Search Results (26)

The functionalisation of lignin-derived phenolics (guaiacol, 4-propylguaiacol, eugenol, isoeugenol, phenol, m-cresol, catechol, syringol, syringaldehyde, and vanillin) for the synthesis of thermoplastic polyurethanes (PUs) and polyester (PE) resins is herein described. Diols were synthesised from phenolics in a one-step reaction using either glycerol carbonate or ethylene carbonate as a greener, solvent-free synthetic route. Nine of the diols were selected for the synthesis of Pus, and two of the diols were used for the synthesis of PE resins, with their physical and thermal properties characterised. Analysis of the PUs by differential scanning calorimetry (DSC) confirmed their amorphous nature, while thermogravimetric analysis (TGA) suggested improved thermal stability for all PUs with the addition of an alkyl or aldehyde substituent on the benzene ring regardless of the diisocyanate used. However, lower PU thermal stabilities were observed with the use of an aliphatic diisocyanate over an aromatic diisocyanate in the absence of an additional substituent. Analysis of the PEs by DSC also confirmed that the clear resins were all amorphous, and gel permeation chromatography (GPC) revealed significantly higher molecular weights and dispersities when an aliphatic diacid was utilised over an aromatic diacid. Full article

Lignin is a natural aromatic macromolecule present in wood and an abundant resource on Earth, yet it is hardly used. In this study, an aqueous solution plasma treatment was investigated for the catalyst-free production of valuable chemicals from lignin. To elucidate the decomposition mechanism, the aqueous solution plasma treatment was applied to the fundamental lignin aromatic model compounds—phenol, guaiacol, and syringol. The results showed that the decomposition rate followed the order syringol > guaiacol > phenol, indicating that electron-donating methoxy groups enhance reactivity. These aromatic model compounds underwent hydroxylation at the ortho and para positions, oxidative ring cleavage, and fragmentation, leading to the formation of various dicarboxylic acids, primarily oxalic acid. All these reactions were promoted by hydroxyl radicals generated from water. Ultimately, decarbonylation and decarboxylation of carboxyl groups resulted in gasification, mainly producing H₂, CO, and CO₂. These results provide fundamental insights into lignin decomposition and demonstrate that aqueous solution plasma is a promising method for producing dicarboxylic acids from lignin under mild conditions without catalysts. Full article

Lignin is one of the main structural components of lignocellulosic biomass and can be utilized to produce phenolic compounds that can be converted downstream to cycloalkanes and aromatics, which are useful as drop-in road or aviation biofuels. Within this study, the hydrodeoxygenation of model phenolic/aromatic compounds and surrogate mixture simulating the light fraction of lignin fast-pyrolysis bio-oil was performed under mild reaction conditions. Ni/BEA zeolite was selected as a catalyst to investigate the conversion and the product selectivity of alkyl phenols (phenol, catechol, cresols), methoxy-phenols (guaiacol, syringol, creosol), aromatics (anisole, 1,2,3-trimethoxybenzene) and dimer (2-phenoxy-1-phenyl ethanol) compounds towards (alkyl)cycloalkanes. The hydrodeoxygenation of a surrogate mixture of eleven phenolic and aromatic compounds was then studied by investigating the effect of reaction conditions (temperature, time, H₂ pressure, surrogate mixture concentration, and catalyst-to-feed ratio). The conversion of model compounds was in the range of 80–100%, towards a 37–81% (alkyl)cycloalkane yield, being strongly dependent on the complexity/side-chain group of the phenolic/aromatic ring. Regarding the hydrodeoxygenation of the surrogate mixture, 59–100% conversion was achieved, with up to a 72% yield of C₆–C₉ cycloalkanes. Characterization of spent catalysts showed that the hydrodeoxygenation of surrogate mixture led to carbonaceous depositions on the catalyst, which can be limited under lower temperatures and longer reaction conditions, while after regeneration, the physicochemical properties of catalysts can be partially recovered. Full article

The potential for grapes and wine to be tainted following vineyard exposure to wildfire smoke is well established, with recent studies suggesting hops and apples (and thus beer and cider) can be similarly affected. However, the susceptibility of other crops to ‘smoke taint’ has not yet been investigated. Smoke was applied to a selection of fruits and vegetables, as well as potted lavender plants, and their volatile phenol composition determined by gas chromatography–mass spectrometry to evaluate their susceptibility to contamination by smoke. Volatile phenols were observed in control (unsmoked) capsicum, cherry, lavender, lemon, spinach and tomato samples, typically at ≤18 µg/kg, but 52 µg/kg of guaiacol and 83–416 µg/kg of o- and m-cresol and 4-methylsyringol were detected in tomato and lavender samples, respectively. However, significant increases in volatile phenol concentrations were observed as a consequence of smoke exposure; with the highest volatile phenol levels occurring in smoke-exposed strawberry and lavender samples. Variation in the uptake of volatile phenols by different crops was attributed to differences in their physical properties, i.e., their surface area, texture and/or cuticle composition, while the peel of banana, lemon, and to a lesser extent apple samples, mitigated the permeation of smoke-derived volatile phenols into pulp. Results provide valuable insight into the susceptibility of different crops to smoke contamination. Full article

The structure of cellulolytic enzyme lignin (CEL) prepared from three bamboo species (Neosinocalamus affinis, Bambusa lapidea, and Dendrocalamus brandisii) has been characterized by different analytical methods. The chemical composition analysis revealed a higher lignin content, up to 32.6% of B. lapidea as compared to that of N. affinis (20.7%) and D. brandisii (23.8%). The results indicated that bamboo lignin was a p-hydroxyphenyl-guaiacyl-syringyl (H-G-S) lignin associated with p-coumarates and ferulates. Advanced NMR analyses displayed that the isolated CELs were extensively acylated at the γ-carbon of the lignin side chain (with either acetate and/or p-coumarate groups). Moreover, a predominance of S over G lignin moieties was found in CELs of N. affinis and B. lapidea, with the lowest S/G ratio observed in D. brandisii lignin. Catalytic hydrogenolysis of lignin demonstrated that 4-propyl-substituted syringol/guaiacol and propanol guaiacol/syringol derived from β-O-4′ moieties, and methyl coumarate/ferulate derived from hydroxycinnamic units were identified as the six major monomeric products. We anticipate that the insights of this work could shed light on the sufficient understanding of lignin, which could open a new avenue to facilitate the efficient utilization of bamboo. Full article

The molecular weight of lignin extracted from lignocellulosic biomass is an important factor in determining its valorization in industrial processes. Herein, this work aims to explore the extraction of high molecular weight and bioactive lignin from water chestnut shells under mild conditions. Five kinds of deep eutectic solvents were prepared and applied to isolate lignin from water chestnut shells. The extracted lignin was further characterized with element analysis, gel permeation chromatography, and Ultraviolet-visible and Fourier-transform infrared spectroscopy. The distribution of pyrolysis products was identified and quantified with thermogravimetric analysis—Fourier-transform infrared spectroscopy and pyrolysis-gas chromatograph-mass spectrometry. The results showed that choline chloride/ethylene glycol/p-toluenesulfonic acid (1:1.8:0.2 molar ratio) exhibited the highest fractionation efficiency for lignin (84.17% yield) at 100 °C for 2 h. Simultaneously, the lignin showed high purity (90.4%), high relative molecular weight (37,077 g/mol), and excellent uniformity. Furthermore, the aromatic ring structure of lignin remained intact, consisting mainly of p-hydroxyphenyl, syringl, and guaiacyl subunits. The lignin generated a large number of volatile organic compounds during the depolymerization process, mainly composed of ketones, phenols, syringols, guaiacols, esters, and aromatic compounds. Finally, the antioxidant activity of the lignin sample was evaluated with the 1,1-diphenyl-2-picrylhydrazyl radical scavenging assay; the lignin from water chestnut shells showed excellent antioxidant activity. These findings confirm that lignin from water chestnut shells has a broad application prospect in valuable chemicals, biofuels and bio-functional materials. Full article

Smoking is used to give food its typical aroma and to obtain the desired techno-functional properties of the product. To gain a deeper knowledge of the whole process of food smoking, a controllable smoking process was developed, and the influence of wood pyrolysis temperature (150–900 °C) on the volatile compounds in the smoking chamber atmosphere was investigated. The aroma profile of smoke was decoded by headspace solid-phase microextraction-gas chromatography-mass spectrometry (HS-SPME-GC-MS). Subsequently, the correlations in the most important substance classes, as well as in individual target components, were investigated by the Pearson test. Phenols and lactones showed an increase over the entire applied temperature range (r_T = 0.94 and r_T = 0.90), whereas furans and carbonyls showed no strict temperature dependence (r_T < 0.6). Investigations on single aroma compounds showed that not all compounds of one substance class showed the same behavior, e.g., guaiacol showed no significant increase over the applied pyrolysis temperature, whereas syringol and hydoxyacetone showed a plateau after 450 °C, and phenol and cyclotene increased linear over the applied temperature range. These findings will help to better understand the production of aroma-active compounds during smoke generation in order to meet consumers preferences. Full article

Drought stress severely threatens plant growth, yield and survivability. Wood vinegar, formed by the condensation of smoke produced during biochar production, has been shown to promote plant growth and enhance stress tolerance. They have now been recognized as a sustainable alternative and are frequently used exogenously to support plants coping with environmental stress. This study aimed to evaluate the efficacy of oil palm wood vinegar (OPWV) in mitigating the adverse effects of drought stress on Pandanus amaryllifolius. The optimal concentrations and frequencies of OPWV application were determined before the drought treatment. The results showed that the imposed drought stress negatively affected the plant growth parameters but applying OPWV at 1:500 dilution at 3-day intervals for 12 days increased its tolerance. These include increased leaf relative water content, root-to-shoot ratio, relative stem circumference, chlorophyll pigments and antioxidant enzyme activities. In contrast, the drought-stressed plants treated with OPWV showed decreased relative electrolyte leakage, hydrogen peroxide, proline, malondialdehyde, and enhanced drought-responsive gene expressions, such as HSP70, GAPDH, and Thau, while ENO and β-Fruc were reduced. These biostimulatory effects of OPWV might be due to several antioxidant compounds, such as anthranilic acid, tetrasiloxane, syringol, guaiacol, and catechol. Altogether, our results showed the effectiveness of OPWV in alleviating the adverse effects of drought stress, and as such, OPWV could be potentially applied in agriculture. Full article

Recovery and reuse of valuable chemicals from hydrothermal carbonization process liquid (HTC-PL) from tomato plant biomass (TPB) was conducted. Different HTC-PLs were characterized with FTIR and Py-GC-MS analyses revealing the presence of low molecular weight linear, cyclic, and aromatics compounds in the HTC-PL. Separation of these valuable chemicals by fractional distillation resulted in eutectic constrains. Solvent extraction separation followed by solvent recovery and reuse provided encouraging results. The non-polar portion of HTC-PLs were extracted by using n-hexane (C₆H₁₄), and diethyl ether (C₂H₅)₂O solvents with 8.5 and 4.3% recoveries, respectively. Characterization by FTIR and Py-GC-MS revealed petrol fuel like materials in the extracts of C₆H₁₄ and (C₂H₅)₂O, irrespective of higher boiling components. Blends of both non-polar extracts were flame tested revealing good burning characteristics with minimal smoke and residue. Bench scale spirit lamp tests showed the blend would be very useful for greenhouse winter heating. The polar extracts using methylene chloride (CH₂Cl₂) resulted in about 55% recovery. Py-GC-MS analysis revealed acetic acid and 5-Hydroxymethyl furfural (5HMF) majors in the extract along with related derivatives. 5HMF is a valued chemical and demonstrated to be a useful building block for many industrial applications, and flatform chemical for various synthesis. Other identified minor components of HTC-PL were vanillin, divinyl terephthalate, and syringol. After the extractions of polar and non-polar components in three steps, the HTC-PL residue was applied as nutrient source after maintaining pH (5.6) and concentration (TOC, 100–200 mg/L) to typical greenhouse plants. Plant growth was encouraging. The paper discusses all the potential valued reuse applications of HTC-PL in greenhouses without discharges, which contributes to environmental protection and economic benefits. Full article

Bimetallic zeolitic imidazolate framework (BMZIF)-decorated Mo carbide catalysts were designed for the catalytic hydrodeoxygenation of guaiacol to produce phenol with high selectivity. A uniform layer of BMZIF was systematically coated onto the surface of the MoO₃ nanorods. During carbonization at 700 °C for 4 h, BMZIF generated active species (ZnO, CoO) on highly dispersed N-doped carbons, creating a porous shell structure. Simultaneously, the MoO₃ nanorod was transformed into the Mo₂C phase. The resulting core@shell type Mo₂C@BMZIF-700 °C (4 h) catalyst promoted a 97% guaiacol conversion and 70% phenol selectivity under 4 MPa of H₂ at 330 °C for 4 h, which was not achieved by other supported catalysts. The catalyst also showed excellent selective cleavage of the methoxy group of lignin derivatives (syringol and vanillin), which makes it suitable for selective demethoxylation in future biomass catalysis. Moreover, it exhibits excellent recyclability and stability without changing the structure or active species. Full article

Lignocellulosic biomass is a renewable resource that contains three major constituents: cellulose, hemicellulose, and lignin. Lignin is a potential source of aromatic phenols. The extraction and subsequent depolymerization of lignin was studied using pine sawdust and pistachio shells. Lignin extraction used 70:30 methyl isobutyl ketone:ethanol followed by 0.1M H₂SO₄. The extraction yield of lignin was 15.78 ± 3.38% from pistachio shells and 18.86 ± 1.52% from pine sawdust. The extracted lignin was characterized using Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and ¹H-NMR spectroscopy. The extracted lignin was depolymerized using subcritical water and a Ni-Graphene catalyst at 240 °C for 10 min. The depolymerization products were identified as phenolic monomers, such as phenol, guaiacol, vanillin, syringol, guaiacylpropane, syringaldehyde, coniferaldehyde, synapyl alcohol, and synapyl aldehyde, using GC-MS. Full article

Industrial symbiosis, which allows the sharing of resources between different industries, could help to improve the overall feasibility of bio-based chemicals production. In that regard, this study focused on integrating the torrefaction of pulp industry sludge with anaerobic digestion. More specifically, anaerobic digestion (AD) of pulp sludge-derived torrefaction condensate (TC) was studied to evaluate the biomethane and volatile fatty acid (VFA) potential. The torrefaction condensate produced at 275 and 300 °C was used in AD. The volatile solid content (VS) was 6.69 and 9.01% for the condensate produced at 275 and 300 °C, respectively. The organic fraction of TC mainly contained acetic acid, 2-furanmethanol, and syringol. The methane yield was in the range of 481–772 mL/g VS for the mesophilic and 401–746 mL/g VS for the thermophilic process, respectively. The VFA yield was in the range of 1.1 to 3.4 g/g VS for mesophilic and from 1.5 to 4.7 g/g VS in thermophilic conditions, when methanogenesis was inhibited. Finally, pulp sludge TC is a feasible feedstock to produce platform chemicals like VFA. However, at higher substrate loading, signs of process inhibition were observed because of the relatively increasing concentration of microbial inhibitors Full article

This work evaluates the effect of feedstock type and composition on the conversion of lignin to liquid by solvolysis with formic acid as hydrogen donor (LtL), by analyzing the yields and molecular composition of the liquid products and interpreting them in terms of both the type and the preprocessing of the lignocellulosic biomass using chemometric data analysis. Lignin samples of different types and purities from softwood, hardwood, and grasses (rice straw and corn stover) have been converted to bio-oil, and the molecular composition analyzed and quantified using GC-MS. LtL solvolysis was found to be a robust method for lignin conversion in terms of converting all samples into bio-oils rich in phenolic compounds regardless of the purity of the lignin sample. The bio-oil yields ranged from 24–94 wt.% relative to lignin input and could be modelled well as a function of the elemental composition of the feedstock. On a molecular basis, the softwood-derived bio-oil contained the most guaiacol-derivatives, and syringol was correlated to hardwood. However, the connection between compounds in the bio-oil and lignin origin was less pronounced than the effects of the methods for biomass fractionation, showing that the pretreatment of the biomass dominates both the yield and molecular composition of the bio-oil and must be addressed as a primary concern when utilization of lignin in a biorefinery is planned. Full article

Near-infrared spectroscopic (NIR) technique was used, for the first time, to predict volatile phenols content, namely guaiacol, 4-methyl-guaiacol, eugenol, syringol, 4-methyl-syringol and 4-allyl-syringol, of aged wine spirits (AWS). This study aimed to develop calibration models for the volatile phenol’s quantification in AWS, by NIR, faster and without sample preparation. Partial least square regression (PLS-R) models were developed with NIR spectra in the near-IR region (12,500–4000 cm⁻¹) and those obtained from GC-FID quantification after liquid-liquid extraction. In the PLS-R developed method, cross-validation with 50% of the samples along a validation test set with 50% of the remaining samples. The final calibration was performed with 100% of the data. PLS-R models with a good accuracy were obtained for guaiacol (r² = 96.34; RPD = 5.23), 4-methyl-guaiacol (r² = 96.1; RPD = 5.07), eugenol (r² = 96.06; RPD = 5.04), syringol (r² = 97.32; RPD = 6.11), 4-methyl-syringol (r² = 95.79; RPD = 4.88) and 4-allyl-syringol (r² = 95.97; RPD = 4.98). These results reveal that NIR is a valuable technique for the quality control of wine spirits and to predict the volatile phenols content, which contributes to the sensory quality of the spirit beverages. Full article

It has been well established that bushfire/wildfire smoke can taint grapes (and therefore wine), depending on the timing and duration of exposure, but the risk of smoke contamination from stubble burning (a practice employed by some grain growers to prepare farmland for sowing) has not yet been established. This study exposed excised bunches of grapes to smoke from combustion of barley straw and pea stubble windrows to investigate the potential for stubble burning to elicit smoke taint. Increased levels of volatile phenols (i.e., chemical markers of smoke taint) were detected in grapes exposed to barley straw smoke (relative to control grapes), with smoke density and the duration of smoke exposure influencing grape volatile phenols. However, the sensory panel did not perceive wine made from grapes exposed to low-density smoke to be tainted, despite the presence of low levels of syringol providing compositional evidence of smoke exposure. During the pea stubble burn, grapes positioned amongst the burning windrows or on the edge of the pea paddock were exposed to smoke for ~15–20 and 30–45 min, respectively, but this only resulted in 1 µg/kg differences in the cresol and/or syringol concentrations of smoke-affected grapes (and 1 µg/L differences for wine), relative to controls. A small, but significant increase in the intensity of smoke aroma and burnt rubber flavor of wine made from the grapes positioned amongst the burning pea stubble windrows provided the only sensory evidence of any smoke taint. As such, had vineyards been located immediately downwind from the pea stubble burn, it is unlikely that there would have been any smoke contamination of unharvested grapes. Full article