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β-sitosterol (BS) is a phytosterol with wide potential in cosmeceutical, biomedical and food applications. In acid sulphite pulp cooking, BS and its derivatives are considered an underutilized natural source of bioactive compounds, which are adsorbed on the resulting pulp or dispersed in the spent liquor. In this work, a new method for the isolation of BS from alkaline extract (AE) of unbleached sulphite pulp purification stage is proposed. BS was recovered by two-step acidification of AE up to pH 3 under pre-selected conditions, followed by fractionation of the formed precipitate with water-miscible organic solvents, having obtained best results (>90% of BS purity; yield of 70-210 mg/dm3 of AE) with methanol fractionation followed by BS crystallization induced via addition of water (ca. 10% vol.). When ethanol was used instead, BS was detected in low amounts in the isolate, being fatty acid sterol esters and fatty acid glycerides the major components, as revealed from analyses by wet chemistry coupled with gas chromatography-mass spectrometry and thin layer chromatography (TLC). The method is adaptable for large-scale industrial production of BS and may represent an important source of sterol-based products. published

Competition issues with food industry have recently boosted the exploration of alternative solutions capable of replacing starch in papermaking to a certain extent. Covalent grafting of quaternary ammonium groups onto LignoBoost® Eucalyptus kraft lignin has recently shown promise in this regard as the cationic products feature excellent water solubility across the entire pH scale. Considering these suitable properties, cationic kraft lignin was applied and evaluated, for the first time, in the perspective of partial substitution of cationic starch in papermaking, using bleached Eucalyptus kraft pulp. Based on an assessment of key paper properties, such as mechanical (tensile, bursting, and tearing indexes), structural (roughness, capillarity rise, air resistance, internal strength, and water contact angle), and optical ones (brightness, opacity, and relative color change), it is safe to conclude that the partial replacement of conventional cationic starch by cationic lignin does not compromise these features. The results also show that properties can be fine-tuned by varying the degree of lignin derivatization, providing paper-specific solutions for replacing starch by lignin potentially available at large-scale at the pulp and paper industry, closing the loop within the circular economy concept.

Reactive washing (RW) is a key process for disinfecting, purifying, and bleaching of cork stoppers to seal bottles with alcoholic beverages. Excessively severe treatment conditions deteriorate the surface properties of cork stoppers and must be strictly controlled. In this study, the conventional RW of natural cork stoppers was optimized employing a fractional factorial design. The RW variables (H

Publisher Copyright: © 2021 The Authors. Published by American Chemical Society. Although extractives have been symbolized as major bioactive pharmacological compounds from Salix (Salicaceae) bark, we speculated that these pharmaceutical effects cannot be solely attributed to phenolic components and their derivatives, but the long-chain suberin acids also contribute to their therapeutic effects. Hence, isolation and deconstruction of suberin were conducted, for the first time, to enrich our knowledge about the macromolecular components at the cell wall of willow bark. Saponification was adopted to obtain suberin extracts at a yield of approximately 5 wt % based on the bark of the studied hybrids. Gas chromatography-mass spectrometry allowed qualification and quantification of 23 compounds from the released suberin monomers, from which fatty acids represented majority of the isolated suberin, namely, fatty acid methyl esters (C17-C19); mono-carboxylic acid (C7-C16); alpha, omega-dicarboxylic acid (C7-C16); and omega-hydroxy long-chain fatty acids (C16-C22). Additionally, the lipophilic extractive was dominated by piceol, heptacosane, β-sitosterol, and fatty acids (C16-C28) from the studied hybrids. These findings could boost our integrative approach toward full valorization of willow bark.

Aiming the sustainability of 3D-printed objects, in this study, pine bark particles were used as filler reinforcement for polyamide 6 (PA). In order to enhance the performance of the produced composites, the biomass was chemically modified via a two-step procedure. In the first step, the OH groups present on the particles surface were reacted with ethylenediamine, which were subsequently reacted with a polyol. Fourier-transform infrared spectroscopy (FTIR), 13C solid-state cross polarization–magic angle spinning nuclear magnetic resonance (13C CPMAS NMR) and scanning electron microscopy coupled with energy-dispersive X-ray analysis confirmed the chemical modification of biomass. The masterbatch was prepared from modified pine bark particles and polymeric matrix (PA) being processed into test specimens. The ensuing composites revealed a significant increase in Young's modulus and maximum stress. Thus, the introduction of 10% modified biomass increases the Young's modulus by 87% and the maximum stress by 15%. Furthermore, analyzing the glass transition temperature (Tg), melting flow index and thermogravimetric analysis results, the modified biomass ensuing composites proved to be suitable for 3D printing. This was attributed to better compatibility between chemically modified biomass and matrix and, further, easier processing.

Laser-induced graphene (LIG) is a foam-like porous material consisting of few-layer graphene obtained by laser irradiation of a wide range of carbon-containing substrates. Among these, the ability to synthesize LIG from paper and other cellulose-related materials is particularly exciting, as it opens the door to a wide assortment of potential applications in the form of low-cost, flexible, and biodegradable devices. Here, the synthesis of this material, dubbed paper-LIG, on different types of filter papers and xylan biopolymer is discussed. In particular, we report the formation of paper-LIG by single-step irradiation, providing an improvement over the conventional multiple lasing approach and giving an explanation of the conditions that allow this simplified synthesis. All the relevant process parameters are covered, assessing their effect on the resulting electrical properties, structure, and morphology. Additionally, we demonstrate the application of LIG obtained from xylan, an abundant and often underutilized biopolymer, for temperature sensing. These results provide a better understanding of the conditions required for the synthesis of highly conductive LIG from paper and related materials, paving the way for its application, with reduced cost and low environmental impact, in fields ranging from biomonitoring to consumer electronics. published

The accessibility of glucuronoxylan from a refined, bleached Eucalyptus globulus industrial kraft pulp in 0–18% aqueous NaOH solution at room temperature (25°C) was studied. The extraction profile revealed a maximum extraction of xylan in the pulp at about 10–12% NaOH concentration and was explained by the maximum swelling of the pulp according to the Gibbs-Donnan equilibrium. The kinetics of xylan removal and the monitoring of its structural features were performed at 5 and 10% NaOH concentrations. The maximum yields of xylans with 10% and 5% NaOH were as high as 90% and 60% for 2 h extraction, respectively. The structural features of xylan were assessed by acid methanolysis and one-dimensional (1D)/two-dimensional (2D) nuclear magnetic resonance (NMR), and the molecular weight by size exclusion chromatography (SEC). The xylan extracted with 10% NaOH had a slightly higher molecular weight and a lower branching with uronic moieties than the xylan extracted with 5% NaOH. The former was less pure (contained more β-cellulose) than the latter. Structural studies by NMR resulted in the conclusion that there are at least two types of xylans removed from the pulp: one xylan with relatively high 4-O-methyl-α-D-glucuronosyl [MeGlcA-(1→] and [→2)-MeGlcA-(1→] substituents and another xylan with a much lower substitution with uronic residues.

The re-profiling from paper-grade to dissolving pulp production is a common trend for acid sulfite cooking of wood. This provides substantial changes in the composition of the spent sulfite liquor (SSL) affecting its potentialities in subsequent processing within the biorefinery concept. In this work, a comparative analysis of the chemical composition of SSL was performed from the magnesium-based acid sulfite cooking of Eucalyptus globulus wood to produce the paper-grade and dissolving pulps. More severe pulping conditions required for dissolving pulp production led to a substantial increase in volatile compounds in SSL, such as acetic acid, methanol, and furfural. At the same time, the amounts of dissolved sugars and lignosulfonates (LS) were increased to a less extent. The main changes detected in LS were related to the increase of its molecular weight, degree of condensation, and sulfonation degree. The increased concentration of the sulfuric acid in SSL was one of the reasons for these change published

In this study, the sulphur oxide anions profile at all stages of the Mg acid sulphite pulping process was evaluated by Ion Chromatography (IC). The concentration of bisulphite anions decreased almost two-third along the cooking, while the sulphate concentration increased progressively. Of the bisulphite consumed, only a third was converted to sulfates. Unexpectedly, the maximum thiosulphate concentration was found in the pulping acid filling step, being further decreased along the cooking. The chloride ions rise progressively during the cooking being extracted essentially from the wood, although a noticeable part of the phosphate anions belongs to pulping reagents and inlet water. The low molecular weight fraction of lignosulphonates (LS) appeared in the cooking liquor in the residual delignification step and, together with xylonic acid, contributed to an overestimation of the fluoride concentration determined by the IC due to the same retention time in the chromatographic column during the analysis.

The increasing demand for cellulosic fibres is continuously driven by the growing earth population and requirements of the textile industry. The annual cotton production of ca. 25 million tons is no longer enough to meet the market demands. This market gap of cellulosic fibres is progressively filled by regenerated cellulosic fibres derived from the dissolving pulp. The conventional industrial process of viscose production is far from being environmentally friendly due to the use of hazardous reagents. Alternatively, new trends in the production of regenerated fibres are related to the direct dissolution of cellulose in appropriate environmentally sound recyclable solvents, allowing high quality rayon fibres. This article reviews the sources of dissolving pulps used for the production of viscose and its quality parameters related to the performance of viscose production. The prospective cellulose regeneration processes, both commercialized and under development, are reviewed regarding current and future developments in the area.

The feasibility of using lignosulfonate (LS) from acid sulphite pulping of eucalyptus wood as an unmodified polyol in the formulation of polyurethane (PU) adhesives was evaluated. Purified LS was dissolved in water to simulate its concentration in sulphite spent liquor and then reacted with 4,4′-diphenylmethane diisocyanate (pMDI) in the presence or absence of poly(ethylene glycol) with Mw 200 (PEG200) as soft crosslinking segment. The ensuing LS-based PU adhesives were characterized by infrared spectroscopy and thermal analysis techniques. The adhesion strength of new adhesives was assessed using Automated Bonding Evaluation System (ABES) employing wood strips as a testing material. The results showed that the addition of PEG200 contributed positively both to the homogenization of the reaction mixture and better crosslinking of the polymeric network, as well as to the interface interactions and adhesive strength. The latter was comparable to the adhesive strength recorded for a commercial white glue with shear stress values of almost 3 MPa. The optimized LS-based PU adhesive formulation was examined for the curing kinetics following the Kissinger and the Ozawa methods by non-isothermal differential scanning calorimetry, which revealed the curing activation energy of about 70 kJ·mol−1.

The production of regenerated cellulosic fibres, such as viscose, modal and lyocell, is based mainly on the use of dissolving wood pulp as raw material. Enzymatic processes are an excellent alternative to conventional chemical routes in the production of dissolving pulp, in terms of energy efficiency, reagent consumption and pulp yield. The two main characteristics of a dissolving pulp are the cellulose purity and the molecular weight, both of which can be controlled with the aid of enzymes. A purification process for paper-grade kraft pulp has been proposed, based on the use of xylanases in combination with hot and cold caustic extraction, without the conventional pre-hydrolysis step before kraft pulping. This enzyme aided purification allowed the production of a dissolving pulp that met the specifications for the manufacture of viscose, < 3% xylan, > 92% ISO brightness and 70% Fock’s reactivity. Endoglucanases (EGs) can efficiently reduce the average molecular weight of the cellulose while simultaneously increasing the pulp reactivity for viscose production. It is shown in this study that lytic polysaccharide monooxygenases act synergistically with EGs in the modification of bleached dissolving pulp.

This work studies the extraction and purification of a novel arabinogalactan from pistachio external hull. It was extracted with a simple method from pistachio hull which is considered as unexploited waste. Based on the results of sugar analysis by GC-FID, glycosidic linkage by GC–MS, NMR spectroscopy, and molecular weight by Size Exclusion Chromatography, pistachio hull water soluble polysaccharides (PHWSP) were identified as a type II arabinogalactan (AG), with characteristic terminally linked α-Araf, (α1 → 5)-Araf, (α1 → 3,5)-Araf, terminally linked β-Galp, (β1 → 6)-Galp, and (β1 → 3,6)-Galp. DEPT-135, HSQC, HMBC and COSY NMR data suggested the presence of (β1 → 3)-Galp mainly branched at O-6 with (β1 → 6)-Galp chains, α-Araf chains, and terminally linked α-Araf. These AG from pistachio external hulls showed in vitro stimulatory activity for B cells, suggesting their possible use as an immunological stimulant in nutraceutical and biomedical applications.

A levan-type fructooligosaccharide was produced by a Paenibacillus strain isolated from Brazilian crude oil, the purity of which was 98.5% after precipitation with ethanol and dialysis. Characterization by FTIR, NMR spectroscopy, GC-FID and ESI-MS revealed that it is a mixture of linear (26) fructosyl polymers with average degree of polymerization (DP) of 18 and branching ratio of 20. Morphological structure and physicochemical properties were investigated to assess levan microstructure, degradation temperature and thermomechanical features. Thermal Gravimetric Analysis highlighted degradation temperature of 218°C, Differential Scanning Calorimetry (DSC) glass transition at 81.47°C, and Dynamic Mechanical Analysis three frequency-dependent transition peaks. These peaks, corresponding to a first thermomechanical transition event at 86.60°C related to the DSC endothermic event, a second at 170.9°C and a third at 185.2°C, were attributed to different glass transition temperatures of oligo and polyfructans with different DP. Levan showed high morphological versatility and technological potential for the food, nutraceutical, and pharmaceutical industries., São Paulo Research Foundation (FAPESP) within Grants 2020/13271-6 and 2018/25511-1. Additionally, the authors acknowledge the financial support by National Council for Scientific and Technological Development – CNPq and by Coordination for the Improvement of Higher Education Personnel (CAPES), Finance Code 001. In addition, this study was supported by the Portuguese Science Foundation (FCT) under the scope of the strategic funding of UID/BIO/04469/2020 unit and the Project FOSYNBIO (POCI-01-0145-FEDER-029549)., info:eu-repo/semantics/publishedVersion

The changes in the cellulose structure of eight Eucalyptus species (E. botryoides, E. globulus, E. grandis, E. maculata, E. propinqua, E. rudis, E. saligna and E. viminalis) in a mild torrefaction (from 160 &deg, C to 230 &deg, C, 3 h) were studied in situ and after cellulose isolation from the wood by solid-state carbon nuclear magnetic resonance (13C NMR), wide angle X-ray scattering (WAXS), Fourier transform infrared spectroscopy (FTIR) and by analytic pyrolysis coupled with gas chromatography and mass spectrometry (Py-GC/MS). Changes in molecular weight were assessed by viscosimetry. A small decrease in cellulose crystallinity (ca. 2%&ndash, 3%) was attributed to its amorphization on crystallite surfaces as a result of acid hydrolysis and free radical reactions resulting in the homolytic splitting of glycosidic bonds. The degree of the cellulose polymerization (DPv) decreased more than twice during the heat treatment of wood. It has been proposed that changes in the supramolecular structure of cellulose and in molecular weight during a heat treatment can be affected by the amount of lignin present in the wood. The limitations of FTIR and Py-GC/MS techniques to distinguish the minor changes in cellulose crystallinity were discussed.

Ionic liquids (ILs), being related to the design of new environmentally friendly solvents, are widely considered for applications within the “green chemistry” concept. Due to their unique properties and wide diversity, ILs allow tailoring new separation procedures and producing new materials for advanced applications. However, despite the promising technical performance, environmental concerns highlighted in recent studies focused on the toxicity and biodegradability of ILs and their metabolites have revealed that ILs safety labels are not as benign as previously claimed. This review refers to the fundamentals about the properties and applications of ILs also in the context of their potential environmental effect. Toxicological issues and harmful effects related to the use of ILs are discussed, including the evaluation of their biodegradability and ecological impact on diverse organisms and ecosystems, also with respect to bacteria, fungi, and cell cultures. In addition, this review covers the tools used to assess the toxicity of ILs, including the predictive computational models and the results of studies involving cell membrane models and molecular simulations. Summing up the knowledge available so far, there are still no reliable criteria for unequivocal attribution of toxicity and environmental impact credentials for ILs, which is a challenging research task.

A sensor consisting of an optical fibre with the exposed tip coated with the polyoxometalate salt [(C4H9)4N]4H[PMo10V2O40], specially designed to be insoluble in water, which UV–Vis spectrum changed in contact with formaldehyde, is presented. The sensor limit of detection for formaldehyde was 0.2 mg L−1, and the limit of quantification was 0.6 mg L−1, which were close to the conventional spectrophotometric method values of 0.2 mg L−1 and 0.5 mg L−1, respectively, and lower than the tolerable limit for ingested food. The sensor was tested for formaldehyde quantification in milk, as its deliberate addition is a matter of concern. The results obtained analysing formaldehyde in milk samples by the optical sensor and by the conventional method were not statistically different (α = 0.05).

This study reports the synthesis of polyurethane&ndash, lignin copolymer blended with carbon multilayer nanotubes to be used in all-solid-state potentiometric chemical sensors. Known applicability of lignin-based polyurethanes doped with carbon nanotubes for chemical sensing was extended to eucalyptus LignoBoost&reg, kraft lignin containing increased amounts of polyphenolic groups from concomitant tannins that were expected to impart specificity and sensitivity to the sensing material. Synthesized polymers were characterized using FT-MIR spectroscopy, electrical impedance spectroscopy, scanning electron microscopy, thermogravimetric analysis, and differential scanning calorimetry and are used for manufacturing of all solid-state potentiometric sensors. Potentiometric sensor with LignoBoost&reg, kraft lignin-based polyurethane membrane displayed theoretical response and high selectivity to Cu (II) ions, as well as long-term stability.

Changes in the lignin structure of eight eucalypt species (E. botryoides, E. globulus, E. grandis, E. maculata, E. propinqua, E. rudis, E. saligna, and E. viminalis) upon mild thermal treatment, where the temperature was gradually raised from 160 to 230 °C over 3 h, were studied by solid-state carbon nuclear magnetic resonance (13C NMR) and after lignin isolation from the wood by acidolysis employing liquid-state 1D and 2D NMR techniques. The molecular weight of the isolated lignins was assessed by size exclusion chromatography (SEC) and their composition by analytic pyrolysis coupled with gas chromatography and mass spectrometry (Py-GC/MS). The thermal treatment induced in lignin partial demethylation (up to ca. 30% from total) and a remarkable reduction in β-O-4 structures (up to ca. 60%), in an extent depending on the ratio of syringyl and guaiacyl units of the specific lignins. The lignin molecular weight reduced only ca. 25% under the thermal treatment due to the likely occurrence of condensation reactions by homolytic and heterolytic mechanisms. The noticeable increase in phenylcoumaran (β-5) and pinoresinol/syringaresinol (β-β) structures in lignin after thermal treatment was tentatively explained by their relative thermal resistance and by newly formed structures as the result of radical coupling reactions occurred during homolytic dissociation of the β-O-4 linkages. Lignins in thermally treated wood contained more than twice phenolic hydroxyls and more aliphatic carboxyl groups than lignins in untreated wood.

Cinnamon is a spice widely used as a flavouring agent in foodstuffs. Despite its commercial availability and low cost, C. burmannii aqueous extracts obtained by decoction originate high viscous solutions (1545 cP) when compared with C. verum (51 cP), preventing its broad use by food industry. Following the hypothesis that cinnamon polysaccharides are responsible for this viscosity, in this work, the hot water-soluble polysaccharides from C. burmannii were structurally characterized, using C. verum for comparison. The results showed that C. burmannii had a higher content of branched arabinoxylans in relation to C. verum. The hot water-soluble polysaccharides from C. verum comprised also glucans, arabinogalactans, and pectic polysaccharides. The partial mild acid-hydrolysis performed to C. burmannii allowed to reach a viscosity value near to the C. verum solutions, keeping the characteristic aroma profile of cinnamon by the predominance of cinnamaldehyde and other varietal compounds, namely mono and sesquiterpenoids. Therefore, C. burmannii can be used as flavouring and thickening agent, whereas low viscosity products can be obtained by a partial acid-hydrolysis, contributing to its wide application in food industry.

The profile of major families of extractives soluble in acetone and dichloromethane during the production of acid sulfite dissolving pulp from Eucalyptus globulus wood was assessed. Nearly 85% of total extractives were removed from wood during pulping and nearly 11% in the course of E-O-P pulp bleaching and secondary pulp screening. Unlike extractives of polyphenolic origin that were almost completely removed after the alkaline extraction stage (E), fatty acids were the main retained component in fully bleached pulp followed by sterols and fatty alcohols. Throughout the bleaching steps, the profiles of extractives were not necessarily decreasing and depended on their reactions with bleaching reagents and the presence of auxiliary chemicals (e.g. antifoams). In this context, the content of fatty acids and fatty alcohols was mostly vulnerable. It has been suggested that Fock reactivity of dissolving pulps is unaffected by extractives at concentrations up to 0.3%.

Reactive washing consists of treating cork stoppers with hydrogen peroxide under strong alkaline conditions at elevated temperature. This causes changes in the surface of the stoppers, affecting their wettability. This study aimed to relate the reactive washing with changes in the surface properties of cork stoppers and their affinity for hydroalcoholic solutions with different concentrations of ethanol. The surface composition was evaluated by Fourier Transform Infrared-Attenuated Total Reflectance spectroscopy, confocal Raman spectroscopy and the free surface energy by contact angle measurements with liquid probes using Owens-Wendt-Rabel-Kaelble method. The surface morphology and topology was assessed by scanning electron microscopy and 3D optical profilometry, respectively. Different wettability of the top and lateral of the cork stoppers is due to the difference in the exposure of phellogen cell wall layers. After reactive washing, the partial degradation of suberin and the increased exposure of hydrophilic biopolymers lead to an increase in the polar component of the free surface energy, thus promoting wettability with aqueous solutions. The changes in the surface observed imply an enhancement in the wettability of cork stoppers towards hydroalcoholic solutions mimicking alcoholic beverages, as revealed by modeling studies employing a wetting envelope.

In this study, aiming to reduce the environmental impact of plastics, new composite materials containing recycled fibers from used paper coffee cups and oil extracted from spent coffee grounds (SCG) were produced. Accordingly, the cellulose fibers were chemically modified using lactic acid to be used as poly(lactic acid) filler reinforcement. The obtained results revealed that its addition improved the mechanical properties of the ensuing composites. The addition of 30% wt/wt of unmodified and modified fibers increased the Young modulus by 53% and 72%, respectively. In addition, enhanced biodegradability was obtained due to higher water absorption (up to 4% wt/wt). In parallel, coffee oil was used as a plasticizer and the affinity between the plasticizer and polymer matrix was confirmed by the lack of phase separation, by the improved flexibility of derived materials (the addition of 40% wt/wt of plasticizer increased the elongation at break by 86%) and by the better processability of the ensuing materials (the addition of 30% wt/wt of plasticizer increased the MFI by 205%). Overall, the results suggest that the use of modified cellulose fibers and the addition of SCG oil-based plasticizer can be promising routes to produce eco-friendly plastics. This study was also performed within the scope of the project CICECO-Aveiro Institute of Materials, UIDB/50011/2020 and UIDP/50011/2020, financed by national funds through the Portuguese Foundation for Science and Technology/MCTES. The NMR spectrometers are part of the National NMR Network (PTNMR) and are partially supported by Infrastructure Project N° 022161 (co-financed by FEDER through COMPETE 2020, POCI and PORL and FCT through PIDDAC). published

Sugarcane bagasse and straw are generated in large volumes as by-products of agro-industrial production. They are an emerging valuable resource for the generation of hemicellulose-based materials and products, since they contain significant quantities of xylans (often twice as much as in hardwoods). Heteroxylans (yields of ca 20% based on xylose content in sugarcane bagasse and straw) were successfully isolated and purified using mild delignification followed by dimethyl sulfoxide (DMSO) extraction. Delignification with peracetic acid (PAA) was more efficient than traditional sodium chlorite (NaClO

This work studies the microwave-assisted extraction conditions for recovery of polysaccharides from spent coffee grounds, including their effect on arabinogalactans and galactomannans polymerization and branching structural features. Temperature (140, 170, and 200 °C) has the most significant impact on total extracted mass (ηtotal soluble solids) and sugars yield (ηsugars), arabinogalactans (ηAG) and galactomannans (ηGM), and polysaccharide mass ratio (ηAG/ηGM). Time (2, 5, and 10 min) and alkali (diluted 0.1 M NaOH) treatments have less influence. Alkali treatment and shorter time (2 min) provided a protective effect against polysaccharides degradation. At 170 °C, the yield of arabinogalactans was found to be significantly higher than that of galactomannans (ηAG/ηGM >1). Increasing temperature to 200 °C leads to decrease the polymerization of polysaccharides, promoting the formation of debranched polysaccharides and oligosaccharides. This study shows that the optimum conditions for polysaccharides extraction cannot be selected only by mass yield but need to be defined according to the desired structural features for the specific applications.

In this work, polysaccharides extracted with hot water from apple pomace were isolated by C18 cartridge solid-phase extraction at pH 7 (Fr7). Dialysis (12–14 kDa) of this fraction allowed to obtain 17% (w/w) of polymeric material composed by 65% of polysaccharides, mainly arabinose (58 mol%), galacturonic acid (16 mol%) and glucose (10 mol%). Folin-Ciocalteu assay showed 62 g of phloridzin equiv/kg of polyphenols. Moreover, adjusting to pH 3, it was possible to retain an additional fraction (Fr3) representing a further 4% of the polymeric material. Fr3 contained 53% of polysaccharides composed mainly by galacturonic acid (66 mol%) and polyphenols accounted for 37 g of phloridzin equiv/kg. Precipitation with ethanol and subsequent methylation and NMR spectroscopic analysis of Fr7 dialysate allowed the identification of covalently-linked pectic-polyphenol-xyloglucan and arabinan-polyphenol complexes. These structures are possibly formed as a result of polyphenol oxidation reactions during the industrial processing of apples, conferring hydrophobic characteristics to apple pomace polysaccharides.

Cellulose/silica hybrid material produced by a sol-gel method from cellulosic fibres and silica precursors (tetraethoxysilane and 3-aminopropyltriethoxysilane) was functionalized with alpha-[SiW9O37Ru3III(H2O)(x)Cl3-x]((10-x)-) (Ru-POM), and thoroughly characterised by C-13 and Si-29 solid state NMR, FTIR spectroscopy, UV-vis reflectance spectroscopy, X-ray diffraction, thermogravimetric analysis, scanning electron microscopy (SEM), and chemical analysis. The supported Ru-POM exhibited catalytic activity for the gas phase heterogeneous aerobic oxidation of formaldehyde (ca. 830 ppm in polluted air) at room temperature, in a packed-bed reactor operating at a linear velocity ca. 0.33 m/s and ca. 0.5 s residence time. Maximum formaldehyde uptake was 1.10 g/min per kg of hybrid material doped with Ru-POM (ca. 1.4% w/w). More than 400 turnovers were achieved without significant loss of catalytic activity and the only detected oxidation products of formaldehyde were carbon dioxide and water. A plausible mechanism for the catalytic oxidation of formaldehyde by supported Ru-POM has been proposed and includes formaldehyde oxidation in oxygenated ruthenium complex. (C) 2015 Elsevier B.V. All rights reserved.

Biofuels are suitable alternatives to conventional and fossil fuels that pose serious environmental adverse effects to society. Bioethanol is the most promising biofuel and can be generated from lignocellulosic biomasses. Forest residues are outside the human food chain and inexpensive raw materials, but they need a previous pretreatment, in order to improve the cellulose accessibility for further bioconversion. The study of bioethanol production from rockrose pretreated by steam explosion (SE) was carried out employing separate enzymatic hydrolysis and fermentation (SHF) or simultaneous saccharification and fermentation (SSF) approaches. Saccharification of untreated rockrose attained only 0.9% of sugars yield. However, the steam explosion pretreatment promoted the disruption of interfibrillar surfaces of fibers with partial degradation of lignin thus enhancing the accessibility of polysaccharides toward enzymatic hydrolysis. Alkaline extraction after steam explosion pretreatment of rockrose residue (R-SE-OH) led to the partial removal of lignin, hemicelluloses, and other degradation products from fibre surface allowing an increase of 75% in the glucose yield. Bioethanol production in SSF mode was faster and slightly more efficient process than SHE providing the best results: ethanol concentration of 16.1 g L-1, fermentation efficiency of 69.8% and a yield of 22.1 g ethanol/100 g R-SE-OH. (C) 2015 Elsevier B.V. All rights reserved.