The monoterpenes of Artemisia tridentata ssp. vaseyana, Artemisia cana ssp. viscidula and Artemisia tridentata ssp. spiciformis.

Monoterpenes from three different members of the Anthemideae family, Artemisia tridentata ssp. vaseyana, Artemisia cana ssp. viscidula and Artemisia tridentata ssp. spiciformis were isolated and their structures determined using spectroscopic techniques. A total of 26 irregular and regular monoterpenes were identified. Among these, 20 had previously been identified in the Anthemideae family. Of the remaining six, four were known, but previously unidentified in this family. 2,2-Dimethyl-6-isopropenyl-2H-pyran, 2,3-dimethyl-6-isopropyl-4H-pyran and 2-isopropenyl-5-methylhexa-trans-3,5-diene-1-ol were isolated from both A. tridentata ssp. vaseyana and A. cana ssp. viscidula. The irregular monoterpene 2,2-dimethyl-6-isopropenyl-2H-pyran has a carbon skeleton analogous to the biologically important triterpene squalene. Two additional irregular monoterpenes, artemisia triene and trans-chrysanthemal were isolated from A. cana ssp. viscidula and lavandulol was isolated from A. tridentata ssp. spiciformis. This is the first time a compound possessing a lavandulyl-skeletal type has been found in the Anthemideae family.

Allergic contact dermatitis caused by Lithraea molleoides and Lithraea brasiliensis: identification and characterization of the responsible allergens.

BACKGROUND: Allergic contact dermatitis caused by species of Lithraea genus (Anacardiaceae) is frequent in South America. Nevertheless, it has been scarcely reported in the literature, hitherto the responsible allergens have not been studied in some species. OBJECTIVE: The purpose of this study was to identify and characterize the allergenic compounds of Lithraea molleoides and brasiliensis, and to investigate the existence of cross-reactions with Toxicodendron allergens. METHODS: Twenty-seven South American subjects (17 with previous Lithraea dermatitis and 10 controls without any plant dermatitis) and four North American subjects who are highly sensitive to poison oak were tested with both purified Lithraea molleoides and brasiliensis extracts and poison oak urushiol. Lithraea extracts were analyzed by gas liquid chromatography (GLC) and gas chromatography-mass spectrometry (GC-MS). RESULTS: All 17 Lithraea-sensitive subjects reacted to poison oak urushiol and 13 of them also reacted to Lithraea molleoides and/or brasiliensis extracts. All 4 poison oak sensitive subjects reacted to poison oak urushiol and to Lithraea extracts. In both groups of sensitive subjects, the responses to poison oak urushiol were stronger and occurred at lower concentration than those to Lithraea extracts. The allergenic fraction in both Lithraea species consisted of: 3-pentadecylcatechol, 3-pentadecenylcatechol, 3-heptadecenylcatechol and 3-hepta-dec-dienilcatechol. CONCLUSION: We concluded that Lithraea molleoides and brasiliensis allergens are closely related to urushiol, although their eliciting potential seems to be lower in comparison with poison oak urushiol, even for Lithraea-sensitive subjects.

Human adipose alpha-tocopherol and gamma-tocopherol kinetics during and after 1 y of alpha-tocopherol supplementation.

Alpha-tocopherol and gamma-tocopherol were monitored in human adipose by using needle biopsies in four subjects during a 1-y supplementation trial with 800 mg all-rac-alpha-tocopherol/d, and for 1 additional year after cessation of supplement. Some increase in adipose alpha-tocopherol (per milligram adipose cholesterol) and a more consistent decrease in gamma-tocopherol were observed during the supplementation period. The alpha-tocopherol/gamma-tocopherol ratio rose consistently during supplementation and fell only gradually after the supplement was stopped. We estimate that > or = 2 y are required for the alpha-tocopherol/gamma-tocopherol ratio to reach a new steady state after a change in alpha-tocopherol intake. In a cross-sectional measurement in five subjects who reported long-term use of alpha-tocopherol supplements (> or = 250 mg/d), and in five other subjects who reported no supplement use, the adipose alpha-tocopherol/gamma-tocopherol ratio clearly discriminated between the two groups (P < 0.002). This ratio may be of value in ranking individuals according to long-term alpha-tocopherol intake.

Unusual contact allergens from plants in the family Hydrophyllaceae.

The dermatitic constituents of the glandular hairs of plants in the family Hydrophyllaceae comprise a class of uncommon natural products called "phacelioids". The chemical structures consist of various elaborations of hydroquinone attached to a C10 to C20 prenyl chain. Certain of these compounds are equivalent to the urushiols of Toxicodendron (Rhus) in their capacity to sensitize humans. Although structurally related to the urushiols, the phacelioids do not appear to cross-react in humans either with urushiol, or between phacelioids with different prenyl chains.

Ultrastructural demonstration of chemical modification of melanogenesis in hairless mouse skin.

We investigated chemical and physical modifications of the genetically determined ultrastructure of melanosomes. The flank skin of hairless mice was treated with ultraviolet energy (UV) shorter than 320 nm or with a combination of a photosensitizer and UV (PUVA treatment). All melanosomes in the induced melanocytes and those in resident melanocytes in the ear skin showed eumelanogenesis, although the degree of melanin deposition differed considerably according to the induction process. Eumelanogenesis was most advanced in the resident melanocytes while PUVA-induced melanocytes showed more immature premelanosomes. We then topically applied 4-tertiary butyl catechol on the skin. The depigmenting agent caused an appearance of pheomelanosomes. The alteration in melanogenesis was seen most distinctly in premelanosomes of the PUVA-induced cells. Altered ultrastructure was also observed in matured melanosomes; this change was most apparent in the resident melanocytes. These findings indicate that cells with eumelanogenesis may undergo pheomelanogenesis. The present study demonstrated effects of chemicals on genetically determined function of melanocytes by quantitative analysis of melanosome ultrastructure.

Sesquiterpene lactone dermatitis. Cross-sensitivity in costus-sensitized patients.

Thirteen costus-sensitive patients were patch tested with 38 sesquiterpene lactones of five different classes over a two-year period. Cross-reacting agents fell into two chemical categories: (1) those that resembled the primary sensitizer, and (2) those belonging to different skeletal classes. An exocyclic methylene group conjugated to a gamma-lactone was present in both chemicals that cross-reacted and those that did not. The difference between these two groups is that cross-reacting chemicals are not highly substituted, tending to be lipophilic, while those giving negative responses all are highly substituted at the C-8/C-6 position. This functional group may hinder binding of exocyclic methylene with skin protein or the actual antigenic site with an immune receptor cell.

In vitro studies of poison oak immunity. I. In vitro reaction of human lymphocytes to urushiol.

Poison oak, ivy, and sumac dermatitis is a T-cell-mediated reaction against urushiol, the oil found in the leaf of the plants. This hapten is extremely lipophilic and concentrates in cell membranes. A blastogenesis assay employing peripheral blood lymphocytes obtained from humans sensitized to urushiol is described. The reactivity appears 1--3 wk after exposure and persists from 6 wk to 2 mon. The dose-response range is narrow, with inhibition occurring at higher antigen concentrations. Urushiol introduced into the in vitro culture on autologous lymphocytes, erythrocytes and heterologous erythrocytes produces equal results as measured by the optimal urushiol dose, the intensity of reaction, and the frequency of positive reactors. This suggests that the urushiol is passed from introducer to some other presenter cell. Although the blastogenically reactive cell is a T cell, there is also a requirement for an accessory cell, found in the non-T-cell population, for reactivity. Evidence is presented that this cell is a macrophage.

In vitro studies of poison oak immunity. II. Effect of urushiol analogues on the human in vitro response.

Studies were performed to ascertain the effect of urushiol analogues on the in vitro lymphocyte blastogenesis elicited by urushiol in peripheral blood lymphocytes taken from individuals sensitized to poison oak or ivy. Urushiol is a mixture of alkylcatechols composed of a catechol ring coupled to mono-, di-, or tri-unsaturated C-15 or C-17 carbon side chains. Each of these two moieties, catechol ring and side chain, was tested for its role in eliciting reactivity. Analogues tested represented the catechol ring (3-methylcatechol), the mono- or di-unsaturated side chain (oleic or linoleic acid), and the saturated side chain coupled to a catechol ring (pentadecylcatechol), a blocked catechol ring (heptadecylveratrole), or a resorcinol (pentadecylresorcinol). Urushiol with a blocked catechol ring (urushiol dimethyl ether) was also included. Of these, only pentadecylcatechol evoked reactivity in sensitized lymphocytes, and this reactivity was only a fraction of that evoked by urushiol. This suggested that the system has some requirement for the side chain, and that the catechol ring is critical for reactivity. This was further investigated by testing the ability of some of these analogues to inhibit urushiol-specific blastogenesis. No inhibition was noted with compounds bearing the saturated side chain with modified ring structures (pentadecylresorcinol and heptadecylveratrole). However, both 3-methylcatechol and pentadecylcatechol (at equimolar concentrations) blocked reactivity. The results of our experiments suggested that although both the side chain and the catechol ring are required for reactivity, the latter is most critical. Unsaturation in the side chain is important for maximal reactivity because the saturated catechols were only partially as active as the urushiol oil. There may be a greater dose requirement for the catechol ring than for the side chain.

Discrimination between Rb+ and K+ by Escherichia coli.

1. The K+ requirment of Escherichia coli is only partially fulfilled by Rb+. The molar growth yield on Rb+ was about 5% of that on K+ and the growth rate in Rb+-supplemented media is lower thatn in K+ influx by any of the four K+ transport systems of E. coli. The high-affinity Kdp system (Km = 2 micron) is poorly traced by 86Rb+. It discriminates against a 86Rb+ tracer at least 1000-fold. The two moderate affinity systems, the high-rate TrkA system (Km = 1.5 mM) and the moderate rate TrkD system (Km = 0.5 mM), discriminate against a 86Rb+ tracer by approximately 10-fold and 25-fold, respectively. 86Rb+ is preferred by the low-rate TrkF system and overestimates its K+ influx by 40%.

The role of sesquiterpene lactones in contact hypersensitivity to some North and South American species of feverfew (Parthenium-Compositae).

Sixteen taxa of the genus Parthenium from North and South America and 20 sesquiterpene lactones derived from plants of the Compositae family were used for patch testing six volunteers who were known to be contact sensitive to plants and lactones of this family. The patterns of cross-sensitivity and structure-activity relationships of the allergenic lactones are evaluated and the clinical and ecological relevance is discussed.

Cation transport in Escherichia coli. VII. Potassium requirement for phosphate uptake.

When Escherichia coli K-12 is grown in media containing limiting amounts of K, growth continues normally until all the extracellular K has been consumed. Thereafter the rates of growth, glucose consumption, and oxygen consumption decrease progressively, and the cell contents of K and P fall. These changes, referred to as K limitation, are all reversed by the addition of K. By specifically altering the ionic composition of the cells it was shown that these metabolic disturbances are not due to changes in the cell content of K or Na, but are directly related to the absence of K from the extracellular medium. The cell pool of inorganic P and the uptake of PO(4) from the medium are low in K-limited cells and are immediately stimulated by the addition of K, suggesting that the primary effect of K limitation is to inhibit PO(4) uptake. All the metabolic effects of K limitation can be attributed to inhibition of PO(4) uptake. The requirement of extracellular K for PO(4) uptake may be due to a coupling between the uptake of K and PO(4).