rosin and dehydroabietic-acid

A novel optically pure dinuclear copper(II) complex of a rosin derivative dehydroabietic acid (DHA, HL) was synthesized and fully characterized. The in vitro antitumor activities of the copper(II) complex Cu2(µ2-O)(L)4(DMF)2 (1) were explored and compared with those of a trinuclear iron(III) complex [Fe3(µ3-O)(L)6(CH3OH)2(CH3O)]·H2O (2). 1 was more cytotoxic than 2, and the in vitro cytotoxicity of 1 was comparable to that of cisplatin and oxaliplatin. The metal coordination improved the cytotoxicity of DHA. 1 could arrest cycle in G1 phase and induce apoptosis in MCF-7 cell. 1 increased reactive oxygen species level, GSSG/GSH ratio, and Ca2+ production, and caused the loss of mitochondrial membrane potential (Δψm) in MCF-7 cells. The up-regulated Bax and down-regulated Bcl-2 expression levels, caspase-9/caspase-3 activation, and the release of Cyt c demonstrate that 1 triggered mitochondria-mediated intrinsic apoptosis in MCF-7 cells. Caspase-8/caspase-4 activation and up-regulated Fas expression indicate that death receptor-mediated extrinsic apoptosis was included. Comet assay and up-regulated γ-H2AX and p53 expressions confirmed that 1 caused DNA damage in MCF-7 cells. Moreover, 1 led to enhancement of the biomarker of lipid peroxidation and the indicator of protein carbonylation in MCF-7 cells. All the results suggest that 1 could kill MCF-7 cells by generating oxidative stress, impairing DNA, promoting lipid peroxidation and protein carbonylation, and inducing apoptosis and autophagy. Furthermore, 1 also displayed antimetastatic activities with inhibition of cell invasion and migration, together with antiangiogenesis properties. On the whole, copper complex based on rosin derivatives is worth developing as metal-based antitumor drugs.

Topics: Abietanes; Antineoplastic Agents; Apoptosis; Cell Cycle; Cell Movement; Coordination Complexes; Copper; DNA Damage; Humans; Iron; Lipid Peroxidation; Membrane Potential, Mitochondrial; Mitochondria; Neoplasms; Oxidative Stress; Protein Carbonylation; Reactive Oxygen Species; Resins, Plant; Tumor Cells, Cultured; Wound Healing

Topics: Abietanes; Adolescent; Bandages, Hydrocolloid; Dermatitis, Allergic Contact; Female; Humans; Patch Tests; Resins, Plant

Exploring the self-assembly of oligomeric surfactants is expected to bridge the gap between conventional and polymeric surfactants. Using the natural resource rosin as the starting material, a bio-based star-shaped trimeric quaternary ammonium surfactant (abbreviated tri-R-4-Phe) was synthesized. With three bulky dehydroabietic acid units in the hydrophobic group, tri-R-4-Phe has a molecular weight of 1684.9 and shows strong affinity towards both water and nonpolar organic compounds. In the presence of tri-R-4-Phe, C12EO3 was able to form lamellar lyotropic liquid crystals over a wide concentration range in water. The tri-R-4-Phe/C12EO3/water tertiary system was investigated by polarizing optical microscopy (POM), small angle X-ray scattering (SAXS) and rheological measurements. The investigated samples with different formulations all showed strong viscoelasticity, and the viscosity increased with the surfactant content. All samples showed interesting shear banding phenomena due to the shear induced mesoscale phase transition in tri-R-4-Phe/C12EO3/water systems. The present work reveals the unique behaviour of trimeric surfactant involved LLC systems and the result may be helpful in investigating delicate molecular self-assembly using natural resources.

Topics: Abietanes; Hydrophobic and Hydrophilic Interactions; Liquid Crystals; Phase Transition; Quaternary Ammonium Compounds; Resins, Plant; Rheology; Solubility; Surface Properties; Surface-Active Agents; Viscoelastic Substances; Viscosity

Colophony (rosin) is a natural product derived from the resin of coniferous trees with many industrial applications including soldering fluxes. Exposure to colophony fume through soldering is one of the leading causes of occupational asthma in the UK.. To assess occupational exposure to colophony from solder fume at selected workplaces in the UK and to investigate the use of dehydroabietic acid (DHA) as a biomarker of exposure.. Six companies in the UK electronics industry were visited and occupational hygiene assessments of extent and control of exposure to rosin-based solder flux fume were undertaken. Urine samples were analysed for one of the main constituents of rosin, DHA.. There was a positive linear relationship between airborne exposure to solder fume and urinary DHA level. The levels of urinary DHA measured in UK workers were significantly lower than those previously measured in African workers because of the use of appropriate exposure control measures, for example, local exhaust ventilation with fixed ducting and flexible hose, tip extraction, etc. It is suggested that good occupational hygiene practice would result in urinary DHA levels of <3 micromol/mol creatinine in a post-shift urine sample.. Urinary DHA is a valid biomarker of exposure to colophony in solder fume. Further work on the excretion kinetics of urinary DHA, the possibility of skin absorption and further occupational hygiene surveys would be beneficial.

Topics: Abietanes; Air Pollutants, Occupational; Biomarkers; Humans; Industry; Occupational Exposure; Resins, Plant; United Kingdom; Ventilation

An investigation was undertaken to establish the concentration in paper products of dehydroabietic (DHA) and abietic (AA) resin acids, present in rosin, which are major toxicants of pulp- and paper-mill effluent. Their migration was studied from paper and paperboard products into various food-simulating solvents and the substitute fatty food simulant Tenax TA (modified polyphenylene oxide). DHA and AA were detected in five of 10 virgin paper products and in all 10 recycled paperboard products for food-contact use at concentrations of 14-500 and 110-1200 microg/g, respectively. In virgin paper products, the highest migration was into 95% ethanol or heptane, with negligible or no migration into other solvents. In recycled paperboard products, migration was highest into 95% ethanol, but was also observed into 20% ethanol, water and heptane. Migration to Tenax TA was also observed and the migration level increased with time. The maximum migration levels of DHA and AA into food simulants were 0.853 and 3.14 microg/g, respectively. The results suggest that, in the worst case, the daily intake of DHA and AA from paper and paperboard products was 50 times lower than the tolerable daily intake of rosin.

Topics: Abietanes; Conservation of Natural Resources; Environmental Pollutants; Ethanol; Food Contamination; Food Packaging; Heptanes; Paper; Phenanthrenes; Polymers; Resins, Plant; Solvents; Temperature; Time Factors

Colophony is known to cause occupational asthma and dermatitis. Biological monitoring may be useful in assessing exposure. This paper describes a method for the analysis of dehydroabietic acid in urine and its potential use as a marker of colophony exposure. The method involves hydrolysis, solvent extraction, derivatization and analysis by gas chromatography-mass spectrometry. Twenty-eight workers from a soldering factory in South Africa were monitored. Results showed that levels of dehydroabietic acid in urine may be correlated with a subjective assessment of exposure.

Topics: Abietanes; Biomarkers; Diterpenes; Environmental Monitoring; Humans; Occupational Exposure; Resins, Plant; Welding

Ponderosa pine needles cause abortion and a poorly described toxicosis when eaten by cattle. In previous trials, the abortifacient compound of pine needles was identified as isocupressic acid. At abortifacient doses, isocupressic acid caused no other toxicosis. However, other pine needle fractions, similar in composition to several commercially available rosin products, caused no abortion but were very toxic. The purpose of this study was to describe the toxicoses of ponderosa pine, compare its toxicity with other rosin and related pine products, and identify the toxin. Four groups of three pregnant beef cows each were treated with either ponderosa pine tips, rosin gum, dehydroabietic acid, or ground alfalfa. The cows treated with pine tips aborted, had retained placentas with endometritis, and developed both renal and neurologic lesions. The cattle treated with rosin gum or dehydroabietic acid did not abort but developed similar signs and lesions of intoxication. Clinical signs of intoxication included anorexia, mild rumen acidosis, dyspnea, paresis progressing to paralysis, and death. Clinical biochemical results, suggestive of renal, hepatic, and muscular disease, included azotemia, hypercreatinemia, hyperphosphatemia, proteinuria, and marked elevations of various serum enzymes. Histologically, all poisoned animals had nephrosis, vacuolation of basal ganglia neuropil with patchy perivascular and myelinic edema, and skeletal myonecrosis. The alfalfa-treated controls were normal. These findings suggest that ponderosa pine needles and tips are both abortifacient and toxic. Because the lesions caused by pine tips, rosin gum, and dehydroabietic acid are similar, toxicosis is most likely due to the diterpene abietane acids, common in all three.

Topics: Abietanes; Abortifacient Agents; Abortion, Veterinary; Animal Feed; Animals; Anorexia; Bison; Cattle; Diterpenes; Female; Kidney; Lumbar Vertebrae; Medicago sativa; Paralysis; Plant Leaves; Pregnancy; Resins, Plant; Trees

As part of the investigation of sources of exposure to rosin allergens, disposable diapers (napkins) common on the Swedish market were analyzed, using gas chromatography, to detect the main rosin compounds. Rosin components were detected in all diapers, the highest amounts in those from the 2 major producers. In these diapers, more rosin was found in the top layer, which is in close contact with the skin than in the fluff. Despite the possibly minimal risk of induction of sensitization to rosin allergens in diapers, there is a real risk of elicitation of dermatitis in sensitive individuals, especially since penetration is enhanced by occlusion and irritation. Such material is not only used for infant diapers, but also for adult incontinence products and feminine hygiene products.

Topics: Abietanes; Adult; Allergens; Chromatography, Gas; Dermatitis, Allergic Contact; Diterpenes; Humans; Incontinence Pads; Infant; Infant Care; Irritants; Menstrual Hygiene Products; Phenanthrenes; Resins, Plant; Risk Factors; Sweden

A connection between patch test reactions to paper extracts and contact allergy to rosin (colophony) has been demonstrated.. We wanted to determine whether a difference in the allergenic activity of various types of paper is related to a difference in the pulp.. Patients with dermatitis who were frequently exposed to paper were patch tested with extracts from various papers and the standard series. The extracts were also tested in volunteers with or without contact allergy to rosin and in animals. The rosin compounds in the papers were analyzed by gas chromatography.. The subjects reacting to paper extracts also reacted to rosin. Most reactions were found to the papers produced from mechanical pulps, which contained the highest analyzed amounts of rosin compounds. Animals sensitized to rosin reacted only to paper from mechanical pulp.. Papers based on mechanical pulps that are considered to be environmentally friendly have a greater potential to elicit positive patch test reactions than papers made from other pulps. The increased use of mechanical pulps in different applications may increase the incidence of rosin-related hand eczema.

Topics: Abietanes; Allergens; Animals; Dermatitis, Allergic Contact; Dermatitis, Irritant; Dermatitis, Occupational; Diterpenes; Eczema; Female; Guinea Pigs; Hand Dermatoses; Humans; Immunization; Male; Paper; Patch Tests; Phenanthrenes; Resins, Plant

Topics: Abietanes; Adhesives; Cosmetics; Diterpenes; Female; Humans; Phenanthrenes; Resins, Plant; Tars

Degradation of abietic, levopimaric and dehydroabietic acids after exposure to air and light over a period of one to several months, as well as examination of degraded French tall oil rosin and Portuguese colophony, led to the isolation of numerous oxidation products. These compounds were synthesized and consigned to experimental sensitization in guinea pigs. From 20 substances studied as acids or as their methyl esters, in the present and preceding paper, at least 2 can be named: 8,12-peroxydo-delta 13(14)-dihydroabietic acid and 12 alpha-hydroxyabietic acid, that contribute a great deal to colophony allergy by both their sensitizing capacity and their determined concentration in the mixture of degradation products. We recommend the preparation of a new mixture of colophony oxidation products for patch testing in the diagnosis of contact allergy to colophony.

Topics: Abietanes; Animals; Dermatitis, Allergic Contact; Diterpenes; Fibrinolytic Agents; Guinea Pigs; Methyl Ethers; Oxidation-Reduction; Patch Tests; Phenanthrenes; Plant Oils; Resins, Plant; Tars

9 oxidation products of abietic acid, dehydroabietic acid, and levopimaric acid were prepared synthetically to determine their sensitizing potential in guinea pigs. It was found that compounds with epoxy and peroxo groups in rings A and B had a notable sensitizing potential. The same result was found with 7-oxode-hydroabietic acid identified earlier in rosin (3) and a polar fraction obtained from commercial abietic acid, suggesting the presence of still unidentified oxidation products. Hydroxylation of rings A or B, or conversion to the methyl esters, considerably decreases the sensitizing potential. A model is presented underlining the importance of hydrophobic and polar domains, in addition to chemically reactive groupings, in the allergen. Insertion into the lipid bilayer may play an important rôle in contact sensitivity.

Topics: Abietanes; Animals; Dermatitis, Contact; Diterpenes; Female; Guinea Pigs; Oxidation-Reduction; Patch Tests; Phenanthrenes; Resins, Plant

A method for detection of rosin (colophony) in technical products has been developed. The technique, using HPLC, is based on the analysis of abietic acid and dehydroabietic acid, major components of rosin. In the procedure described in this paper, the limit of detection was 0.001% for abietic acid and 0.015% for dehydroabietic acid. An average recovery of 88.9% for abietic acid and 88.2% for dehydroabietic acid was obtained. The lowest detectable amount of abietic acid (0.001%) corresponds to a content of 0.003% unmodified rosin in the product, assuming that the resin acid content in rosin is 90%, of which 30-50% is abietic acid. This is an acceptable limit compared to the reactivity in patients with known allergy to rosin. Technical products for analysis were supplied by different Swedish manufacturers, who also gave the approximate content of rosin in the various products. The content of rosin determined in the products was in accordance with the contents given by the manufacturers.

Topics: Abietanes; Chromatography, High Pressure Liquid; Diterpenes; Phenanthrenes; Resins, Plant

Abietic acid is the main component of rosin. It is readily oxidized by air and its oxidation products are considered to be mainly responsible for the allergenic effect. Hydrogenation of the conjugated double bonds of abietic acid decreases its susceptibility to air oxidation and would thus reduce the allergenicity of rosin. Portuguese gum rosin was therefore hydrogenated and its allergenicity was compared with that of unmodified rosin in animal experiments and by patch testing in humans. Its sensitizing potential was determined in 2 studies. No response was found according to the FCAT method while the GPMT gave significant response in the animals challenged with the highest test concentration. Hydrogenated rosin showed no eliciting activity in animals induced with unmodified rosin according to the GPMT method. A marked decrease was found in the frequency of allergic reactions to hydrogenated rosin compared to the reactions to unmodified rosin in patients with known allergy to gum rosin. We conclude that elimination of the unsaturated non-aromatic compounds by hydrogenation considerably reduces the allergenicity of Portuguese gum rosin.

Topics: Abietanes; Allergens; Animals; Chemical Phenomena; Chemistry; Dermatitis, Contact; Diterpenes; Female; Guinea Pigs; Humans; Hydrogen; Patch Tests; Phenanthrenes; Resins, Plant

7-oxodehydroabietic acid and 15-hydroxydehydroabietic acid were isolated as their methyl esters from Portuguese colophony of the gum rosin type and identified as contact allergens. Another oxidation product of dehydroabietic acid, 15-hydroxy-7-oxodehydroabietic acid, was synthesized and identified as a component of Portuguese gum rosin. 7-oxodehydroabietic acid was found to a be a grade III allergen according to the GPMT method. Guinea pigs induced with gum rosin showed only a low response to the isolated compounds, while patients with a known allergy to gum rosin reacted to a greater extent. The results imply that the content of oxidized dehydroabietic acids in gum rosin is too low to give a marked sensitization in the animals. However, the patients might have come in contact with the allergens in technically modified rosins. The compounds showed a pattern of cross-reactivity in the animal experiments as well as among the patch tested patients.

Topics: Abietanes; Allergens; Animals; Chromatography; Chromatography, High Pressure Liquid; Dermatitis, Contact; Diterpenes; Guinea Pigs; Humans; Immunization; Patch Tests; Portugal; Resins, Plant