Hydroperoxy Group Research Articles

New polycyclic polyprenylated acylphloroglucinols with antidepressant activities from Hypericum perforatum L.

Six new polycyclic polyprenylated acylphloroglucinols (PPAPs), hyperidiones A-F (1–6), were obtained from Hypericum perforatum L. Their structures were characterized via extensive spectroscopic analyses, the circular dichroism data of the in situ formed [Mo2(OCOCH3)4] complexes, the nuclear magnetic resonance calculation with DP4 + probability analysis, and the calculated electronic circular dichroism (ECD) spectra. Compounds 1–6 are bicyclic polyprenylated acylphloroglucinols with a major bicyclo[3.3.1]nonane-2,4,9-trione skeleton. Notably, compound 1 is a rare PPAP with a hydroperoxy group, and a plausible biosynthetic pathway for 1 was proposed. Compounds 4 and 6 exhibited significant neuroprotective effects under 10 μM against corticosterone (CORT)-injured SH-SY5Y cells. Furthermore, compound 4 demonstrated a noteworthy antidepressant effect at the dose of 5 mg/kg in the tail suspension test (TST) of mice, which was equivalent to 5 mg/kg of fluoxetine. And it potentially exerted an antidepressant effect through the hypothalamic–pituitary–adrenal (HPA) axis.

Theoretical structural and spectroscopic characterization of peroxyacetic acid (CH3-CO-OOH): study of the far infrared region.

Peroxyacetic acid, a non-rigid oxygenated organic molecule which acts in the atmosphere as a reservoir of HOX and ROX radicals, is studied using highly correlated ab initio methods with the aim of its spectroscopic characterization in the gas phase. The study focuses on the far infrared region providing reliable rovibrational parameters such as energy levels and splittings. The molecule presents three conformers that inter-convert by internal rotation, drawing a potential energy surface of 12 minima. One of them shows prominent stability due to the formation of one weak intramolecular bond between the hydrogen atom of the hydroperoxy group and the oxygen atom of the carbonyl group. For the three minimum energy structures, rotational constants and centrifugal distortion constants are provided. It may be expected that the most stable conformer is the only one contributing to the spectral features in further measurements at low temperature. In this structure, the methyl torsional barrier has been found to be very low, V3 = 88.6 cm-1 producing a splitting of 2.262 cm-1 for the ground vibrational state. The study confirms that the ν20 torsional mode interacts strongly with the other two torsional modes ν19 and ν21, but slightly with the remaining vibrations. Then, a variational procedure in three dimensions allows the exploration of the low-frequency modes. The methyl torsional fundamental ν21 was found to be 49.1 cm-1 (Ai) and 33.4 cm-1 (E). The fundamentals of ν20 (C-O bond torsion) and ν19 (OH torsion) have been computed to be 216.7 cm-1 (A2) and 218.5 cm-1 (E) and 393.6 cm-1 (A2) and 394.1 cm-1. Since non-rigidity can have effects on the reactivity due to the conformer interconversion, and transitions involving low-lying levels can be observed with many spectroscopic techniques, this work can help kinetic studies and assignments of further spectroscopic studies needed for the detection in the gas phase of trace molecules.

Preparation of saturated fatty acid hydroperoxide isomers and determination of their thermal decomposition products – 2-alkanones and lactones

As known for quite a long time now, even saturated fatty acids can be oxidized at high temperatures to produce unique aroma compounds, such as 2-alkanones and lactones. Hydroperoxide positional isomers with a hydroperoxy group at the 2-, 3-, 4-, or 5-position are hypothesized to be responsible for the formation of these aroma components, but this hypothesis has not been verified. For the first time, this study successfully prepared a series of glyceryl trioctanoate hydroperoxide (C8TG;OOH) isomers. The isomers were thermally decomposed, proving that 2-heptanone was selectively formed from C8TG;3-OOH, and γ- and δ-octalactones were mainly formed from C8TG;4- and 5-OOH, respectively. C8TG;2-OOH was also involved in lactone formation, whereas C8TG;6- and 7-OOH were not. This proves the long-standing hypothesis. The mechanism revealed in this work is expected to be useful to create favorable aromas (i.e., 2-alkanones and lactones) from saturated fatty acids.

Highly Efficient Autoxidation of Triethylamine.

Autoxidation has been acknowledged as a major oxidation pathway in a broad range of atmospherically important compounds including isoprene and monoterpenes. More recently, autoxidation has also been identified as central and even dominant in the atmospheric oxidation of the rather small nonhydrocarbons dimethyl sulfide (DMS) and trimethylamine (TMA). Here, we find even faster autoxidation in the aliphatic amine triethylamine (TEA). The atmospherically dominating autoxidation leads to highly oxygenated and functionalized compounds. Products with as many as three hydroperoxy (OOH) groups and an O:C ratio larger than 1 are formed. We present theoretical multiconformer transition-state theory (MC-TST) calculations of the unimolecular reactions in the autoxidation following the OH + TEA reaction and calculate peroxy radical H-shift rate coefficients >20 s-1 for the first two generations of H-shifts. The efficient autoxidation in TEA is verified by the observation of the proposed highly oxidized products and radicals in flow-tube experiments. We find that the initial OH hydrogen abstraction at the α-carbon is strongly favored, with the β-carbon abstraction yield being less than a few percent.

Sesquiterpene coumarins isolated from Ferula bungeana and their anti-neuroinflammatory activities

This is the first study to profile natural sesquiterpene coumarins (SCs) in Ferula bungeana, a medicinal plant of the genus Ferula in China. Eight undescribed sesquiterpene coumarins (1–8), along with six known ones (9–14) were obtained from the whole plant of F. bungeana. These unreported SCs (1–8) enriched the structural diversity of natural SCs, especially these with the hydroxy or carbonyl group at C-7′ and a hydroperoxy group at C-7′ or C-8′. Compounds (9–14) were reported for the first time from this plant. The in vitro anti-neuroinflammatory activity assay showed that compounds 2 and 9 showed stronger inhibitory effect on nitric oxide (NO) production in lipopolysaccharide (LPS)-induced BV-2 microglia, compared with positive control minocycline, and compounds 5 and 10 showed moderate inhibitory effects.

Watching a hydroperoxyalkyl radical (•QOOH) dissociate.

A prototypical hydroperoxyalkyl radical (•QOOH) intermediate, transiently formed in the oxidation of volatile organic compounds, was directly observed through its infrared fingerprint and energy-dependent unimolecular decay to hydroxyl radical and cyclic ether products. Direct time-domain measurements of •QOOH unimolecular dissociation rates over a wide range of energies were found to be in accord with those predicted theoretically using state-of-the-art electronic structure characterizations of the transition state barrier region. Unimolecular decay was enhanced by substantial heavy-atom tunneling involving O-O elongation and C-C-O angle contraction along the reaction pathway. Master equation modeling yielded a fully a priori prediction of the pressure-dependent thermal unimolecular dissociation rates for the •QOOH intermediate-again increased by heavy-atom tunneling-which are required for global models of atmospheric and combustion chemistry.

Spectral fingerprint of stabilized •QOOH

Chemical Kinetics Carbon-centered radicals containing the hydroperoxy group, commonly denoted as •QOOH, are elusive but are among the most critical intermediate species for kinetic modeling of hydrocarbon oxidation in various atmospheric and combustion processes. Their direct experimental observation is a long-standing challenge, with only one successful previous attempt. Using a combination of infrared activation spectroscopy and ultraviolet laser–induced fluorescence detection, Hansen et al. directly characterized the vibrational structure of a •QOOH intermediate in isobutane oxidation, collisionally stabilized and isolated, and followed its dissociative evolution under infrared activation with time and energy resolution. High-level electronic structure calculations revealed an important role of heavy-atom tunneling in this process. Science , abj0412, this issue p. [679][1] [1]: /lookup/doi/10.1126/science.abj0412

1H NMR Study of the In Vitro Digestion of Highly Oxidized Soybean Oil and the Effect of the Presence of Ovalbumin.

Oxidized lipids containing a wide variety of potentially toxic compounds can be ingested through diet. However, their transformations during digestion are little known, despite this knowledge being essential in understanding their impact on human health. Considering this, the in vitro digestion process of highly oxidized soybean oil, containing compounds bearing hydroperoxy, aldehyde, epoxy, keto and hydroxy groups, among others, is studied by 1H nuclear magnetic resonance. Lipolysis extent, oxidation occurrence and the fate of oxidation products both present in the undigested oil and formed during digestion are analyzed. Furthermore, the effect during digestion of two different ovalbumin proportions on all the aforementioned issues is also addressed. It is proved that polyunsaturated group bioaccessibility is affected by both a decrease in lipolysis and oxidation occurrence during digestion. While hydroperoxide level declines throughout this process, epoxy-compounds, keto-dienes, hydroxy-compounds, furan-derivatives and n-alkanals persist to a great extent or even increase. Conversely, α,β-unsaturated aldehydes, especially the very reactive and toxic oxygenated ones, diminish, although part of them remains in the digestates. While a low ovalbumin proportion hardly affects oil evolution during digestion, at a high level it diminishes oxidation and reduces the concentration of potentially bioaccessible toxic oxidation compounds.

Regulatory Phenomena in the Glutathione Peroxidase Superfamily.

Significance: The selenium-containing Glutathione peroxidases (GPxs)1-4 protect against oxidative challenge, inhibit inflammation and oxidant-induced regulated cell death. Recent Advances: GPx1 and GPx4 dampen phosphorylation cascades predominantly via prevention of inactivation of phosphatases by H2O2 or lipid hydroperoxides. GPx2 regulates the balance between regeneration and apoptotic cell shedding in the intestine. It inhibits inflammation-induced carcinogenesis in the gut but promotes growth of established cancers. GPx3 deficiency facilitates platelet aggregation likely via disinhibition of thromboxane biosynthesis. It is also considered a tumor suppressor. GPx4 is expressed in three different forms. The cytosolic form proved to inhibit interleukin-1-driven nuclear factor κB activation and leukotriene biosynthesis. Moreover, it is a key regulator of ferroptosis, because it reduces hydroperoxy groups of complex lipids and silences lipoxygenases. By alternate substrate use, the nuclear form contributes to chromatin compaction. Mitochondrial GPx4 forms the mitochondrial sheath of spermatozoa and, thus, guarantees male fertility. Out of the less characterized GPxs, the cysteine-containing GPx7 and GPx8 are unique in contributing to oxidative protein folding in the endoplasmic reticulum by reacting with protein isomerase as an alternate substrate. A yeast 2-Cysteine glutathione peroxidase equipped with CP and CR was reported to sense H2O2 for inducing an adaptive response. Critical Issues: Most of the findings compiled are derived from tissue culture and/or animal studies only. Their impact on human physiology is sometimes questionable. Future Directions: The expression of individual GPxs and GPx-dependent regulatory phenomena are to be further investigated, in particular in respect to human health.

Sulfuric Acid Formation via H2SO3 Oxidation by H2O2 in the Atmosphere.

With the help of quantum mechanical methods, the formation of H2SO4 by the oxidation of H2SO3 with H2O2 was studied theoretically. Both stepwise and concerted mechanisms were calculated. It was found that the direct oxidation of H2SO3 by H2O2 alone requires prohibitive activation energies of >38.6 kcal/mol. However, the addition of one water molecule exhibits a strong catalytic effect that dramatically reduces the overall reaction barrier to 6.2 (2.3 with PCM) kcal/mol. The deprotonated HSO3- species also reduces the overall reaction barrier to 5.6 (-5.8 with PCM) kcal/mol. Both of these proceed via concerted pathways. On the other hand, the stepwise mechanisms generally produce intermediates with a hydroperoxy group (-O-O-H), which is a result of a nucleophilic attack by the oxygens of H2O2. While studying the catalytic effect of water, a previously unknown hydroperoxy intermediate (HOO)S(OH)3, where sulfur is coordinated with three OH groups, was found. This work also reveals a rearrangement step of another hydroperoxy intermediate (HOO)SO2- to HSO4- that was found in earlier experimental studies. For all of the mechanisms calculated, the final H2SO4 is formed with a significant exothermicity of >60 kcal/mol. In general, even without sunlight, it was found that the formation of sulfuric acid by hydrogen peroxide can occur in a heterogeneous moisturized environment.

First oxidation products from the reaction of hydroxyl radicals with isoprene for pristine environmental conditions

Isoprene, C5H8, inserts about half of the non-methane carbon flux of biogenic origin into the atmosphere. Its degradation is primarily initiated by the reaction with hydroxyl radicals. Here we show experimentally the formation of reactive intermediates and corresponding closed-shell products from the reaction of hydroxyl radicals with isoprene for low nitric oxide and low hydroperoxy radical conditions. Detailed product analysis is achieved by mass spectrometric techniques. Quantum chemical calculations support the usefulness of applied ionization schemes. Observed peroxy radicals are the isomeric HO-C5H8O2 radicals and their isomerization products HO-C5H8(O2)O2, bearing most likely an additional hydroperoxy group, and in traces HO-C5H8(O2)2O2 with two hydroperoxy groups. Main closed-shell products from unimolecular peroxy radical reactions are hydroperoxy aldehydes, C5H8O3, and smaller yield products with the composition C5H8O4 and C4H8O5. Detected signals of C10H18O4, C10H18O6, and C5H10O2 stand for products arising from peroxy radical self- and cross-reactions.

Triterpene glycosides from the Vietnamese sea cucumber Holothuria edulis

From the MeOH extract of the Vietnamese sea cucumber Holothuria edulis, eight triterpene glycosides (1–8), including one new compound namely holothurin A5 (1), were isolated by using various chromatographic separations. Their structures were established by spectroscopic experiments including 1D, 2D NMR and HR-ESI-MS. Holothurin A5 (1) has a hydroperoxy group at C-25. To the best of our knowledge, this is the first report of this group in triterpene saponins obtained from sea cucumbers to date. In addition, the in vitro cytotoxicity against five human cancer cell lines (HepG2, KB, LNCaP, MCF7 and SK-Mel2) of all isolated compounds was also evaluated using SRB assays.

Involvement of the Hydroperoxy Group in the Irreversible Inhibition of Leukocyte-Type 12-Lipoxygenase by Monoterpene Glycosides Contained in the Qing Shan Lu Shui Tea.

We have previously found two novel monoterpene glycosides, liguroside A and liguroside B, with an inhibitory effect on the catalytic activity of the enzyme leukocyte-type 12-lipoxygenase in the Qing Shan Lu Shui tea. Here, two new monoterpene glycosides, liguroside C and liguroside D which inhibit this enzyme, were isolated from the same tea. The spectral and chemical evidence characterized the structures of these compounds as (5E)-7-hydroperoxy-3,7-dimethyl-1,5-octadienyl-3-O-(α-l-rhamnopyranosyl)-(1′′→3′)-(4′′′-O-trans-p-coumaroyl)-β-d-glucopyranoside and (2E)-6-hydroxy-3,7-dimethyl-2,7-octadienyl-3-O-(α-l-rhamnopyranosyl)-(1′′→3′)-(4′′′-O-trans-p-coumaroyl)-β-d-glucopyranoside, respectively. These ligurosides, which irreversibly inhibited leukocyte-type 12-lipoxygenase, have a hydroperoxy group in the monoterpene moiety. Additionally, monoterpene glycosides had the same backbone structure but did not have a hydroperoxy group, such as kudingoside A and lipedoside B-III, contained in the tea did not inhibit the enzyme. When a hydroperoxy group in liguroside A was reduced by using triphenylphosphine, the resultant compound, kudingoside B, showed a lower inhibitory effect on the enzyme. These results strongly suggest the involvement of the hydroperoxy group in the irreversible inhibition of the catalytic activity of leukocyte-type 12-lipoxygenase by the monoterpene glycosides contained in the Qing Shan Lu Shui tea.

Cytotoxic Triterpenoids from the Stembark of <i>Aglaia argentea</i> (Meliaceae)

Four dammarane-type triterpenoid compounds, dammar-24-en-3a-ol (1), 3-epi-cabraleahydroxy lactone (2), (E)-25-hydroperoxydammar-23-en-3b,20-diol (3), and dammar-24-en-3β,20-diol (4), were isolated from the methanolic extract of the stembark of Aglaia argentea. Compounds 1-4 were isolated for first time from this plant. The structure of isolated compounds were elucidated by spectroscopic methods including one and two-dimensional NMR as well as mass spectrometric analysis. Compounds, 1-4, along with a known synthetic analog, 20-hydroxy-dammar-24-en-3-on (5), were evaluated their cytotoxic activity against P-388 murine leukemia cells in vitro. The IC50 values of compounds, 1-5 were 9.09 ± 0.10, 68.53 ± 0.08, 5.89 ± 0.08, 22.40 ± 0.11, and 11.53 ± 0.08 µg/mL, respectively. Among the dammarane-type triterpenoids, compounds 1, 3, 4 and 5 having opened side chain showed the stronger activity, wheres compound 2 with cyclic side chain showed weak or no activity. In addition, compound 3 showed strongest activity, indicate that hydroperoxy group at side chain increase cytotoxic activity.

Computational Comparison of Different Reagent Ions in the Chemical Ionization of Oxidized Multifunctional Compounds.

High pressure anion chemical ionization is commonly used for the detection of neutral molecules in the gas phase. The detection efficiency in these measurements depends on how strongly the reagent ion binds to the neutral target molecule. We have calculated the binding strength of nitrate (NO3-), acetate (CH3C(O)O-), lactate (CH3CH(OH)C(O)O-), trifluoroacetate (CF3C(O)O-), trifluoromethanolate (CF3O-), bromide (Br-), and iodide (I-) reagent ions to ten different products derived from the OH radical-initiated oxidation of butadiene. We found that the binding of these oxidation products to the reagent ions depends almost linearly on the number of oxygen atoms in the target molecule, with the precise chemical identity of the compound (e.g., the number and relative position of hydroxyl or hydroperoxy groups) playing a more minor role. For acetate, the formation free energy decreases on average by around 4 kcal/mol when the number of oxygen atoms in the sample molecule increases by one. For the other reagent ions the corresponding decrease is around 3 kcal/mol. For all of the molecules studied, acetate forms the most stable clusters and I- the least stable. We also investigated the effect of humidity on the chemical ionization by calculating how strongly water molecules bind to both the reagent ions and the ion-molecule clusters. Water binds much more strongly to the reagent ion monomers compared to the reagent ion "dimers" (defined here as a cluster of the reagent anion with the corresponding neutral conjugate acid, e.g., HNO3(NO3-)) or the ion-molecule clusters. This likely leads to a stronger humidity dependence when using reagent ions that are not able to form reagent ion dimers (such as CF3C(O)O-, CF3O-, Br-, and I-).

Unraveling the structure and chemical mechanisms of highly oxygenated intermediates in oxidation of organic compounds

Decades of research on the autooxidation of organic compounds have provided fundamental and practical insights into these processes; however, the structure of many key autooxidation intermediates and the reactions leading to their formation still remain unclear. This work provides additional experimental evidence that highly oxygenated intermediates with one or more hydroperoxy groups are prevalent in the autooxidation of various oxygenated (e.g., alcohol, aldehyde, keto compounds, ether, and ester) and nonoxygenated (e.g., normal alkane, branched alkane, and cycloalkane) organic compounds. These findings improve our understanding of autooxidation reaction mechanisms that are routinely used to predict fuel ignition and oxidative stability of liquid hydrocarbons, while also providing insights relevant to the formation mechanisms of tropospheric aerosol building blocks. The direct observation of highly oxygenated intermediates for the autooxidation of alkanes at 500-600 K builds upon prior observations made in atmospheric conditions for the autooxidation of terpenes and other unsaturated hydrocarbons; it shows that highly oxygenated intermediates are stable at conditions above room temperature. These results further reveal that highly oxygenated intermediates are not only accessible by chemical activation but also by thermal activation. Theoretical calculations on H-atom migration reactions are presented to rationalize the relationship between the organic compound's molecular structure (n-alkane, branched alkane, and cycloalkane) and its propensity to produce highly oxygenated intermediates via extensive autooxidation of hydroperoxyalkylperoxy radicals. Finally, detailed chemical kinetic simulations demonstrate the influence of these additional reaction pathways on the ignition of practical fuels.

QM/MM simulations provide insight into the mechanism of bioluminescence triggering in ctenophore photoproteins.

Photoproteins are responsible for light emission in a variety of marine ctenophores and coelenterates. The mechanism of light emission in both families occurs via the same reaction. However, the arrangement of amino acid residues surrounding the chromophore, and the catalytic mechanism of light emission is unknown for the ctenophore photoproteins. In this study, we used quantum mechanics/molecular mechanics (QM/MM) and site-directed mutagenesis studies to investigate the details of the catalytic mechanism in berovin, a member of the ctenophore family. In the absence of a crystal structure of the berovin-substrate complex, molecular docking was used to determine the binding mode of the protonated (2-hydroperoxy) and deprotonated (2-peroxy anion) forms of the substrate to berovin. A total of 13 mutants predicted to surround the binding site were targeted by site-directed mutagenesis which revealed their relative importance in substrate binding and catalysis. Molecular dynamics simulations and MM-PBSA (Molecular Mechanics Poisson-Boltzmann/surface area) calculations showed that electrostatic and polar solvation energy are +115.65 and -100.42 kcal/mol in the deprotonated form, respectively. QM/MM calculations and pKa analysis revealed the deprotonated form of substrate is unstable due to the generation of a dioxetane intermediate caused by nucleophilic attack of the substrate peroxy anion at its C3 position. This work also revealed that a hydrogen bonding network formed by a D158- R41-Y204 triad could be responsible for shuttling the proton from the 2- hydroperoxy group of the substrate to bulk solvent.

Hygroscopicity of Organic Compounds as a Function of Carbon Chain Length and Carboxyl, Hydroperoxy, and Carbonyl Functional Groups.

The albedo and microphysical properties of clouds are controlled in part by the hygroscopicity of particles serving as cloud condensation nuclei (CCN). Hygroscopicity of complex organic mixtures in the atmosphere varies widely and remains challenging to predict. Here we present new measurements characterizing the CCN activity of pure compounds in which carbon chain length and the numbers of hydroperoxy, carboxyl, and carbonyl functional groups were systematically varied to establish the contributions of these groups to organic aerosol apparent hygroscopicity. Apparent hygroscopicity decreased with carbon chain length and increased with polar functional groups in the order carboxyl > hydroperoxy > carbonyl. Activation diameters at different supersaturations deviated from the -3/2 slope in log-log space predicted by Köhler theory, suggesting that water solubility limits CCN activity of particles composed of weakly functionalized organic compounds. Results are compared to a functional group contribution model that predicts CCN activity of organic compounds. The model performed well for most compounds but underpredicted the CCN activity of hydroperoxy groups. New best-fit hydroperoxy group/water interaction parameters were derived from the available CCN data. These results may help improve estimates of the CCN activity of ambient organic aerosols from composition data.

N-Hexanal and (Z)-3-hexenal are generated from arachidonic acid and linolenic acid by a lipoxygenase in Marchantia polymorpha L.

Most terrestrial plants form green leaf volatiles (GLVs), which are mainly composed of six-carbon (C6) compounds. In our effort to study the distribution of the ability of lipoxygenase (LOX) to form GLVs, we found that a liverwort, Marchantia polymorpha, formed n-hexanal and (Z)-3-hexenal. Some LOXs execute a secondary reaction to form short chain volatiles. One of the LOXs from M. polymorpha (MpLOX7) oxygenized arachidonic and α-linolenic acids at almost equivalent efficiency and formed C6-aldehydes during its catalysis; these are likely formed from hydroperoxides of arachidonic and α-linolenic acids, with a cleavage of the bond between carbon at the base of the hydroperoxy group and carbon of double bond, which is energetically unfavorable. These lines of evidence suggest that one of the LOXs in liverwort employs an unprecedented reaction to form C6 aldehydes as by-products of its reaction with fatty acid substrates.

Lipoxygenase-mediated peroxidation of model plant extractives

Three unsaturated fatty acids, namely 9-cis,12-cis-linoleic acid, 1,2,3-tri-cis, cis-9,12-octadecadienoyl (glycerol trilinolein) and 1,2,3-tri-cis-9-octadecenoyl (triolein) were selected as models of components of plant extractives to monitor the hydroperoxygenation induced by soybean lipoxygenase (LOX), which was applied as an oxidative catalyst at room temperature. The fatty acids were monitored in colloidal dispersions in relation to their molecular changes using 1H/13C nuclear magnetic resonance (NMR), Fourier transform infrared (FTIR) and UV spectroscopies. The detection of the hydroperoxy group was limited due to its unstable nature. However, the reduction of protons associated with the diene groups and the substitution of hydroperoxy groups at the allylic positon in conjugated lipids were detected by the induced chemical shift of HOO-bearing 13C and 1H resonances and the oxygen absorption owing to changes in the molecule. Moreover, compared to the two other substrates, no oxygen substitution was observed in triolein, in accordance with its lower level of saturation and the absence of bis-allylic carbon. Our results are of relevance to plant fiber processing, since fatty acids are major constituents of hydrophobic deposits that cause a range of manufacturing challenges.