16, no 21, article id 3055Article in journal (Refereed) Published
Abstract [en]

Currently, industrial water pollution represents a significant global challenge, with the potential to adversely impact human health and the integrity of ecosystems. The continuous increase in global consumption has resulted in an exponential rise in the use of dyes, which have become one of the major water pollutants, causing significant environmental impacts. In order to address these concerns, a number of wastewater treatment methods have been developed, with a particular focus on physicochemical approaches, such as adsorption. The objective of this study is to investigate the potential of a bio-based material derived from olive oil pomace (OOP) as an environmentally friendly bio-adsorbent for the removal of methylene blue (MB), a cationic dye commonly found in textile effluents. The biobased material was initially characterized by determining the point of zero charge (pHpzc) and using scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR). Subsequently, a comprehensive analysis was conducted, evaluating the impact of specific physicochemical parameters on MB adsorption, which included a thorough examination of the kinetic and thermodynamic aspects. The adsorption process was characterized using Langmuir, Freundlich, Brunauer-Emmett-Teller (BET), and Dubinin Radushkevich (D-R) isotherms. The results suggest that the equilibrium of adsorption is achieved within ca. 200 min, following pseudo-second-order kinetics. The optimal conditions, including adsorbent mass, temperature, bulk pH, and dye concentration, yielded a maximum adsorption capacity of ca. 93% (i.e., 428 mg g−1) for a pomace concentration of 450 mg L−1. The results suggest a monolayer adsorption process with preferential electrostatic interactions between the dye and the pomace adsorbent. This is supported by the application of Langmuir, BET, Freundlich, and D-R isotherm models. The thermodynamic analysis indicates that the adsorption process is spontaneous and exothermic. This work presents a sustainable solution for mitigating MB contamination in wastewater streams while simultaneously valorizing OOP, an agricultural by-product that presents risks to human health and the environment. In conclusion, this approach offers an innovative ecological alternative to synthetic adsorbents. 

Place, publisher, year, edition, pages
MDPI AG, 2024
Keywords
absorption kinetics, bio-based adsorbent, methylene blue, olive oil pomace, wastewater treatment
National Category
Physical Chemistry
Identifiers
urn:nbn:se:miun:diva-53110 (URN)10.3390/polym16213055 (DOI)001351810700001 ()2-s2.0-85208540483 (Scopus ID)
Available from: 2024-11-19 Created: 2024-11-19 Last updated: 2024-11-25
Melro, E., Duarte, H., Eivazi, A., Costa, C., Faleiro, M. L., da Costa, A. M., . . . Medronho, B. (2024). Poly(butylene succinate)-Based Composites with Technical and Extracted Lignins from Wood Residues. ACS Applied Polymer Materials, 6(2), 1169-1181
Open this publication in new window or tab >>Poly(butylene succinate)-Based Composites with Technical and Extracted Lignins from Wood Residues
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2024 (English)In: ACS Applied Polymer Materials, ISSN 2637-6105, Vol. 6, no 2, p. 1169-1181Article in journal (Refereed) Published
Abstract [en]

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. 1%), and high contact angle (>ca. 100°). 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. 

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2024
Keywords
bio-PBS, biocomposites, levulinic acid-based solvent, Poly(butylene succinate)-lignin composites, wood residues
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:miun:diva-50357 (URN)10.1021/acsapm.3c02103 (DOI)001152647100001 ()2-s2.0-85183040872 (Scopus ID)
Available from: 2024-01-31 Created: 2024-01-31 Last updated: 2024-02-09Bibliographically approved
Dahlström, C., Eivazi, A., Nejström, M., Zhang, R., Pettersson, T., Iftikhar, H., . . . Norgren, M. (2024). Regenerated cellulose properties tailored for optimized triboelectric output and the effect of counter-tribolayers. Cellulose, 31(4), 2047-2061
Open this publication in new window or tab >>Regenerated cellulose properties tailored for optimized triboelectric output and the effect of counter-tribolayers
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2024 (English)In: Cellulose, ISSN 0969-0239, E-ISSN 1572-882X, Vol. 31, no 4, p. 2047-2061Article in journal (Refereed) Published
Abstract [en]

Cellulose has shown great potential in the development of green triboelectric nanogenerators. Particularly, regenerated cellulose (R-cellulose) has shown remarkably high output power density but the structural features and key parameters that explain such superior performance remain unexplored. In this work, wood cellulose fibers were dissolved in a LiOH(aq)-based solvent to produce a series of R-cellulose films. Regeneration in different alcohols (from methanol to n-pentanol) was performed and the films’ structural features and triboelectric performance were assessed. Nonsolvents of increased hydrophobicity led to R-cellulose films with a more pronounced (1–10) diffraction peak. An open-circuit voltage (VOC) of up to ca. 260 V and a short-circuit current (ISC) of up to ca. 150 µA were measured for R-cellulose against polytetrafluoroethylene (as negative counter-layer). However, R-cellulose showed an increased VOC of 175% (from 88.1 V) against polydimethylsiloxane when increasing the alcohol hydrocarbon chain length from methanol to n-pentanol. The corresponding ISC and output power also increased by 76% (from 89.9 µA) and by 382% (from 8.8 W m–2), respectively. The higher R-cellulose hydrophilicity, combined with soft counter-tribolayer that follow the surface structures increasing the effective contact area, are the leading reasons for a superior triboelectric performance.

Place, publisher, year, edition, pages
Springer Nature, 2024
National Category
Materials Chemistry Polymer Chemistry
Identifiers
urn:nbn:se:miun:diva-50421 (URN)10.1007/s10570-024-05745-8 (DOI)001154303000002 ()2-s2.0-85184163338 (Scopus ID)
Available from: 2024-02-04 Created: 2024-02-04 Last updated: 2024-03-08Bibliographically approved
Dahlström, C., Duan, R., Eivazi, A., Magalhães, S., Alves, L., Engholm, M., . . . Norgren, M. (2024). Stacking self-gluing cellulose II films: A facile strategy for the formation of novel all-cellulose laminates. Carbohydrate Polymers, 344, Article ID 122523.
Open this publication in new window or tab >>Stacking self-gluing cellulose II films: A facile strategy for the formation of novel all-cellulose laminates
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2024 (English)In: Carbohydrate Polymers, ISSN 0144-8617, E-ISSN 1879-1344, Vol. 344, article id 122523Article in journal (Refereed) Published
Abstract [en]

Cellulose laminates represent a remarkable convergence of natural materials and modern engineering, offering a wide range of versatile applications in sustainable packaging, construction, and advanced materials. In this study, novel all-cellulose laminates are developed using an environmentally friendly approach, where freshly regenerated cellulose II films are stacked without the need for solvents (for impregnation and/or partial dissolution), chemical modifications, or resins. The structural and mechanical properties of these all-cellulose laminates were thoroughly investigated. This simple and scalable procedure results in transparent laminates with exceptional mechanical properties comparable to or even superior to common plastics, with E-modulus higher than 9 GPa for a single layer and 7 GPa for the laminates. These laminates are malleable and can be easily patterned. Depending on the number of layers, they can be thin and flexible (with just one layer) or thick and rigid (with three layers). Laminates were also doped with 10 wt% undissolved fibers without compromising their characteristics. These innovative all-cellulose laminates present a robust, eco-friendly alternative to traditional synthetic materials, thus bridging the gap between environmental responsibility and high-performance functionality. 

Place, publisher, year, edition, pages
Elsevier BV, 2024
Keywords
All-cellulose laminates, Dissolution, Fibers, LiOH/urea, Regeneration
National Category
Composite Science and Engineering
Identifiers
urn:nbn:se:miun:diva-52072 (URN)10.1016/j.carbpol.2024.122523 (DOI)001281080500001 ()2-s2.0-85199263320 (Scopus ID)
Available from: 2024-08-08 Created: 2024-08-08 Last updated: 2024-08-09
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