Phenolic Aldehydes Research Articles

Quercus humboldtii(Colombian oak): Characterisation of wood phenolic composition with respect to traditional oak wood used in oenology

The use of new oak barrels and the demand for oak wood in oenology is increasing. Thus, it is necessary to search for new wood sources to supply the current demand in cooperage. The aim of this work was to study the composition of ellagitannins and low molecular weight phenolic compounds (LMWP) by HPLC-DAD of green wood Quercus humboldtii Bonpl. (Colombian), compared to the species typically used in cooperage: Quercus sessiliflora Salisb. (French and Romanian) and Quercus alba L. (USA). In Colombian oak wood, the same LMWP and ellagitannins as in the traditional species were identified. The most abundant LMWP was ellagic acid, and its concentration was lower in Q. humboldtii and Q. alba than in Q. sessiliflora , so these two presented a lower content of phenolic acids. As regards phenolic aldehydes, Colombian oak wood only showed significant differences in the content of coniferyl and sinapic aldehydes in relation to French oak. Finally, the total ellagitannin content of Q. humboldtii was lower than that of European oaks and similar to that of American oak ( Q. alba ). None of the ellagitannins studied presented significant differences compared to Q. alba . Therefore, Q. humboldtii wood was more similar in terms of phenolic composition to Q. alba than to Q. sessiliflora .

An assessment of potential applications with pulsed electric field in wines

Pulsed electric fields (PEF) is a non-thermal processing technology that uses instantaneous, pulses of high voltage for a short period in the range of milliseconds to microseconds; the application of high intensity electric field on toasted wood chips leads to a quick diffusion of extractable molecules. Currently most PEF studies, in the field of oenology, have been focusing on the application of PEF as a pretreatment of grape musts by examining the microbial inactivation and the enhancement of polyphenol extraction. In this study a post-treatment of wine is introduced as method to enhance the wood flavor in the wine with a green noninvasive technology. Major phenolic aldehydes that have been identified as the characteristic compounds of oak volatile compounds were selected as markers and were analyzed instrumentally to compare the influence of PEF processing to non-treated samples. PEF treated samples brought about higher concentrations of the examined oak compounds in the samples treated with PEF, which may explain the advantages of its application. The modulation of the intensity of the electric field and the period of pulses influenced the concentrations of the volatile phenols that were leached out. Differences found between the assayed treatments indicate that PEF application could be a potential practice for a rapid extraction of volatile compounds from oak.

Phenolic Acids, Phenolic Aldehydes and Furanic Derivatives in Oak Chips: American vs. French Oaks

Phenolic acids (gallic, vanillic, syringic and ellagic acids), phenolic aldehydes (vanillin, syringaldehyde, coniferaldehyde and sinapaldehyde) and furanic derivatives (furfural, 5-methylfurfural and 5-hydroxymethylfurfural) were quantified in commercial American and French oak chips. Chips with different sizes and toast degrees were used. Compounds were extracted directly from the wood samples in order to determine possible differences among woods as well as toast degree. Likewise, the compounds were extracted from a synthetic wine solution to which the chip woods had been added. The results show that French wood chips are generally richer than the American ones. The total amount of phenolic compounds increases with toasting level, with the non-toasted chips being the poorest ones. The degree of extraction from the synthetic wine solution seems to be related to the shape of the chips, rather than to the wood type or toast degree.

Structure and mechanism of NOV1, a resveratrol-cleaving dioxygenase

Stilbenes are diphenyl ethene compounds produced naturally in a wide variety of plant species and some bacteria. Stilbenes are also derived from lignin during kraft pulping. Stilbene cleavage oxygenases (SCOs) cleave the central double bond of stilbenes, forming two phenolic aldehydes. Here, we report the structure of an SCO. The X-ray structure of NOV1 from Novosphingobium aromaticivorans was determined in complex with its substrate resveratrol (1.89 Å), its product vanillin (1.75 Å), and without any bound ligand (1.61 Å). The enzyme is a seven-bladed β-propeller with an iron cofactor coordinated by four histidines. In all three structures, dioxygen is observed bound to the iron in a side-on fashion. These structures, along with EPR analysis, allow us to propose a mechanism in which a ferric-superoxide reacts with substrate activated by deprotonation of a phenol group at position 4 of the substrate, which allows movement of electron density toward the central double bond and thus facilitates reaction with the ferric superoxide electrophile. Correspondingly, NOV1 cleaves a wide range of other stilbene-like compounds with a 4'-OH group, offering potential in processing some solubilized fragments of lignin into monomer aromatic compounds.

Natural antimicrobial/antioxidant agents in meat and poultry products as well as fruits and vegetables: A review

ABSTRACTSynthetic preservatives are widely used by the food industry to control the growth of spoilage and pathogenic microorganisms and to inhibit the process of lipid oxidation extending the shelf-life, quality and safety of food products. However, consumer's preference for natural food additives and concern regarding the safety of synthetic preservatives prompted the food industry to look for natural alternatives. Natural antimicrobials, including plant extracts and their essential oils, enzymes, peptides, bacteriocins, bacteriophages, and fermented ingredients have all been shown to have the potential for use as alternatives to chemical antimicrobials. Some spices, herbs and other plant extracts were also reported to be strong antioxidants. The antimicrobial/antioxidant activities of some plant extracts and/or their essential oils are mainly due to the presence of some major bioactive compounds, including phenolic acids, terpenes, aldehydes, and flavonoids. The proposed mechanisms of action of these natural preservatives are reported. An overview of the research done on the direct incorporation of natural preservatives agents into meat and poultry products as well as fruit and vegetables to extend their shelf-life is presented. The development of edible packaging materials containing natural preservatives is growing and their applications in selected food products are also presented in this review.

Substituent Effect of Phenolic Aldehyde Inhibition on Alcoholic Fermentation by Saccharomyces cerevisiae

Phenolic compounds significantly inhibit microbial fermentation of biomass hydrolysates. To understand the quantitative structure–inhibition relationship of phenolic aldehydes on alcoholic fermentation, the effect of 11 different substituted benzaldehydes on the final ethanol yield was examined. The results showed that the degree of phenolic benzaldehyde inhibition was strongly associated with the position of phenolic hydroxyl groups but not the number of phenolic hydroxyl groups. It was observed that ortho-substituted 2-hydroxybenzaldehyde resulted in 15–20-fold higher inhibition than the meta- or para-substituted analogues of 3- and 4-hydroxybenzaldehydes. From the correlation of the molecular descriptors to inhibition potency in yeast fermentation, we found a strong relationship between the octanol/water partition coefficient (log P) of aldehydes and the EC50 value. The most inhibitory 2-hydroxybenzaldehyde has the highest log P and possesses an ortho −OH group capable of forming an intramolecular hydr...

Urease Inhibitors of Agricultural Interest Inspired by Structures of Plant Phenolic Aldehydes

The plant phenolic natural products (PNPs) protocatechuic aldehyde, syringaldehyde and vanillin were used as platforms for obtaining four urease inhibitors. Urea (urease substrate) or thiourea (urease inhibitor) core was added to the structure of newly synthesized compounds to provide inhibitors up to 230-fold more active than the PNPs they originated from. The PNP derivatives are mixed inhibitors with higher affinity to urease active site. Two compounds were as efficient as N-(butyl)thiophosphoric triamide (NBPT) toward soil. Overall, PNPs derivatives are promising urease inhibitors for use as additive in urea-based fertilizers formulations.

The color expression of copigmentation between malvidin-3-O-glucoside and three phenolic aldehydes in model solutions: The effects of pH and molar ratio

Copigmentation was investigated in model solutions between the anthocyanin malvidin-3-O-glucoside and three phenolic aldehydes (vanillic, syringic and coniferyl aldehydes) as a function of the pH and the pigment/copigment molar ratio. Tristimulus colorimetry was applied to evaluate the chromatic variations induced by copigmentation process. The results indicated that the greatest magnitude of copigmentation was obtained at pH 3.0 and molar ratio of 1:100, being significantly higher with coniferyl aldehyde, followed by syringic and vanillic aldehydes. The equilibrium constant (K) and Gibbs free energies (ΔG°) determined here show a spontaneous exothermic reaction. Theoretical calculations (ΔGbinding, ΔE) specified the relative arrangement of the pigment and copigment molecules within the complexes. In addition, an atoms in molecules (AIM) analysis was used to explore the main driving forces contributing to the formation of copigmentation complexes.

ChemInform Abstract: Synthesis of 4H‐Chromenes Promoted by NbCl5 Through Multicomponent Reaction.

AbstractThe optimized conditions allow the synthesis of 4H‐chromenes from phenol (I), β‐ketoester (II), and various aromatic aldehydes under mild conditions.

Transcriptome analysis of Zymomonas mobilis ZM4 reveals mechanisms of tolerance and detoxification of phenolic aldehyde inhibitors from lignocellulose pretreatment.

BackgroundPhenolic aldehydes generated from lignocellulose pretreatment exhibited severe toxic inhibitions on microbial growth and fermentation. Numerous tolerance studies against furfural, 5-hydroxymethyl-2-furaldehyde (HMF), acetate, and ethanol were reported, but studies on inhibition of phenolic aldehyde inhibitors are rare. For ethanologenic strains, Zymomonas mobilis ZM4 is high in ethanol productivity and genetic manipulation feasibility, but sensitive to phenolic aldehyde inhibitors. Molecular mechanisms of tolerance for Z. mobilis toward phenolic aldehydes are not known.ResultsWe took the first insight into genomic response of Z. mobilis ZM4 to the phenolic aldehyde inhibitors derived from lignocellulose pretreatment. The results suggest that the toxicity to cells is caused by the functional group of phenolic aldehyde, similar to furfural and HMF, rather than aromatic groups or phenolic hydroxyl groups. Transcriptome response against 4-hydroxybenzaldehyde, syringaldehyde, and vanillin, representing phenolic groups H, S, and G, respectively, was investigated. The atlas of the important genes responsible for significantly enhanced and repressed genes at the genomic level was illustrated. 272 genes with twofold greater expressions than non-treated controls and 36 gene clusters in response to challenges of these phenolic aldehydes were identified. Several reductases encoded by ZMO1116, ZMO1696, and ZMO1885 were found to play the key roles in reducing phenolic aldehydes into the corresponding phenolic alcohols. Reduction of phenolic aldehydes by overexpression of ZMO1116, ZMO1696, and ZMO1885 in Z. mobilis ZM4 resulted in the increased inhibitor conversion and ethanol productivity, especially for 4-hydroxybenzaldehyde and vanillin. Several transporter genes such as ZMO0282, ZMO0283, ZMO0798, ZMO0799, and ZMO0800 was also displayed significantly increased expressions against the phenolic aldehydes.ConclusionsThe genes encoding reductases are with potentials on phenolic aldehydes-tolerant genes contributing to the reduction of phenolic aldehydes into the corresponding phenolic alcohols forms for Z. mobilis ZM4. Overexpression of the key genes improved the conversion ratio and ethanol productivity of 4-hydroxybenzaldehyde and vanillin with high toxicity. New knowledge obtained from this research aids understanding the mechanisms of bacterial tolerance and the development of the next-generation biocatalysts for advanced biofuels production.Electronic supplementary materialThe online version of this article (doi:10.1186/s13068-015-0333-9) contains supplementary material, which is available to authorized users.

Chemical and structural changes associated with Cu-catalyzed alkaline-oxidative delignification of hybrid poplar.

BackgroundAlkaline hydrogen peroxide pretreatment catalyzed by Cu(II) 2,2′-bipyridine complexes has previously been determined to substantially improve the enzymatic hydrolysis of woody plants including hybrid poplar as a consequence of moderate delignification. In the present work, cell wall morphological and lignin structural changes were characterized for this pretreatment approach to gain insights into pretreatment outcomes and, specifically, to identify the extent and nature of lignin modification.ResultsThrough TEM imaging, this catalytic oxidation process was shown to disrupt cell wall layers in hybrid poplar. Cu-containing nanoparticles, primarily in the Cu(I) oxidation state, co-localized with the disrupted regions, providing indirect evidence of catalytic activity whereby soluble Cu(II) complexes are reduced and precipitated during pretreatment. The concentration of alkali-soluble polymeric and oligomeric lignin was substantially higher for the Cu-catalyzed oxidative pretreatment. This alkali-soluble lignin content increased with time during the catalytic oxidation process, although the molecular weight distributions were unaltered. Yields of aromatic monomers (including phenolic acids and aldehydes) were found to be less than 0.2 % (wt/wt) on lignin. Oxidation of the benzylic alcohol in the lignin side-chain was evident in NMR spectra of the solubilized lignin, whereas minimal changes were observed for the pretreatment-insoluble lignin.ConclusionsThese results provide indirect evidence for catalytic activity within the cell wall. The low yields of lignin-derived aromatic monomers, together with the detailed characterization of the pretreatment-soluble and pretreatment-insoluble lignins, indicate that the majority of both lignin pools remained relatively unmodified. As such, the lignins resulting from this process retain features closely resembling native lignins and may, therefore, be amenable to subsequent valorization.Electronic supplementary materialThe online version of this article (doi:10.1186/s13068-015-0300-5) contains supplementary material, which is available to authorized users.

Separation and concentration of hydroxycinnamic acids in alkaline hydrolyzate from rice straw by nanofiltration

Alkali pretreatment could cause the degradation of the lignin of lignocellulose, releasing hydroxycinnamic acids and phenolic aldehydes into the hydrolyzate. Hydroxycinnamic acids (ferulic and p-coumaric acids) found in alkaline lignocellulosic hydrolyzate are high value-added products. Their separation and concentration from phenolic aldehydes were investigated using nanofiltration (NF) membrane with model solution and practical hydrolyzate. The effect of main operating parameters such as feed pH, permeate flux, NaCl concentration and the synergistic effect of pH and salt on the retentions of phenolic acids and aldehydes in the model solution were studied. Results indicated that the separation performance of hydroxycinnamic acids from aldehydes was optimal at neutral pH. All the phenolics retentions decreased with increasing NaCl concentration, especially for aldehydes. Salt and pH acted synergistic effect on phenolic aldehydes retention. When the practical alkaline hydrolyzate was treated under concentration–diafiltration mode, the mass percentage of hydroxycinnamic acids reached as high as 91.4%. This work demonstrated that NF could accomplish the separation and concentration of hydroxycinnamic acids from practical alkaline lignocellulosic hydrolyzate.

High tolerance and physiological mechanism of Zymomonas mobilis to phenolic inhibitors in ethanol fermentation of corncob residue.

Corncob residue as the lignocellulosic biomass accumulated phenolic compounds generated from xylitol production industry. For utilization of this biomass, Zymomonas mobilis ZM4 was tested as the ethanol fermenting strain and presented a better performance of cell growth (2.8 × 10(8) CFU/mL) and ethanol fermentability (54.42 g/L) in the simultaneous saccharification and fermentation (SSF) than the typical robust strain Saccharomyces cerevisiae DQ1 (cell growth of 2.9 × 10(7) CFU/mL, ethanol titer of 48.6 g/L). The physiological response of Z. mobilis ZM4 to the twelve typical phenolic compounds derived from lignocellulose was assayed and compared with that of S. cerevisiae DQ1. Z. mobilis ZM4 showed nearly the same tolerance to the phenolic aldehydes with S. cerevisiae DQ1, but the stronger tolerance to the phenolic acids existing in corncob residue (2-furoic acid, p-hydroxybenzoic acid, p-coumaric acid, vanillic acid, ferulic acid, and syringic acid). The tolerance mechanism of Z. mobilis was investigated in terms of inhibitor degradation, cell morphology and membrane permeability under the stress of phenolics using GC-MS, scanning and transmission electron microscopies (SEM and TEM), as well as fluorescent probes. The results reveal that Z. mobilis ZM4 has the capability for in situ detoxification of phenolic aldehydes, and the lipopolysaccharide aggregation on the cell outer membrane of Z. mobilis ZM4 provided the permeable barrier to the attack of phenolic acids.

Fast Pyrolysis of Spent Coffee Waste and Oak Wood Chips in a Micro-tubular Reactor

Fast pyrolysis of spent coffee waste, a major non-cellulosic material, and oak wood chips, a cellulosic material, was carried out in a micro tubular reactor over a temperature range of 550 to 750°C with sweep gas flow rates of 20 and 500 mL/min. When the temperature was raised from 550 to 750°C, the gas yields were significantly enhanced, but the liquid yields were reduced. The highest liquid yield, 63.4 wt%, was obtained after pyrolysis of spent coffee waste at 550°C at a sweep gas rate of 500 mL/min. The highest gas yield, 65.74 wt%, was obtained after pyrolysis of the oak wood chips at 750°C at a sweep gas flow rate of 20 mL/min. The gas products primarily included considerable amounts of CO, CO2, and hydrocarbon-rich gases but no hydrogen. Furthermore, regardless of the biomass source, the hydrocarbon-rich gases were qualitatively similar and largely consisted of methane, ethane, ethylene, propane, and propylene. The gas chromatography-mass spectrometry analysis of the pyrolyzed bio-oils demonstrated that the major compounds were phenol derivatives, aldehydes, ketones, acids, and alcohols.

ChemInform Abstract: Solvent‐Free Mechanochemical Route for Green Synthesis of Pharmaceutically Attractive Phenol‐Hydrazones.

AbstractVarious substituted organic hydrazines and phenol aldehydes efficiently react in a vibratory ball‐mill leading to hydrazones with high level of purity and without the use of any environmentally unadvisable reagents, additives or catalysts.

ChemInform Abstract: A Base‐Catalyzed Cascade Route to Phenolic 6‐Cyanopurines via O‐Alkylformamidoximes.

N-[1,2-Dicyano-2-(hydroxyphenylideneamino)vinyl]-O-alkylformamidoximes were prepared from the reaction of N-(2-amino-1,2-dicyanovinyl)-O-alkylformamidoximes with phenolic aldehydes. These compounds generated 2-hydroxyphenyl-4,5-dicyano-N-(N'-alkoxyformimidoyl)imidazoles in the presence of manganese oxide, whereas in triethylamine 6-cyano-8-hydroxy-phenylpurines were isolated. The reaction was followed by 1H NMR spectroscopy and a plausible mechanism is presented.

Antioxidant activity of some phenolic aldehydes and their diimine derivatives: A DFT study

Phenolic compounds are known as antioxidant and/or radical scavengers via H-atom transfer or single electron transfer pathway. Density functional theory (DFT) calculations have been performed on some phenolic aldehydes and some of their designed diimine derivatives with different spacer lengths. Both H-atom transfer and single electron transfer pathways have been investigated by calculating the phenolic O–H bond dissociation energy (BDE) and vertical ionization potentials (IPV). Moreover, the polarity of the solvent medium has been included in calculating BDE and IPV. The radical scavenging activity of these derivatives has been compared with 1,1-diphenyl-2-picrylhydrazyl (DPPH) free radical.

Effect of Brazilian green propolis in patients with type 2 diabetes: A double-blind randomized placebo-controlled study

Propolis contains a variety of chemical compounds, including polyphenols, flavonoids, phenolic aldehydes, amino acids and vitamins, and presents numerous biological and pharmacological properties. The aim of the present study was to evaluate the effect of propolis on blood examination data in patients with type 2 diabetes. In the double-blind, 8-week randomized controlled study, 80 patients with type 2 diabetes were enrolled. Patients were randomly assigned to receive Brazilian green propolis (226.8 mg/day for 8 weeks) (n=41) or the placebo (n=39). The primary endpoint was to detect changes in blood examination data associated with metabolic disorders in patients suffering from diabetes mellitus, including the homeostasis model assessment of insulin resistance (HOMA-IR), uric acid and estimated glomerular filtration rate (eGFR) from baseline to the end of this study. The value of HOMA-IR was not significantly changed by the 8-week administration of propolis or placebo from the baseline data. Values of blood uric acid and eGFR in patients taking the placebo became worse at 8 weeks compared to the baseline, whereas this did not occur in patients consuming Brazilian green propolis. However, HOMA-IR was not improved by propolis intake. A randomized, controlled 8-week trial suggests that Brazilian green propolis (226.8 mg/day) prevents patients with type 2 diabetes from developing worse blood uric acid and eGFR.

Phenolic thio- and selenosemicarbazones as multi-target drugs

A series of isosteric phenolic thio- and selenosemicarbazones have been obtained by condensation of naturally-occurring phenolic aldehydes and thio(seleno)semicarbazides. Title compounds were designed as potential multi-target drugs, and a series of structure-activity relationships could be established upon their in vitro assays: antioxidant activity, α-glucosidase inhibition and antiproliferative activity against six human tumor cell lines: A549 (non-small cell lung), HBL-100 (breast), HeLa (cervix), SW1573 (non-small cell lung), T-47D (breast) and WiDr (colon). For the antiradical activity, selenium atom and 2 or 3 phenolic hydroxyl groups proved to be essential motifs; remarkably, the compound with the most potent activity, with a trihydroxyphenyl scaffold (EC50 = 4.87 ± 1.57 μM) was found to be stronger than natural hydroxytyrosol, a potent antioxidant present in olive oil (EC50 = 13.80 ± 1.41 μM). Furthermore, one of the thiosemicarbazones was found to be a strong non-competitive inhibitor of α-glucosidase (Ki = 9.6 ± 1.6 μM), with an 8-fold increase in activity compared to acarbose (Ki = 77.9 ± 11.4 μM), marketed for the treatment of type-2 diabetes. Most of the synthesized compounds also exhibited relevant antiproliferative activities; in particular, seleno derivatives showed GI50 values lower than 6.0 μM for all the tested cell lines; N-naphthyl mono- and dihydroxylated derivatives behaved as more potent antiproliferative agents than 5-fluorouracil or cisplatin.

Pollen diversity and volatile variability of honey from Corsican Anthyllis hermanniae L. habitat.

Melissopalynological, physicochemical, and volatile analyses of 29 samples of Corsican 'summer maquis' honey were performed. The pollen spectrum was characterized by a wide diversity of nectariferous and/or polleniferous taxa. The most important were Anthyllis hermanniae and Rubus sp., associated with some endemic taxa. Castanea sativa was also determined in these honeys with a great variation. The volatile fraction was characterized by 37 compounds and dominated by phenolic aldehydes and linear acids. The major compounds were phenylacetaldehyde, benzaldehyde, and nonanoic acid. Statistical analysis of pollen and volatile data showed that 18 samples were characterized by a high abundance of phenylacetaldehyde, which might relate to the high amount of A. hermanniae and Rubus sp. Eleven other samples displayed a higher proportion of phenolic ketones and linear acids, which characterized the nectar contribution of C. sativa and Thymus herba-barona, respectively.