Phenolic Monomers Research Articles

Altered Metabolism in Knockdown Lines of Two HXXXD/BAHD Acyltransferases During Wound Healing in Potato Tubers

Suberin biosynthesis involves the coordinated regulation of both phenolic and aliphatic metabolisms. HXXXD/BAHD acyltransferases occupy a unique place in suberization, as they function to crosslink phenolic and aliphatic monomers during suberin assembly. To date, only one suberin-associated HXXXD/BAHD acyltransferase, StFHT, has been described in potatoes, whereas, in Arabidopsis, at least two are implicated in suberin biosynthesis. RNAseq data from wound-induced potato tubers undergoing suberization indicate that transcripts for 28 HXXXD/BAHD acyltransferase genes accumulate in response to wounding. In the present study, we generated RNAi knockdown lines for StFHT and another highly wound-induced HXXXD/BAHD acyltransferase, designated StHCT, and characterized their wound-induced suberin phenotype. StFHT-RNAi and StHCT-RNAi knockdown lines share the same aliphatic suberin phenotype of reduced esterified ferulic acid and ferulates, which is similar to the previously described StFHT-RNAi knockdown suberin phenotype. However, the phenolic suberin phenotype differed between the two knockdown genotypes, with StHCT-RNAi knockdown lines having proportionately more p-hydroxyphenyl-derived moieties than either StFHT-RNAi knockdown or empty vector control lines. Analysis of soluble polar metabolites revealed that StHCT catalyzes a step upstream from StFHT. Overall, our data support the involvement of more than one HXXXD/BAHD acyltransferase in potato suberin biosynthesis.

Conversion of kraft lignin to hydrocarbons using an integrated molten salt pyrolysis/catalytic hydrotreatment approach

Thermochemical conversion of underutilized lignocellulosic streams such as kraft lignin from the pulp and paper industry has the potential to produce sustainable chemicals and biofuels. We here report a process to continuously convert softwood-based lignoboost lignin to hydrocarbons using a three-step approach: i) liquefaction/dispersion of the lignin in a suitable molten salt, ii) pyrolysis of the liquefied/dispersed lignin in a molten salt mixture (ZnCl2, KCl, and NaCl), to obtain a crude lignin oil and iii) upgrading of the lignin oil using a catalytic hydrotreatment to yield hydrocarbons. Step 1 and 2 were integrated using a twin screw extruder with different heating sections at a scale of 20 g/h lignin input. Besides char, a lignin oil, mainly composed of monomeric phenolics, and propylene were the major products. The highest yield of the latter two products was around 32 wt% (23 wt% crude lignin oil and 9 wt% propylene). The lignin oil was subsequently converted to hydrocarbons using a two-step catalytic hydrotreatment approach (stabilization step using CoMo/Al2O3 catalyst and a further deep hydrotreatment over a NiMo/Al2O3 catalyst). The final liquid product contained less than 0.5 wt% of oxygen and was shown to be rich in (cyclo)alkanes and aromatic hydrocarbons. The carbon yield for the overall conversion of lignin to hydrocarbons was 23 %.

A deep eutectic solvent with a lignin stabilization and functionalization for lignocellulosic biomass pretreatment

This study synthesized a functional deep eutectic solvent (DES) using betaine and glyoxylic acid (GA) for lignocellulosic biomass pretreatment. The Betaine/GA DES pretreatment resulted a high delignification efficiency of 81.89% and xylan removal of 83.25% while preserving most of cellulose. During pretreatment, lignin was stabilized by GA, preventing its condensation and introducing carboxyl groups onto its molecular backbone. The GA stabilized lignin (GASL), with a high β-O-4 linkage content of 62.92%, was depolymerized for phenolic monomer production with a bio-oil yield of 55.40%. Additionally, the functional lignin was used as a surfactant for GASL-based O/W emulsion (GA-O/W emulsion) preparation. With 0.5% of lignin addition and an optimal O/W ratio of 6:4, the resulting GA-O/W emulsion exhibited a high cream index value of 100% and excellent storage stability without any phase transition or emulsion aggregation. When using the lignin to prepare curcumin-encapsulated microcapsules, a cumulative curcumin remaining of 74.19% under UV radiation and an extraordinary encapsulation efficiency of 62.86% were achieved. Furthermore, this DES pretreatment promoted enzymatic saccharification of the pretreated cellulose substrate, resulting in a glucose yield of 91.49%. After adding 15 wt% of the fibers in soft wood pulp for papermaking, the tear index, ring crush strength index, and tensile index of the produced paper-sheets reached 112.04%, 98.58%, and 83.55% of those of the pure softwood pulp papers, respectively.

Enhancing nutritional composition and aroma characteristics of kiwifruit wines through indigenous non-Saccharomyces yeast extracellular extract treatment

To unlock the potential of strains for further enhancing the aromatic complexity of kiwifruit wines while avoiding undesirable flavors, indigenous non-Saccharomyces yeast extracellular extract treatment for fermentation was established. The extracellular extract from Zygosaccharomyces rouxii, Pichia kudriavzevii, and Meyerozyma guilliermondii were prepared and supplemented individually or in pairs to the kiwifruit wine fermentation system. Subsequently, the changes in physicochemical properties, antioxidants, and volatile characteristics of kiwifruit wines produced by different protocols were comprehensively evaluated, and the major aroma descriptors affecting sensory acceptability were analyzed by sensory evaluation and partial least squares regression. The results showed that extracellular extract treatment significantly improved the organic acids and monomeric phenols content, antioxidant capacity, and volatiles of kiwifruit wines. Compared to Sc, the increase in esters and alcohols, along with the decrease in aldehydes and acids in Pk-Zr and Mg-Zr, enhanced the aromatic complexity while reduce grassy and fungal flavors, resulting in higher sensory acceptability.

Reversibly crosslinked polyurethane fibres from sugar-based 5-chloromethylfurfural: Synthesis, fibre-spinning and fibre-to-fibre recycling.

The development of recyclable crosslinked thermosetting fibres is a challenging research topic. In the present work, we have designed and synthesized polyurethane fibres from fructose-derived 5-chloromethylfurfural (CMF) and lignin-derived monomeric phenols. The greenhouse gas emissions associated with the production of CMF showed comparable results to that of 5-hydroxymethylfurfural (HMF), a high potential sugar-based platform molecule. The wet-spun biobased polyurethane fibres produced could be conveniently crosslinked using Diels-Alder chemistry to effectively enhance the glass transition temperature and mechanical properties. At a mildly elevated temperature (140 °C), the chemically crosslinked fibres could be effectively de-crosslinked, which enabled complete separation from a mixture with poly(ethylene terephthalate) (PET) and cotton fibres. These results outline a potential strategy to design and fabricate new biobased fibres with reversible crosslinking, which may enable fibre-to-fibre recycling.

Effect of low molecular weight phenols on the in-mouth sensory perception of high molecular weight phenols by analyzing reconstituted wines

This research aimed to assess the contribution of monomeric phenols to the perception of bitterness and astringency by means of wine reconstitution experiments. Six wines with distinct total polyphenol indexes were selected and fractioned by preparative liquid chromatography into two fractions. Thirty-one reconstituted wines were prepared by combining distinct low molecular weight fractions (L) with different high molecular weight fractions (H). In-mouth attributes of reconstituted and reference wines were described by a trained sensory panel. Fractions were chemically characterized by UPLC-MS. No significant differences among sensory results were found between reference and reconstituted wines. Bitterness and astringency perception were strongly influenced by total proanthocyanidins content. Flavan-3-ol monomers and dimers were only responsible for astringency in wines with a low content of proanthocyanidins, as was the case in rosé wine. Quercetin-3-O-glucuronide and several anthocyanins presented correlations with bitterness in the reconstituted wines; notwithstanding, several interactions with this attribute were observed.

Unlocking biomass valorization: Machine Learning insights for Reductive Catalytic Fractionation of cotton stalks

Lignocellulosic biomass valorization has become an intensive area of research due to the importance of renewable nature and availability of biomass. However, biomass fractionation and depolymerization produce numerous datasets, that are difficult to visualise and interpret for the scale-up of the process. Therefore, machine learning algorithms, which can discover hidden patterns in data are applied to these datasets. Reductive Catalytic Fractionation (RCF) of lignocellulosic biomass is an emerging methodology to valorize biomass completely and effectively. Herein, the present work includes the Correlation Analysis and the Principal Component Analysis (PCA) of product distribution obtained from RCF of cotton stalks. Interactions between process variables and delignification (DL), sugar retention (SR), total phenolic monomers (PM), and individual phenolic monomers yield were evaluated. Correlations among DL, SR, and PM yields were also evaluated at different reaction conditions through PCA, which were explained using the reaction mechanism and molecular chemistry of lignin.

Reductive catalytic fractionation of cotton stalks: catalytic strategy for tuning the selectivity of phenolic monomers

Reductive catalytic fractionation of cotton stalks: catalytic strategy for tuning the selectivity of phenolic monomers

Investigation of ruthenium loaded beta zeolite catalyst performance in vanillin hydrodeoxygenation yielding both monomeric and dimeric cycloalkanes

The valorization of lignin-derived bio-oil is studied extensively due to its promising contribution to sustainability. Among these studies, many have focused on the hydrodeoxygenation (HDO) of phenolic model compounds as it is a crucial process in obtaining valuable oxygen-free hydrocarbons. In this work, vanillin HDO was performed on various bifunctional ruthenium-based zeolite catalysts with different zeolite supports (Y, ZSM-5, and beta) in a batch reactor. Ru-loaded beta zeolite catalysts (Ru/Hβ) exhibited the highest HDO activity among them, and the formation of dimeric cycloalkanes of high value were also observed specifically when using the Ru/Hβ catalyst. Due to their benefits of direct use in blending of biofuel, factors promoting the dimerization of phenolic monomers were extensively examined through a series of experiments using a mix of phenolic model compounds as HDO reactants. Specific oxygen containing functional groups contributed to the aldol condensation of aromatic species, and the structure and kinetic diameter of the monomers had a profound effect on the ability to participate in dimerization. Additionally, the metal loading of the catalyst and reaction conditions such as temperature and hydrogen pressure were varied to observe each of their effects on the product distribution. The change in metal loading had a remarkable impact on the preferred reaction pathway and product selectivity, while a high temperature of 200 °C and hydrogen pressure of 50 bar was determined to be necessary to fully achieve HDO to cycloalkanes. Consequently, this study has provided useful information on the production of both monomeric and dimeric cycloalkanes and has contributed to the development of the bio-oil upgrading process.

Effects of different low-temperature maceration times on the chemical and sensory characteristics of Syrah wine

This study aimed to investigate the effects of three different cold maceration times on the color, volatiles, and sensory of Syrah wine. The results showed that the physicochemical parameters were not influenced by maceration time. Extending the maceration time significantly increased the color intensity and decreased the hue of the wines. The content of monomeric anthocyanins and monomeric phenols increased gradually with the prolongation of immersion time, however, there was no significant difference between 72 and 120 h. Malvidin-3-O-glucoside was the most abundant monomer in anthocyanins, accounting for 67 % of the total content. Moreover, the highest flavanol content (95.42 ± 0.66 mg/L) was found in 120-h sample. The aroma contents of wines macerated for 72 and 120 h were significantly higher than that of 24 h (p < 0.05). Sensory evaluations showed that extended maceration enhanced the color intensity and floral-fruity aromas of the Syrah wines, while increasing astringency.

Quality of jujube wines fermented by different jujube varieties: Physicochemical parameters, antioxidant activity, non-volatile and volatile substances

The varieties of raw materials are significant to the quality of jujube wine. In this study, the physicochemical quality, antioxidant activity, non-volatile and volatile substances of different jujube wines were analyzed. The alcohol content of the different wines ranged from 12.70% (v/v) to 14.19% (v/v). Wine fermented by J60Z showed the highest alcohol content. ZHDZ-fermented wine was the yellowest and its color quality was the best. The main monomeric phenols in date wine are chlorogenic acid, epicatechin and catechin. DZ-fermented wine had the strongest DPPH, ABTS radical scavenging activity and FRAP. The organic acids in date wine were mainly succinic acid, malic acid and lactic acid. JUZ-fermented wine had the highest content of total free amino acids, essential amino acids, and sweet amino acids, which were 817.42, 53.23, and 751.01 mg/L, respectively. Seventy-nine volatile compounds were found in the nineteen jujube wines. Wine fermented by JUZ had the highest total volatiles content (8329.52 mg/L). Principal component analysis and sensory evaluation revealed that DZ-fermented date wine had the highest composite and sensory scores. Therefore, this study showed that DZ was more suitable for making jujube wine. This study provides theoretical guidance for screening suitable varieties for jujube wine fermentation.

Maturation-induced changes in phenolic forms and their antioxidant activities of walnuts: A dual view from kernel and pellicle

The phenolic profiles and antioxidant activities during walnut maturation are not well understood. This study used UPLC-MS/MS to evaluate phenolic content in walnuts, including free, esterified, and bound forms, at different maturation stages. Findings showed that free phenolics were predominant, comprising 44.57 % in kernels and 56.54 % in pellicles. In vitro assays showed antioxidant capacity decreased with maturation, with IC50 values of 0.87–84.43 μg/mL in pellicles and 48.51–712.30 μg/mL in kernels. Most monomeric phenols decreased in concentration as the fruit ripened. OPLS-DA identified 5 and 8 maturity-sensitive phenolics (MSPs) in kernels and pellicles, respectively, with fold changes from 2.32 to 1664.72. Pearson correlation analysis showed a significant correlation between MSPs and antioxidant activity (r > 0.75, p < 0.05). Bioinformatics analysis elucidated three key metabolic pathways involved in these changes. This research provides insights into walnut phenolic composition, important for optimizing harvest practices and enhancing nutritional value.

Catalytic depolymerization of Camellia oleifera shell lignin to phenolic monomers: Insights into the effects of solvent, catalyst and atmosphere

Camellia oleifera shell (COS) is a renewable biomass resource abundant in lignin with significant potential for producing phenolic monomers. However, the dearth of research has led to considerable resource wastage and environmental pollution. Herein, reductive catalytic fractionation (RCF) of COS was performed using noble metal catalysts in different solvents. An 11.1 wt% yield of phenolic monomers was achieved with 91% selectivity toward propylene-substituted monomers in H2O/EtOH (3:7, v/v) cosolvent under N2 atmosphere. Notably, the highest phenolic monomer yield of 17.0 wt% was obtained with impressive selectivity (86.9%) toward propanol-substituted monomers in the presence of H2. The GPC analysis and 2D HSQC NMR spectra indicated the effective depolymerization of lignin oligomers with catalysts. Phenolic monomers with ethyl, propyl, or propanol side chain could be produced from lignin-derived oligomers through hydrogenolysis, hydrogenation, and decarboxylation reactions. Overall, this study has paved the way for the valorization of COS lignin through the RCF strategy.

Role of solvent in selective hydrodeoxygenation of monomeric phenols

The current production of aromatic hydrocarbons, crucial in fuel and polymer production, relies heavily on fossil resources. Finding carbon-neutral alternatives is necessary to address the current environmental challenges. Lignin emerges as a promising source for bio-based aromatics. However, existing catalytic hydrodeoxygenation processes often yield mixtures of cycloalkanes and aromatics. In our study, we investigated a selective route to obtain aromatics from phenols using the keto-tautomer reaction mechanism. According to this mechanism, the initial hydrogenation of the carbonyl group while a phenol compound is in its keto form leads to the removal of the hydroxyl group while preserving the aromatic structure. Our experiments focused on p-cresol, guaiacol, and mequinol, employing Pd/C and Ru/C catalysts. Experimental results revealed that aromatic hydrocarbons were favored during the hydrodeoxygenation of p-cresol and mequinol, while steric effects from the methoxy group hindered guaiacol's conversion. Furthermore, we observed significantly higher conversion rates when using hydrocarbon solvents compared to water, with toluene yields of up to 13.5 % by mass achieved on Pd/C. Our computational simulations confirmed the feasibility of the keto-tautomer mechanism on Pd cluster surfaces, similar to those found in Pd/C catalysts.

Synergetic effect of Accentuated Cut Edges (ACE) and macerating enzymes on the phenolic composition of Marquette red wines

One of the challenges of cold-hardy grape cultivars is their typical low content of tannins, alongside the presence of anthocyanin diglucoside and high acidity, which can lead to unbalanced red wines. This study hypothesized that the combination of Accentuated Cut Edges (ACE) and macerating enzymes would improve phenolics extraction from grape skins after disruption. The effects of those two winemaking techniques, either used separately or together, on red wine quality characteristics were investigated at crushing, bottling, and after six or nine months of aging. Overall, the combination of treatments improved the concentration of monomeric phenolics (20 %) and tannins (21 %) after nine months of aging. ACE or enzyme treatment separately applied had little impact on phenolics extraction in finished wines. This study exhibited a potential strategy to modify phenolics profile through the synergistic effect of ACE and macerating enzymes by causing cellular breakdown in a cold-hardy red grape cultivar.

Synthesis and Antibacterial Activity of Capsaicin Derivatives Containing Phenolic Hydroxyl Groups

AbstractBacterial infections tend to cause a series of cytopathic reactions and have become a major threat to human life. Among them, phenolic compounds are widely used as a natural antibacterial derivative for antifouling and antibacterial applications. In this study, four phenolic hydroxyacrylamide monomers have been successfully prepared using capsaicinoid derivatives as inspiration (named as OHABA, PHABA, AHMA, and AMTHBA, respectively) and the chemical structures were confirmed by FT‐IR, 1H‐NMR, 13C‐NMR. The minimum inhibitory concentration (MIC) assay and plate antibacterial assay were measured to explore the antibacterial properties of the monomer. The results showed that four capsaicin derivatives exhibited antibacterial activity, and the antibacterial properties of the four monomers from strong to weak were PHABA, OHABA, AHMA and AMTHBA. The best antibacterial activity was PHABA (MIC for E. coli: 1.6 mg/mL, bacteriostasis rate: 82.46 %, MIC for S. aureus: 1.6 mg/mL, bacteriostasis rate: 69.58 %). Both the cluster effect of monomers and the spatial distribution of phenolic hydroxyl groups in the structure of derivatives affect the antibacterial properties.

Enhancing monolignol ferulate conjugate levels in poplar lignin via OsFMT1

BackgroundThe phenolic polymer lignin is one of the primary chemical constituents of the plant secondary cell wall. Due to the inherent plasticity of lignin biosynthesis, several phenolic monomers have been shown to be incorporated into the polymer, as long as the monomer can undergo radicalization so it can participate in coupling reactions. In this study, we significantly enhance the level of incorporation of monolignol ferulate conjugates into the lignin polymer to improve the digestibility of lignocellulosic biomass.ResultsOverexpression of a rice Feruloyl-CoA Monolignol Transferase (FMT), OsFMT1, in hybrid poplar (Populus alba x grandidentata) produced transgenic trees clearly displaying increased cell wall-bound ester-linked ferulate, p-hydroxybenzoate, and p-coumarate, all of which are in the lignin cell wall fraction, as shown by NMR and DFRC. We also demonstrate the use of a novel UV–Vis spectroscopic technique to rapidly screen plants for the presence of both ferulate and p-hydroxybenzoate esters. Lastly we show, via saccharification assays, that the OsFMT1 transgenic p oplars have significantly improved processing efficiency compared to wild-type and Angelica sinensis-FMT-expressing poplars.ConclusionsThe findings demonstrate that OsFMT1 has a broad substrate specificity and a higher catalytic efficiency compared to the previously published FMT from Angelica sinensis (AsFMT). Importantly, enhanced wood processability makes OsFMT1 a promising gene to optimize the composition of lignocellulosic biomass.

Strong and tough semi-crystalline poly(aryl ether nitrile) with low coefficient of thermal expansion

The crystallization of poly (aryl ether nitrile) (PEN) has an essential impact on improving heat resistance, mechanical properties, chemical resistance, and dielectric properties. However, during the synthesis process, high crystallinity PEN is prone to precipitate out, which makes it difficult to carry out the synthesis reaction, which poses a significant challenge to synthesizing high crystallinity and high molecular weight PEN. In this work, hydroquinone (HQ) as the main phenolic monomer and 4,4′-biphenol (BP) as the second phenolic monomer were used to solve the technical difficulties in synthesis by copolymerization. The crystalline PEN with high molecular weight and significant crystallinity was obtained by regulating the molar ratio of BP to HQ. The effects of isothermal heat treatment on its crystalline, mechanical, and thermal properties were investigated. The influence laws of molecular chain structure and heat treatment process on the properties of PEN films were revealed. Among them, when the isothermal treatment temperature was 270 °C and the HQ: BP was 85:15, the mechanical strength reached 130 MPa, and the elongation at break could be up to an astonishing 50 %. Besides, the CTE value from 50 °C–150 °C is 40.84 ppm/°C, which is lower than most thermoplastics. Therefore, PEN with the HQ to BP molar ratio of 85:15 is suitable for large-scale production, providing new crystalline plastic specifications for high-performance special engineering plastics. A crystal bridge-tie chain model is summarized by the properties of HQ/BP-PEN films under different crystallization conditions, which provides an idea for preparing stiff and tough films.

Enhanced reductive catalytic fractionation of lignocellulose using a water-resistant RuNiZnOx/Nb2O5 catalyst with synergistic hydrogen spillover and acidic properties

Eco-friendly lignin depolymerization into monomeric phenols in an aqueous system is essential for the sustainable and green valorization of lignocellulosic biomass. However, a major challenge in this process is the development of efficient and stable catalysts for aqueous reductive catalytic fractionation (RCF), as water can cause catalyst deactivation and reduce monomer yields. In this study, a water-resistant RuNiZnOx/Nb2O5 catalyst is developed that demonstrates excellent catalytic activity and stability in aqueous systems, achieving a near-theoretical monomeric phenol yield of 40.1 wt% under reaction conditions of 240℃ and 3 MPa H2 for 4 h. The excellent performance of this catalyst is attributed to the synergistic hydrogen spillover effect between Ni and Ru and the strong acidic properties of ZnO, as revealed by in-situ XPS analysis and NH3-TPD, respectively. This hydrogen spillover effect significantly alters the product composition, promoting the generation of POH-S/G from lignin model compounds. Additionally, screening of the catalyst support materials revealed that Nb2O5 not only enhances Ru dispersion but also improves its stability, resulting in a minor decrease in lignin monomer yield observed after three cycles.

Characterization and properties of phenolic resin doped modified lignin

Phenolic resins occupy an important position in industrial applications, but phenol, one of the raw materials for synthesis, is a non-renewable resource. Lignin, as a natural polymer containing phenolic hydroxyl groups, alcohol hydroxyl groups and other reactive groups, can replace some of the phenol in the synthesis of phenolic resins, which can reduce the amount of phenol, thus reducing the cost of phenolic resins, while effectively promoting the high value-added use of renewable biomass resources. Due to its low reactivity, alkaline lignin is usually discharged as production waste, unaware that lignin macromolecules can be modified. In this paper, the phenolic monomers were obtained by acid-catalyzed depolymerization of DES (choline chloride/p-toluenesulfonic acid or choline chloride/lactic acid) from waste alkaline lignin, and the recovery rate of the DES solution during the catalytic treatment was more than 85 %, in which the main monomer was 2-methoxy-4-(1-propyl) phenol. The degradation of alkaline lignin is still favorable after five times of DES solvent recovery. The depolymerized lignin monomer replaced phenol by 50 wt% and then ternary co-polymerized with phenol and formaldehyde to form a biomass phenol-based phenolic resin, providing a green route for phenolic resin production. The cost of resin preparation was economically calculated, and it was found that the cost of resin after accumulating 4 cycles of DES treatment was only 51.1 % of that of pure phenolic resin. The density functional theory (DFT) was used to simulate the possible radical reactions in the intermediate process of phenolic resin reaction, to explore the microscopic mechanism and competition, to provide theoretical reference for further experimental realization of resin structure control and optimization, and to improve the theoretical system of resin synthesis.