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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.

Lignin obtained by Lignoboost® procedure from black liquor after kraft pulping of Eucalyptus globulus wood was characterized and converted into liquid polyols via an innovative and safe procedure using base catalyzed oxyalkylation with propylene carbonate (PC). The effect of four catalysts, Potassium carbonate (K2CO3), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), dicyanodiamide (DICY), and 1,4-diazabicyclo [2.2.2] octane (DABCO) was evaluated in terms of lignin polyol yield and weight gain. The ensuing polyols were also characterized by fourier transform infrared (FTIR), 1H NMR, 13C NMR, and size exclusion chromatography (SEC) to determine the degree of the substitution (DS), degree of polymerization (DP), and the molecular weight, respectively. Only a minor proportion of PC (ca. 3–15%) was converted to propylene glycol/homooligomers as revealed by high performance liquid chromatography (HPLC). All catalysts promoted preferential derivatization of lignin phenolic OH groups by oxypropyl moieties. The maximum average DP of propylene oxide chains in oxyalkylated Lignoboost® kraft lignin (oKL) was 1.85 per one phenylpropane unit (PPU) using DBU. Conversely, the DP of oKL using DICY was very low (0.27/PPU). DICY’s catalytic activity seems to be jeopardized due to the formation of unreactive adducts with lignin. The oKL obtained using DBU, DABCO, and K2CO3 have potential to be used as polyols in the production of polyurethanes as the corresponding hydroxyl number (IOH) is in the range of 198–410 mg KOH g−1.

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.

The structural features of macromolecular components of cork (suberin, lignin, cellulose and hemicelluloses) from Quercus suber L. used for the production of stoppers were assessed after their isolation and purification. Suberin is the major component of cork (ca. 44%) and is constituted mainly by hydroxy fatty acids (C14–C26). Cork lignin was found to be highly condensed (16.2%) and revealed a syringyl:guaiacyl:p-hydroxyphenyl (S:G:H) ratio of 26:71:3 with predominant β-O-4′ (0.38%), β-5′, β-β and tetrahydrofuran (THF) type (totally ca. 27%) structures. Cork lignin also has a remarkable amount of ferulic acid structures, which are considered the binding point between lignin and suberin. The cellulose of cork cells (17.2%) is a typical cellulose I polymorph with a degree of crystallinity (DC) of 70.3% and an average crystallite width of 3.5 nm. The major hemicellulose of cork is glucuronoxylan (near 6.0%) possessing a molar Xylp:MeGlcpA ratio of 14:1.

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.

Non-enzymatic transglycosylation reactions are known to occur under high sugar concentrations, high temperatures, low moisture environments and acidic conditions. Although honey is not a thermally processed food, its high sugars concentration under an acidic and low moisture environment for prolonged periods of time may also promote these reactions. To test this hypothesis six model solutions containing combinations of sucrose and glucose or fructose, prepared with water and diluted citric acid at pH 4.0 and 2.0, were incubated at 35 °C during up to 5 months, similar to the honey under hive conditions. Electrospray ionization mass spectrometry (ESI-MS) allowed to observe polymerization products soon after their incubation. After 5 months, a degree of polymerization of 6 was detected, similarly to the honey samples used for comparison. Maltose, isomaltose, inulobiose, sophorose, gentiobiose, 1-kestose and panose were detected in both model solutions and honey samples, showing that non-enzymatic transglycosylation reactions also contribute to oligosaccharides origin and diversity in honey.

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.

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

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).

Water absorption capacity is a key characteristic of cellulosic pulps used for different commodities. This property is influenced by the affinity of the pulp fiber surface with water, chemical composition of the pulp, morphology, and organization of fibers in the network. In this study, surface properties of six industrial Eucalyptus bleached kraft pulps (fluff pulps) dry-defiberized in a Hammermill, which were obtained by wood pulping and pulp bleaching under different production conditions, were studied while employing dynamic water vapor sorption and contact angles measurements. The absorption properties of air-laid pulp pads were analyzed following the absorbency testing procedure and the relationship between these properties and pulp&rsquo, s chemical composition and fiber network structure were assessed by multivariate analysis. The results showed that the accessibility of the fiber surface is related to the reduction of the contact angles, but, at the same time, to the longer absorption time and less absorption capacity of the fiber network. Therefore, the absorption properties of the pulps are not necessarily directly related to their surface properties. Indeed, absorptivity is related to the surface chemical composition, fiber morphology, and fiber network structure. Thus, surface carboxylic groups promote total water uptake, resulting in better absorption capacity. Greater fiber coarseness and deformations (curl and kink) provide a less wettable surface, but a more porous network with higher specific volume, resulting in more absorbent air-laid formulations.

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.

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.

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

The identification of paper composition, pH, early signs of paper degradation, and emitting volatile organic compounds (VOCs) are mandatory for effective preventive conservation of paper/books. Sampling restrictions in the analysis of cultural heritage materials limit the choice of appropriate analytical methods. Solvent-free analytical techniques with nondestructive sampling are needed. Addressing this challenge, an electronic nose based on six-coated piezoelectric quartz crystals was assembled and used to analyze VOCs emitted from books. Careful selection of sensor coatings and cluster analysis allowed us to achieve a clear distinction between cotton/linen rag and wood pulp paper, and among the letter group, the discrimination between papers manufactured from alkaline and acidic stocks. This six-element sensor array was therefore able to replace destructive tests as the ones ordinarily used for paper pH measurements. The same electronic nose was able to separate aged pale-yellow paper, a visible initial sign of paper degradation, from well-preserved still white papers, even when made from the same raw material. One of the used sensors detected furfural, often seen as a marker of cellulose degradation, at lower levels than the detection limit found in the literature with gas chromatography-mass spectrometry, a much more complex bulky and expensive instrument.

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.

A series of six industrial bleached hardwood kraft pulps produced from Eucalyptus globulus (BEKPs) under variable process conditions were dry-defiberized on a pilot scale hammermill at 3500 rpm and the nonwoven air-laid fabrics evaluated for their specific volume, absorption capacity/absorption rate and fiber network strength. The effect of non-defiberized fiber aggregates (knots) on the former properties was evaluated. Processual variations in pulping and bleaching conditions revealed variability within 15% in the absorption capacity of fluff pulps and within 25% in the network strength of the air-laid formulations. These variations were attributed to changes in the chemical composition of BEKPs and fiber morphology. The importance of pulp bleaching sequence on the quality of BEKPs for fluff applications was highlighted. BEKPs, having a high residual xylan content with a greater amount of uronic/hexenuronic moieties and coarser/deformed fibers, revealed the best performance in fluff applications. The coarseness was considered a critical morphological parameter of the fibers, strongly affecting the porosity of air-laid formulations, which determined the absorption capacity and the network strength. The absorption capacity of fluffed BEKP was comparable of commercial bleached softwood kraft pulp (BSKP), although the latter showed almost triple the network strength of air-laid formulations produced with BEKP. BSKP proved to be much more vulnerable to dry defiberization conditions than BEKP and suffered a pronounced cut of fibers, producing larger amounts of fines (dust) and stronger undesirable peeling and straightening of fibers. BEKPs can be considered a promising raw material for fluff applications, whose basic properties can be adjusted according to the needs by varying conditions in the pulping and bleaching process steps.

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

In this work bleached E. globulus kraft pulp was doped with polyhexamethylene biguanide (PHMB) from an aqueous solution or from a suspension of silica capsules (PHMB@silica) by impregnation under atmospheric or ultra-high pressure (UHP) conditions (500MPa). The antimicrobial properties of pulps were evaluated towards gram-negative E. coli and gram-positive L. innocua bacteria. PHMB loads below 500mg per kg of pulp revealed negligible bacteriostatic properties, whereas PHMB loads of ca 3000-4000mg per kg demonstrated bactericidal properties of pulp without significant deterioration of its mechanical strength. The UHP impregnation allowed significant improvement of PHMB uptake. Thus, under equal conditions, PHMB uptake was ca 25% greater under UHP than under atmospheric pressure impregnation, whereas the leachable amounts of PHMB in both pulps were comparable. The sorption of PHMB@silica on pulp in suspension under UHP conditions was ca 17% greater than under atmospheric pressure with almost 70% increase of leachable PHMB.

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 relevance of microalgae biotechnology for producing high-value compounds with biomedical application, such as polysaccharides, has been increasing. Despite this, the knowledge about the composition and structure of microalgae polysaccharides is still scarce. In this work, water-soluble polysaccharides from Nannochloropsis oculata were extracted, fractionated, structurally analysed, and subsequently tested in terms of immunostimulatory activity. A combination of sugar and methylation analysis with interaction data of carbohydrate-binding proteins using carbohydrate microarrays disclosed the complex structural features of the different polysaccharides. These analyses showed that the water-soluble polysaccharides fractions from N. oculata were rich in (β1→3, β1→4)-glucans, (α1→3)-, (α1→4)-mannans, and anionic sulphated heterorhamnans. The immunostimulatory assay highlighted that these fractions could also stimulate murine B-lymphocytes. Thus, the N. oculata water-soluble polysaccharides show potential to be further explored for immune-mediated biomedical applications.

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.

Hardwood spent sulphite liquors (HSSLs) are by-products from the pulping industry rich in pentoses, which are not yet fully exploited for bioprocessing, namely for the production of bioethanol. The sustainable fermentation of pentoses into bioethanol is a challenge to overcome. Besides sugars, HSSLs contains inhibitors that decrease the possibility of bioprocessing of these by-products. Nevertheless, recent studies have brought new insights in using HSSLs for bioethanol production. This paper reviews the results of relevant studies carried out with HSSLs towards bioprocessing to bioethanol. The composition of SSLs was compared and related with the wood origin stressing specificity of microbial inhibitors from HSSL and their anti-microbial effect. The different fermentative processes, the microorganisms used, and the strategies to improve yield and productivity used so far were also reviewed. This review allowed concluding that research is still needed in several areas, including optimization of detoxification processes, fermentation strategies and selection of suitable microbial strains in order to achieve the integration of the different steps needed for HSSLs bioconversion into ethanol thus contributing for sustainability of pulping mills within biorefinary concept. (C) 2012 Elsevier Ltd. 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.

Three mixtures containing different molar proportions of (beta 1-4)-D-mannotriose and (alpha 1 -> 5)-L-arabinotriose, oligosaccharides structurally related to coffee polysaccharides (galactomannans and arabinogalactans), were roasted at 200 degrees C for different periods. Electrospray ionization mass spectrometry (ESI-MS) and tandem mass spectrometry (ESI-MSn) analyses of labeled (180) and unlabeled samples allowed identification of not only nonhybrid oligosaccharides but also hybrid oligosaccharides composed of both hexose and pentose units. The identification of hybrid oligosaccharides allowed us to infer the occurrence of nonenzymatic transglycosylation reactions involving both oligosaccharides in the starting mixtures. Also, it was observed that using different proportions of the oligosaccharides in the starting mixtures and extents of thermal treatment led to a variation in the composition of the compounds formed. These results have led to the conclusion that, depending on the distribution of the polysaccharides in the bean cell walls and the roasting conditions, different nonhybrid and hybrid structures can be formed during coffee roasting.

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 oxidation kinetics of lignosulfonates (LS) from acidic magnesium-based sulfite pulping of Eucalyptus globulus wood with oxygen under alkaline conditions was studied. The analysis of oxidation products in the reaction system O(2)/NaOH revealed a predominance of aromatic aldehydes (vanillin and syringic aldehyde) though small amounts of vanillic and syringic acids and acetophenone/phenylacetaldehyde derivatives have also been detected. The rate constant of syringic aldehyde formation was roughly twice of that for vanillin. The effective activation energies for the oxidation of LS to aromatic aldehydes (ca. 60-70 kJ/mol) were rather different to those found for the formation of aromatic acids (ca. 110 kJ/mol) indicating different mechanisms involved in the rate-determining reaction step. The addition of catalyst (copper salt, 20% w/w) promoted the LS oxidation with increments of aromatic aldehyde yields by 25-50%. The maximum yields of syringic aldehyde and vanillin upon LS oxidation were 16.1 and 4.5%, respectively (150 degrees C, 20 min, P(O2) = 10 bar, 0.9 M NaOH solution). The highly negative effect of concomitant sugars in sulfite liquor to the yield of aromatic aldehydes was highlighted.

The correct choice of the specific lignocellulosic biomass pretreatment allows obtaining high biomass conversions for biorefinery implementations and cellulosic bioethanol production from renewable resources. Cynara cardunculus (cardoon) pretreated by steam explosion (SE) was involved in second-generation bioethanol production using separate hydrolysis and fermentation (SHF) or simultaneous saccharification and fermentation (SSF) processes. Steam explosion pretreatment led to partial solubilisation of hemicelluloses and increased the accessibility of residual polysaccharides towards enzymatic hydrolysis revealing 64% of sugars yield against 11% from untreated plant material. Alkaline extraction after SE pretreatment of cardoon (CSEOH) promoted partial removal of degraded lignin, tannins, extractives and hemicelluloses thus allowing to double glucose concentration upon saccharification step. Bioethanol fermentation in SSF mode was faster than SHF process providing the best results: ethanol concentration 18.7 g L-1, fermentation efficiency of 66.6% and a yield of 26.6 g ethanol/100 g CSEOH or 10.1 g ethanol/100 g untreated cardoon. (C) 2015 Elsevier Ltd. All rights reserved.

The residual lignin (LR sample) was isolated from unbleached acid sulphite pulp from Eucalyptus globulus with kappa number 18.2 by acidolysis and structurally characterized by wet chemistry and NMR techniques. The main structural features of LR were compared with lignin isolated from sulphite spent liquor (LSSL sample) and dioxane lignin (DL sample) from eucalypt wood. LR contains less sulphonic groups (4.4%) compared to LSSL (11.3%), and its molecular weight (2200 Da) is very close to that of DL (2600 Da). A part of sulphonic groups is located at the benzylic carbon in β-O-4′ and β-5′ structures. LR revealed ca. 20% lower abundance of β-O-4′ structures than DL, but ca. 40% higher abundance of these structures than LSSL. The degree of condensation of LR was higher than that of DL but lower than that of LSSL. The condensed structures in LR mainly originate from C6-linked syringyl units. The structural peculiarities of LR consisted of the relatively high proportion of syringyl units compared to DL and the strong structural association with hemicelluloses via benzyl ether linkages. The differences in the structure of residual lignins from eucalypt sulphite and kraft pulps have been discussed.

The feasibility of using sequential microwave superheated water extraction (MAE) for the recovery of mannans from spent coffee grounds (SCG) was studied. Due to the high contents of mannose still present in the SCG residue left after two consecutive MAE, the unextracted material was re-suspended in water and submitted to a third microwave irradiation (MAE3) at 200 degrees C for 3 min. With MAE3, mannose recovery achieved 48%, increasing to 56% by MAE4, and reaching a maximum of 69% with MAE5. Glycosidic-linkage analysis showed that in MAE3 mainly galactomannans were recovered, while debranched galactomannans were recovered with MAE4 and MAE5. With increasing the number of extractions, the average degree of polymerization of the mannans decreased, as observed by size-exclusion chromatography and by methylation analysis. Scanning electron microscopy images showed a decrease on cell walls thickness. After final MAE5, the remaining un-extracted insoluble material, representing 22% of the initial SCG, was composed mainly by cellulose (84%). (C) 2013 Elsevier Ltd. All rights reserved.

The chemical structure of lignin from grape stalks, an abundant waste of winemaking, has been studied. The dioxane lignin was isolated from extractive- and protein-free grape stalks (Vitis vinifera L.) by modified acidolytic procedure and submitted to a structural analysis by wet chemistry (nitrobenzene and permanganate oxidation (PO)) and spectroscopic techniques. The results obtained suggest that grape stalk lignin is an HGS type with molar proportions of p-hydroxyphenyl (H), guaiacyl (G) and syringyl (S) units of 3:71:26. Structural analysis by H-1 and C-13 NMR spectroscopy and PO indicates the predominance of beta-O-4' structures (39% mol) in grape stalk lignin together with moderate amounts of beta-5', beta-beta, beta-1', 5-5', and 4-O-5' structures. NMR studies also revealed that grape lignin should be structurally associated with tannins. The condensation degree of grape stalks lignin is higher than that of conventional wood lignins and lignins from other agricultural residues.

The photochemical degradation of 2-mercaptobenzothiazole (MBT) and 1,2,3-benzotriazole (BTA) inhibitors was studied in the present work in aqueous and in organic solutions. The extent of photo-degradation was assessed by UV-Vis spectroscopy and the main reaction products were identified by tandem electrospray ionization mass spectrometry (ESI-MS/MS). The analysis of degradation products upon UV irradiation revealed the predominant formation of dimeric compounds from MBT and oligomeric structures from BTA, which were further converted into aniline. The increase of the quantum yield of MBT and BTA photodegradation reactions under aerobic conditions both in aqueous and organic solvents was explained by an increase of the spin-orbit conversion of the singlet radical pairs into the triplet radical pairs in the presence of oxygen. These triplet pairs further dissociate into free radicals, or convert to the parent compounds. At the early stage of UV irradiation, free radical coupling leads essentially to dimer formation in the case of MBT and to the formation of oligomers in the case of BTA irradiation.

The polyoxometalate (POM)-laccase catalytic system was applied for the first time to aerobic delignification of kraft pulps at moderate (40-60 degreesC) temperatures. Laccase was found to readily catalyze the re-oxidation of different kinds of polyoxometalates, including those, which cannot be re-oxidized by dioxygen even at high temperatures (PMo11V1, SiW11V1. etc.). This allows a sequence of catalytic redox cycles similar to that in the laccase-mediator system (LMS) where electrons are transferred from the substrate (lignin) via POM and laccase to oxygen. Results obtained showed that the POM-laccase system could decrease kappa number of eucalypt kraft pulp from 13.7 to 8.5 though the reaction rate is relatively slow. Among different POM used, SiW11V showed the best results. The effect of the process variables on the delignification was studied. The best results in delignification of eucalypt pulp were obtained at 60 degreesC, oxygen pressure of 5 bar, pH 6.3, SiW11V concentration of 4.2 mM and laccase concentration of 0.65 U/ml. The reaction temperature appears to be one of the crucial factors in the achievement of a delignification rate acceptable for practical application. (C) 2001 Elsevier Science B.V. All rights reserved.

An approach for the integrated utilization of grape skins from white grape pomaces has been proposed. This consists of consecutive or simultaneous extraction of grape skins with neutral organic solvent and water under reflux. Organic extract is a valuable raw material for the isolation of oleanolic acid. The aqueous extract (ca 50%, w/w) is composed of essentially hexoses and suitable for the high yield (till 51%) bioethanol production at a maximum specific cell growth rate (mu(max)) of 0.29 h(-1). The remained extracted grape skins are the complex of structural polysaccharides embedded into cutinous matrix. Extracted grape skins were shown to be a prospective raw material for the production of low-density boards (d

Cellulose/silica derived hybrids materials (CSH), functionalized with aluminium, calcium, and propylammonium ions, were tested for their possible use in the removal of arsenic from aqueous solutions with controlled compositions to levels lower than 10 μg As/L. CSH were synthesized by sol-gel method using bleached pulp, as source of cellulose fiber, and tetraethoxysilane (TEOS) as main silica precursor. The silica network, made in situ, contained various anchored cations such as propylammonium (CSH-PA), aluminium (CSH-Al) and, calcium (CSH-Ca). Thin films or mesoparticles of silica were deposited on cellulose fibers as shown by SEM and XRD. These hybrid materials were immersed in controlled ionic strength aqueous solutions with arsenic concentrations lower than 0.2 mg As/L. The best performance was shown by CSH-PA that was able to remove a maximum of 20 % of the total arsenic concentration.