Guaiacyl Moieties Research Articles

Theoretical Study on the Multiple Free Radical Scavenging Reactions of Pyranoanthocyanins.

The free radical trapping capacities of multiple pyranoanthocyanins in wine storage and ageing were theoretically explored by density functional theory (DFT) methods. Intramolecular hydrogen bonds were detected in all pyranoanthocyanins, and the planarity of the compounds worsened with an increasing dielectric constant in the environment. Solvents significantly influenced the reaction enthalpies; thus, the preferred thermodynamic mechanisms of the free radical scavenging reactions were modified in different phases. This study incorporates hydrogen atom transfer (HAT), proton loss (PL), electron transfer (ET) reactions, and demethylation (De) of methoxy group mechanisms. The three pyranoanthocyanins have the capacity to capture n1+1 free radicals, where n1 represents the number of methoxy groups. In the gas phase, they prefer employing the n1-De-HAT mechanism on the guaiacyl moiety of the B ring, resulting in the formation of a stable quinone or a quinone radical to scavenge free radicals. In the benzene phase, pyranoanthocyanins trap free radicals via a PL-n1-De-HAT mechanism. In the water phase, the targeted pyranoanthocyanins may dissociate in the form of carboxylate and tend to utilize the n2-PL-n1-De-ET mechanism, where n2 and n1 represent the number of phenolic groups and methoxy groups, respectively, facilitating multiple H+/e- reactions.

Multiple free radical scavenging reactions of aurones

A series of naturally occurring 3′,4′-dihydroxy aurones have been studied with regard to multiple free radical scavenging reactions in the gas and two liquid phases using density functional theory (DFT). All of the aurones prefer to perform (2 + n)-HAT mechanism to trap 2 + n free radicals, where n is the sum of the numbers of catechol and guaiacyl units in the gas and benzene phases. The second HAT reaction favours occurring in the same catechol moiety of the first HAT mechanism occurring OH group due to the formation of a stable quinone and the highly exothermic step of the final stable product formation. The catechol and guaiacyl moieties show increased potency for the second and fourth H+/e‒ reactions. In the water phase, aurones can perform multiple H+/e‒ reactions through n1PL-ET-n2HAT-(n+1-n2)ET mechanism, where n1 is the number of OH groups and n2 is the number of guaiacyl moieties.

Free radical scavenging potency of ellagic acid and its derivatives in multiple H+/e‒ processes

The reaction energetics of the multiple free radical scavenging mechanisms of ellagic acid and its derivatives were studied by DFT method. Ellagic acid and its derivatives that bear catechol or guaiacyl moieties can proceed multiple free radical scavenging processes. Intramolecular hydrogen-bonds were found in the most stable geometries of the investigated compounds and can influence the antioxidant activity of the related groups and hydrogen atom/proton loss sequence. The stronger hydrogen-bond, the weaker antioxidant activity of the hydrogen atom/proton-donating group. The preferred mechanisms vary among different phases. All of the investigated compounds prefer to trap free radicals by multiple HAT mechanisms in gas and benzene phases. The second HAT reaction preferably occurs in the same catechol or guaiacyl unit of the first HAT group with the formation of stable quinone or benzodioxole. The catechol and guaiacyl moieties not only retain high free radical scavenging ability of the parent compounds but even show increased potency for the second and fourth H+/e‒ reactions. In water phase, ellagic acid and its derivatives would proceed consecutively PL reactions from the OH groups. The formed di/tri/tetra-anion would proceed one/four electron transfers following with single/double SPLET mechanism and electron donation reactions until forming the stable quinone or benzodioxole.

Structural investigation of coal humic substances by selective isotopic exchange and high-resolution mass spectrometry.

Here, we report the application of a selective liquid-phase hydrogen/deuterium exchange (HDX) coupled to ultra-high resolution FTICR MS for structural investigations of individual constituents of humic substances (HS) isolated from three coal samples of different geographical origin. Selectivity was achieved by conducting reactions in DCl or NaOD solutions for catalyzing HDX in aromatic ring and side-chain positions with enhanced C-H acidity, respectively. FTICR MS analysis showed a significant overlap of molecular compositions in the HS samples under study, with 2000 common formulae. Using HDX, we demonstrated that the determined common formulae are presented by different structural isomers. We found that aromatic compounds varied both in the substitution pattern and the number of aromatic protons. Depending on the sample, lignin components with the same molecular formulae were composed of coumaryl, coniferyl or sinapyl moieties. Enumeration of HDX series for the 800 most abundant compounds showed that the results of HDX agreed well with the model structures suggested for humic components occupying a van Krevelen plot. In addition, we explored chemical transformations, which could connect individual constituents of coal HS. These transformations included hydrolysis of a guaiacyl moiety and reduction of a catechol unit, which corresponds to the conversion of a coniferyl fragment into a coumaryl unit. The obtained results were supportive of the hypothesis of the reducing humification pathway suggested for lignin transformation in the environment. The conclusion was made that the molecular ensemble of coal HS is composed of individual constituents produced at different humification stages.

The role of guaiacyl moiety in free radical scavenging by 3,5-dihydroxy-4-methoxybenzyl alcohol: thermodynamics of 3H+/3e− mechanisms

ABSTRACTParticipation of guaiacyl moiety of 3,5-dihydroxy-4-methoxybenzyl alcohol (DHMBA) in inactivation of free radicals was investigated using the DFT method. The thermodynamics of triple (3H+/3e−) free radical scavenging mechanisms was investigated. The Gibbs free energies of reactions of inactivation of selected 10 free radicals indicate DHMBA as a potent scavenger. Obtained results allow us to suggest that the contribution of guaiacyl moiety to antioxidant activity of phenolic compounds should be taken into account, what has been scarcely considered until now.

Functional Annotation of LigU as a 1,3-Allylic Isomerase during the Degradation of Lignin in the Protocatechuate 4,5-Cleavage Pathway from the Soil Bacterium Sphingobium sp. SYK-6.

Sphingobium sp. SYK-6 is a Gram-negative soil bacterium that contributes to the degradation of lignin. Lignin provides structural support and protection to plants as a complex aromatic heteropolymer. The lignin degradation pathway of guaiacyl moieties leads to the intermediate, protocatechuate (PCA), which is further degraded via the 4,5-cleavage pathway in which PCA is ultimately metabolized to pyruvate and oxaloacetate. In this pathway, LigI has been shown to catalyze the hydrolysis of 2-pyrone-4,6-dicarboxylate to (4 E)-oxalomesaconate (OMA). Here we have demonstrated, using 1H and 13C nuclear magnetic resonance spectroscopy, that LigU catalyzes the isomerization of the double bond between C4 and C5 in (4 E)-OMA to (3 Z)-2-keto-4-carboxy-3-hexenedioate (KCH), where the double bond has migrated to be between C3 and C4 via a 1,3-allylic isomerization. LigU is most closely related in amino acid sequence to methylaconitate isomerase (PrpF) from Shewanella oneidensis and methylitaconate-Δ-isomerase (Mii) from Eubacterium barkeri. The kinetic constants for the isomerization of OMA to KCH by LigU at pH 8.0 were determined to be 1300 ± 120 s-1 and (7.7 ± 1.5) × 106 M-1 s-1 for kcat and kcat/ Km, respectively. We have also shown that the product of the LigU-catalyzed reaction is the preferred substrate for the LigJ hydratase. In this reaction, LigJ catalyzes the hydration of KCH to 4-carboxy-4-hydroxy-2-oxoadipate.

Theoretical study of the thermodynamics of the mechanisms underlying antiradical activity of cinnamic acid derivatives

The role of antiradical moieties (catechol, guaiacyl and carboxyl group) and molecular conformation in antioxidative potency of dihydrocaffeic acid (DHCA) and dihydroferulic acid (DHFA) was investigated by density functional theory (DFT) method. The thermodynamic preference of different reaction paths of double (2H+/2e−) free radical scavenging mechanisms was estimated. Antiradical potency of DHCA and DHFA was compared with that exerted by their unsaturated analogs − caffeic acid (CA) and ferulic acid (FA). Cis/trans and anti-isomers of studied cinnamic acid derivatives may scavenge free radicals via double processes by involvement of catechol or guaiacyl moiety. Carboxyl group of syn-isomers may also participate in the inactivation of free radicals. Gibbs free energies of reactions with various free radicals indicate that syn-DHCA and syn-DHFA, colon catabolites that could be present in systemic circulation in low μM concentrations, have a potential to contribute to health benefits by direct free radical scavenging.

Application of FTIR spectroscopy to the characterization of archeological wood

Two archeological wood samples were studied by attenuated total reflectance Fourier transform infrared (FTIR–ATR) spectroscopy. They originate from a shipwreck in Ribadeo Bay in the northwest of Spain and from a beam wood of an old nave of the Cathedral of Segovia in the central Spain. Principal component analysis was applied to the transposed data matrix (samples as columns and spectral bands as rows) of 43 recorded spectra (18 in the shipwreck and 25 in the beam wood). The results showed differences between the two samples, with a larger proportion of carbohydrates and smaller proportion of lignin in the beam than in the shipwreck wood. Within the beam wood, lignin content was significantly lower in the recent than the old tree rings (P=0.005). These variations can be attributed to species differences between the two woods (oak and pine respectively), with a mixture of guaiacyl and syringyl in hardwood lignin, whereas softwood lignin consists almost exclusively of guaiacyl moieties. The influence of environmental conditions on the FTIR fingerprint was probably reflected by enhanced oxidation of lignin in aerated conditions (beam wood) and hydrolysis of carbohydrates in submerged-anoxic conditions (shipwreck wood). Molecular characterization by analytical pyrolysis of selected samples from each wood type confirmed the interpretation of the mechanisms behind the variability in wood composition obtained by the FTIR–ATR.

The Characteristics and Reactivity of Acid-Labile Aryl Ether Units in Wood Lignin

Wood lignin contains significant amounts of acid-labile aryl ether units, which play a significant role in lignin modification or delignification processes. We have evaluated the rate and reaction kinetics on the acid-catalyzed cleavages of aryl ether structures for wood lignin in situ based on the formation of phenolic hydroxyl groups. The content of acid-labile aryl ether units was quite uniform for a variety of softwood wood lignins (∼4% per C9 unit) and it varied appreciably among hardwood species, ranging from 4% for aspen to 9% for beech wood lignin. These variations, however, appear to be related to the content of syringyl units in wood lignin. The reactivity of these reactive aryl ether structures was noticeably higher for the spruce than for the aspen wood lignin. This difference in reactivity, based on the behavior of lignin model compound reactions, can be attributed to the influence of syringyl moieties in aspen wood lignin. It appears that most of the acid-labile aryl ether units in hardwood were associated with the syringy moiety being present as a benzyl unit, which is much less reactive than the corresponding guaiacyl moiety.

Chemical Groups and Structural Characterization of Lignin via Thiol-Mediated Demethylation

A new approach to increase the reactivity of lignin by thiol-mediated demethylation was investigated in this study. Demethylated lignin was characterized by the changes in its hydroxyl and methoxyl groups, molecular weight, and other properties using titration and spectroscopy methods including FT-IR, 1H NMR, UV, and GPC. The total, phenolic, and aliphatic hydroxyl contents in lignin increased while the methoxyl content decreased after demethylation reaction, which indicated the occurrence of demethylation reaction. The results from FT-IR and UV analysis also indicated that the kraft lignin in this study contains mainly guaiacyl moiety and demethylated lignin has a higher guaiacyl content than original lignin. The average molecular weight of lignin decreased after demethylation reaction due to the cleavage of ether linkages in lignin macromolecules. No severe degradation of lignin was observed during the demethylation reaction.

Pyrolysis reactions of coniferyl alcohol as a model of the primary structure formed during lignin pyrolysis

It has been suggested that cinnamyl alcohol-type structures are formed during lignin primary pyrolysis using model dimers. In this article, the pyrolysis reactions of trans-coniferyl alcohol (CA) bearing a guaiacyl moiety were studied under N2 at temperatures in the range of 200–350̊C, with particular emphasis on the evaporation/degradation processes. Some (less than 15%) of the CA evaporated without undergoing any degradation reactions, whereas large portions of the CA were converted to polymerization products together with monomers (up to ∼15% in total) with various side-chains. The cis-isomer of CA and 4-vinylguaiacol with a C2 side-chain were also identified. Methylation of the phenolic OH group of CA substantially reduced the formation of polymerization products, whereas the influence of the methylation on the side-chain-converted monomers was limited. Since the methylated CA was not effective for quinine methide formation, quinine methide and radical pathways were indicated as more important reaction mechanisms for the polymerization and side-chain-conversion processes, respectively. These results suggest that CA, if it was formed through pyrolytic cleavage of lignin β-ether linkages, tended to be degraded before it could be recovered through evaporation. Furthermore, the recovery of different monomers suggested the process was greatly dependent on the relative evaporation/degradation efficiencies.

Antihypertensive Evaluation of Lignin Related High-Added-Value 4-Aryl-Hexahydroquinolines

4-Aryl-hexahydroquinolines prepared by Hantzsch reaction from aromatic aldehydes obtained from lignin had been proved to be excellent antioxidant property. In view of polyhydroquinoline containing similarities in structure to the biologically important compound, 1,4-dihydropyridine, their antihypertensive activities were herein determined in spontaneously hypertensive rats (SHRs) during different time. The results show that those compounds possessing excellent antioxidant activity exhibit good antihypertensive property, and the compound containing syringyl moiety exhibit better antihypertensive activity than that containing guaiacyl moiety. This study suggests that those compounds may serve as promising agents for cure hypertension and free radical-related diseases.

Source and transformations of lignin in Carex-dominated peat

We identified the effects of vegetation changes, and aerobic and anaerobic decay on the lignin composition in the Penido Vello peat record (Galicia, Spain). The ombrotrophic part of this peat record was dominated by graminoids and has significant contributions of ericoids at some depths. The organic matter (OM) of different peat fractions (bulk, NaOH-extractable fraction, and non-extractable residues) of 15 samples from the upper meter was analysed with pyrolysis-gas chromatography/mass spectrometry (pyrolysis-GC/MS). In addition, the dominant plant species were analysed, including Carex durieui, Agrostis curtisii, Molinia caerulea, Deschampsia flexuosa, Festuca rubra, Eriophorum angustifolium, Erica mackaiana and Calluna vulgaris, and their lignin composition compared to that of the peat OM. The high abundance of guaiacol and 4-formylguaiacol in fresh plant tissue compared to peat OM suggests that in addition to p-coumaric and ferulic acid (which are abundant in graminoids), other non-lignin phenolic monomers are contributed by graminoid species. For the non-lignin phenolics, graminoids differed from ericoids in the high abundance of ferulic acid (4-vinylguaiacol), while p-coumaric acid (4-vinylphenol) showed high and similar abundances in ericoids and graminoids. This result suggests that ratios between p-hydroxyphenyl (or p-coumaric acid) and other lignin moieties in (pyrolysates of) peat cannot be used as source indicator. Comparison of plant and peat fractions using factor analysis allowed a distinction between the effects of source (plant identity) and decay on the lignin composition of the Penido Vello peat, and different stages of decomposition were identified. Preferential decay of guaiacyl over syringyl moieties was found for the first stage of decay. This preferential decay is probably related to the large abundance of guaiacyl moieties in easily degradable non-lignin phenolics. Preferential decay of syringyl moieties occurred during subsequent aerobic decay.

Biodegradation of Hardwood Lignocellulosics by the Western Poplar Clearwing Borer, Paranthrene robiniae (Hy. Edwards)

Lignin in plant cell wall is a source of useful chemicals and also the major barrier for saccharification of lignocellulosic biomass for producing biofuel and bioproducts. Enzymatic lignin degradation/modification process could bypass the need for chemical pretreatment and thereby facilitate bioprocess consolidation. Herein, we reveal our new discovery in elucidating the process of hardwood lignin modification/degradation by clearwing borer, Paranthrene robiniae . The wood-boring clearwing borer, P. robiniae , effectively tunnels hardwood structures during the larval stage; its digestion products from wood components, however, has not yet been investigated. A series of analysis conducted in this study on tunnel walls and frass produced provided evidence of structural alterations and lignin degradation during such hardwood digestion process. The analysis included solid state (13)C cross-polarization magic angle spinning (CP/MAS) nuclear magnetic resonance (NMR) spectroscopy, attenuated total reflectance Fourier transform infrared (ATR-FTIR), pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS), and thermogravimetric (TG) analysis; the results strongly suggest that the structural alteration of lignin primarily involved a preferential degradation of syringyl units accompanied by oxidation on the side chains of lignin guaiacyl moieties. This study also further indicated that unlike the wood-feeding termite the clearwing borer does not target cellulose as an energy source, and thus its lignin degradation ability should provide potential information on how to disassemble and utilize hardwood lignin. Overall, this biological model with an efficient lignin disruption system will provide the new insight into novel enzyme system required for effective plant cell wall disintegration for enhanced cellulose accessibility by enzymes and production of value-added lignin derived products.

Chemical and physico-chemical characterization of lignins obtained from ethanol-water fractionation of bagasse

Organosolv lignins can replace petroleum chemicals such as phenol either partially or totally in various applications. Eight lignins, seven of which corresponded to the ethanol-water fractionation of bagasse and the other to a reference lignin (Alcell®) were analyzed with the aim to evaluate their chemical and physicochemical characteristics. The purity of the lignin fractions was determined by high pressure liquid chromatography (HPLC) and by ash content. Fourier Transform-Infrared Spectroscopy (FTIR) techniques and differential UV spectroscopy were applied to identify the chemical groups in the lignin samples. The molecular weight distribution was determined by size exclusion chromatography (HPSEC). Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) techniques were used to determine the mass loss due to the high temperature treatment. The lignins studied showed the presence of p-hydroxyphenyl (H unit) and a greater proportion of guaiacyl (G unit) moieties, lower purity, similar or greater amount of phenolic hydroxyl groups, and higher degradation temperatures, than the Alcell® lignin.

Influence of steaming pressure on steam explosion pretreatment of Lespedeza stalks (Lespedeza cyrtobotrya). II. Characteristics of degraded lignin

AbstractLignin fractions obtained by steam explosion pretreatment and subsequent alkaline ethanol solution post‐treatment from Lespedeza cyrtobotrya stalks were studied in terms of chemical characteristics, to reflect the influence of elevating steam pressure from 15 to 25 kg/m2. Because of the remarkable selectivity with respect to lignin, the post‐treatment with 60% ethanol solution containing 1% NaOH yielded 8.3, 13.0, 16.0, 16.4, and 17.8% lignin fractions from the samples steam‐exploded at 15, 17.5, 20, 22.5, and 25 kg/m2 for 4 min, respectively, comparing to 7.7% lignin removal from the raw material. Steam explosion pretreatment, not only obviously cleaved the linkage between carbohydrates and lignin resulting in the significantly decrease of the associated hemicelluloses in lignin fractions, but also broke the β‐O‐4 bond between lignins to some degrees. In particular, slightly more guaiacyl moieties than syringyl units were affected. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010

Chemical Changes Induced by High-Speed Rotation Welding of Wood — Application to Two Canadian Hardwood Species

The chemical changes occurring upon rotational welding with dowels of Canadian wood species sugar maple (Acer saccharum) and yellow birch (Betula alleghaniensis) were examined by pyrolysis-GC/MS, DSC and XPS anlayses. The analyses performed separately on wood substrate (reference wood) and welded material by pyrolysis-GC/MS, DSC and XPS indicate that the differences in mechanical performances of the two welded woods are due mainly to the differences in original lignin structures as well as in the welding temperatures determined for the two wood species. The more pronounced guaiacyl character of the maple wood lignin seems to explain the preferential condensation reactions of the guaiacyl moieties in maple lignin with formaldehyde and furanic compounds released from lignin and carbohydrates during the fast pyrolysis associated with the welding process. The higher temperature determined for maple wood welding than for birch could be responsible for enhanced miscibility of wood polymers in the welding zone, explaining, therefore, the more significant presence of xylan polymer together with newly formed lignin carbohydrate complex (LCC) in the welded material. The detailed analysis of the compounds identified by pyrolysis-GC/MS, together with the results of the other two methods applied in this study, has confirmed that the S/G ratio cannot be taken as the sole criterion for the discussion of the chemical changes in lignins during welding of wood.

Structure–activity relationships of the ultrapotent vanilloid resiniferatoxin (RTX): The side chain benzylic methylene

The side chain benzylic methylene is a critical element for the vanilloid activity of resiniferatoxin ( 2a, RTX), and introduction of branching, oxygen functions, or isosteric substitution at this center proved detrimental, with a decrease of potency of 2–3 orders of magnitude compared to the natural product. Conversely, only a modest erosion of activity was observed upon α-methylation and α-methylenation of the side chain. Surprisingly, introduction of an iodine atom in the guaiacyl moiety of the oxygen isoster 2h led to an unexpected and remarkable (>1000-fold) increase of potency, affording 2i, a compound that outperforms RTX in terms of vanilloid agonism and represents the first one-digit picomolar ligand of a TRP channel discovered to date.

Decomposition of plant residues used in no-tillage systems as revealed by flash pyrolysis

Changes in organic composition of crop residues (soybean, radish, white lupine, blue lupine, black oat and mucuna) that are utilized in crop rotations in no-tillage farming systems in the southern part of Brazil were evaluated by analytical flash pyrolysis. The pyrolysis allowed the identification of five groups of compounds in the residues: guaiacyl moieties in lignin (Lg), syringyl moities in lignin (Ls), polysaccharide (Ps), chlorophyll (Chl) and fatty acid (Fa) derivatives. The decomposition rates of the plant residues ranged from 4.7 to 5.9 g kg −1 day −1, with a mean value of 5.2 g kg −1 day −1, corresponding to a mean loss of 41% (37–47%) of the initial biomass after 80 days of incubation. The Ps and lignin contents were strongly affected by incubation; relative lignin content increased at the expense of polysaccharide derivatives. In the original samples, Ps was the principal group of organic compounds in green manure plant materials, with maximum values in blue and white lupine (67%); after incubation, Ps fractions decreased by 26–51% (average 40%), with the greatest value observed with mucuna and the lowest in white lupine. In soybean plant material the Ps fraction decreased only by 9%. Greater increases in relative lignin content were observed with Ls (156%) than with Lg (59%) derivatives, demonstrating that guaiacyl moieties are easier to biochemically degrade than syringyl moieties. A significant correlation between residue-weight loss and organic groups after 80 days incubation was only found with Ls. Plant materials showing a higher content of syringyl moieties after decomposition might aid in increasing soil organic matter. Flash pyrolysis was shown to be an adequate technique to follow the process of transformation of plant residues into stabilized soil organic matter.

THERMAL INDUCED HOMOLYTIC SCISSIONS OF LIGNIN INTERUNITARY BONDS IN THE HARDWOOD LIGNIN SOLUTION. AN ESR STUDY COMBINED WITH A SPIN TRAPPING METHOD

An electron spin resonance (ESR) method combined with a spin trapping reagent was successfully applied to trap and characterize unstable free radicals which were generated by heat-treatment of the dimethylsulfoxide (DMSO) solution of a hardwood, Japanese beech (Fagus crenata) lignin. It was found, consequently, that two unstable secondary carbon radicals, ∼ CH• in the solution were created and the resulting radicals were trapped as the stable nitroxide spin adducts when the DMSO solution was heat-treated in the presence of a spin trapping reagent: 2,4,6-tri-tert-butylnitrosobenzene (BNB) at ca. 91°C. This means that so-called alkyl phenyl ether bonds, ∼ CH-O- phenyl, known as important lignin interunitary bonds were homolytically scissoned by the heat-treatment of the lignin solution. Further the detailed analysis of the observed ESR spectrum revealed that two positions of alkyl phenyl ether bonds, i.e., β-O-4 and/or α-O-4 bonds as the interunitary linkages in the lignin are homolytically scissioned, although the phenoxy radical, Ph-O • as the counter radical of the secondary carbon radicals was not trapped by the BNB spin trap. This suggests that fairly large steric hindrances operate between the syringyl with two methoxy moieties at the ortho positions and/or guaiacyl moieties with a methoxy moiety at the ortho position, and the BNB molecule bearing two bulky ortho tert-butyl groups in the phenyl ring.