Volume 74, Issue 2 - Special Issue: The 15th European Workshop on Lignocellulosics and Pulp (Aveiro, Portugal, June 26–29, 2018) / Issue Editor: Thomas Rosenau

Plants of the Lamiaceae family are important ornamental, medicinal and aromatic plants, with many of them producing essential oils that are used in traditional and modern medicine as well as in the pharmaceutical industry. This review summarizes research on selected Lamiaceae species from the Uzbekistan flora with regard to their chemical constituents and biological activity. These plants contain many bioactive compounds, such as ecdysteroids, iridoids, flavonoids, terpenoids, phenolics and alkaloids, exhibiting different antibacterial, antifungal, cytotoxic and antioxidant activities. The botanical description, taxonomy, habitat and ethnopharmacology of the investigated Lamiaceae species that have been used in Uzbek traditional medicine are presented as well, including the local names.

Wood chips from a novel type of drum chipper were compared to wood chips from a conventional disc chipper in an evaluation based on demonstration-scale and industrial-scale machinery. The evaluation was performed as the wood chippers were used as production machines in a kraft pulp mill using softwood. The average bulk density of the wood chips from the disc chipper and the drum chipper was similar and within the range of 138–140 kg/m 3 . The size distribution of the wood chips was investigated using a conventional screening method, and by using an automatized image-analysis system based on laser scanning. The average length was set to be the same, but the wood chips from the drum chipper had a more uniform length. The average thickness was similar, but the drum chipper generated slightly more thinner wood chips. Compared to the disc chipper and using the screening method, the drum chipper generated a similar fraction of oversized and overthick wood chips, 51% more large accept chips, 11% more total accept chips, and 74% less pin chips and fines. Image analysis resulted in similar data. The results indicate that drum chippers warrant further attention as an alternative to conventional industrial-scale disc chippers.

Xylose-rich solutions were produced by applying water pre-hydrolysis on mixed hardwood chips followed by an enzymatic treatment of the filtrate. The liquid phase obtained after water pre-hydrolysis contained xylose and xylans as the major components as well as other hemicelluloses and monosaccharides, acetic acid, and some degradation products of the monosaccharides [furfural, 5-(hydroxymethyl)furfural]. This hydrolysate underwent a two-step enzymatic treatment successively with endo-1,4-β-xylanase and 1,4-β-xylosidase to specifically depolymerize xylans into xylose without producing monosaccharides from the other oligosaccharides. After this treatment, 20.5% of the xylose units remained as oligomers. Matrix-assisted laser desorption ionization time-of-flight (MALDI-ToF) mass spectrometry was applied after each step of the treatment to approach the structure of hemicellulose oligomers, to follow their depolymerization and to understand the reason for the resistance of some of them to enzymatic hydrolysis. It was found that highly acetylated xylans and/or xylans still substituted with 4-O-methylglucuronic groups were particularly resistant to this treatment.

The kraft process remains the dominant chemical pulping process but still struggles with extensive hemicellulose degradation. Such degradation has previously been mitigated through the use of anthraquinone; but due to it recently being found to have carcinogenic properties, anthraquinone is now being phased out. One alternative, sodium dithionite, was initially investigated in the 1950s but was found to be unviable. The present study investigated whether sodium dithionite could be made viable through the use of different processing parameters, using mannose as a model compound and measuring the yield of mannitol in the various systems using gas chromatography with flame ionization detection (GC-FID) and nuclear magnetic resonance (NMR). Alkalinity was found to be crucial; at pH 14 as well as pH 7, dithionite indeed proved unviable, but if pH was kept at either 8 or 10 significant reduction was seen to occur. The best results were obtained at pH 10 when a lower temperature (70°C) was used to compensate for alkaline degradation of the mannose reactant.

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

The Klason method is adequate for quantifying lignin in softwood (SWD) but is less so for hardwood (HWD). The latter contains a fraction of acid-soluble lignin (ASL) that is not measurable under the conditions prevailing in the Klason method and that must be quantified by other means. This study aimed at investigating the composition of ASL obtained from eucalypt and pine woods by using pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS). About 2.7% and 0.9% ASL by dry wood weight were measured in the acid filtrate of eucalypt and pine, respectively, by the Technical Association of the Pulp and Paper Industry (TAPPI) UM 250 method. The acid filtrate was lyophilized and processed by Py-GC-MS, allowing identification of 26 primary pyrolysis products, with 2% and 52% relative molar abundance coming from lignin and carbohydrates, respectively, for eucalypt and 24 primary pyrolysis products, with 1% and 54% relative molar abundance from lignin and carbohydrates, respectively, for pine. The main products derived from lignin were phenol, 4-methylphenol, guaiacol, 4-methylcatechol, syringol, acetosyringone and vanillin. It was concluded that measurements of ASL remain a requirement for accurate eucalypt and pine wood lignin quantification because lignin derivatives remain in the acid filtrate from the Klason lignin quantification method. Corrections for carbohydrate-derived compounds are not necessary, despite their predominance in the filtrate, because these derivatives do not interfere with ultraviolet (UV) absorption.

Recent developments in enzymatic bleaching processes have led to replacement strategies of harsh chemicals by haloperoxidases. For this purpose, it is important to control the haloperoxidase-mediated formation of adsorbable organic halides (AOX). In this study, we studied the chlorination of monomeric and dimeric lignin model substrates. Guaiacol, acetovanillone, veratryl alcohol, pinoresinol and adlerol were treated with Curvularia verruculosa haloperoxidase and compared to a sodium hypochlorite treatment. High-performance liquid chromatography-diode array detection-mass spectrometry (HPLC-DAD-MS) analysis was employed for the characterization of the reaction products. Our results show that while treatment with haloperoxidases in the presence of sodium chloride and hydrogen peroxide leads to no improvement in AOX formation compared to chemical treatment with NaOCl, addition of ammonium chloride substantially lessens chlorination and promotes β-O-4 ether bond cleavage. The use of ammonium chloride in conjunction with enzymatic haloperoxidase-based bleaching could be a route to minimize lignin chlorination.

Lignin is a renewable and abundant source for production of bio-based chemicals and is a valuable alternative to crude oil to obtain aromatic building blocks. It is built from aromatic units with strong chemical linkages, which need to be cleaved to enable the use of the aromatic compounds in industrial applications. In addition to depolymerizing lignin, efficient fractionation and conversion of the resulting complex mixtures is an essential step in the valorization of lignin derivatives for different applications. In this work, we studied the separation of a lignin oil obtained by catalytic cleavage in supercritical ethanol (scEtOH) of technical lignin produced by means of soda pulping of wheat straw. The use of six commercial polymeric nanofiltration (NF) membranes and one in-house developed Grignard-functionalized ceramic membrane was investigated for the fractionation of a mixture of lignin derivatives. Separation by molecular weight (MW) was observed with the polymeric NP030 membrane but not with the other membranes tested. The development of a protocol using this membrane in the diafiltration mode for fractionation of crude lignin oils (CLOs) is discussed.

The substitution of phenol by lignin in phenol-formaldehyde (PF) resins is one of the most promising end uses of lignin valorization. Lignin from grasses and softwood has been the focus of the studies in this field as they present a higher number of theoretical reactive sites for resin synthesis. Herein we examined the composition and chemical reactivity of “less-reactive” hardwood lignin fractions and their performance in PF resins, synthesized by substituting 50 wt% of the phenol with lignin. Before resin synthesis, the samples were hydroxymethylated and the maximum formaldehyde consumption was recorded. By doing so, we observed that hardwood fractions consumed formaldehyde close to the theoretical calculation, whereas the reference softwood lignin consumed only about ¼ of the theoretical value. In the resin synthesis, we added formaldehyde to the formulation according to the measured maximum formaldehyde consumption. Thus, low values of free formaldehyde in lignin-PF (LPF) resins were achieved (<0.23%). Moreover, the resin bonding strength displayed similar performance irrespective of whether the LPF resins were made with softwood or hardwood lignin (range of 3.4–4.8 N mm −2 at 150°C and 45–480 s of press time). Furthermore, we concluded that hardwood kraft lignins present no disadvantage compared to softwood lignins in PF resin applications, which have significant practical implications.

Commercial birch xylan (CX) and alkali-soluble birch xylan (ASX) were subjected to controlled acetylation and used for film formation in the presence (20% and 40%) or absence of plasticizers (i.e. glycerol, sorbitol and xylitol). Although the content of Klason lignin was similar (1.2–1.4%), the acetylation process was favored by the high-purity CX (97% xylan) over the ASX (89% xylan). On the other hand, the presence of residual pectin heteropolysaccharides rather than xylan in the ASX sample was beneficial for film formation. These heteropolysaccharides seemed to act as natural plasticizers during film formation, allowing the formation of coherent films from ASX, even in the absence of an external plasticizer. The use of plasticizers favored the mechanical properties of films, especially in a dosage of 40%, when plastic behavior was created. Acetylation favored the film formation and slightly improved the mechanical properties of the films, and this improvement was in the same range as that achieved when using 20% plasticizer in non-acetylated ASX.

Coniferyl alcohol is considered to be a potent antioxidant and a precursor of several bioactive products. In addition, it is a frequently used as a model compound in lignin chemistry. Coniferyl thiol is used analogously to study the sulfur chemistry in technical lignins. Coniferyl alcohol was synthesized in a large scale from commercially available ferulic acid by a mixed anhydride reduction method which affords high yields (84%) under very mild conditions and allows using sodium borohydride. The nucleophilic substitution of 4-O-acetylated coniferyl alcohol ( 3 ) with thioacetic acid in the presence of dimethylformamide (DMF) dineopentylacetal afforded 4-O-acetylated coniferyl thioacetate ( 5 ) in a 70% yield, which, in a 72% yield, was deprotected to the respective thiol ( 6 ). Both coniferyl alcohol and coniferyl thiol were comprehensively analytically characterized [one-dimensional (1D) and two-dimensional (2D) nuclear magnetic resonance (NMR) spectroscopy]. The presented approach renders the two model substances readily available on a gram scale and according to low-risk, environmentally compatible protocols.

Usage of lignin and its derivatives as chemical and carbon source, i.e. in processes other than burning, is one of the most active fields in renewable resource chemistry today. In this study, the synthesis of lignosulfonate (LS)-based polyurethane (PU) materials from non-toxic reagents and through environmentally friendly processes is presented. LS, modified with bio-based (glycerin-derived) cyclic carbonate moieties, was reacted with 1,6-hexamethylenediamine (HMDA) to form characteristic PU material. For mechanistic studies and reaction optimization, cyclic carbonates and 1,2-diol derivatives of vanillyl alcohol (VA), as a simplifying lignin model compound, were employed. An LS-bound cyclic carbonate can be formed in one pot without a transesterification step, which simplifies the route toward non-isocyanate lignin-based PU materials. Attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectra showed typical linkages of cyclic carbonates and 1,2-diols on LS. Further analytical characterization, in both the model compound and the LS polymer case, was provided by liquid-state nuclear magnetic resonance (NMR) spectroscopy [one-dimensional (1D), two-dimensional (2D) and 31 P] and 13 C solid-state (ss) NMR. The production of PU materials from sulfonated lignin and glycerol carbonate, synthesized through a non-isocyanate reaction pathway, confirms the good potential of LS utilization in the development of PU composites based on renewable resources.

The technical viability was investigated for the conversion of Pinus pinaster stumps to value-added products via a chain of pretreatments and simultaneous saccharification and fermentation (SSF) steps to obtain bioethanol. Sequential steam explosion (SE), organosolv (OS) pretreatment and soda-anthraquinone pulping (Na/AQ) were performed resulting in an unbleached pulp (UBP), which was successfully converted via SSF to bioethanol with concentrations up to 79 g l −1 , which corresponds to a conversion yield of 97% and productivity of 1.09 g l −1 h −1 at 15% total solids. Accordingly, delignification steps by oxygen bleaching are not necessary for bioethanol production. Different industrial softwood (SW) pulps were also tested as reference materials. Total lignin contents up to 4.5% in SW-based pulps had no adverse effects on SSF efficiency.

A scalable, fixed-bed adsorption system for the removal and selective recovery of polyphenols (lignans and stilbenes) from medium-density fiberboard (MDF) process waters was developed. Before adsorption, fibers and non-colloidal substances were removed from process water by centrifugation, while colloidal fatty and resin acids were removed by filtration through a 30-kDa cut-off membrane. Polyphenols were then isothermally adsorbed on a medium-pressure liquid chromatography (MPLC) column packed with Divergan ® RS, a regenerable macroporous, cross-linked pyrrolidone-based [polyvinylpolypyrrolidone (PVPP)] resin. Loading at acidic pH and subsequent gradient elution of polyphenols with methanol were monitored at 280 nm, and elution conditions for selective polyphenol recovery were optimized based on gas chromatography/mass spectrometry (GC/MS) analyses of the obtained fractions. Lignans were eluted in successive fractions containing the individual lignans in different proportions, followed by pinosylvin in a separate fraction. The capacity of the PVPP for hydroxymatairesinol (HMR) as a model lignan was determined to be 37.4 mg g −1 at 1% breakthrough. Highly polar substances such as sugars and sugar alcohols, however, were not retained on the column and remained in the flow-through. The results revealed the benefits of PVPP for the recovery of potentially valuable polyphenols from MDF process waters while reducing carbon load and toxicity for subsequent biological treatment.

Benchtop nuclear magnetic resonance (NMR) spectroscopy is an emerging field with an appealing profile for industrial applications. The instrumentation offers the possibility to measure NMR spectra in situations where high-field NMR spectroscopy is considered too expensive or complicated. In this study, we investigated the scope and limitations of 1 H NMR measurements on kraft lignins and black liquors at low magnetic field strengths (1.0 and 1.5 T). The ability to quantify different classes of compounds was investigated and found to be promising. NMR-based diffusion measurements were performed, with the aim of gaining insight into the molar mass of the lignins at hand. These measurements were fast, repeatable and in good agreement with established methods.