phenanthrenes and Dermatitis--Contact

Topics: Abietanes; Dermatitis, Atopic; Dermatitis, Contact; Diterpenes; Environmental Exposure; Humans; Music; Phenanthrenes; Resins, Plant

In Asia, there is still a high usage of traditional Chinese medicament by the general population. Some patients with contact dermatitis to these medicaments have been found to be sensitive to colophony on patch testing. Dehydroabietic acid (DHAA) and abietic acid (AA) are the main components of colophony and believed to be the agents responsible for skin sensitization. This paper describes a reliable high-performance liquid-chromatographic method for determining these two resin acids in ointment samples. The samples were either pretreated with diethyl ether or treated with acetonitrile directly by ultrasonication for 30 min. One volume of this sample was added to an equal volume of water and purified by solid-phase extraction. The mobile phase used was methanol-water-phosphoric acid (87:13:0.02, v/v) and the flow-rate was 1 ml/min. DHAA and AA were detected at 4.3 and 6.3 men with ultraviolet detection at wavelength 200 and 239 nm, respectively. However, fluorimetric detection with an excitation wavelength of 225 nm and emission wavelength of 285 nm, provided more selective determination of DHAA. The detection limits for DHAA and AA were 1 ng. Analytical recovery generally exceeded 90%. We analyzed nine types of commonly used topical Chinese medicaments and two types of Western medical ointments in Singapore. The results showed that most of these medicaments contain colophony below 5 ppm (micrograms g-1). Only one Chinese medicament contained > 70 ppm of both allergens and one of the Western medical ointments contained 0.2% of DHAA and 2.2% of AA.

Topics: Abietanes; Chromatography, High Pressure Liquid; Dermatitis, Contact; Diterpenes; Drugs, Chinese Herbal; Humans; Phenanthrenes; Reproducibility of Results; Sensitivity and Specificity

A 56-year-old man, working in a food processing factory, developed contact dermatitis of his hands, forearms, and face after the introduction of a new herb extract (Rosmanox) made from the leaves of rosemary (Rosmarinus officinalis). He reacted to carnosol, the main constituent of Rosmanox. 226 controls were negative. To our knowledge, this is the 1st reported case of contact dermatitis from carnosol.

Topics: Abietanes; Antioxidants; Dermatitis, Contact; Dermatitis, Occupational; Humans; Male; Middle Aged; Phenanthrenes; Plant Extracts; Spices

Rosin has a complex chemical composition. The aim of this study was to investigate if it is possible to define 1 or 2 compounds as the rosin allergens. 2 compounds, 13, 14(beta)-epoxyabietic acid and 7-oxodehydroabietic acid, identified in gum rosin and tall oil rosin, were used as screening substances for patch testing in addition to the standard series. The rosin patch detected more cases of contact allergy than the isolated allergens did. Our suggestion is to patch test with a preparation of gum rosin, as well-defined as possible, for screening. The content of oxidation products should be kept at a constant and rather high level, since these are the main allergens. A rosin series for additional testing of patients with allergic contact dermatits suspected to be caused by rosin could be a valuable tool. Gum rosin and tall oil rosin from different countries should be included, since the amounts of allergens in rosin varies due to source and mode of production. Testing with identified allergens from modified rosin products and with modified rosins could also be performed.

Topics: Abietanes; Case-Control Studies; Dermatitis, Contact; Diterpenes; Epoxy Compounds; Humans; Patch Tests; Phenanthrenes; Plant Oils; Portugal; Resins, Plant; Sweden

A methanol extract of the leaves of the plant Rosmarinus officinalis L. (rosemary) was evaluated for its effects on tumor initiation and promotion in mouse skin. Application of rosemary to mouse skin inhibited the covalent binding of benzo(a)pyrene [B(a)P] to epidermal DNA and inhibited tumor initiation by B(a)P and 7,12-dimethylbenz[a]anthracene (DMBA). Topical application of 20 nmol B(a)P to the backs of mice once weekly for 10 weeks, followed 1 week later by promotion with 15 nmol 12-O-tetradecanoylphorbol-13-acetate (TPA) twice weekly for 21 weeks, resulted in the formation of 7.1 tumors per mouse. In a parallel group of animals that were treated topically with 1.2 or 3.6 mg of rosemary 5 min prior to each application of B(a)P, the number of tumors per mouse was decreased by 54 or 64%, respectively. Application of rosemary to mouse skin also inhibited TPA-induced ornithine decarboxylase activity, TPA-induced inflammation, arachidonic acid-induced inflammation, TPA-induced hyperplasia, and TPA-induced tumor promotion. Mice initiated with 200 nmol DMBA and promoted with 5 nmol TPA twice weekly for 19 weeks developed an average of 17.2 skin tumors per mouse. Treatment of the DMBA-initiated mice with 0.4, 1.2, or 3.6 mg of rosemary together with 5 nmol TPA twice weekly for 19 weeks inhibited the number of TPA-induced skin tumors per mouse by 40, 68, or 99%, respectively. Topical application of carnosol or ursolic acid isolated from rosemary inhibited TPA-induced ear inflammation, ornithine decarboxylase activity, and tumor promotion. Topical application of 1, 3, or 10 mumol carnosol together with 5 nmol TPA twice weekly for 20 weeks to the backs of mice previously initiated with DMBA inhibited the number of skin tumors per mouse by 38, 63, or 78%, respectively. Topical application of 0.1, 0.3, 1, or 2 mumol ursolic acid together with 5 nmol TPA twice weekly for 20 weeks to DMBA-initiated mice inhibited the number of tumors per mouse by 45-61%.

Topics: 9,10-Dimethyl-1,2-benzanthracene; Abietanes; Animals; Anticarcinogenic Agents; Antioxidants; Arachidonic Acid; Benzo(a)pyrene; Dermatitis, Contact; DNA; Drug Interactions; Enzyme Induction; Epidermis; Female; Hyperplasia; Magnoliopsida; Mice; Mice, Inbred Strains; Ornithine Decarboxylase; Phenanthrenes; Plant Extracts; Skin; Skin Neoplasms; Spices; Tetradecanoylphorbol Acetate; Triterpenes; Tritium; Ursolic Acid

Abietic acid isolated from colophony (W.W. grade) was selectively oxidized in the presence of KMnO4, into 13beta,14beta-dihydroxy-14alpha-isopropylabietic acid. The structure of the compound was elucidated using UV, IR, and NMR spectroscopy. Epicutaneous application of the dihydroxy acid to colophony-sensitized guinea pigs suggested the compound as an elicitor of contact allergy that had not been tested before in contact-sensitization reactions.

Topics: Abietanes; Animals; Dermatitis, Contact; Diterpenes; Guinea Pigs; Oxidation-Reduction; Phenanthrenes

Two groups of patients were studied, one with known contact allergy to colophony and hand eczema, 'colophony patients', and the other consisted of patients who suspected that their eczema was caused by contact with paper, 'paper patients'. The 'colophony patients' were patch tested with samples of newsprint paper, while the 'paper patients' were tested with samples of their own paper. Extracts of the paper and paper were applied. Testing with paper caused no reactions. All 'colophony patients' showed strong reactions to the tested extracts of newsprint paper. None of the 'paper patients' reacted to the extracts of their own paper, except those patch-test positive to colophony or maleopimaric acid, the main component of one type of modified colophony in paper size and shown experimentally to be a potent sensitizer. Colophony in paper may contribute to hand eczema in sensitized patients and the use of cotton gloves when in contact with paper might alleviate the dermatitis.

Topics: Abietanes; Dermatitis, Contact; Diterpenes; Female; Fibrinolytic Agents; Hand Dermatoses; Humans; Male; Newspapers as Topic; Occupational Diseases; Paper; Patch Tests; Phenanthrenes; Resins, Plant; Triterpenes

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

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

Colophony (rosin) is a widespread material which is obtained from species of the family Pinaceae. It has a complex chemical composition, which differs depending mainly on the recovery process. The global production is about one million tons a year and the largest single consumption is in the sizing of paper and paper board. Rosin is a common cause of contact allergy and is included in the standard tray for patch testing at dermatological clinics. Unmodified gum rosin is the material mainly used in the routine series. It is desirable to test with identified allergens in order to make the testing and diagnosis more reliable and establish a strategy for prevention. The principal aims of the present study were to compare the allergenicity of rosin of different origins, to isolate and identify some of the allergens in unmodified gum rosin, and to attempt to diminish the allergenic potential of rosin preparations. Tall oil rosin and different types of gum rosin were tested in guinea pigs and in man. The test reactivity corresponded well when comparing gum rosin from different sources, while tall oil rosin showed a lower reactivity. However, testing with more than one rosin preparation in the routine series detected additional cases. A clear dose-response relationship was obtained by patch testing with gum rosin, implying that a concentration of 10% in petrolatum is well worth considering for routine testing. Unmodified Portuguese gum rosin was fractionated by chromatographic methods. Isolated fractions and components were tested for eliciting activity in guinea pigs sensitive to gum rosin. Pure compounds were also tested in patients with known allergy to gum rosin. The structures of the isolated allergens were elucidated using spectroscopic methods. Abietic acid, the classical colophony allergen, was found not to be allergenic, while oxidation products of abietic acid and dehydroabietic acid were identified as allergens. The isolated allergens showed a pattern of cross-reactivity in the animal experiments as well as among patients with known allergy to gum rosin. 15-Hydroperoxyabietic acid was identified as one of the main allergens, apparently formed by air oxidation of abietic acid. Gum rosin was hydrogenated in order to minimize the content of easily oxidized acids of the abietic type. The hydrogenated gum rosin showed a reduced allergenic activity compared to unmodified rosin both in animal experiments and patch testing in man.

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

Topics: Abietanes; Aged; Dermatitis, Contact; Diterpenes; Humans; Male; Phenanthrenes; Trees; Turpentine

In order to investigate whether abietic acid itself is the allergenic component of colophony, 2 commercial samples were extensively purified and tested in guinea pigs and in colophony-sensitive patients. In the modified FCAT method, sensitization was obtained with Portuguese colophony and when challenged with purified abietic acid, the animals showed no reaction. In the GMPT method, the animals were exposed to purified abietic acid. Challenging with 2 different samples of it gave no significant reaction. When patch tested, patients sensitive to colophony showed no reactions to abietic acid which had been purified immediately before the test. It is concluded that abietic acid itself is not a contact allergen.

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

Topics: Abietanes; Aniline Compounds; Dermatitis, Contact; Diterpenes; Eczema; Formaldehyde; Humans; Organophosphates; Organophosphorus Compounds; Paper; Phenanthrenes; Thiourea; Trityl Compounds

Using several chromatographic and spectrometric procedures, it was established that the allergens present in pharmaceutical and cosmetic petrolatums are probably polycyclic aromatic hydrocarbons. These substances are impurities, and the quantity present is largely a function of the source of the petrolatum and the purification procedures. As the aromatic portion in petrolatum is a very complex and unstable mixture of chemically-related agents, only 2 out of the several possible allergens present could be identified: they were most probably phenanthrene derivatives with molecular weights of 230 and 244.

Topics: Allergens; Chromatography, Gas; Chromatography, High Pressure Liquid; Chromatography, Thin Layer; Dermatitis, Contact; Humans; Mass Spectrometry; Petrolatum; Phenanthrenes; Polycyclic Compounds

Topics: Abietanes; Cosmetics; Dermatitis, Contact; Diterpenes; Humans; Immunization; Phenanthrenes

Patch-tests made in 13 persons who were allergic to colophony revealed quite different allergologic profiles. Some patients reacted only to abietylic alcohol while others did not react to abietic acid. Methylabietate used as plasticizer in sticking-plasters and especially "hypoallergic" ones, had an allergizing effect in 6 out of 12 cases.

Topics: Abietanes; Carboxylic Acids; Dermatitis, Contact; Diterpenes; Humans; Patch Tests; Petrolatum; Phenanthrenes; Resins, Plant

A nickel-sensitized female patient developed a contact dermatitis reaction to her mascara that was maintained by her spectacle frames, which contained nickel. On patch testing, she reacted to dihydroabietyl alcohol (Abitol), which was present in her mascara, and to hypoallergenic adhesive tape containing methyl abietate. There was also cross-reactivity with colophony and abietic acid.

Topics: Adult; Cosmetics; Cross Reactions; Dermatitis, Contact; Diterpenes; Female; Humans; Nickel; Patch Tests; Phenanthrenes

Topics: Absorption; Acetylcholine; Alkaloids; Animals; Birds; Breeding; Cardiac Glycosides; Cyanides; Dermatitis, Contact; Disease Outbreaks; Eulipotyphla; Female; Heterocyclic Compounds; Histamine Release; Insecta; Mice; Ovum; Phenanthrenes; Plants, Edible; Skin; Toxins, Biological