Advancements in Detection and Mitigation Strategies for Petroleum-Derived Contaminants in Aquatic Environments: A Comprehensive Review.

The 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.

The European Polysaccharide Network of Excellence (EPNOE) research roadmap 2040: Advanced strategies for exploiting the vast potential of polysaccharides as renewable bioresources.

Polysaccharides are among the most abundant bioresources on earth and consequently need to play a pivotal role when addressing existential scientific challenges like climate change and the shift from fossil-based to sustainable biobased materials. The Research Roadmap 2040 of the European Polysaccharide Network of Excellence (EPNOE) provides an expert's view on how future research and development strategies need to evolve to fully exploit the vast potential of polysaccharides as renewable bioresources. It is addressed to academic researchers, companies, as well as policymakers and covers five strategic areas that are of great importance in the context of polysaccharide related research: (I) Materials & Engineering, (II) Food & Nutrition, (III) Biomedical Applications, (IV) Chemistry, Biology & Physics, and (V) Skills & Education. Each section summarizes the state of research, identifies challenges that are currently faced, project achievements and developments that are expected in the upcoming 20 years, and finally provides outlines on how future research activities need to evolve.

On the Valorization of Arbutus unedo L. Pomace: Polyphenol Extraction and Development of Novel Functional Cookies.

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.

Eco-Friendly Methods for Extraction and Modification of Cellulose: An Overview.

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.

Engineering novel phenolic foams with lignin extracted from pine wood residues via a new levulinic-acid assisted process.

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.

Levulinic Acid-Based "Green" Solvents for Lignocellulose Fractionation: On the Superior Extraction Yield and Selectivity toward Lignin.

The high potential use of lignin in novel biomaterials and chemicals represents an important opportunity for the valorization of the most abundant natural resource of aromatic molecules. From an environmental perspective, it is highly desirable replacing the hazardous methods currently used to extract lignin from lignocellulosic biomass and develop more sustainable and environmentally friendly approaches. Therefore, in this work, levulinic acid (a "green" solvent obtained from biomass) was successfully used, for the first time, to selectively extract high-quality lignin from pine wood sawdust residues at 200 °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 reduce the temperature and reaction times needed (i.e., 140 °C, 2 h) for complete lignin extraction without compromising its purity. NMR data suggests that condensed OH structures and acidic groups are present in the lignin following extraction. Levulinic acid can be easily recycled and efficiently reused several times without affecting its performance. Furthermore, excellent solvent reusability and performance of extraction of other wood residues has been successfully demonstrated, thus making the developed levulinic acid-based procedure highly appealing and promising to replace the traditional less sustainable methodologies.

Perspectives on the Lindman Hypothesis and Cellulose Interactions.

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.

On Hair Care Physicochemistry: From Structure and Degradation to Novel Biobased Conditioning Agents.

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.

Ultrasound-Assisted Extraction of Polyphenols from Maritime Pine Residues with Deep Eutectic Solvents.

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.

Acacia Wood Fractionation Using Deep Eutectic Solvents: Extraction, Recovery, and Characterization of the Different Fractions.

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, ChCl:LA in a ratio of 1:3, was found to not significantly depolymerize the extracted lignin, which presented a similar molecular weight to a kraft lignin. Additionally, the 31P 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.

Extraction and Characterization of Microplastics from Portuguese Industrial Effluents.

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.

On the Development of Phenol-Formaldehyde Resins Using a New Type of Lignin Extracted from Pine Wood with a Levulinic-Acid Based Solvent.

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.

On the formation and stability of cellulose-based emulsions in alkaline systems: Effect of the solvent quality.

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).

Lignin enhances cellulose dissolution in cold alkali.

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.

Lignin Extraction from Waste Pine Sawdust Using a Biomass Derived Binary Solvent System.

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.

Enhancing Lignin Dissolution and Extraction: The Effect of Surfactants.

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 octyltrimethylammonium 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.

On the Development of All-Cellulose Capsules by Vesicle-Templated Layer-by-Layer Assembly.

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 carboxymethylcellulose (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.

Hydrophobic interactions control the self-assembly of DNA and cellulose.

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.

New deep eutectic solvent assisted extraction of highly pure lignin from maritime pine sawdust (Pinus pinaster Ait.).

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.

Cellulose-stabilized oil-in-water emulsions: Structural features, microrheology, and stability.

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.