Mid Sweden University

The gelation of cellulose in alkali solutions is quite relevant, but still a poorly understood process. Moreover, the role of certain additives, such as urea, is not consensual among the community. Therefore, in this work, an unusual set of characterization methods for cellulose solutions, such as cryo-transmission electronic microscopy (cryo-TEM), polarization transfer solid-state nuclear magnetic resonance (PTssNMR) and diffusion wave spectroscopy (DWS) were employed to study the role of urea on the dissolution and gelation processes of cellulose in aqueous alkali. Cryo-TEM reveals that the addition of urea generally reduces the presence of undissolved cellulose fibrils in solution. These results are consistent with PTssNMR data, which show the reduction and in some cases the absence of crystalline portions of cellulose in solution, suggesting a pronounced positive effect of the urea on the dissolution efficiency of cellulose. Both conventional mechanical macrorheology and microrheology (DWS) indicate a significant delay of gelation induced by urea, being absent until ca. 60 degrees C for a system containing 5wt % cellulose, while a system without urea gels at a lower temperature. For higher cellulose concentrations, the samples containing urea form gels even at room temperature. It is argued that since urea facilitates cellulose dissolution, the high entanglement of the cellulose chains in solution (above the critical concentration, C*) results in a strong three-dimensional network.

Cellulose can be dissolved in concentrated acidic aqueous solvents forming extremely viscous solutions, and, in some cases, liquid crystalline phases. In this work, the concentrated phosphoric acid aqueous solvent is revisited implementing a set of advanced techniques, such as cryo-transmission electronic microscopy (cryo-TEM), polarization transfer solid-state nuclear magnetic resonance (PTssNMR), and diffusing wave spectroscopy (DWS). Cryo-TEM images confirm that this solvent system is capable to efficiently dissolve cellulose. No cellulose particles, fibrils, or aggregates are visible. Conversely, PTssNMR revealed a dominant CP signal at 25 °C, characteristic of C-H bond reorientation with correlation time longer than 100 ns and/or order parameter above 0.5, which was ascribed to a transient gel-like network or an anisotropic liquid crystalline phase. Increasing the temperature leads to a gradual transition from CP to INEPT-dominant signal and a loss of birefringence in optical microscopy, suggesting an anisotropic-to-isotropic phase transition. Finally, an excellent agreement between optical microrheology and conventional mechanical rheometry was also obtained. 

Gas chromatography (GC) and mass spectrometry (MS) are widely used techniques in the analysis of complex mixtures due to their various advantages, such as high selectivity, reproducibility, precision, and sensitivity. However, the data processing is often complex and time-consuming and requires a great deal of experience, which might be a serious drawback in certain areas, such as quality control, or regarding research in the field of medicine or forensic sciences, where time plays a crucial role. For these reasons, some authors have proposed the use of alternative data processing approaches, such as the total ion chromatogram or total mass spectrum, allowing these techniques to be treated as sensors where each retention time or ratio m/z acts as a sensor collecting total intensities. In this way, the main advantages associated with both techniques are maintained, but the outcomes from the analysis can be reached in a faster, simpler, and an almost automated way. In this review, the main features of the GC- and MS-based analysis methodologies and the ways in which to apply them are highlighted. Moreover, their implementation in different fields, such as agri-food, forensics, environmental sciences, or medicine is discussed, highlighting important advantages as well as limitations.

Aqueous sodium hydroxide solutions are extensively used as solvents for lignin in kraft pulping. These are also appealing systems for cellulose dissolution due to their inexpensiveness, ease to recycle and low toxicity. Cellulose dissolution occurs in a narrow concentration region and at low temperatures. Dissolution is often incomplete but additives, such as zinc oxide or urea, have been found to significantly improve cellulose dissolution. In this work, lignin was explored as a possible beneficial additive for cellulose dissolution. Lignin was found to improve cellulose dissolution in cold alkali, extending the NaOH concentration range to lower values. The regenerated cellulose material from the NaOH-lignin solvents was found to have a lower crystallinity and crystallite size than the samples prepared in the neat NaOH and NaOH-urea solvents. Beneficial lignin-cellulose interactions in solution state appear to be preserved under coagulation and regeneration, reducing the tendency of crystallization of cellulose. 

Emulsion stabilization by native cellulose has been mainly hampered because of its insolubility in water. Chemical modification is normally needed to obtain water-soluble cellulose derivatives. These modified celluloses have been widely used for a range of applications by the food, cosmetic, pharmaceutic, paint and construction industries. In most cases, the modified celluloses are used as rheology modifiers (thickeners) or as emulsifying agents. In the last decade, the structural features of cellulose have been revisited, with particular focus on its structural anisotropy (amphiphilicity) and the molecular interactions leading to its resistance to dissolution. The amphiphilic behavior of native cellulose is evidenced by its capacity to adsorb at the interface between oil and aqueous solvent solutions, thus being capable of stabilizing emulsions. In this overview, the fundamentals of emulsion formation and stabilization by biomolecules are briefly revisited before different aspects around the emerging role of cellulose as emulsion stabilizer are addressed in detail. Particular focus is given to systems stabilized by native cellulose, either molecularly-dissolved or not (Pickering-like effect). 

With amphiphilic properties, cellulose molecules are expected to adsorb at the O/W interface and be capable of stabilizing emulsions. The effect of solvent quality on the formation and stability of cellulose-based O/W emulsions was evaluated in different alkaline systems: NaOH, NaOH-urea and tetrabutylammonium hydroxide (TBAH). The optimal solvency conditions for cellulose adsorption at the O/W interface were found for the alkaline solvent with an intermediate polarity (NaOH-urea), which is in line with the favorable conditions for adsorption of an amphiphilic polymer. A very good solvency (in TBAH) and the interfacial activity of the cation lead to lack of stability because of low cellulose adsorption. However, to achieve long-term stability and prevent oil separation in NaOH-urea systems, further reduction in cellulose's solvency was needed, which was achieved by a change in the pH of the emulsions, inducing the regeneration of cellulose at the surface of the oil droplets (in-situ regeneration).

Cellulose-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. 

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. 

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.

Cellulose has shown great potential in the development of green triboelectric nanogenerators (TENG) [1]. 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 higher hydrophilic character; the films showed a (1- 10) diffraction peak of larger amplitude and higher apparent crystallinity. 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 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-layer that follow the surface structures increasing the effective contact area, are the leading reasons for a superior triboelectric performance.

[1] Zhang, R., Dahlström, C., Zou, H., Jonzon, J., Hummelgård, M., Örtegren, J., Blomquist, N., Yang, Y., Andersson, H., Olsen, M., Norgren, M., Olin, H. & Wang, Z.L. Adv. Mater. 32, 2002824, 2020; https://doi.org/10.1002/adma.202002824

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 phytochemicals from grapevine shoots. Three levulinic acid-based DESs were tested for the first time, and their performance 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 (proanthocyanins, 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 polyphenols. 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.

The fruits of Arbutus unedo L. have a crimson colour and are enriched with remarkable concentrations of bioactive compounds such as anthocyanins and polyphenols. These fruits are commonly used in the production of a Portuguese Protected Geographical Indication distillate called “Aguardente de Medronho”. During this process, a solid pomace is generated and presently discarded without valuable applications. In this work, two strategies have been developed for the valorisation of A. unedo pomace. The first approach considers the extraction of polyphenols from this by-product through the optimization of an ultrasound-assisted method using a Box-Behnken design coupled with response surface methodology. The results indicate that the temperature and the percentage of methanol, along with their interaction, significantly influence the total concentration of polyphenols and the antioxidant activity of the extracts obtained. The optimal conditions identified consider the extraction of 0.5 g of sample with 20 mL of a solvent containing 74% MeOH (aq), at a pH of 4.8, maintained at 70 °C for 15 min. On the other hand, the second valorisation strategy considered the use of A. unedo pomace in the development of functional cookies. The incorporation of 15–20% pomace in the cookie formulation was well-received by consumers. This incorporation results in an intake of ca. 6.55 mg of polyphenols per gram of cookie consumed, accompanied by an antioxidant activity of 4.54 mg Trolox equivalents per gram of cookie consumed. Overall, these results encourage the employment of A. unedo pomace either as a reliable source of extracts enriched in polyphenols or as a nutraceutical active ingredient in functional cookies, thereby positively impacting human health. 

Abstract: In the present investigation, the optimization of a pressurized solid–liquid extraction of polyphenols from Pinus pinaster Aiton needles and bark residues has been carried out using new deep eutectic solvent systems (DES). A Box–Behnken design with response surface methodology was implemented, with six variables, including solid:liquid ratio, water content, temperature, extraction time, reactor closure state, and catalyst concentration. The DES consisting of levulinic acid: formic acid exhibited the highest content, and the optimal conditions were determined to be 0.10 g of residue in 10 mL of solvent (without water) and without catalyst, at 60 °C for 5 min. The method demonstrated excellent repeatability and intermediate precision, with a coefficient of variation of less than 5%. In addition, the antimicrobial and antioxidant activities of the polyphenol-enriched extracts were evaluated, obtaining a total reduction in S. aureus cell growth and remarkable antioxidant levels of 144.72 ± 4.24 and 161.01 ± 4.70 mg Trolox equivalents/gram for needle and bark residues, respectively. Under the optimized conditions, the new DES are remarkably superior to conventional solvents and can be recycled and reused, demonstrating that these systems have a promising environmental profile, making them valuable alternatives for biomass fractionation. 

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 polyphenol-enriched extracts from forest residues that are commonly discarded without any clear application, thus opening an important window toward the valorization of such residues. 

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. 

Polymeric multilayer capsules formed by the layer-by-layer (LbL) technique are interesting candidates for the purposes of storage, encapsulation, and release of drugs and biomolecules for pharmaceutical and biomedical applications. In the current study, cellulose-based core-shell particles were developed via the LbL technique alternating two cellulose derivatives, anionic carboxymethyl-cellulose (CMC), and cationic quaternized hydroxyethylcellulose ethoxylate (QHECE), onto a cationic vesicular template made of didodecyldimethylammonium bromide (DDAB). The obtained capsules were characterized by dynamic light scattering (DLS), ζ potential measurements, and high-resolution scanning electron microscopy (HR-SEM). DLS measurements reveal that the size of the particles can be tuned from a hundred nanometers with a low polydispersity index (deposition of 2 layers) up to micrometer scale (deposition of 6 layers). Upon the deposition of each cellulose derivative, the particle charge is reversed, and pH is observed to considerably affect the process thus demonstrating the electrostatic driving force for LbL deposition. The HR-SEM characterization suggests that the shape of the core-shell particles formed is reminiscent of the spherical vesicle template. The development of biobased nano-and micro-containers by the alternating deposition of oppositely charged cellulose derivatives onto a vesicle template offers several advantages, such as simplicity, reproducibility, biocompatibility, low-cost, mild reaction conditions, and high controllability over particle size and composition of the shell. 

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. 

Hair is constantly exposed to various adverse external stimuli, such as mechanical or thermal factors, that may cause damage or cause it to lose its shine and smooth appearance. These undesirable effects can be minimized by using hair conditioners, which repair the hair and restore the smooth effect desired by the consumer. Some of the currently used conditioning agents present low biodegradability and high toxicity to aquatic organisms. Consumers are also becoming more aware of environmental issues and shifting their preferences toward natural-based products. Therefore, developing novel, sustainable, natural-based derivatives that can act as conditioning agents in hair care products and thus compete with the traditional systems obtained from non-renewable sources is highly appealing. This paper presents the key physicochemical aspects of the hair conditioning process, including hair structure and degradation, and reviews some of the new alternative conditioning agents obtained from natural resources. 

Lignocellulosic biomass is a renewable and sustainable feedstock, mainly composed of cellulose, hemicellulose, and lignin. Lignin, as the most abundant natural aromatic polymer occurring on Earth, has great potential to produce value-added products. However, the isolation of highly pure lignin from biomass requires the use of efficient methods during lignocellulose fractionation. Therefore, in this work, novel acidic deep eutectic solvents (DESs) were prepared, characterized and screened for lignin extraction from maritime pine wood (Pinus pinaster Ait.) sawdust. The use of cosolvents and the development of new DES were also evaluated regarding their extraction and selectivity performance. The results show that an 1 h extraction process at 175 °C, using a novel DES composed of lactic acid, tartaric acid and choline chloride, named Lact:Tart:ChCl, in a molar ratio of 4:1:1, allows the recovery of 95 wt% of the total lignin present in pine biomass with a purity of 89 wt%. Such superior extraction of lignin with remarkable purity using a “green” solvent system makes this process highly appealing for future large-scale applications. 

In this study, the effect of different alcohols and esters as a coagulation medium in the regeneration of cellulose dissolved in an aqueous LiOH-urea-based solvent was thoroughly investigated using various methods such as solid state NMR, X-ray diffraction, water contact angle, oxygen gas permeability, mechanical testing, and scanning electron microscopy. It was observed that several material properties of the regenerated cellulose films follow trends that correlate to the degree of cellulose II crystallinity, which is determined to be set by the miscibility of the coagulant medium (nonsolvent) and the aqueous alkali cellulose solvent rather than the nonsolvents’ polarity. This article provides an insight, thus creating a possibility to carefully tune and control the cellulose material properties when tailor-made for different applications. 

Cellulose dissolution and regeneration are old topics that have recently gained renewed attention. This is reflected in both applications - earlier and novel - and in scientific controversies. There is a current discussion in the literature on the balance between hydrogen bonding and hydrophobic interactions in controlling the solution behavior of cellulose. Some of the key ideas are recalled.

Desoxyribosenucleic acid, DNA, and cellulose molecules self-assemble in aqueous systems. This aggregation is the basis of the important functions of these biological macromolecules. Both DNA and cellulose have significant polar and nonpolar parts and there is a delicate balance between hydrophilic and hydrophobic interactions. The hydrophilic interactions related to net charges have been thoroughly studied and are well understood. On the other hand, the detailed roles of hydrogen bonding and hydrophobic interactions have remained controversial. It is found that the contributions of hydrophobic interactions in driving important processes, like the double-helix formation of DNA and the aqueous dissolution of cellulose, are dominating whereas the net contribution from hydrogen bonding is small. In reviewing the roles of different interactions for DNA and cellulose it is useful to compare with the self-assembly features of surfactants, the simplest case of amphiphilic molecules. Pertinent information on the amphiphilic character of cellulose and DNA can be obtained from the association with surfactants, as well as on modifying the hydrophobic interactions by additives.

Recently, milk consumption has been declining and there is a high demand for non-dairy beverages. However, market offers are mainly cereal and nut-based beverages, which are essentially poor in protein (typically, less than 1.5% against the 3.5% in milk) and are not true milk replacers in that sense. In this work, new beverages from different pulses (i.e., pea, chickpea and lupin) were developed using technologies that enable the incorporation of a high level of seed components, with low or no discharge of by-products. Different processing steps were sequentially tested and discussed for the optimization of the sensorial features and stability of the beverage, considering the current commercial non-dairy beverages trends. The lupin beverage protein contents ranged from 1.8% to 2.4% (w/v) and the chickpea beverage varied between 1.0% and 1.5% (w/v). The “milk” yield obtained for the optimized procedure B was 1221 g/100 g of dry seed and 1247 g/100 g of dry seed, for chickpea beverage and lupin beverage, respectively. Sensory results show that chickpea beverage with cooking water has the best taste. All pulses-based beverages are typical non-Newtonian fluids, similarly to current non-dairy alternative beverages. In this respect, the sprouted chickpea beverage, without the cooking water, presents the most pronounced shear-thinning behavior of all formulations. 

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.

Microplastics (MPs) are contaminants present in the environment. The current study evaluates the contribution of different well-established industrial sectors in Portugal regarding their release of MPs and potential contamination of the aquifers. For each type of industry, samples were collected from wastewater treatment plants (WWTP), and different parameters were evaluated, such as the potential contamination sources, the concentration, and the composition of the MPs, in both the incoming and outcoming effluents. The procedures to extract and identify MPs in the streams entering or leaving the WWTPs were optimized. All industrial effluents analysed were found to contribute to the increase of MPs in the environment. However, the paint and pharmaceutical activities were the ones showing higher impact. Contrary to many reports, the textile industry contribution to aquifers contamination was not found to be particularly relevant. Its main impact is suggested to come from the numerous washing cycles that textiles suffer during their lifetime, which is expected to strongly contribute to a continuous release of MPs. The predominant chemical composition of the isolated MPs was found to be polyethylene terephthalate (PET). In 2020, the global need for PET was 27 million tons and by 2030, global PET demand is expected to be 42 million tons. Awareness campaigns are recommended to mitigate MPs release to the environment and its potential negative impact on ecosystems and biodiversity.

The 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.

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.

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. 

Cellulose is the most abundant renewable polymer on Earth and can be obtained from several different sources, such as trees, grass, or biomass residues. However, one of the issues is that not all the fractionation processes are eco-friendly and are essentially based on cooking the lignocellulose feedstock in a harsh chemical mixture, such as NaOH + Na2S, and water, to break loose fibers. In the last few years, new sustainable fractionation processes have been developed that enable the obtaining of cellulose fibers in a more eco-friendly way. As a raw material, cellulose’s use is widely known and established in many areas. Additionally, its products/derivatives are recognized to have a far better environmental impact than fossil-based materials. Examples are textiles and packaging, where forest-based fibers may contribute to renewable and biodegradable substitutes for common synthetic materials and plastics. In this review, some of the main structural characteristics and properties of cellulose, recent green extraction methods/strategies, chemical modification, and applications of cellulose derivatives are discussed. 

Lignocellulosic biomass fractionation is typically performed using methods that are somehow harsh to the environment, such as in the case of kraft pulping. In recent years, the development of new sustainable and environmentally friendly alternatives has grown significantly. Among the developed systems, bio-based solvents emerge as promising alternatives for biomass processing. Therefore, in the present work, the bio-based and renewable chemicals, levulinic acid (LA) and formic acid (FA), were combined to fractionate lignocellulosic waste (i.e., maritime pine sawdust) and isolate lignin. Different parameters, such as LA:FA ratio, temperature, and extraction time, were optimized to boost the yield and purity of extracted lignin. The LA:FA ratio was found to be crucial regarding the superior lignin extraction from the waste biomass. Moreover, the increase in temperature and extraction time enhances the amount of extracted residue but compromises the lignin purity and reduces its molecular weight. The electron microscopy images revealed that biomass samples suffer significant structural and morphological changes, which further suggests the suitability of the newly developed bio-fractionation process. The same was concluded by the FTIR analysis, in which no remaining lignin was detected in the cellulose-rich fraction. Overall, the novel combination of bio-sourced FA and LA has shown to be a very promising system for lignin extraction with high purity from biomass waste, thus contributing to extend the opportunities of lignin manipulation and valorization into novel added-value biomaterials. 

Plastics are widely used due to their excellent properties, inexpensiveness and versatility leading to an exponential consumption growth during the last decades. However, most plastic does not biodegrade in any meaningful sense; it can exist for hundreds of years. Only a small percentage of plastic waste is recycled, the rest being dumped in landfills, incinerated or simply not collected. Waste-water treatment plants can only minimize the problem by trapping plastic particles of larger size and some smaller ones remain within oxidation ponds or sewage sludge, but a large amount of microplastics still contaminate water streams and marine systems. Thus, it is clear that in order to tackle this potential ecological disaster, new strategies are necessary. This review aims at briefly introducing the microplastics threat and critically discusses emerging technologies, which are capable to efficiently clean aqueous media. Special focus is given to novel greener approaches based on lignocellulose flocculants and other biomaterials. In the final part of the present review, it was given a proof of concept, using a bioflocculant to remove micronized plastic from aqueous medium. The obtained results demonstrate the huge potential of these biopolymers to clean waters from the microplastics threat, using flocculants with appropriate structure.

Adhesives 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. 

Microplastics (MPs) awareness has been growing particularly after several alarming reports about “garbage patches” in the world. Plastics do not biodegrade in any meaningful way and, up to now, only a small percentage of plastic waste is recycled, being all the rest dumped in landfills, incinerated or simply not collected. The distribution of MPs within the water ecosystem depends on particle density and size and environmental characteristics, such as winds and currents. In the present study, different Portuguese industrial effluents were analysed and characterised to determine which MPs in the treated water released from wastewater treatment plants (WWTP), predominate and contribute the most to the environmental contamination of aquifers which, eventually, will end up in the coast of Continental Portugal. Overall, this work suggests strategies for MPs analysis in WWTP, thus allowing mapping of the different types of MPs prevalent in Portugal. The establishment of such database will enable the creation of reliable laboratory models to test new and green removal processes, based on the flocculation by, for instance, bio-based flocculants.

Bombyx mori L. silk fibroin (SF) is widely used in different areas due to its ability to form durable and resilient materials with notable mechanical properties. However, in some of these applications the dissolution of SF is required, and this is not often straightforward due to its inability to be dissolved in the majority of common solvents. This work reports a novel approach to dissolve SF using 40 wt % aqueous tetrabutylammonium hydroxide, TBAOH(aq), at mild temperature. A thorough rheological study combined with small-angle X-ray scattering is presented to correlate the SF state in solution with changes in the rheological parameters. The scattering data suggest that the SF conformation in TBAOH(aq) is close to a random coil, possibly having some compact domains linked with flexible random chains. The radius of gyration (Rg) and the molecular weight (Mw) were estimated to be ca. 17.5 nm and 450 kDa, respectively, which are in good agreement with previous works. Nevertheless, a lower Mw value was deduced from rheometry (i.e., 321 kDa) demonstrating a low degree of depolymerization during dissolution in comparison to other harsh processes. The transition from a dilute to a semidilute regime coincides with the estimated critical concentration and is marked by the presence of a shear-thinning behavior in the flow curves, violation of the empirical Cox-Merz rule, and an upward increase in the activation energy. This work paves the way toward the development of advanced high-tech SF-based materials. © 2019 American Chemical Society.

The molecular self-diffusion coefficients were accessed, for the first time, in solutions of microcrystalline cellulose, dissolved in 30 wt% and 55 wt% aqueous tetrabutylammonium hydroxide, TBAH (aq), and in mixtures of 40 wt% TBAH (aq) with an organic co-solvent, dimethylsulfoxide (DMSO), through pulsed field gradient stimulated echo NMR measurements. A two-state model was applied to estimate α (i.e., average number of ions that “bind” to each anhydroglucose unit) and Pb (i.e., fraction of “bound” molecules of DMSO, TBAH or H2O to cellulose) parameters. The α values suggest that TBA+ ions can bind to cellulose within 0.5 TBA+ to 2.3 TBA+/AGU. On the other hand, the Pb parameter increases when raising cellulose concentration for TBA+, DMSO and water in all solvent systems. Data suggests that TBAH interacts with the ionized OH groups from cellulose forming a sheath of bulky TBA+ counterions which consequently leads to steric hindrance between cellulose chains. 

Resole resins have many applications, especially for foam production. However, the use of phenol, a key ingredient in resoles, has serious environmental and economic disadvantages. In this work, lignin extracted from pine wood using a “green” solvent, levulinic acid, was used to partially replace the non-sustainable phenol. The physicochemical properties of this novel resin were compared with resins composed of different types of commercial lignins. All resins were optimized to keep their free formaldehyde content below 1 wt%, by carefully adjusting the pH of the mixture. Substitution of phenol with lignin generally increases the viscosity of the resins, which is further increased with the lignin mass fraction. The addition of lignin decreases the kinetics of gelification of the resin. The type and amount of lignin also affect the thermal stability of the resins. It was possible to obtain resins with higher thermal stability than the standard phenol-formaldehyde resins without lignin. This work provides new insights regarding the development of lignin-based resoles as a very promising sustainable alternative to petrol-based resins. 

Phenolic foams are typically produced from phenolic resins, using phenol and formaldehyde precursors. Therefore, common phenolic foams are non-sustainable, comprising growing environmental, health, and economic concerns. In this work, lignin extracted from pine wood residues using a “green” levulinic acid-based solvent, was used to partially substitute non-sustainable phenol. The novel engineered foams were systematically compared to foams composed of different types of commercially available technical lignins. Different features were analyzed, such as foam density, microstructure (electron microscopy), surface hydrophilicity (contact angle), chemical grafting (infrared spectroscopy) and mechanical and thermal features. Overall, it was observed that up to 30 wt% of phenol can be substituted by the new type of lignin, without compromising the foam properties. This work provides a new insights on the development of novel lignin-based foams as a very promising sustainable and renewable alternative to petrol-based counterparts. 

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. 

Lignin is a complex organic polymer found in the plant cell wall with important biological functions, such as water transport, mechanical support, and resistance to various stresses. It is considered the second most abundant biopolymer on earth and the largest natural source of aromatics. Despite being annually co-produced in massive amounts, during cellulose fragmentation in the pulp industry and ethanol biorefinery, it is clearly undervalued; most of it is discarded or burned as fuel for energy production and, so far, only ca. 1-2% of lignin has been utilized as a high-value product. This underuse makes lignin the future resource of choice to produce green fuels and a wide range of added-value biomaterials and chemicals, which can contribute to the transition to more sustainable industries. However, its great variability between plant families combined with its complex and chemically inert structure is challenging researchers who seek for strategies regarding its valorization. With this scope, several different approaches have emerged regarding the development of better and efficient isolation methods, purification and characterization techniques, and improved methodologies for lignin chemical modification and blending with other compounds. These improvements represent important opportunities for the creation of value-added lignin-based biopolymers and materials and some have already shown potential to be scaled up. All these aspects are pedagogically introduced and discussed in this review.

Lignins are among the most abundant renewable resources on the planet. However, their application is limited by the lack of efficient dissolution and extraction methodologies. In this work, a systematic and quantitative analysis of the dissolution efficiency of different alkaline-based aqueous systems (i.e. lithium hydroxide, LiOH; sodium hydroxide, NaOH; potassium hydroxide, KOH; cuprammonium hydroxide, CuAOH; tetrapropylammonium hydroxide, TPAOH and tetrabutylammonium hydroxide, TBAOH) is reported, for the first time, for kraft lignin. Phase maps were determined for all systems and lignin solubility was found to decrease in the following order: LiOH &gt; NaOH &gt; KOH &gt; CuAOH &gt; TPAOH &gt; TBAOH, thus suggesting that the size of the cation plays an important role on its solubility. The π∗ parameter has an opposite trend to the solubility, supporting the idea that cations of smaller size favor lignin solubility. Dissolution was observed to increase exponentially above pH 9–10 being the LiOH system the most efficient. The soluble and insoluble fractions of lignin in 0.1 M NaOH were collected and analyzed by several techniques. Overall, data suggests a greater amount of simple aromatic compounds, preferentially containing sulfur, in the soluble fraction while the insoluble fraction is very similar to the native kraft lignin.

Lignin is a natural, renewable resource with potential to be used in biomaterials. Due to its complex structure, its efficient dissolution is still challenging, which hinders its applicability at large scale. This challenge become harder considering the current need of sustainable and environmentally friendly solvents. To the best of our knowledge, this work reports for the first time the dissolution of kraft lignin in levulinic acid, a “green” solvent, and compares its efficiency with common carboxylic acids and sulfuric acid. It has been found that levulinic acid has a high capacity to dissolve kraft lignin at room temperature (40 wt% solubility), and it efficiency is not compromised when diluting the acid with water (up to 40 wt% water content). The Kamlet-Taft π⁎ parameter of the different acidic solvents was estimated and found to correlate well with their solubility performance. Lignins previously dissolved in levulinic and formic acids were selected to be regenerated and minor differences were found in thermal stability and morphological structure, when compared to native kraft lignin. However, an increase in the content of the carbonyl groups in the regenerated lignin material was observed. 

The high potential use of lignin in novel biomaterialsand chemicalsrepresents an important opportunity for the valorization of the mostabundant natural resource of aromatic molecules. From an environmentalperspective, it is highly desirable replacing the hazardous methodscurrently used to extract lignin from lignocellulosic biomass anddevelop more sustainable and environmentally friendly approaches.Therefore, in this work, levulinic acid (a "green" solventobtained from biomass) was successfully used, for the first time,to selectively extract high-quality lignin from pine wood sawdustresidues at 200 degrees C for 6 h (at atmospheric pressure). Moreover,the addition of catalytic concentrations of inorganic acids (i.e.,H2SO4 or HCl) was found to substantially reducethe temperature and reaction times needed (i.e., 140 degrees C, 2 h)for complete lignin extraction without compromising its purity. NMRdata suggests that condensed OH structures and acidic groups are presentin the lignin following extraction. Levulinic acid can be easily recycledand efficiently reused several times without affecting its performance.Furthermore, excellent solvent reusability and performance of extractionof other wood residues has been successfully demonstrated, thus makingthe developed levulinic acid-based procedure highly appealing andpromising to replace the traditional less sustainable methodologies.

The dissolution and extraction of lignin from biomass represents a great challenge due to the complex structure of this natural phenolic biopolymer. In this work, several surfactants (i.e., non-ionic, anionic, and cationic) were used as additives to enhance the dissolution efficiency of model lignin (kraft) and to boost lignin extraction from pine sawdust residues. To the best of our knowledge, cationic surfactants have never been systematically used for lignin dissolution. It was found that ca. 20 wt.% of kraft lignin is completely solubilized using 1 mol L−1 octyltrimethylammo-nium bromide aqueous solution. A remarkable dissolution efficiency was also obtained using 0.5 mol L−1 polysorbate 20. Furthermore, all surfactants used increased the lignin extraction with formic acid, even at low concentrations, such as 0.01 and 0.1 mol L−1. Higher concentrations of cationic surfactants improve the extraction yield but the purity of extracted lignin decreases. 

In the history of cellulose chemistry, hydrogen bonding has been the predominant explanation when discussing intermolecular interactions between cellulose polymers. This is the general consensus in scholarly textbooks and in many research articles, and it applies to several other biomacromolecules’ interactions as well. This rather unbalanced description of cellulose has likely impacted the development of materials based on the processing of cellulose—for example, via dissolution in various solvent systems and regeneration into solid materials, such as films and fibers, and even traditional wood fiber handling and papermaking. In this review, we take as a starting point the questioning of the general description of the nature of cellulose and cellulose interactions initiated by Professor Björn Lindman, based on generic physicochemical reasoning about surfactants and polymers. This dispute, which became known as “the Lindman hypothesis”, highlights the importance of hydrophobic interactions in cellulose systems and that cellulose is an amphiphilic polymer. This paper elaborates on Björn Lindman’s contribution to the subject, which has caused the scientific community to revisit cellulose and reconsider certain phenomena from other perspectives. 

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.

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.