Resin acids. V. Preparation and reactions of ring-A olefins from dehydroabietic acid

AbstractThe balm of the Norway spruce (Picea abies) is a well-known traditional herbal medicine used to cure wounds. Even though clinical trials have confirmed its empirical use, the active constituents, their mode of action, and the exact composition of this natural product are still unknown. In this study, the balm was subjected to fractionated extraction and further purified employing flash chromatography, HPLC-PDA-ELSD, preparative and analytical TLC. Hydroxycinnamic acids ( 1– 3), the lignan pinoresinol ( 4), four hydroxylated derivatives of dehydroabietic acid (DHAA) ( 5 – 8), and dehydroabietic acid ( 9) were isolated. Their structures were elucidated by LC-MS, 1D- and 2D-NMR. Four extracts, two commercially available resin acids–pimaric acid ( 10) and isopimaric acid ( 11)–and the isolated compounds were tested for increased re-epithelialization of cell-free areas in a human adult low calcium high temperature keratinocytes monolayer. Lysophosphatidic acid (10 µM) served as positive control and ranged between 100% and 150% rise in cell-covered area related to the vehicle control. Two extracts containing carboxylic acids and non-acidic apolar constituents, respectively, boosted wound closure by 47% and 36% at 10 and 3 µg/mL, respectively. Pinoresinol, DHAA, three of its hydroxylated derivatives, and pimaric and isopimaric acid as well as defined combinations of the hydroxylated DHAA derivatives led to a significantly enhanced wound closure by up to 90% at concentrations between 1 and 10 µM. Overall, lignans and diterpene resin acids, main constituents of Norway spruce balm, are able to increase migration or proliferation of keratinocytes in vitro. The presented data link the phytochemistry of this natural wound healing agent with boosted re-epithelialization.

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Chemical Composition of Lipophilic Bark Extracts from Pinus pinaster and Pinus pinea Cultivated in Portugal

Applied Sciences ◽

10.3390/app8122575 ◽

2018 ◽

Vol 8 (12) ◽

pp. 2575 ◽

Cited By ~ 2

Author(s):

Joana L. C. Sousa ◽

Patrícia A. B. Ramos ◽

Carmen S. R. Freire ◽

Artur M. S. Silva ◽

Armando J. D. Silvestre

Keyword(s):

Chemical Composition ◽

Pinus Pinaster ◽

Primary Source ◽

Dehydroabietic Acid ◽

Resin Acids ◽

Pinus Pinea ◽

Gas Chromatography Mass Spectrometry ◽

Major Constituent ◽

Main Components ◽

Micro Organisms

The chemical composition of lipophilic bark extracts from Pinus pinaster and Pinus pinea cultivated in Portugal was evaluated using gas chromatography-mass spectrometry. Diterpenic resin acids were found to be the main components of these lipophilic extracts, ranging from 0.96 g kg−1 dw in P. pinea bark to 2.35 g kg−1 dw in P. pinaster bark. In particular, dehydroabietic acid (DHAA) is the major constituent of both P. pinea and P. pinaster lipophilic fractions, accounting for 0.45 g kg−1 dw and 0.95 g kg−1 dw, respectively. Interestingly, many oxidized compounds were identified in the studied lipophilic extracts, including DHAA-oxidized derivatives (7-oxo-DHAA, 7α/β-hydroxy-DHAA, and 15-hydroxy-DHAA, among others) and also terpin (an oxidized monoterpene). These compounds are not naturally occurring compounds, and their formation might occur by the exposure of the bark to light and oxygen from the air, and the action of micro-organisms. Some of these compounds have not been previously reported as lipophilic constituents of the bark of the referred pine species. Other constituents, such as aromatic compounds, fatty acids, fatty alcohols, and sterols, are also present in the studied extracts. These results can represent an opportunity to valorize P. pinaster and P. pinea by-products as a primary source of the bioactive resin acids that are integrated into the current uses of these species.

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Resin acid degradation by bacterial strains grown on CTMP effluent

Water Science & Technology ◽

10.2166/wst.1997.0476 ◽

1997 ◽

Vol 35 (2-3) ◽

pp. 33-39

Author(s):

Yi Zhang ◽

P. A. Bicho ◽

C. Breuil ◽

J. N. Saddler ◽

S. N. Liss

Keyword(s):

Biological Treatment ◽

Resin Acid ◽

Pulp Mill ◽

Dehydroabietic Acid ◽

Operating Conditions ◽

Resin Acids ◽

Organic Substrates ◽

Bacterial Strains ◽

Pulp Mill Effluents ◽

Chemithermomechanical Pulping

All resin acids are diterpenoid carboxylic acids that are components of softwood extractives and they are known to contribute to much of the toxicity of pulp mill effluents. Although biological treatment systems can efficiently remove resin acids during normal operating conditions, resin acid breakthroughs occasionally occur. Recently we isolated five bacterial strains from bleach kraft effluents that degrade dehydroabietic acid (DHA), a resin acid commonly found in effluents. In this study we examined the ability of two bacterial strains (BKME 5 and BKME 9) to grow on chemithermomechanical pulping (CTMP) effluent and degrade DHA. Both of the strains could grow on CTMP effluents, but did not degrade DHA. COD measurement showed that both strains used other organic substrates in CTMP effluent. When nutrients (NH4⊕, PO43−, minerals and vitamins) were added to the effluent, both growth and DHA degradation increased significantly. The strains used DHA and other organic sources in the CTMP effluent simultaneously. The stimulated growth resulting from use of other organic material did not increase the rate of DHA degradation. It was found that ammonium played an important role in the DHA degradation of both strains. Without added ammonium, DHA degradation did not occur. Other nutrients also played important roles in DHA degradation by BKME 9.

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Isolation and characterization of thermophilic bacteria capable of degrading dehydroabietic acid

Canadian Journal of Microbiology ◽

10.1139/w99-028 ◽

1999 ◽

Vol 45 (6) ◽

pp. 513-519 ◽

Cited By ~ 21

Author(s):

Zhongtang Yu ◽

William W Mohn

Keyword(s):

Thermophilic Bacteria ◽

Resin Acid ◽

Pulp Mill ◽

Maximum Growth ◽

Dehydroabietic Acid ◽

Resin Acids ◽

Bacterial Strains ◽

Rdna Sequences ◽

Isolation And Characterization ◽

Continuous Enrichment

Using a semi-continuous enrichment method, we isolated two thermophilic bacterial strains, which could completely degrade abietane resin acids, including dehydroabietic acid (DhA). Strain DhA-73, isolated from a laboratory-scale bioreactor treating bleached kraft mill effluent at 55°C, grew on DhA as sole carbon source; while DhA-71, isolated from municipal compost, required dilute tryptic soy broth for growth on DhA. DhA-71 grew on DhA from 30°C to 60°C with maximum growth at 50°C; while, DhA-73 grew on DhA from 37°C to 60°C with maximum growth at 55°C. At 55°C, the doubling times for DhA-71 and DhA-73 were 3.3 and 3.7 h, respectively. DhA-71 and DhA-73 had growth yields of 0.26 and 0.19 g of protein per g of DhA, respectively. During growth on DhA, both strains converted DhA to CO2, biomass, and dissolved organic carbon. Analyses of the 16S-rDNA sequences of these two strains suggest that they belong to two new genera in theRubrivivax subgroup of the beta subclass of the Proteobacteria. Strains DhA-71 and DhA-73 are the first two bacteria isolated and characterized that are capable of biodegradation of resin acids at high temperatures. This study provided direct evidence for biodegradation of resin acids and feasibility for biotreatment of pulp mill effluent at elevated temperatures.Key words: biodegradation, resin acid, semi-continuous enrichment, thermophiles.

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Metabolites of the honey mushroom, Armillariamellea

Canadian Journal of Chemistry ◽

10.1139/v87-002 ◽

1987 ◽

Vol 65 (1) ◽

pp. 7-14 ◽

Cited By ~ 24

Author(s):

William A. Ayer ◽

John B. Macaulay

Keyword(s):

Liquid Culture ◽

Fruit Production ◽

Dehydroabietic Acid ◽

Resin Acids ◽

Fungal Metabolites ◽

Isopimaric Acid ◽

Levopimaric Acid ◽

Sandaracopimaric Acid

The fungus Armillariamellea (Vahl ex. Fr.) Kummer is responsible for severe losses in timber and fruit production. The metabolites isolated when certain strains of this fungus are grown in liquid culture have been identified as diterpenoid acids possessing the abietane (1) and pimarane (2) skeletons. These compounds, known collectively as resin acids, have not been reported previously from a fungal source. In addition to the resin acids dehydroabietic acid (3), pimaric acid (4), isopimaric acid (5), and sandaracopimaric acid (6), three additional acids, levopimaric acid endo-peroxide (7), 7-oxodehydroabietic acid (9), and 7-oxo-15-hydroxydehydroabietic acid (10) were obtained. On one occasion three orange pigments, austocystin F (11), averufin (12), and averufanin (13), all previously known fungal metabolites, were isolated.

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THE SIBERIAN LARCH GROUP COMPOSITION AND ACID NEEDLES AT DIFFERENT VEGETATION PERIODS

chemistry of plant raw material ◽

10.14258/jcprm.2019045477 ◽

2019 ◽

pp. 207-214

Author(s):

Dar'ya Sergeyevna Mikson ◽

Viktor Ivanovich Roshchin

Keyword(s):

Fatty Acids ◽

Group Composition ◽

Siberian Larch ◽

Dehydroabietic Acid ◽

Resin Acids ◽

Hydroxy Acids ◽

Isopimaric Acid ◽

Isopropanol Extract ◽

Extractive Substances ◽

Higher Fatty Acids

The research results of the Siberian larch needle extractives are presented in paper. The content of extractive substances from green and yellow needles extracted by organic solvents with different polarities is determined. It is found out that the double increase of the yellow needle extractive substances content soluble in hydrocarbon extractant is observed, whereas it is decreased by 30 per cent when extracted with propan-2-ol. The group composition of needle extracts derived from isopropanol extract by petroleum ether is determined. The neutral substances content in both needle collections is practically the same, although the yellow needles contain less acid “bound” in the form of esters. There is a high content of waxes in the needles, which mainly consist of secondary nonacosanol-10 alcohol. The composition of free and “bound” acids in Siberian larch needles of different vegetation periods is established. The needles are dominated by groups of higher unsaturated C-18 fatty acids. Resin acids are represented by isopimaric acid (isopimaric and sandaracopimaric) and abietic acids: abietic, dehydroabietic and levopiric acids. In yellow needles, the content of dehydroabietic acid is increased quadrupled and the hydroxy acids are identified: 15-hydroxyabietic acid and 15-hydroxyhydroabietic acid. The tri- and tetraenic C-20 acids are identified among higher fatty acids.

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Preparation, composition analysis and practical application of terpenoid-maleic adducts

Известия СПбЛТА ◽

10.21266/2079-4304.2017.221.294-308 ◽

2017 ◽

Author(s):

И.А. Латышевич ◽

А.Ю. Клюев ◽

Н.Г. Козлов ◽

Н.Р. Прокопчук ◽

М.М. Огородникова

Keyword(s):

Maleic Anhydride ◽

Total Concentration ◽

Chemical Properties ◽

Dehydroabietic Acid ◽

Acid Number ◽

Resin Acids ◽

Composition Analysis ◽

Unknown Composition ◽

Total Composition ◽

Kinetics Of

Представлено описание способа получения терпеноидномалеиновых аддуктов. Приведены данные физико-химических свойств полученных образцов: кислотное число, температура размягчения, вязкость. Изучен с использованием метода ЯМР-спектроскопии групповой состав терпеноидномалеиновых аддуктов. Установлено, что при модифицировании терпентина состава от 30/70 до 70/30 мас. % малеиновым ангидридом наблюдаются значительные изменения составов полученных канифолетерпеномалеиновых аддуктов. Так, содержание малеопимаровой кислоты возрастает соответственно с 24,3 до 51,9 мас. %, а содержание терпеномалеинового аддукта понижается с 70 до 30 мас. %. Наблюдается увеличение общего содержания смоляных кислот с 5,7 до 18,1 мас. %, в том числе содержание дегидроабиетиновой кислоты увеличивается с 2,0 до 3,7 мас. %, изопимаровой – с 1,2 до 6,2 мас. % и пимаровой кислоты – с 1,4 до 7,4 мас. %. При этом содержание смоляных кислот неустановленного состава составляет 0,8–1,1 мас. %. Приведена зависимость изменения содержания группового состава канифолетертпеномалеиновых аддуктов в процессе модифицирования терпентина (состава 60/40 мас. %) малеиновым ангидридом без отгонки остатков скипидара и малеинового ангидрида. Терпеноидномалеиновые аддукты представляют собой многокомпонентные системы, содержащие в различных количествах малеопимаровую кислоту, терпеномалеиновые аддукты и смоляные кислоты, не вступившие в реакцию с малеиновым ангидридом. Варьируя состав терпентина и количество вводимого малеинового ангидрида, можно получать терпеноидномалеиновые аддукты с различным содержанием компонентов, улучшая при этом их потребительские свойства. Доказано, что терпеноидномалеиновые аддукты являются эффективными отвердителями эпоксидных смол. Термоотверждаемые лаки, полученные с использованием в качестве отвердителя данных аддуктов, могут найти широкое применение в электротехнической промышленности. This study describes the technique of obtaining terpenoid-maleic adducts. The data on of the physic-chemical properties of the samples such as softening point, viscosity and acid number are given. The group composition of terpenoid-maleic adducts was studied using NMR-spectroscopy. The significant differences in composition of resin-terpenemaleic adducts were revealed when terpene composition was modified from 30/70 to 70/30 mas. % by maleic anhydride. Thus, concentration of maleic acid increased from 24.3 to 51.9 mas. %, while the concentration of terpenoidmalene adducts decreased from 70 to 30 mass% and total concentration of resin acids increased from 5.7 to 18.1 mas. %. Contents of dehydroabietic acid increased from 2.0 to 3.7 mas. %, isopimaric asid – from 1.2 to 6.2 mas. % and pimaric acid – from 1.4 to 7.4 mas. %. Concentration of resin acids of unknown composition were 0.8–1.1 mas. %. Kinetics of variation in content of total composition of resinterpenemaleic adducts during the process of modification of turpentine (composition 60/40) with maleic anhydride without distillation of residue of pitch and maleic anhydride were given. In this way, terpenoid-maleic adducts were multicomponent systems, which containes terpenomaleic adducts, maleapimaric acids and resin acids in different concentration. These products didn’t react with maleic anhydride. Terpenomaleic adducts with different concentration of components were obtained, by changing the composition of turpentine with maleic anhydride. It was proved that terpenoid-maleic adducts were effective hardener for epoxy resins. Heat-harden lacquers were obtained using these adducts as a hardener, and can be used in electrical industry.

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The resin acids dehydroabietic acid and isopimaric acid release calcium from intracellular stores in rainbow trout hepatocytes

Aquatic Toxicology ◽

10.1016/s0166-445x(98)00115-5 ◽

1999 ◽

Vol 46 (1) ◽

pp. 55-65 ◽

Cited By ~ 10

Author(s):

Christina M.I. Råbergh ◽

Henrik Lilius ◽

John E. Eriksson ◽

Boris Isomaa

Keyword(s):

Rainbow Trout ◽

Dehydroabietic Acid ◽

Resin Acids ◽

Isopimaric Acid ◽

Acid Release

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Microbial Conversion of Toxic Resin Acids

Molecules ◽

10.3390/molecules24224121 ◽

2019 ◽

Vol 24 (22) ◽

pp. 4121 ◽

Cited By ~ 1

Author(s):

Natalia A. Luchnikova ◽

Kseniya M. Ivanova ◽

Ekaterina V. Tarasova ◽

Victoria V. Grishko ◽

Irina B. Ivshina

Keyword(s):

Paper Industry ◽

Resin Acid ◽

Microbial Transformation ◽

Dehydroabietic Acid ◽

Pulp And Paper ◽

Resin Acids ◽

Microbial Conversion ◽

Fundamental Interest ◽

Depth Study ◽

Living Organisms

Organic wood extractives—resin acids—significantly contribute to an increase in the toxicity level of pulp and paper industry effluents. Entering open ecosystems, resin acids accumulate and have toxic effects on living organisms, which can lead to the ecological imbalance. Among the most effective methods applied to neutralize these ecotoxicants is enzymatic detoxification using microorganisms. A fundamental interest in the in-depth study of the oxidation mechanisms of resin acids and the search for their key biodegraders is increasing every year. Compounds from this group receive attention because of the need to develop highly effective procedures of resin acid removal from pulp and paper effluents and also the possibility to obtain their derivatives with pronounced pharmacological effects. Over the past fifteen years, this is the first report analyzing the data on distribution, the impacts on living organisms, and the microbial transformation of resin acids. Using the example of dehydroabietic acid—the dominant compound of resin acids in effluents—the review discusses the features of interactions between microorganisms and this pollutant and also highlights the pathways and main products of resin acid bioconversion.

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Pinus pinaster Oleoresin in Plus Trees

Holzforschung ◽

10.1515/hf.2002.043 ◽

2002 ◽

Vol 56 (3) ◽

pp. 261-266 ◽

Cited By ~ 15

Author(s):

C. Arrabal ◽

M. Cortijo ◽

B. Fernández de Simón ◽

M.C. García-Vallejo ◽

E. Cadahía:

Keyword(s):

Mass Spectrometry ◽

Pinus Pinaster ◽

Dehydroabietic Acid ◽

Resin Acids ◽

Plus Tree ◽

Main Components ◽

Level Of Significance ◽

And Control ◽

The Relationship

Summary The present paper establishes the relationship between certain components of oleoresin and the character of a tree as high producer (plus tree). The composition of the oleoresin (monoterpenes, sesquiterpenes, neutral diterpenes and resin acids) of Pinus pinaster in plus trees was studied by gaschromatography/mass spectrometry. The main components of the monoterpenes are α-pinene, β-pinene, limonene + β-phellandrene; of the sesquiterpenes β-caryophylene and longifolene; of neutral diterpenes isoabienol, abienol, isopimaral, pimaral, 11,13-labdien-8-ol and of resin acids levopimaric + palustric, neoabietic, abietic, isopimaric, pimaric, dehydroabietic, sandaracopimaric and 7,13,15 abietatrienoic acid. The components which enable us to distinguish between plus and control trees are myrcene and noracid 1 at a level of significance of 1%, and abienol and dehydroabietic acid at 5%. The composition of diterpenes permits a certain approach to distinguish between control and plus trees.

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