7-oxodehydroabietic Acid Research Articles

Chemical composition and antioxidant capacity of purified extracts of Prosopis pallida(Humb. & Bonpl. ex Willd.) Kunth (Fabaceae) fruits from Northern Peru

The purpose of this work was to evaluate the antioxidant capacity of Prosopis pallida(Fabaceae) fruits “algarrobo”, in addition to determine their main chemical components. Fruit purified extracts from the regions of Tumbes, Piura, Lambayeque, and La Libertad (Peru) were evaluated using infusion, decoction, and alcoholic extraction at concentrations of 45, 70 and 96%. To measure the antioxidant capacity of the extracts, the determination of total phenolics content was performed, followed by the antioxidant evaluation using DPPH, FRAP and ABTS. The chemical identification was carried out through UHPLC-UV-MS/MS. The results showed that the decoction of the sample from the region of La Libertad, as well as the ethanol extracts at 45% of the samples from Tumbes and Lambayeque presented greater antioxidant capacity. Moreover, ten major substances of these extracts were identified: nine phenolic derivatives (vicenin II as the main constituent of the extracts) and one diterpene (7-oxodehydroabietic acid).

EFFECT OF SUBMERGED FERMENTATION ON THE ANTIBACTERIAL AND ANTIOXIDANT PROPERTIES OF AQUEOUS EXTRACTS OBTAINED FROM VOACANGA AFRICANA STAPF SEED

Voacanga africana Stapf which belongs to the family, Apocynaceae is among useful medicinal plants of West Africa. The present study investigates the antibacterial and antioxidant properties of aqueous extracts obtained from raw and fermented V. africana. One portion of V. africana was subjected to submerged fermentation for 7 days. Aqueous extracts of the raw and fermented samples of V. africana were obtained using standard methods. Antibacterial effect of the aqueous exracts was assessed by agar well diffusion while a battery of antioxidant test which include DPPH scavenging, ABTS, and Fe2+ chelation was employed. The bioactive compounds present in the extract were assessed using gas chromatography-mass spectrophotometer. Extract obtained from the fermented seed of V. africana had good antimicrobial effect with zones of inhibition ranging from 4.67 to 22.00 mm. Aqueous extract obtained from fermented V. africana exhibited better antioxidant capacity with DPPH scavenging effect being the highest (27.93) when compared with extract obtained from raw V. africana. Bioactive compounds such as Eicosane, 1,14-Dibromotetradecane, 7-Oxodehydroabietic acid, oleic acid and so on were present in the aqueous extract obtained from fermented V. africana. Data gathered from this study revealed that fermentation enhances the antimicrobial and anoxidant properties of V. africana. The presence of bioactive compounds in the aqueous extract of V. africana indicates that it could be a good source of natural antimicrobial and antioxidant compounds for the improvement of human health.

Tricyclic diterpenes from the resin of Daemonorops draco and their activities on oxidative stress-induced mesenchymal stromal cells

A bioassay-guided chemical investigation of the resin exudates from Daemonorops draco (dragon’s blood, Palmaceae) has resulted in the isolation of two new trinorditerpenes, 7β-13-dihydroxypodocarpa-8,11,13-trien-15-oic acid (1) and 7α-13-dihydroxypodocarpa-8,11,13-trien-15-oic acid (2), along with ten previously described abietane diterpenes, 7β-15-dihydroxydehydroabietic acid (3), 7α-15-dihydroxydehydroabietic acid (4), 15-hydroxydehydroabietic acid (5), 7-oxodehydroabietic acid (6), dehydroabietic acid (7), 15-hydroxyabietic acid (8), 12α-hydroxyabietic acid (9), abietic acid (10), 7,13,15-abietatrien-18-oic acid (11), and cephasinene B (12). The structures of 1 and 2 were elucidated using spectroscopic techniques, including HR-ESIMS and 1D/2D NMR. The absolute configurations were determined by comparing the experimental electronic circular dichroism (ECD) spectra with the calculated ECD data based on time-dependent density functional theory. The bioactivity of the extracts, fractions, and isolated compounds was assessed in oxidative stress-induced mesenchymal stromal cells (MSCs). The crude extract and the hexanes, ethyl acetate, and aqueous fractions exhibited high potency against oxidative stress-induced apoptosis of MSCs. Among the isolated compounds, compounds 1 (3 μM) and 10 (100 μM) demonstrated good recovery of MSCs against oxidative stress.

Bioactive Compounds Involved in the Formation of the Sparse Understory Vegetation in Pine Forests

The spices of Pinus, the most widespread genus of the Pinaceae family in the northern hemisphere, often have sparse understory vegetation. However, sunlight intensity on the pine forest floor is sufficient for undergrowth. Allelopathy, therefore, is considered to be involved in the formation of sparse understory vegetation. The evidence for the allelopathy of several pine species has accumulated in the literature over the decades. Extracts of pine needle- like leaves, roots, litter, and soil under pine trees suppressed several plant species, including undergrowth plant species of pine forests. A substantial number of secondary metabolites such as terpenoids, phenolics, cinnamic acids, carboxylic acids, fatty acids, and flavonoids have been identified in pine needles and roots, litter and soil under pine trees. The evidence also suggests that some of these compounds are probably released into the soil through the decomposition of the plant litter, and into the surrounding environment as volatiles. The most active compounds found in the pine soil were methyl 15-hydroxy-7-oxodehydroabietate and 7-oxodehydroabietic acid; both compounds may also be formed through the degradation of resin acids, which were found abundantly in pine trees. Bioactive compounds released into the soil and surrounding environment possibly act as allelochemicals and suppress the invasion of undergrowth plants into the forests, resulting in the establishment of the sparse understory vegetation. The paper summarized the allelopathic activity of 16 Pinus species and 38 allelochamicals.

Tracing colophonium in consumer products.

Colophonium (rosin) can cause allergic contact dermatitis, mainly due to autoxidation of abietic acid (AbA). Products containing ≥0.1% colophonium should be labeled with EUH208 - "Contains rosin; colophony. May produce an allergic reaction." How should this be measured? To compare the results from different strategies for estimating colophonium levels in consumer products: (a) from AbA, and (b) the sum of all major resin acids. To investigate the ratio of 7-oxodehydroabietic acid (7-O-DeA)/AbA as indication of autoxidation. Resin acids were extracted from consumer products, derivatized, and then separated by gas chromatography/mass spectrometry (GC/MS). Resin acids were detected in 9 of 15 products. No product contained colophonium ≥0.1%. Estimation based on AbA resulted in underestimation of the colophonium levels in four of nine products. For three products, the obtained levels from this strategy were only one of two compared to when estimating from the sum of all resin acids. The ratio 7-O-DeA/AbA varied from 74% to 1.4%. We propose to measure colophonium based on the sum of all detectable major resin acids, including 7-O-DeA. The ratio of 7-O-DeA/AbA should be used as a marker of autoxidation, indicating an increased risk of sensitization. The presented analytical method is simple to use and suitable for further screening studies.

Phytochemical, Antiplasmodial, Cytotoxic and Antimicrobial Evaluation of a Southeast Brazilian Brown Propolis Produced by Apis mellifera Bees.

Seven phenolic compounds (ferulic acid, caffeic acid, 4-methoxycinnamic acid, 3,4-dimethoxycinnamic acid, 3-hydroxy-4-methoxybenzaldehyde, 3-methoxy-4-hydroxypropiophenone and 1-O,2-O-digalloyl-6-O-trans-p-coumaroyl-β-D-glucopyranoside), a flavanonol (7-O-methylaromadendrin), two lignans (pinoresinol and matairesinol) and six diterpenic acids/alcohol (19-acetoxy-13-hydroxyabda-8(17),14-diene, totarol, 7-oxodehydroabietic acid, dehydroabietic acid, communic acid and isopimaric acid) were isolated from the hydroalcoholic extract of a Brazilian Brown Propolis and characterized by NMR spectral data analysis. The volatile fraction of brown propolis was characterized by CG-MS, composed mainly of monoterpenes and sesquiterpenes, being the major α-pinene (18.4 %) and β-pinene (10.3 %). This propolis chemical profile indicates that Pinus spp., Eucalyptus spp. and Araucaria angustifolia might be its primary plants source. The brown propolis displayed significant activity against Plasmodium falciparum D6 and W2 strains with IC50 of 5.3 and 9.7 μg/mL, respectively. The volatile fraction was also active with IC50 of 22.5 and 41.8 μg/mL, respectively. Among the compounds, 1-O,2-O-digalloyl-6-O-trans-p-coumaroyl-β-D-glucopyranoside showed IC50 of 3.1 and 1.0 μg/mL against D6 and W2 strains, respectively, while communic acid showed an IC50 of 4.0 μg/mL against W2 strain. Cytotoxicity was determined on four tumor cell lines (SK-MEL, KB, BT-549, and SK-OV-3) and two normal renal cell lines (LLC-PK1 and VERO). Matairesinol, 7-O-methylaromadendrin, and isopimaric acid showed an IC50 range of 1.8-0.78 μg/mL, 7.3-100 μg/mL, and 17-18 μg/mL, respectively, against the tumor cell lines but they were not cytotoxic against normal cell lines. The crude extract of brown propolis displayed antimicrobial activity against C. neoformans, methicillin-resistant Staphylococcus aureus, and P. aeruginosa at 29.9 μg/mL, 178.9 μg/mL, and 160.7 μg/mL, respectively. The volatile fraction inhibited the growth of C. neoformans at 53.0 μg/mL. The compounds 3-hydroxy-4-methoxybenzaldehyde, 3-methoxy-4-hydroxypropiophenone and 7-oxodehydroabietic acid were active against C. neoformans, and caffeic and communic acids were active against methicillin-resistant Staphylococcus aureus.

Four new neo-clerodane diterpenes from the stem bark of Croton oligandrus

Four new neo-clerodanes, crotonolins C-F (3-6), were isolated from the stem bark of Croton oligandrus together with the known clerodane crotonzambefuran A, the abietanes 7-β-hydroxydehydroabietic acid and 7-oxodehydroabietic acid, and ferulic acid. Their structures were elucidated by spectroscopic analyses including 1D and 2D NMR and HRESIMS and by comparison with previously reported data. The cytotoxicity of the isolated compounds against A549, MCF7, PC3 and PNT2 cells was evaluated using the MTT assay. Only 7-β-hydroxydehydroabietic acid showed a moderate level of activity against PC3 cells with an IC50 value of 68.9 ± 6.6 µM.

Involvement of allelopathy in inhibition of understory growth in red pine forests

Japanese red pine (Pinus densiflora Sieb. et Zucc.) forests are characterized by sparse understory vegetation although sunlight intensity on the forest floor is sufficient for undergrowth. The possible involvement of pine allelopathy in the establishment of the sparse understory vegetation was investigated. The soil of the red pine forest floor had growth inhibitory activity on six test plant species including Lolium multiflorum, which was observed at the edge of the forest but not in the forest. Two growth inhibitory substances were isolated from the soil and characterized to be 15-hydroxy-7-oxodehydroabietate and 7-oxodehydroabietic acid. Those compounds are probably formed by degradation process of resin acids. Resin acids are produced by pine and delivered into the soil under the pine trees through balsam and defoliation. Threshold concentrations of 15-hydroxy-7-oxodehydroabietate and 7-oxodehydroabietic acid for the growth inhibition of L. multiflorum were 30 and 10μM, respectively. The concentrations of 15-hydroxy-7-oxodehydroabietate and 7-oxodehydroabietic acid in the soil were 312 and 397μM, respectively, which are sufficient concentrations to cause the growth inhibition because of the threshold. These results suggest that those compounds are able to work as allelopathic agents and may prevent from the invasion of herbaceous plants into the forests by inhibiting their growth. Therefore, allelopathy of red pine may be involved in the formation of the sparse understory vegetation.

Conifer Diterpene Resin Acids Disrupt Juvenile Hormone-Mediated Endocrine Regulation in the Indian Meal Moth Plodia interpunctella.

Diterpene resin acids (DRAs) are important components of oleoresin and greatly contribute to the defense strategies of conifers against herbivorous insects. In the present study, we determined that DRAs function as insect juvenile hormone (JH) antagonists that interfere with the juvenile hormone-mediated binding of the JH receptor Methoprene-tolerant (Met) and steroid receptor coactivator (SRC). Using a yeast two-hybrid system transformed with Met and SRC from the Indian meal moth Plodia interpunctella, we tested the interfering activity of 3704 plant extracts against JH III-mediated Met-SRC binding. Plant extracts from conifers, especially members of the Pinaceae, exhibited strong interfering activity, and four active interfering DRAs (7α-dehydroabietic acid, 7-oxodehydroabietic acid, dehydroabietic acid, and sandaracopimaric acid) were isolated from roots of the Japanese pine Pinus densiflora. The four isolated DRAs, along with abietic acid, disrupted the juvenile hormone-mediated binding of P. interpunctella Met and SRC, although only 7-oxodehydroabietic acid disrupted larval development. These results demonstrate that DRAs may play a defensive role against herbivorous insects via insect endocrine-disrupting activity.

Thin‐layer chromatography and gas chromatography–mass spectrometry examination of shoe materials from patients with shoe dermatitis

Keywords: 2(3H)-benzothiazolone; 7-oxodehydroabietic acid methyl ester; colophonium; contact dermatitis; gas chromatography–mass spectrometry (GCMS); methyl dehydroabietate; patch testing; shoes; thin-layer chromatography (TLC)

Determination of resin acids during production of wood pellets—a comparison of HPLC/ESI-MS with the GC/FID MDHS 83/2 method

Resin acids are constituents of natural and technical products of widespread use. Exposure is known to cause health effects in the airways and on the skin. Liquid chromatography/positive ion electrospray-mass spectrometry (HPLC/pos ESI-MS) was investigated for determination of 7-oxodehydroabietic (7-OXO), dehydroabietic (DHAA) and abietic acid (AA) in wood dust-containing air samples as a derivatisation-free alternative to the GC/FID HSE method 83/2, developed by the Health and Safety Executive UK. The resin acid 7-OXO was measured as a marker for oxidised resin acids, which are known to be the main contact allergens in colophonium. The found detection limits were 0.42 ng m(-3) for 7-OXO, 5.2 ng m(-3) for DHAA and 9.4 ng m(-3) for AA, respectively, which are considerably lower than with the GC/FID method (24, 115 and 89 ng m(-3)). The two methods correlated well, although consistently and significantly lower concentrations of 7-OXO were detected with LC/MS. The higher concentration of this compound with MDHS 83/2 is suggested to be an artefact from the derivatisation step in the presence of soluble wood dust remains.

SPE and HPLC/UV of resin acids in colophonium‐containing products

A new method, involving SPE and HPLC/UV diode-array detection (DAD), was developed for the quantification of colophonium components in different consumer products, such as cosmetics. Colophonium is a common cause of contact dermatitis since its components can oxidize into allergens on exposure to air. Three different resin acids were used as markers for native and oxidized colophonium, abietic acid (AbA), dehydroabietic acid (DeA), and 7-oxodehydroabietic acid (7-O-DeA). The SPE method, utilizing a mixed-mode hydrophobic and anion exchange retention mechanism, was shown to yield very clean extracts. The use of a urea-embedded C(12) HPLC stationary phase improved the separation of the resin acids compared to common C(18). Concentrations higher than 2 mg/g of both AbA and DeA were detected in wax strips. In this product also 7-O-DeA, a marker for oxidized colophonium, was detected at a level of 28 microg/g. The LODs were in the range of 7-19 microg/g and the LOQs 22-56 microg/g. The method is simple to use and can be applied on many types of technical products, not only cosmetics. For the first time, a method for technical products was developed, which separates AbA from pimaric acid.

Exposure to Wood Dust, Resin Acids, and Volatile Organic Compounds During Production of Wood Pellets

The main aim of this study was to investigate exposure to airborne substances that are potentially harmful to health during the production of wood pellets, including wood dust, monoterpenes, and resin acids, and as an indicator of diesel exhaust nitrogen dioxide. In addition, area measurements were taken to assess background exposure levels of these substances, volatile organic compounds (VOCs), and carbon monoxide. Measurements were taken at four wood pellet production plants from May 2004 to April 2005. Forty-four workers participated in the study, and a total of 68 personal measurements were taken to determine personal exposure to wood dust (inhalable and total dust), resin acids, monoterpenes, and nitrogen dioxide. In addition, 42 measurements of nitrogen dioxide and 71 measurements of total dust, resin acids, monoterpenes, VOCs, and carbon monoxide were taken to quantify their indoor area concentrations. Personal exposure levels to wood dust were high, and a third of the measured levels of inhalable dust exceeded the Swedish occupational exposure limit (OEL) of 2 mg/m 3 . Parallel measurements of inhalable and total dust indicated that the former were, on average, 3.2 times higher than the latter. The data indicate that workers at the plants are exposed to significant amounts of the resin acid 7-oxodehydroabietic acid in the air, an observation that has not been recorded previously at wood processing and handling plants. The study also found evidence of exposure to dehydroabietic acid, and exposure levels for resin acids approached 74% of the British OEL for colophony, set at 50 μg/m 3 . Personal exposure levels to monoterpenes and nitrogen dioxide were low. Area sampling measurements indicated that aldehydes and terpenes were the most abundant VOCs, suggesting that measuring personal exposure to aldehydes might be of interest. Carbon monoxide levels were under the detection limit in all area measurements. High wood dust exposure levels are likely to have implications for worker health; therefore, it is important to reduce exposure to wood dust in this industry.

Tape-stripping as a method for measuring dermal exposure to resin acids during wood pellet production

The purpose of this study was to develop a sensitive and specific method for quantifying dermal exposure to the resin acids 7-oxodehydroabietic acid (7-OXO), dehydroabietic acid (DHAA), abietic acid (AA), and pimaric acid (PA). In addition the method was evaluated in occupational settings during production of wood pellets. Tape-strips were spiked with the substances to evaluate the recovery of the acids from the tape. The removal efficiency of the tape was assessed by tape-stripping a specified area on a glass plate spiked with resin acids. The recovery of the acids from human skin in vivo was evaluated by applying acids in methanol onto the skin of volunteers. Occupational dermal exposure to the resin acids was assessed by tape-stripping the skin of workers involved in the production of wood pellets. The resin acids were analyzed by liquid chromatography mass spectrometry (LC-MS). The limit of detection was 15 pg (7-OXO), 150 pg (DHAA), 285 pg (AA) and 471 pg (PA) per injection. The recovery from spiked tapes was in general 100%. The removal efficiency of the tape was 48-101%. Recovery tests from human skin in vivo showed a mean recovery of 27%. Quantifiable amounts of resin acids were observed on four different skin areas with an increase in exposure during a work shift. This study shows that occupational dermal exposure to resin acids can be assessed by tape-stripping and quantified by LC-MS.

Direct exposure electron ionization mass spectrometry and gas chromatography/mass spectrometry techniques to study organic coatings on archaeological amphorae

Two different analytical approaches, direct exposure electron ionization mass spectrometry (DE-MS) and gas chromatography/mass spectrometry (GC/MS), were compared in a study of archaeological resinous materials. DE-MS was found to be an efficient fingerprinting tool for the fast screening of organic archaeological samples and for providing information on the major components. GC/MS appeared to be more efficient in unravelling the sample composition at a molecular level, despite the long analysis time and the need for a wet chemical pretreatment. Both procedures were applied to characterize the organic material present as coatings in Roman and Egyptian amphorae. DE-MS successfully identified abietanic compounds, hence a diterpenic resinous material could be identified and its degree of oxidation assessed. GC/MS enabled us to identify dehydroabietic acid, 7-oxodehydroabietic acid, 15-hydroxy-7-oxodehydroabietic acid, 15-hydroxydehydroabietic acid, retene, tetrahydroretene, norabietatriene, norabietatetraene and methyl dehydroabietate. These oxidized and aromatized abietanes provided evidence that the amphorae examined were waterproofed with a pitch produced from resinous wood of plants from the Pinaceae family. The chemometric evaluation of the GC/MS data highlighted significant chemical differences between the pitches found in the two archaeological sites, basically related to differences in the production techniques of the materials and in their degradation pathways.

New Abietane‐Type Diterpenes from the Heartwood of Picea morrisonicola.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Dermal exposure to terpenic resin acids in Swedish carpentry workshops and sawmills.

The aim of this study was to evaluate dermal exposure to the resin acids abietic acid, dehydroabietic acid and 7-oxodehydroabietic acid during collecting in sawmills and during sawing in carpentry workshops, respectively. Sampling was performed by fastening patches at 12 different areas on a sampling overall, one patch on the front of a cap, one patch on the chest inside the clothing and one patch on the inner lower right leg. Exposure of the hands was assessed by fastening patches on cotton gloves representing the dorsal sides and the palms of the left and right hands. Sampling was performed on 30 different occasions in the sawmills and in the carpentry workshops with mean sampling times of 120 and 59 min, respectively. The acids were solvent desorbed from the patches. Identification and quantification of the resin acids was performed by gas chromatography-mass spectrometry. The geometric means (GMs) of the potential body exposures to abietic acid, dehydroabietic acid and 7-oxodehydroabietic acid during sawing and collecting of wood from pine and spruce were 3346 and 17 247 micro g/h, respectively. The GM of the potential exposure on the hands was 3020 micro g/h in the carpentry workshops and 4365 micro g/h in the sawmills. Resin acids were detected on the inner chest and inner lower front right leg, respectively. There is a potential dermal exposure to terpenic resin acids in carpentry workshops as well as in sawmills. The hands have the highest exposure during sawing as well as during collecting. There is a spatial distribution of contaminants, with the outer chest, arms and legs showing the highest exposures. Resin acids also contaminated the inner chest and inner lower leg. It is necessary to take action to reduce dermal exposure to these allergenic substances.

New abietane-type diterpenes from the heartwood of Picea morrisonicola.

New abietane-type diterpenes, 15-acetoxy-7-oxodehydroabietic acid (1), picealactones A (2), B (3), and C (4), together with the known 7-oxodehydroabietic acid (5) were isolated and identified from the heartwood of Picea morrisonicola. The structures of 1-4 were determined on the basis of spectral data explanation. Compounds 2-4 possessed a rare 5-dehydro-18, 6-olide functionality. Compounds 1 and 2 were first isolated from natural source.

Genetic investigation of the catabolic pathway for degradation of abietane diterpenoids by Pseudomonas abietaniphila BKME-9.

We have cloned and sequenced the dit gene cluster encoding enzymes of the catabolic pathway for abietane diterpenoid degradation by Pseudomonas abietaniphila BKME-9. The dit gene cluster is located on a 16.7-kb DNA fragment containing 13 complete open reading frames (ORFs) and 1 partial ORF. The genes ditA1A2A3 encode the alpha and beta subunits and the ferredoxin of the dioxygenase which hydroxylates 7-oxodehydroabietic acid to 7-oxo-11,12-dihydroxy-8, 13-abietadien acid. The dioxygenase mutant strain BKME-941 (ditA1::Tn5) did not grow on nonaromatic abietanes, and transformed palustric and abietic acids to 7-oxodehydroabietic acid in cell suspension assays. Thus, nonaromatic abietanes are aromatized prior to further degradation. Catechol 2,3-dioxygenase activity of xylE transcriptional fusion strains showed induction of ditA1 and ditA3 by abietic, dehydroabietic, and 7-oxodehydroabietic acids, which support the growth of strain BKME-9, as well as by isopimaric and 12, 14-dichlorodehydroabietic acids, which are diterpenoids that do not support the growth of strain BKME-9. In addition to the aromatic-ring-hydroxylating dioxygenase genes, the dit cluster includes ditC, encoding an extradiol ring cleavage dioxygenase, and ditR, encoding an IclR-type transcriptional regulator. Although ditR is not strictly required for the growth of strain BKME-9 on abietanes, a ditR::Km(r) mutation in a ditA3::xylE reporter strain demonstrated that it encodes an inducer-dependent transcriptional activator of ditA3. An ORF with sequence similarity to genes encoding permeases (ditE) is linked with genes involved in abietane degradation.

Photolysis of the Resin Acid Dehydroabietic Acid in Water

The effects of UV254-radiation and artificial solar radiation on the degradation of dehydroabietic acid (DHAA) in humic water and in humus-free control water were examined. The reaction rates were determined, the degradation products were tentatively identified, and the toxicity changes of the solutions were monitored. Our results demonstrate that the presence of dissolved organic matter (DOM) in water affects the light-induced degradation rate of DHAA. In the UV-experiments, the degradation was substantially slower in humic water than in humus-free control water, whereas the degradation rate was accelerated by the presence of DOM in the simulated sunlight-experiments. These differences are obviously due to different reaction pathways in the experiments. Irradiation of the aqueous DHAA solutions gave rise to a great number of degradation products of which e.g. 7-oxodehydroabietic acid and 7-oxodehydroabietin were formed in high amounts. During photolysis of DHAA in humic water, decarboxylation of DHAA to ...