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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.

The dioxane lignin was isolated from extractives- and suberin-free cork (Quercus suber L.) by a modified acidolytic procedure and submitted to structural analysis by permanganate oxidation, analytical pyrolysis coupled with gas chromatography and mass spectrometry (Py-GC-MS), liquid- and solid-state nuclear magnetic resonance (NMR) spectroscopy, and Fourier transform infrared (FTIR) spectroscopy. The molecular weight (Mw = 2500 Da) was assessed by size exclusion chromatography (SEC). The results obtained show that the cork lignin is of syringyl (S)/guaiacyl (G) type with a small proportion of p-hydroxyphenyl (H) units (S:G:H molar ratio of 23:72:5). Among a dozen detected lignin structures, those linked by ether bonds, such as β-O-4' (38 mol %) and 4-O-5' (5 mol %), were the most abundant. The frequency of occurrence of β-5', β-β', 5-5', tetrahydrofuran type, and structures arising from the condensation with concomitant procyanidins was assessed. Ferulates were the only cinnamic structure detected in the cork dioxane lignin.

Three industrial Eucalyptus globulus acid sulphite dissolving pulps of different intrinsic viscosity (ca. 490–570 cm3/g) with similar xylan content (2.4–3.0%) were partially (ca. 60%) converted to cellulose II by treatment with 12% NaOH and hornified by drying for 8 h at 105 °C to induce changes in physical structure. All three initial and modified pulps were analysed on their Fock reactivity method and Chinese filterability. These dissolving pulps were also examined for the crystallinity degree and the crystallite dimensions assessed by wide-angle X-ray scattering and the fibril aggregation assessed by solid-state 13C nuclear magnetic resonance. The results showed that the reactivity of the dissolving pulp was negatively correlated with the degree of cellulose crystallinity and depended almost linearly on the lateral dimension of the fibril and the dimensions of the fibril aggregates. In hornified pulps, the effect of cellulose physical structure on reactivity was even more pronounced than the intrinsic viscosity of the dissolving pulp. In addition, no unambiguous dependence between the reactivity and the filterability of dissolving pulps was found. Filterability did not correlate clearly with lateral dimension of fibril or fibril aggregates, but depended only on pulp viscosity.

Lignosulfonates (LS) from acidic magnesium-based sulfite cooking of Eucalyptus globulus wood were modified via laccase-catalyzed oxidative treatment with the aim to improve their performance as plasticizing additives in concrete formulations. The target parameters were the increment of molecular weight (Mw) and the amount of oxidized groups. The laccase-assisted oxidation under optimized conditions (40°C, pH 4.5, enzyme loads of 83–500 U g−1 for 90 min) allowed Mw increment up to 11-fold and almost doubled the amount of carbonyl and carboxyl groups without using any mediators. Modified LS maintained their solubility in water and possessed a zeta- potential close to that of initial LS. The characterization of modified LS has been carried out by ultraviolet-visible (UV-Vis), Fourier transform infrared-attenuated total reflectance (FTIR-ATR) and quantitative 13C nuclear magnetic resonance (NMR) spectroscopy, and the sulfonic and phenolic groups were assessed by conductometric titration. It was concluded that LS polymerization occurred mostly via the formation of new aryl ether bonds (two thirds of the modification) and biphenyl bonds (the remaining third). However, part of the newly formed bonds of unknown origin are temperature labile and cleaved during the concentration of LS at pH 4 and 80°C under vacuum, which led to the reduction of the Mw of the modified lignin to almost one third.

Lignosulfonates (LS) are products from the sulfite pulping process that could be applied as renewable environmentally-friendly polymeric surfactants. Being widely used as plasticizers and water-reducing admixtures in concrete formulations LS compete in the market with petroleum-based superplasticizers, such as naphthalene sulfonate formaldehyde polycondensate (NSF) and copolymer polycarboxylate ethers (PCE). In this work, different chemical modification strategies were used to improve LS performance as dispersants for concrete formulations. One strategy consisted in increasing the molecular weight of LS through different approaches, such as laccase and polyoxometalate-mediated polymerization, glyoxalation, and reversible addition-fragmentation chain transfer (RAFT) polymerization. The other strategy consisted of preparing LS-based non-ionic polymeric dispersants using two different epoxidized oligomer derivatives of poly(ethylene glycol) (PEG) and poly(propylene glycol) (PPG). Modified LS were used to prepare cement pastes, which were examined for their fluidity. Results revealed that the most promising products are PPG-modified LS due to the introduction of PPG chains by reaction with phenolic moieties in LS. The enhanced dispersant efficiency of the ensuing products is probably related not only to electrostatic repulsion caused by the sulfonic ionizable groups in LS but also to steric hindrance phenomena due to the grafted bulky PPG chains.

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.

In this study, lignosulfonate (LS) from the acid sulfite pulping of eucalypt wood was used to synthesize LS-based polyurethanes (PUs) doped with multiwalled carbon nanotubes (MWCNTs) within the range of 0.1–1.4% w/w, yielding a unique conducting copolymer composite, which was employed as a sensitive material for all-solid-state potentiometric chemical sensors. LS-based PUs doped with 1.0% w/w MWCNTs exhibited relevant electrical conductivity suitable for sensor applications. The LS-based potentiometric sensor displayed a near-Nernstian or super-Nernstian response to a wide range of transition metals, including Cu(II), Zn(II), Cd(II), Cr(III), Cr(VI), Hg(II), and Ag(I) at pH 7 and Cr(VI) at pH 2. It also exhibited a redox response to the Fe(II)/(III) redox pair at pH 2. Unlike other lignin-based potentiometric sensors in similar composite materials, this LS-based flexible polymeric membrane did not show irreversible complexation with Hg(II). Only a weak response toward ionic liquids, [C2mim]Cl and ChCl, was registered. Unlike LS-based composites comprising MWCNTs, those doped with graphene oxide (GO), reduced GO (rGO), and graphite (Gr) did not reveal the same electrical conductivity, even with loads up to 10% (w/w), in the polymer composite. This fact is associated, at least partially, with the different filler dispersion abilities within the polymeric matrix.

In order to close the water cycle in pulp mills with condensates instead of fresh water, the malodorous/hazardous volatile compounds and colored substances have to be removed by appropriate efficient methods. In the present work, the condensate from the evaporation of black liquor (BL) from a kraft mill was purified by a batch adsorptive process by means of commercial activated carbon (AC). The effluent was found to contain a wide range of aromatic and organosulfur volatile compounds, including toluene, ethylguaicol, syringaldehyde, dimethyl disulfide (DMDS), dimethyl trisulfide (DMTS), 2,3-dimethylthiophene, benzothiol and benzothiophene derivatives. Methanol was the major volatile organic component in the condensate (201 mg l−1), which was, however, poorly adsorbed on the AC surface. Aromatics and organosulfur contaminants were adsorbed almost completely in 2–5 min at 23°C under the optimized AC load (900 mg l−1). The treatment allowed the elimination of up to 99% of the obnoxious odor, color and turbidity of the condensate. The adsorption equilibrium followed the Langmuir model and the pseudo-second-order kinetics. The new process could be incorporated in the pulp mill with relatively low additional reagent costs.

During the hydrolytic degradation of cellulose caused by acidic transition metal sulphates, new low molecular products such as monosaccharides and their degradation products are usually formed which can increase the cellulose sensitivity to oxidation. This work was aimed at elucidation of the chemical and structural changes of cellulose in silver fir (Abies alba Mill.) wood treated with iron, copper and zinc salts to achieve a detailed understanding of cellulose deterioration during accelerated ageing. Cellulose samples were isolated from the wood by the Kurschner-Hoffer method and the Seifert method. Changes in cellulose structure were evaluated by wide-angle X-ray scattering (WAXS) measurements, Fourier transform infrared spectroscopy (FTIR), and high performance liquid chromatography. The presence of metal cations (Cu2+, Zn2+, Fe3+) caused a significant loss in the content of cellulose for treated and aged wood samples. Wet-thermal accelerated ageing led to a decrease (~ 20%) in the content of monosaccharides. The Seifert cellulose samples had a higher crystallinity than the Kurschner-Hoffer samples. A strong correlation was found between crystallinity indices obtained from the FTIR and WAXS measurements. Two cluster groups of cellulose samples, segregated from each other, were identified within each cellulose type in a multivariate cellulose trait analysis.

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.

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).

Ellagitannins (ETs), characterized by their diversity and chemical complexity, belong to the class of hydrolysable tannins that, via hydrolysis under acidic or alkaline conditions, can yield ellagic acid (EA). They are mostly found as a part of extractives in angiosperms. As known antioxidants and chelators, EA and EA derivatives are drawing an increasing interest towards extensive technical and biomedical applications. The latter ones include possible antibacterial, antifungal, antiviral, anti-inflammatory, hepato- and cardioprotective, chemopreventive, neuroprotective, anti-diabetic, gastroprotective, antihyperlipidemic, and antidepressant-like activities, among others. EA’s synthesis and production challenges prompt further research on new methods and alternative sources. Conventional and prospective methods and raw materials for the production of EA and its derivatives are reviewed. Among the potential sources of EA, the residues and industrial streams of the pulp industry have been highlighted and considered as an alluring alternative in terms of commercial exploitation.

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%.

In this study, modification of LignoBoost™ softwood kraft lignin with epichlorhydrin in water-organic solvents media was realized. Lignin-based epoxy resins were obtained by two ways: acetone extraction of glycidylated lignin or glycidylation of the acetone soluble lignin fraction. The effect of glycidylation regimes on the yields of acetone soluble fractions, their functional composition and physical-chemical characteristics was investigated using wet chemistry methods, FTIR spectroscopy, size exclusion chromatography (SEC) and differential scanning calorimetry (DSC). The positive effect of the biphasic phase transfer catalytic system – KOH/quaternary ammonium salt – on glycidylation of both phenolic and aliphatic hydroxyl groups was testified, exemplified using a lignin-like model compound – 4-hydroxy-3-methoxylbenzyl alcohol (vanillyl alcohol). The partial substitution (up to 10%) of commercial epoxy resin on the basis of bisphenol A (Araldite® LY1564) by lignin-based epoxy resin significantly increased the viscosity of resin. Therefore, the possible practical application of lignin-containing epoxies as adhesive, mastic or crack filler instead of binder for fiber reinforced composites was considered. A tendency towards increasing Young’s modulus of cured lignin-containing epoxies, compared with the case of the reference composition, was observed. The lignin chemically incorporated into the matrix of cured commercial epoxy resin acts as a charcoal formation promoter in high temperature treatment.

A new method for the quantification of acetaldehyde in a water matrix, namely commercial ciders, was developed using solid phase micro-extraction (SPME) followed by detection with a coated acoustic wave sensor. The sensitive coating was a polyoxometalate salt specially synthesised for this application, a compound tailored to be insoluble in water. Although the sample gaseous flow reaching the sensor needed to be dried, as the sensor itself responds to water, there was no sensitivity deterioration after contacting with water vapour, as frequency recover under dried nitrogen carrier was complete. Calibration lasted at least for two months. Comparing this sensor with the analogue previously coated with the soluble decamolybdodivanado phosphoric acid, the main advantage comes from the superior stability, and the possibility of keeping it in a wet environment without deterioration. The flow injection analysis (FIA) methodology here reported for the first time for acetaldehyde analysis in cider, allowed to obtain results not statistically different from the ones obtained with Gas Chromatography-Flame Ionization Detection (GC-FID) (α = 0.05). Besides, the new methodology does not use expensive instrumentation and the analysis time is similar. Detection limit of this new method was 2.0 mg L−1, and quantification limit was 6.7 mg L−1, not much higher than the values of 1.4 mg L−1 and 4.6 mg L−1, respectively, of the GC-FID.

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

Two functionalized xylans, namely a carboxymethyl xylan (CMX) and a 2-dodecenyl succinic anhydride-modified xylan (X-2-DSA) were, i) synthesized from beechwood xylan (BX) and characterized for their structural properties, thermal behaviour and molar mass and, ii) used in the production of paper/xylan laminates for food packaging. Films prepared from the functionalized xylans by solvent casting were applied onto paper employing the calendering moulding under pre-selected conditions in order to produce the laminates. The obtained laminates, as well as the starting base paper and the xylan-derived films, were characterized for their mechanical and barrier properties. The novel type of laminates demonstrated a synergistic effect with respect to its individual constituents, as the Young's modulus, tensile, tear and burst strengths of laminates were significantly improved in comparison to those of the starting paper or the xylan films. The xylan-coated paper laminates showed good moisture barrier properties, reducing up to 30-fold the water vapor permeability of the paper. At the same time, despite of fairly good oxygen barrier properties of the bio-based films from functionalized xylan, their application in paper laminates did not permit maintaining the same order of magnitude of oxygen transfer rates, which were, however, comparable to those reported for packaging papers coated by polyethylene films.

High concentrations of 5-hydroxymethylfurfural (HMF) in honey provide an indication of overheating under inappropriate storage conditions or aging. Conventional methods for determining HMF are cumbersome and require expensive equipment or hazardous reagents. Hence the aim of this study was to propose a new analytical tool for HMF determination in honey, using a low cost acoustic wave sensor. Volatile organic compounds (VOCs) of honey samples were extracted, using the solid phase microextraction (SPME) technique, and HMF was quantified, using a piezoelectric quartz crystal with gold electrodes coated with a layer of decamolybdodivanado phosphoric acid, sensitive to HMF. The reliability of the proposed method was confirmed after comparing the results of HMF quantification with those obtained by the conventional spectrophotometric White method, and no statistical differences were found (α=0.05).

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.

The valorization of lignins as renewable aromatic feedstock is of utmost importance in terms of the use of sustainable resources. This study provides a deductive approach towards market-oriented lignin-derived antioxidants by ascertaining the direct effect of different structural features of lignin on the reactivity of its phenolic OH groups in the radical scavenging reactions. The antioxidant activity of a series of compounds, modeling lignin structural units, was experimentally characterized and rationalized, using thermodynamic descriptors. The calculated O&ndash, H bond dissociation enthalpies (BDE) of characteristic lignin subunits were used to predict the modification pathways of technical lignins. The last ones were isolated by soda delignification from different biomass sources and their oligomeric fractions were studied as a raw material for modification and production of optimized antioxidants. These were characterized in terms of chemical structure, molecular weight distribution, content of the functional groups, and the antioxidant activity. The developed approach for the targeted modification of lignins allowed the products competitive with two commercial synthetic phenolic antioxidants in both free radical scavenging and stabilization of thermooxidative destruction of polyurethane films.

Grape pectic polysaccharides-malvidin-3-O- β - d -glucoside binding was studied, aiming to unveil the impact of structural diversity of polysaccharides on anthocyanins-polysaccharides interactions. Polysaccharides were extracted with solutions of imidazole (ISP) and carbonate at 4 °C (CSP-4 °C) and room temperature (CSP-RT) and also recovered from the dialysis supernatant of the remaining cellulosic residue after the aqueous NAOH extraction of hemicellulosic polysaccharides (Sn-CR). Polysaccharides richer in homogalacturonan domains, like those present in the CSP-4 °C fraction had approximately 50–fold higher binding affinity to malvidin-3-O- β- d -glucoside, than polysaccharides with side chains (as ISP and CSP-RT extractable polysaccharides). CSP-4 °C polysaccharides showed a positive effect on malvidin-3-O- β- d -glucoside colour fading. Hydration equilibrium constant of malvidin-3-O- β- d -glucoside in the presence of CSP-4 °C polysaccharides was higher, showing the preferential stabilization of the flavylium cation. The results showed that anthocyanins colour stabilization can be promoted by pectic polysaccharide structures such as those extracted by cold carbonate.

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.

Bioethanol production potential from cardoon ( Cynara cardunculus ) and rockrose ( Cistus ladanifer ), pretreated by diluted acid hydrolysis (DAH), was studied and compared by both, separate enzymatic hydrolysis and fermentation (SHF) and simultaneous saccharification and fermentation (SSF) processes. DAH pretreatment allowed an increase of 5 fold to cardoon and 16 fold to rockrose in cellulose accessibility towards enzymatic hydrolysis. Both plants showed better overall fermentation efficiency and ethanol yield in SSF than in SHF also with shorter processing periods, 24 h against 72 + 24 h, respectively. Results obtained for rockrose are about half the concentration and volumetric productivity of ethanol and 60% of the overall fermentation efficiency of those obtained for cardoon. The recalcitrance of rockrose to enzymatic hydrolysis was explained by higher abundance of lignin and extractives than in cardoon. Comparing the steam explosion (SE) and DAH pretreatments, the former was more advantageous for the recalcitrant rockrose in terms of enzymatic saccharification yield., This research was funded by INALENTEJO 2007.2013/QREN (BioEcos Project – Valorização Integrada de Biomassa (ALENT-09-0140-FEDER-000705 (QREN)). The author’s thanks, FCT (Fundação para a Ciência e Tecnologia) under projects CICECO-Aveiro Institute of Materials (Ref.FCTUID/CTM/50011/2013) and ICAAM-Instituto de Ciências Agrárias e Ambientais Mediterrânicas (Ref.FCTUID/AGR/00115/2013). Agrarian School from Instituto Politécnico de Beja and Associação de Defesa do Património de Mértola, are greatly acknowledged for kindly supplying cardoon and rockrose, respectively.

BACKGROUND Brightness stability of bleached chemical pulps is often associated with the final bleaching stages that should provide the removal of chromogenic species responsible for brightness reversion without compromising the papermaking potential. Aiming at promoting higher brightness stability, a partially bleached Eucalyptus globulus pulp (DED) of c. 88% ISO brightness was involved in a study of a final enzymatic stage (X) alternative to conventional chlorine dioxide (D) and hydrogen peroxide (P) bleaching stages (DEDX vs. DEDD and DEDX vs. DEDP). X stage was also applied before and after the final P or D stages (DEDDX/DEDXD and DEDPX/DEDXP) to produce high brightness pulps (c. 91%). RESULTS X stage with xylanase Pulpzyme HC allowed an increase of c. 1.5% in pulp brightness while decreasing the brightness reversion and a concomitant pulp yield loss of only 0.5%. Significant chemical savings were obtained in the final D (70%) or P (45%) stages to achieve targeted final brightness of c. 91%. DEDXD or DEDXP sequences had advantage over DEDDX and DEDPX, respectively, in terms of brightness stability of fully bleached pulps. CONCLUSIONS Xylanase interferes with structures responsible for the brightness reversion. X stage allows production of pulp with extra brightness in sequences with a final P stage. © 2014 Society of Chemical Industry

The oxidation of α-(1 → 5)-L-arabinotriose (Ara3), an oligosaccharide structurally related to side chains of coffee arabinogalactans, was studied in reaction with hydroxyl radicals generated under conditions of Fenton reaction (Fe(2+)/H2O2). The acidic and neutral oxidation products were separated by ligand exchange/size-exclusion chromatography, subsequently identified by electrospray ionisation mass spectrometry (ESI-MS) and structurally characterised by tandem MS (ESI-MS/MS). In acidic fraction were identified several oxidation products containing an acidic residue at the corresponding reducing end of Ara3, namely arabinonic acid, and erythronic, glyceric and glycolic acids formed by oxidative scission of the furanose ring. In neutral fractions were identified derivatives containing keto, hydroxy and hydroperoxy moieties, as well as derivatives resulting from the ring scission at the reducing end of Ara3. In both acidic and neutral fractions, beyond the trisaccharide derivatives, the corresponding di- and monosaccharide derivatives were identified indicating the occurrence of oxidative depolymerisation. The structural characterisation of these oxidation products by ESI-MS/MS allowed the differentiation of isobaric and isomeric species of acidic and neutral character. The species identified in this study may help in detection of roasting products associated with the free radical-mediated oxidation of coffee arabinogalactans.

The acid-catalyzed reaction of 5-(hydroxymethyl)-2-furfural with ethanol is a promising route to produce biofuels or fuel additives within the carbohydrate platform; specifically, this reaction may give 5-ethoxymethylfurfural, 5-(ethoxymethyl)furfural diethylacetal, and/or ethyl levulinate (bioEs). It is shown that sulfonated, partially reduced graphene oxide (S-RGO) exhibits a more superior catalytic performance for the production of bioEs than several other acid catalysts, which include sulfonated carbons and the commercial acid resin Amberlyst-15, which has a much higher sulfonic acid content and stronger acidity. This was attributed to the cooperative effects of the sulfonic acid groups and other types of acid sites (e.g., carboxylic acids), and to the enhanced accessibility to the active sites as a result of the 2D structure. Moreover, the acidic functionalities bonded to the S-RGO surface were more stable under the catalytic reaction conditions than those of the other solids tested, which allowed its efficient reuse.

The oxidative modification of Biolignin (BL) has been investigated to make it more suitable as an adsorbent for transition/heavy metals. BL is a by-product of a wheat straw organosolv process for the production of pulp, ethanol, and pentoses (CIMV S.A. pilot plant, Levallois Perret, France). It was subjected to oxidation by a polyoxometalate (POM) H3[PMo12O40], aiming at the increment of oxygen-containing adsorption-active sites. The POM oxidation of BL was performed under moderate conditions (1 bar, 60–90°C, and 200°C) with the co-oxidants O2 or H2O2. The resulting lignin functionality and structure was evaluated by pyrolysis-gas chromatography/mass spectrometry, solid-state 13C nuclear magnetic resonance, Fourier transform infrared, and chemical analysis. The condensation degree of BL and its COOH and aliphatic OH group contents increased significantly, whereas the polymer structure was maintained. Under optimal conditions with POM/H2O2, the sorption capacity of lignins toward Cd(II) and Pb(II) was increased threefold and twofold, respectively.

The chemical composition and the structural features of macromolecular components from red grape skins (variety Touriga Nacional) have been evaluated. The results of chemical analyses revealed the following contents of the main constituents: cellulose (20.8%), hemicelluloses (12.5%), proteins (18.8%), tannins (13.8%), extractives soluble in dichloromethane (5.0%) and ash (7.8%). Cellulose of grape skins is typical cellulose I polymorph with a degree of crystallinity of 66.1% as assessed by X-ray scattering. The hemicelluloses were analyzed by neutral sugars analysis, methylation analysis and 1D/2D H-1 NMR. The water-soluble compounds (26.4%) are composed mainly of monomeric sugars (glucose and fructose) and a complex mixture of hemicelluloses, the most abundant being pectin and acetylated glucomannan. The major part of structural polysaccharides (cellulose, xylan, xyloglucan, etc.) is embedded in cuticular layer and is poorly accessible to the acid hydrolysis. The cuticular substances contributed to ca. 8.5% of grape skins and their chemical structure has been evaluated by methanolysis. The possibility of comprehensive utilization of grape skins has been discussed. (C) 2012 Elsevier B.V. All rights reserved.

Industrially produced bleached recycled pulp (R) comprising essentially hardwood fibres was subjected to enzymatic treatment with endo-xylanase from Thermomyces lanuginosus with or without ultra-high hydrostatic pressure (UHP) pre-treatment at 300–600 MPa for 10 min. The kinetics and the extent of enzymatic hydrolysis after UHP pre-treatment under different conditions have been evaluated by released reducing sugars and the analysis of neutral sugars in pulps, respectively. The changes in surface chemical composition of pulps were assessed by UV-vis diffuse reflectance spectroscopy. UHP-pre-treated R under optimal conditions (400 MPa), with or without posterior enzymatic treatment, was used for the production of handsheets and evaluation of its mechanical properties. It was suggested that enzymatic modification improves significantly the papermaking properties of recycled pulp. These improvements were related with selective removal of xylan bound to impurities and to aggregated cellulose fibrils on the fibre surface, thus favouring the ensuing swelling and inter-fibre bonding in paper. UHP pre-treatment and posterior enzymatic treatment revealed a synergetic effect on the mechanical properties of recycled pulp. This fact was assigned to enhanced accessibility of fibres towards xylanase and by forced hydration and favourable rearrangement of cellulosic fibrils in fibres after UHP pre-treatment. The increase of basic strength properties after UHP-promoted xylanase treatment was up to 30 % being the most pronounced for the tensile strength and the burst resistance.

High pressure laminates (HPLs) are attractive, resistant to environmental effects and good cost-benefit decorative surface composite materials whose properties can be tailored to meet specific market demands. In this study, the substantial improvement of dirt repellence of HPLs with simultaneous enhancement of its abrasion resistance was achieved for the first time by incorporating nonafluorohexyl polyhedral oligomeric silsesquioxane (FH-POSS) nanoparticles (up to 1% w/w) into a melamine formaldehyde (MF) resin matrix used to impregnate decorative and overlay papers required for HPLs production. FH-POSS particles were synthesized and thoroughly characterized by C-13 and Si-29 solid state nuclear magnetic resonance (NMR) spectroscopy, and by X-ray diffraction (XRD) analysis. Fluoroalkyl moieties in FH-POSS afforded increased hydrophobicity to HPLs thus providing improved surface clean ability, whereas abrasion resistance was improved due to the robust silica core of the POSS particles. Hydrophobicity of HPLs doped with FH-POSS increased with time, after resin curing, and this was attributed to migration of FH-POSS nanoparticles to the composite surface. (C) 2016 Elsevier B.V. All rights reserved.

Many chemicals are used to prolong wood lifetime and protect wood against wood-destroying organisms and fire but there is not sufficient information about their possible corrosive effects on wood and its structural components from the perspective of long-term exposition in unsuitable condition. This study evaluated the combined effects of inorganic chemicals (borates, phosphates containing ammonia, sulphates with metal cations, chlorides) and wet-thermal accelerated ageing (T=80 °C, RH=65 %, for 30 days) on chemical composition of treated wood. Used analyses indicated that selected chemicals cause a decomposition of all wood constituents in varying degrees. Cellulose was degraded in the greatest extent due to acidic sulphates (Fe3+, Cu2+) and almost no deterioration of polysaccharides was caused with H3BO3. A negative effect on lignin had almost only Na2B4O7.10H2O and NaCl. At the same time the amount of extractives in hot water and acetone and ash content were compared at all samples. The wet-thermal ageing played an important role in wood degradation, but the effect of chemical treatment was certainly stronger.

In this work, the successful derivatization of a beechwood xylan (BX) by carboxymethylation and hydroxypropylation was achieved aimed to produce bio-based films. Carboxymethyl xylan (CMX) and hydroxypropyl xylan (HPX) with a substitution degree of 0.3 and 1.1, respectively, as determined by H-1 NMR, were synthesised. The xylan's characterization by thermogravimetric analysis showed that HPX is thermally more stable than CMX or BX. The ability of the xylan derivatives to form films and the effect of the glycerol addition on the films performance were evaluated. Tensile strength, Young's modulus and water vapour permeability of self-supporting CMX films were higher and the elongation at break lower than those of the corresponding HPX films. The water vapour barrier properties of CMX and HPX films were improved with 10% glycerol addition. Oxygen barrier property was exceptionably good for a CMX film plasticized with 25% of glycerol (oxygen permeability of 0.5 cm(3) mu m m(-2) d(-1) kPa(-1)) while higher oxygen permeability values were obtained for HPX films. Favourable characteristics were found that may enable the use of these films in, e.g., coatings for packaging. (C) 2016 Elsevier B.V. All rights reserved.

The effect of urea on the cellulose degradation under conditions of alkaline pulping has been studied using purified cellulose powder. The increased cellulose yield in the presence of urea was assigned essentially to the carbamation reactions which were confirmed by elemental analysis, UV-resonance Raman and solid-state 13C nuclear magnetic resonance spectroscopy. The stabilizing effect of urea on the cellulose peeling reactions during heating up period of pulping process was suggested based on kinetic studies and additionally confirmed in model reactions using cellobiose. The reaction products formed in alkaline urea solutions were analysed by tandem electrospray ionization mass spectrometry and the occurrence of Maillard type reactions between reducing end groups of cellobiose and urea were evidenced. Both Maillard type reactions and carbamation of reducing end groups were proposed to be a part of cellulose protection mechanism against peeling under the conditions of alkaline pulping.

This study puts particular emphasis on the role of copper ions in the performance of hydrogen peroxide bleaching (P-stage). Owing to their variable levels across the bleaching line due to washing filtrates, bleaching reagents, and equipment corrosion, these ions can play a major role in hydrogen peroxide decomposition and be detrimental to polysaccharide integrity. In this study, a Cu-contaminated D0(EOP)D1 prebleached pulp was subjected to an acidic washing (A-stage) or chelation (Q-stage) before the alkaline P-stage. The objective was to understand the isolated and combined role of copper ions in peroxide bleaching performance. By applying an experimental design, it was possible to identify the main effects of the pretreatment variables on the extent of metals removal and performance of the P-stage. The acid treatment was unsuccessful in terms of complete copper removal, magnesium preservation, and control of hydrogen peroxide consumption in the following P-stage. Increasing reaction temperature and time of the acidic A-stage improved the brightness stability of the D0(EOP)D1AP bleached pulp. The optimum conditions for chelation pretreatment to maximize the brightness gains obtained in the subsequent P-stage with the lowest peroxide consumption were 0.4% diethylenetriaminepentaacetic acid (DTPA), 80ºC, and 4.5 pH.

The focus of this study is the chemistry of reductive bleaching of kraft pulps with sodium dithionite. A set of model compounds mimicking quinone structures, residual lignin structures with conjugated carbonyl/carboxyl groups and muconic acid, among others, was reduced with sodium dithionite and monitored by ultraviolet-visible (UV-vis) spectroscopy. Depending on the chromophore models, either reductive or sulfonation reactions are thought to be responsible for the degradation. No reductive degradation of hexeneuronic acid (HexA) residues was detected, but unsaturated structures of unknown origin were eliminated from the xylan. Additionally, the potential of the reductive stage with either sodium dithionite or sodium borohydride was tested using an industrial pine kraft pulp bleached by OOZEDD sequence. This pulp, with a 88.8% ISO brightness ceiling, exhibited a brightness increase to 90 ± 0.5% in the final reduction stage.

The reasons for the improved brightness stability of pulp bleached in the final stage with hydrogen peroxide than with chlorine dioxide have been studied. UV–vis Diffuse Reflectance and UV Resonance Raman micro-spectroscopy @ 325 nm were employed to evaluate the chromophores formation/degradation in fully bleached eucalypt kraft pulp while applying a final chlorine dioxide or a hydrogen peroxide bleaching stages. Spectroscopic data were coupled to wet chemistry and mass spectrometry analyses of degradation products arisen during hydrothermal ageing of bleached pulps. The complementary analyses have revealed the important role of partially oxidised carbohydrates and of the residual xylan–lignin complex in ageing reactions. The leaching of degradation products from pulp during the final bleaching stage, rather than specific oxidation patterns of pulp polysaccharides with the bleaching agent was suggested to be a crucial factor predetermining the extent of brightness reversion of pulp.

Ultrahigh hydrostatic pressure (UHP) was applied to enhance the enzymatic hydrolysis of xylan in cellulosic fibers. The pretreatment improved xylan accessibility in the fiber cell wall and a 5–10-fold increase in the initial hydrolysis rate of xylan by xylanase was observed when Eucalyptus globulus kraft bleached pulp was pretreated at hydrostatic pressures of 300–400 MPa for 15–45 min. The rate and the extent of hydrolysis can be controlled by varying the pressure and the exposure time of UHP treatment prior to enzymatic hydrolysis. Sequential UHP pretreatment and hydrolysis by xylanase disaggregated the hydrated cellulose fibrils and led to the gelation of cell wall regions accessible to enzymatic attack. UHP could therefore become a tool for the engineering of enzymatic reactions within cellulosic fibers to obtain products with tailored properties.

Modified eucalyptus kraft lignin doped with multiwall carbon nanotubes (MWCNTs) was used as a macromonomer in step-growth polymerization with tolylene 2,4-diisocyanate terminated poly(propylene glycol) with the aim of producing a conductive copolymer for all-solid-state potentiometric chemical sensor applications. The crosslinked elastomeric polyurethane obtained was characterized by Fourier transform infrared attenuated total reflection spectroscopy, scanning electron microscopy, tunnelling electron microscopy and atomic force microscopy. Doping of lignin-based polyurethane with MWCNTs produced a significant enhancement of its electrical conductivity without deterioration of thermal and viscoelastic properties. The polymer composite displayed a low percolation threshold at an MWCNT concentration of 0.18% (w/w), which was explained by the oriented distribution of MWCNTs along lignin clusters. All lignin-based polyurethanes doped with MWCNTs at concentrations above the percolation threshold are suitable for sensor applications. Copyright © 2012 Society of Chemical Industry

Cellulosic fibre/silica hybrid materials functionalized with Keggin-type polyoxometalates ([PV2Mo10O40]52, [PVMo11O40]42, ([PMo12O40]32 or [PW12O40]32) were prepared by a sol–gel method at room temperature. The novel materials are composed of ca. 56 wt% of polysaccharides, ca. 37 wt% of propylamine-modified silica, 2 wt% of polyoxometalate, and 5% of hydration water. The silica network of these hybrids exhibits relatively high degree of condensation being distributed mainly on the surface of the cellulosic fibres as a dense film. The functionalization of silica with polyoxometalates via electrostatic interactions with protonated propylamino groups of modified silica was unambiguously confirmed. Despite their high silica content cellulose/silica hybrids retained basic cellulosic pulp properties—supramolecular and fibrous structure, porosity, relatively low density, etc. The novel bio-based material functionalized with 2% of [PVMo11O40]42 shows particularly high activity towards the oxidation of volatile organic compounds (VOCs) present in urban air thus anticipating future environmental applications. published

The hydroxyl radicals are widely implicated in oxidation of carbohydrates during biological and industrial processes being responsible for their structural modifications and causing functional damage. The identification of intermediate oxidation products is hampered by a lack of reliable sensible methods for their detection. In this study, the oxidation of two models of galactomannans (Man 3 and GalMan 2 ) has been studied in reaction with hydroxyl radical generated by Fenton reaction. The oxidation patterns were assessed using preparative ligand-exchange/size-exclusion chromatography (LEX/SEC) coupled with tandem electrospray mass spectrometry (ESI-MS/MS). This allowed the identification of derived oligosaccharides (OS) containing hexuronic, hexonic, pentonic and erythronic acid residues and neutral OS bearing hydroperoxy, hydrated carbonyl moieties and residues from pyranosyl ring cleavage. The depolymerization products have been also detected upon oxidation of oligomers. This study allowed developing a simple, effective ‘fingerprinting’ protocol for detecting the damage done to mannans by oxidative radicals.