Phenolic Monomers Research Articles

Efficient hydrogenolysis of lignin over CeO2/AC catalyst prepared by a simple impregnation method

There are limited renewable sources of aromatic chemicals, with lignin being one of the most prominent, accounting for approximately 30% of the planet's organic carbon. Due to its intricate and irregular structure, lignin is recalcitrant to chemical conversion, often resulting in low yields of mixtures of products when it is depolymerized. This study synthesized a CeO2/AC catalyst via an impregnation technique and then explored its ability to depolymerize lignin via an oxidation-reduction strategy. The CeO2/AC catalyst efficiently depolymerized lignin by an oxidation-reduction strategy. At 200 °C, an argon pressure of 1 MPa, and a reaction time of 4 h, the conversion of the lignin model compound reached 98.5%. When using lignin derived from poplar, birch, pine, and cotton stalk, the total yields of phenolic monomers were 36.2 wt.%, 31.2 wt.%, 17.4 wt.%, and 12.1 wt.%, respectively. The CeO2/AC catalyst exhibited a higher surface oxygen vacancy concentration than CeO2, which was crucial for facilitating the hydrogenolysis of lignin.

The bifunctional active sites on carbon supported Fe-Mo bimetallic catalyst to improve Kraft lignin liquefaction

Carbon-supported Fe-Mo bimetallic catalysts were synthesized for the thermal catalytic ethanolysis of lignin to liquid fuels composed of aromatic monomers. A yield of 40.7 wt % of lignin oil, consisting of 38.8 wt % phenol monomers and 39.3 wt % benzeneacetaldehyde monomers, was obtained in the presence of Fe-Mo-P catalysts (1:0.5) at 290 °C for 4 h in the supercritical ethanol solvent (6.5 MPa). The catalysts exhibited a rich distribution of α-MoC nanoparticles, Fe0 nanoclusters, surface oxygen defects, and active species of Mo6+ and phosphoric acid on the graphitized microporous carbon substrate. The synergistic effects of these active components were crucial for enhancing lignin liquefaction efficiency. The ethanolysis of the lignin model compound revealed that the Fe-Mo bimetallic catalyst can facilitate double cracking of C-C/C-O bonds under supercritical ethanol conditions. In situ Raman and FT-IR characterization were performed to monitor the transformation of the Fe-Mo bimetallic catalyst from the precursor to the carbon material, including the dehydration and carbonization of the organic precursor.

Catalytic hydrogenolysis of lignin in isopropanol as hydrogen donor over nickel-cobalt supported on zeolite to produce aromatic and phenolic monomers

Due to its high catalytic activity and good hydrogenating properties, bimetallic catalysts are gaining increasing attention for lignin valorization. Herein, transition bimetallic catalysts Ni-Co/HZSM-5 were proposed to investigate the catalytic hydrogenolysis reaction of lignin. The activity was demonstrated in an 80 mL stainless-steel reactor. At 250 ℃ temperature in 4 h of reaction using isopropanol as the hydrogen donor solvent. 45 wt% yields of total monomer products and 91% lignin conversion were obtained with Ni-Co/HZSM-5 catalysts. This is superior to the catalytic activity of Ni/HZSM-5 and Co/HZSM-5 monometallic catalysts. BET, SEM, XPS, and EDX techniques were used to characterize the catalysts. The results revealed that the synergistic effect between the two metal species (Ni-Co) was the major cause of their high catalytic activity, which resulted in better hydrogen transformation and better hydrogenolysis activity. The electronic interactions between Co and Ni enhanced the transfer of electrons and accelerated catalytic reactions. Also, well-dispersed Ni and Co on HZSM-5 support enhanced the surface area, providing more active sites for lignin to adsorb and participate in hydrogenolysis reactions. In addition, a series of measurements such as FT-IR, GPC, and GC-MS were performed to examine the hydrogenolysis reaction products. A total of 19 monomer products were successfully identified in GC-MS analysis. These results confirmed the great potential of bimetallic catalysts Ni-Co/HZSM-5 due to their synergistic effect.

Targeted metabolic reveals different part of maize in polyphenolic metabolites during germination and hypoglycemic activity analysis.

In this study, qualitative and quantitative analyses of phenolic compounds in the maize germinating seed embryo, radicle, and germ were performed at 0, 48, and 96h post-germination, followed by the evaluation of their hypoglycemic activity. The results revealed the accumulation of 80 phenolics in different parts of germinated maize, of which 47, 48, and 53 were present in the seed embryo, radicle, and germ. After germination 22, 26, and 34 polyphenols were found to differential accumulate in the seed embryo, radicle, and germ. At 96h post-germination, the content of monomeric phenols in the germ was higher than that in the radicle and seed embryo. Moreover, the inhibitory activity of polyphenols in the germ towards α-glucosidase and α-amylase was higher than that in the radicle and seed embryo. These results indicate that germination can effectively improve the type and content of phenolic compounds in different parts of maize.

Production of phenolic compounds from argan shell waste by reductive catalytic fractionation

AbstractFor efficient utilization of lignocellulosic biomass components, reductive catalytic fractionation appears as a promising biorefinery strategy. In this work, this concept of biomass valorization was used to study the potential of an unexplored feedstock, argan shells. This material was processed in a non-catalytic route and over a Pd/C catalyst in two different reaction media. The effects of the treatment temperature (250, 275, and 300 °C), as well as the catalyst loading (catalyst/argan shells mass ratio of 0.05 and 0.1 g/g), were also studied. The main product (lignin-derived oil) was thoroughly characterized using GC/MS/FID, SEC, and NMR. The highest monomer yields of 48–49 wt% based on the lignin content were obtained for n-butanol/water reaction medium at 300 °C using a Pd/C catalyst load of 0.1 g/g and for methanol reaction medium at 275 °C and 0.05 g/g. Significantly lower monomeric phenol yields were obtained in the non-catalytic route (4–19 wt% for n-butanol/water and 9–16 wt% for methanol). The main phenolic monomers in the catalytic pathway were 4-n-propanolguaiacol, 4-n-propanolsyringol, and 4-alkyl guaiacols and syringols, with some differences in the selectivities from one solvent to another. Graphical Abstract

Tetrabutylammonium Halides as Selectively Bifunctional Catalysts Enabling the Syntheses of Recyclable High Molecular Weight Salicylic Acid‐Based Copolyesters

AbstractTo synthesize high molecular weight poly(phenolic ester) via a living ring‐opening polymerization (ROP) of cyclic phenolic ester monomers remains a critical challenge due to serious transesterification and back‐biting reactions. Both phenolic ester bonds in monomer and polymer chains are highly active, and it is difficult so far to distinguish them. In this work, an unprecedented selectively bifunctional catalytic system of tetra‐n‐butylammonium chloride (TBACl) was discovered to mediate the syntheses of high molecular weight salicylic acid‐based copolyesters via a living ROP of salicylate cyclic esters (for poly(salicylic methyl glycolide) (PSMG), Mn=361.8 kg/mol, Ð<1.30). Compared to previous catalysis systems, the side reactions were suppressed remarkably in this catalysis system because phenolic ester bond in monomer can be selectively cleaved over that in polymer chains during ROP progress. Mechanistic studies reveal that the halide anion and alkyl‐quaternaryammonium cation work synergistically, where the alkyl‐quaternaryammonium cation moiety interacts with the carbonyl group of substrates via non‐classical hydrogen bonding. Moreover, these salicylic acid‐based copolyesters can be recycled to dimeric monomer under solution condition, and can be recycled to original monomeric monomers without catalyst under sublimation condition.

Tetrabutylammonium Halides as Selectively Bifunctional Catalysts Enabling the Syntheses of Recyclable High Molecular Weight Salicylic Acid-Based Copolyesters.

To synthesize high molecular weight poly(phenolic ester) via a living ring-opening polymerization (ROP) of cyclic phenolic ester monomers remains a critical challenge due to serious transesterification and back-biting reactions. Both phenolic ester bonds in monomer and polymer chains are highly active, and it is difficult so far to distinguish them. In this work, an unprecedented selectively bifunctional catalytic system of tetra-n-butylammonium chloride (TBACl) was discovered to mediate the syntheses of high molecular weight salicylic acid-based copolyesters via a living ROP of salicylate cyclic esters (for poly(salicylic methyl glycolide) (PSMG), Mn =361.8 kg/mol, Ð<1.30). Compared to previous catalysis systems, the side reactions were suppressed remarkably in this catalysis system because phenolic ester bond in monomer can be selectively cleaved over that in polymer chains during ROP progress. Mechanistic studies reveal that the halide anion and alkyl-quaternaryammonium cation work synergistically, where the alkyl-quaternaryammonium cation moiety interacts with the carbonyl group of substrates via non-classical hydrogen bonding. Moreover, these salicylic acid-based copolyesters can be recycled to dimeric monomer under solution condition, and can be recycled to original monomeric monomers without catalyst under sublimation condition.

Thiourea resole polymers for recovery of noble element

The recovery of noble elements from secondary source, industrial effluent, which are classified as high concentrated noble elements solution are very essential. Liquid-solid extraction systems are an attractive process used for the separation and purification of noble elements. For this purpose, a solid-phase extraction system was investigated for the recovery of noble metals (Au(III), Pd(II), and Rh(III)). Chelating resins were synthesized by a polycondensation reaction between phenolic thiourea monomers and formaldehyde under alkaline conditions. The resulting polymers were characterized and evaluated for their chelating properties with regard to noble metal sorption. Also, the selectivity of sorption of noble elements was studied in the presence of competitive elements that can be present in effluent waste, such as Zn, Cu, Ni, Fe, and Al. Here, we present a promising materials based on formo-phenolic thiourea resins as a potential candidate for high-capacity (> 350 mg/g for Au; > 50 mg/g for Pd; > 30 mg/g for Rh) and high-selectivity solid-liquid sorption of noble elements, particularly for Au.

Herbaceous lignin valorization through integrated copper-catalyzed hydrogenolysis and chemical functionalization

Lignin is an important biomass resource to replace petrochemical industry for carbon neutrality. However, it is challenged by unyielding the trade-off between activity and selectivity owing to the chemical complexity and inherent heterogeneity of lignin biomacromolecule. Herein, we report that copper nanomaterial (CuO/C) derived from metal-organic framework (HKUST-1) could effectively catalytic hydrogenolysis of herbaceous plants into monomeric phenols (up to 29.5 wt%) through a lignin-first strategy, affording methyl 3-(4-hydroxyphenyl) propionate (1-H) and methyl 3-(4-hydroxy-3-methoxyphenyl) propionate (2-G) as the main monophenols with high selectivity of 31.9% and 17.3%. Moreover, we proposed two synthetic routes based on the purification and functionalization of those two compounds (1-H and 2-G) to synthesis 3-(4-carboxyphenyl) propionic acid and functional polyesters. Subsequent studies revealed that the temperature of 50% mass loss of the two polyesters reached 430–440 °C, indicating their robust thermal stability; while the DSC curves showed the difference between the two polymers in glass conversion temperature (Tg) and crystallization. In brief, this work opens a new avenue for the production of lignin-derived chemicals and materials.

Continuous-Flow Microreactor Accelerates Molecular Collisions for Lignin Depolymerization to Phenolic Monomers and Oligomers.

Effective depolymerization of lignin is the most important step for its comprehensive utilization. So far, most of the studies on depolymerization of lignin focused on batch processing, whereas only a few studies relied on the microreactor. In this study, we developed a continuous-flow microreactor for depolymerization of lignin into monomeric and oligomeric compounds. The yields of monomers and oligomers can be adjusted by varying the temperature, pressure, residence time, NaOH dosage, and solvent. Under optimized conditions, the lignin conversion rate was 77.73 wt %, and the monomer yield was 13.26 wt %, with 77.81% being phenolic compounds. In addition, comparative characterizations on the raw lignin and products demonstrated that the oil products were mainly composed of phenolic tetramers and trimers, and the effective cleavage of the β-O-4 linkage of S-type lignin was responsible for the high yield of 2,6-dimethoxyphenol. It indicated that raw lignin could be effectively depolymerized continuously using the continuous-flow microreactor, and it will be a new strategy for comprehensive utilization of lignin to produce fine-chemical intermediates.

Effects of rice bran rancidity on the release of phenolics and antioxidative properties of rice bran dietary fiber in vitro gastrointestinal digestion products

Rice bran (RB) as the raw material for rice bran dietary fiber (RBDF) extraction, is rapidly rancidified prior to stabilization. To enhance the RBDF utilization in food industry, effects of RB rancidity (RB was stored for 0, 1, 5, 7, and 10 d) on the bioaccessibility and bioavailability of RBDF-bound phenolics were investigated. With the increase in RB storage time, the RB rancidity degree significantly increased (the acid value of rice bran oil from 5.08 mg KOH/g to 60.59 mg KOH/g), and the endogenous phenolics content in RBDF also increased. Simultaneously, RB rancidity reduced the antioxidant activity of RBDF digestion products during the gastric digestion phase, while RB rancidity increased the antioxidant activity of RBDF digestion products during the intestinal digestion phase. In addition, in vitro gastrointestinal digestion stimulated the release of RBDF-bound phenolics. The released monomeric phenolics (especially ferulic acid and p-coumaric acid) were the major contributors to the increased antioxidant properties of RBDF digestion products. RBDF digestion products could inhibit H2O2-induced oxidative stress and apoptosis of HUVECs. In conclusion, the study found that RB rancidity could improve the antioxidant capacity of RBDF in the small intestine by promoting RB endogenous phenolics bound to RBDF release.

Metal catalyst-free selective acetosyringone synthesis from rice straw lignin.

In recent decades, due to abundance (second most abundant natural polymer after cellulose) and sustainability, lignin has attracted much interest from different researchers to use as a raw material for producing various value-added materials such as polymer and fuel. In addition to that, the aromatic structure of lignin makes it a suitable candidate for producing platform chemicals with aromatic rings. As a result, lignin depolymerization has become an interesting process to derive different phenolic monomers like vanillin, acetosyringone, and guaiacol. Among them, due to the bioactive characteristics and efficiency of acetosyringone in plant regulatory systems, the production of acetosyringone from lignin has been presented in this work. A green and cost-effective method was developed for the selective formation of acetosyringone via depolymerization of isolated rice straw lignin (RSL) by using metal catalyst-free conditions in the biphasic medium and described. The RSL was characterized with various spectroscopic techniques such as FT-IR, solid-state 13C NMR, XPS, and TGA. The selectivity of synthesized acetosyringone during depolymerization of RSL was checked from GC-MS analysis. The molecular structure and purity of acetosyringone isolated from preparative thin layer chromatography (TLC) were confirmed with the help of 1H NMR and HRMS, respectively.

Stereoselective hydrogenation of guaiacol to cis-2-methoxycyclohexanol using supported rhodium catalysts in supercritical carbon dioxide

Selective hydrogenation of lignin-derived phenolic monomer to valuable chemicals has attracted attention and investigated well; however, stereoselective hydrogenation is required for practical applications, and is still challenging. In this study, we examined the stereoselective hydrogenation of guaiacol to cis-2-methoxycyclohexanol over supported metal catalysts in several solvents at mild reaction conditions. Rh/C in supercritical CO2 gave a higher proportion of cis-2-methoxycyclohexanol in total 2-methoxycyclohexanol compared to water solvent. Finally, guaiacol could be stereoselectively hydrogenated to cis-2-methoxycyclohexanol with the yield 83.9 % (total 2-methoxycyclohexanol yield was 95.5 %) even at 313 K for 1 h using the Rh/C catalyst in supercritical CO2 (CO2 25 MPa, H2 1.5 MPa).

Production of Antioxidant Additives and High-quality Activated Biochar from Pyrolysis of Argan Shells

An integral valorization route based on a pyrolysis process has been proposed to find sustainable applications for argan shells focused on the simultaneous production of activated biochar and antioxidant additives from bio-oil. The bio-oil obtained in the pyrolysis process was furtherly upgraded (hydrothermal treatment and extraction process) to obtain antioxidant additives. On the other hand, the biochar obtained in the pyrolysis was used as a feedstock to produce high-quality activated biochar (by physical activation with CO2). The increase in the pyrolysis temperature (350–550 °C) hardly affected the pyrolysis products distribution (biochar yields of 28–34 wt.% and bio-oil yields between 51 and 55 wt.%), but it led to a slight decrease in the content of phenolic monomers extracted from bio-oil (from 63 wt.% at 350 °C to 53 wt.% at 550 °C). When these extracted fractions were blended with biodiesel (<1 wt.%), improvements of up to 300% in biodiesel oxidation stability were attained. The hydrothermal treatment of the bio-oil did not show noteworthy effects either on the production or antioxidant performance of the extracted fractions if compared with the fractions extracted from the raw bio-oil. Regarding the valorization of argan shells biochar, the activated biochar prepared from it showed considerable potential as an adsorbent material for CO2 (125 mg of CO2 per g of the activated biochar) or phenols (complete removal of 99.6% in 4 h of contact time). It was characterized by a high BET surface area (up to 1500 m2/g), a high carbon content (up to 95 wt.%), low ash content (around 2 wt.%), and a pH of around 8.

Lignin Depolymerization to Guaiacol and Vanillin Derivatives via Catalytic Transfer Hydrogenolysis using Pd-Lewis Metal Oxide Supported on Activated Carbon Catalysts

Lignin valorization is the key to sustainability of second-generation bioethanol refineries. In this study, the catalytic activities of Pd-Lewis acid metal oxides (Mo, Zr) supported on commercial activated carbon (AC) and activated biochar (ABC) were evaluated for the selective production of monomeric phenols from alkali lignin through transfer hydrogenolysis. The catalysts were thoroughly characterized for phase, degree of graphitization, textural properties, and metal dispersion. The Pd crystallite size was 2.1-2.5 Å in the case of AC-supported catalysts, while it was smaller (1.4-1.5 Å) for ABC-supported catalysts. AC exhibited better degree of graphitization than ABC. 2%Pd-5%Mo supported on AC showed good catalytic activity for the production of guaiacol, alkyl guaiacols, alkene guaiacols, and vanillin derivatives, and their respective yields were 4.2, 10.3, 3.4, and 12 wt.%. Compared to other alcohols like methanol and ethanol, the use of isopropyl alcohol as solvent resulted in better yields of guaiacol, alkyl guaiacols and alkene guaiacols. Condensation reactions of the guaiacyl unit and syringyl unit were confirmed through Fourier transform infrared spectroscopic analysis of the residue. Dimerization of monomeric phenols was observed with Pd-metal oxide supported on ABC than with AC-based catalyst.

Sustainable Electropolymerization of Zingerone and Its C2 Symmetric Dimer for Amperometric Biosensor Films.

Polymeric permselective films are frequently used for amperometric biosensors to prevent electroactive interference present in the target matrix. Phenylenediamines are the most commonly used for the deposition of shielding polymeric films against interfering species; however, even phenolic monomers have been utilized in the creation of these films for microsensors and biosensors. The purpose of this paper is to evaluate the performances of electrosynthesized polymers, layered by means of constant potential amperometry (CPA), of naturally occurring compound zingerone (ZING) and its dimer dehydrozingerone (ZING DIM), which was obtained by straight oxidative coupling reaction. The polymers showed interesting shielding characteristics against the main interfering species, such as ascorbic acid (AA): actually, polyZING exhibited an AA shielding aptitude comprised between 77.6 and 99.6%, comparable to that obtained with PPD. Moreover, a marked capability of increased monitoring of hydrogen peroxide (HP), when data were compared with bare metal results, was observed. In particular, polyZING showed increases ranging between 55.6 and 85.6%. In the present work, the molecular structures of the obtained polymers have been theorized and docking analyses were performed to understand their peculiar characteristics better. The structures were docked using the Lamarckian genetic algorithm (LGA). Glutamate biosensors based on those polymers were built, and their performances were compared with biosensors based on PPD, which is the most widespread polymer for the construction of amperometric biosensors.

An Overview of Plant Phenolics and Their Involvement in Abiotic Stress Tolerance

Secondary metabolites, such as phenols and salicylic, play a crucial role in the regulation of development and tolerance mechanisms against a wide range of stresses. During adverse conditions such as biotic and abiotic stresses, plants induce the biosynthesis of phenolic compounds to provide tolerance. Phenolics are secondary aromatic metabolites synthesized through the shikimate/phenylpropanoid pathway or polyketide acetate/malonate pathway, which produce monomeric and polymeric phenolics. Phenolic compounds in plants not only take part in preventing stresses but also in regulating physiological activities. These compounds significantly regulate both below- and above-ground defense mechanisms. Plants synthesize thousands of phenolic compounds throughout their evolution to survive in changing environments. Environmental factors, such as high light, cold, drought, heavy metals, etc., increase the accumulation of phenolics to neutralize any toxic effects. This review focuses on the biosynthesis of phenolic compounds and their updated studies against abiotic stresses.

Calix[4]arene–pyrazole conjugates as potential cancer therapeutics

Tumor selectivity is yet a challenge in chemotherapy-based cancer treatment. A series of calixarenes derivatized at the lower rim with 3-phenyl-1H-pyrazole units with variable upper-rim substituent and conformations of macrocyclic core, alkyl chain length between heterocycle and core, as well as phenolic monomer (5-(4-tert-butylphenyloxy)methoxy-3-phenyl-1H-pyrazole) have been synthesized and characterized in a range of therapeutically relevant cellular models (M-HeLa, MCF7, A-549, PC3, Chang liver, and Wi38) from different target organs/systems. Specific cytotoxicity for M-HeLa cells has been observed in tert-butylcalix[4]arene pyrazoles in 1,3-alternate (compound 7b) and partial cone (compound 7c) conformations with low mutagenicity and haemotoxicity and in vivo toxicity in mice. Compounds 7b,c have induced mitochondrial pathway of apoptosis of M-HeLa cells through caspase-9 activation preceded by the cell cycle arrest at G0/G1 phase. A concomitant overexpression of DNA damage markers in pyrazole-treated M-HeLa cells suggests that calixarene pyrazoles target DNA, which was supported by the presence of interactions between calixarenes and ctDNA at the air–water interface.

Profiles of Free and Bound Phenolics and Their Antioxidant Capacity in Rice Bean (Vigna umbellata).

Rice bean (Vigna umbellata) is a medicinal and dietary legume rich in polyphenols. In this study, the free and bound phenolics in rice bean were extracted by water, 80% methanol, and acid, base, and composite enzymatic hydrolysis, respectively. The polyphenol profiles of the extracted fractions were analyzed. The outcome demonstrated that base hydrolysis was the most effective way to liberate bound phenolics from rice bean (14.18 mg GAE/g DW), which was 16.68 and 56.72 folds higher than those extracted by acid and enzymatic hydrolysis, respectively. The bound polyphenols released by base hydrolysis contributed to 71.15% of the total phenolic content. A total of 35 individual phenolics was identified, of which isoquercitrin, procyanidin B1, rutin, taxifolin, and catechin were the main monomeric phenolics in the free fraction, while gallic acid, protocatechuic acid, p-hydroxybenzoic acid, catechin, and phloroglucinol were the main monomeric phenolics in the bound fraction. In comparison to the free phenolics extracted by water and 80% methanol and the bound phenolics extracted using acid and composite enzymatic hydrolysis, the bound phenolics from base hydrolysis had a superior antioxidant capacity. The antioxidant activity of rice bean is primarily attributed to individual phenolics such as catechin, abundant both in free and bound fractions, and also p-hydroxybenzoic acid, gallic acid, and protocatechuic acid in bound fractions. The bound phenolics of rice bean were first reported and showed large differences with the composition of free phenolics. This work suggests that the bound fraction of rice bean must be taken into account in assessing its potential benefits to health.

Lignin Catalytic Depolymerization for Phenolic Monomers: Boosting the Selective Cleavage of β-O-4 Bonds of Lignin by Mo═O and Al(IV)–O–BO2 Interfacial Sites in B–Mo/Sepiolite

Lignin Catalytic Depolymerization for Phenolic Monomers: Boosting the Selective Cleavage of β-O-4 Bonds of Lignin by Mo═O and Al(IV)–O–BO₂ Interfacial Sites in B–Mo/Sepiolite