UV irradiation of polycyclic aromatic hydrocarbons in ices: production of alcohols, quinones, and ethers.
(1/902)
Polycyclic aromatic hydrocarbons (PAHs) in water ice were exposed to ultraviolet (UV) radiation under astrophysical conditions, and the products were analyzed by infrared spectroscopy and mass spectrometry. Peripheral carbon atoms were oxidized, producing aromatic alcohols, ketones, and ethers, and reduced, producing partially hydrogenated aromatic hydrocarbons, molecules that account for the interstellar 3.4-micrometer emission feature. These classes of compounds are all present in carbonaceous meteorites. Hydrogen and deuterium atoms exchange readily between the PAHs and the ice, which may explain the deuterium enrichments found in certain meteoritic molecules. This work has important implications for extraterrestrial organics in biogenesis. (+info)
Divinyl ether fatty acid synthesis in late blight-diseased potato leaves.
(2/902)
We conducted a study of the patterns and dynamics of oxidized fatty acid derivatives (oxylipins) in potato leaves infected with the late-blight pathogen Phytophthora infestans. Two 18-carbon divinyl ether fatty acids, colneleic acid and colnelenic acid, accumulated during disease development. To date, there are no reports that such compounds have been detected in higher plants. The divinyl ether fatty acids accumulate more rapidly in potato cultivar Matilda (a cultivar with increased resistance to late blight) than in cultivar Bintje, a susceptible cultivar. Colnelenic acid reached levels of up to approximately 24 nmol (7 microgram) per g fresh weight of tissue in infected leaves. By contrast, levels of members of the jasmonic acid family did not change significantly during pathogenesis. The divinyl ethers also accumulated during the incompatible interaction of tobacco with tobacco mosaic virus. Colneleic and colnelenic acids were found to be inhibitory to P. infestans, suggesting a function in plant defense for divinyl ethers, which are unstable compounds rarely encountered in biological systems. (+info)
Adaptation of bulk constitutive equations to insoluble monolayer collapse at the air-water interface.
(3/902)
A constitutive equation based on stress-strain models of bulk solids was adapted to relate the surface pressure, compression rate, and temperature of an insoluble monolayer of monodendrons during collapse at the air-water interface. A power law relation between compression rate and surface pressure and an Arrhenius temperature dependence of the steady-state creep rate were observed in data from compression rate and creep experiments in the collapse region. These relations were combined into a single constitutive equation to calculate the temperature dependence of the collapse pressure with a maximum error of 5 percent for temperatures ranging from 10 degrees to 25 degrees C. (+info)
Phospholipid metabolism in ehrlich ascites tumor cells. II. Turnover rate of ether phospholipids.
(4/902)
1. Radioactive precursors of phospholipids, i.e., 32Pi, [1-14C]glycerol, [2-3H]glycerol, and [1-14C]acetate, were individually injected into the peritoneal cavity of mice bearing Ehrlich ascites tumor cells and the rates of incorporation were estimated. 2. Although [2-3H]glycerol was not practically incorporated into ether phospholipids, the other three radioactive precursors were incorporated into diacyl, 1-O-alkenyl-2-acryl-, and 1-O-alkyl-2-acryl-GPE (GPC). 3. In the experiments on 32Pi or [1-14C]acetate incorporation, 1-O-alkyl compounds in the ethanolamine phosphoglyceride fraction showed high specific activities in comparison with 1-acyl compounds. In the case of [1-14C]glycerol incorporation, a high rate of incorporation into 1-O-alkyl compounds was not found. In the choline phosphoglyceride fraction, a high rate of incorporation of the above precursors into 1-O-alkyl compounds was not observed. 4. The specific activities of 1-O-alkenyl compounds were fairly low compared with those of 1-acyl- and 1-O-acyl- and 1-O-alkyl compounds throughout the incorporation experiments with [1-14C]glycerol and [1-14C]acetate, but in 32Pi incorporation, 1-O-alkenyl compounds showed higher specific activities than 1-acyl compounds in ethanolamine phosphoglyceride, suggesting an exchange reaction of the phosphorylethanolamine moiety. 5. From the above findings, it appears that alkyl ether phospholipids of ethanolamine from may have a significant role in ascites tumor cells, based on their rapid turnover. (+info)
The class B, type I scavenger receptor promotes the selective uptake of high density lipoprotein cholesterol ethers into caveolae.
(5/902)
The uptake of cholesterol esters from high density lipoproteins (HDLs) is characterized by the initial movement of cholesterol esters into a reversible plasma membrane pool. Cholesterol esters are subsequently internalized to a nonreversible pool. Unlike the uptake of cholesterol from low density lipoproteins, cholesterol ester uptake from HDL does not involve the internalization and degradation of the particle and is therefore termed selective. The class B, type I scavenger receptor (SR-BI) has been identified as an HDL receptor and shown to mediate selective cholesterol ester uptake. SR-BI is localized to cholesterol- and sphingomyelin-rich microdomains called caveolae. Caveolae are directly involved in cholesterol trafficking. Therefore, we tested the hypothesis that caveolae are acceptors for HDL-derived cholesterol ether (CE). Our studies demonstrate that in Chinese hamster ovary cells expressing SR-BI, >80% of the plasma membrane associated CE is present in caveolae after 7.5 min of selective cholesterol ether uptake. We also show that excess, unlabeled HDL can extract the radiolabeled CE from caveolae, demonstrating that caveolae constitute a reversible plasma membrane pool of CE. Furthermore, 50% of the caveolae-associated CE can be chased into a nonreversible pool. We conclude that caveolae are acceptors for HDL-derived cholesterol ethers, and that caveolae constitute a reversible, plasma membrane pool of cholesterol ethers. (+info)
The movement of an unemulsified oil test meal and aqueous- and oil-phase markers through the intestine of normal and bile-diverted rats.
(6/902)
An unemulsified oil test meal containing aqueous- and oil-phase markers (PEG and 3-H labelled triether) was fed to control and bile fustula rats. PEG moved ahead of the lipid phase in all groups, and was of limited value as a marker for the test meal. Triether was an excellent marker for studies of gastric emptying. An unexpectedly high correlation was seen between the triether and the test meal and its digestion products in the intestine. The results suggest that triether is a valid marker for following the movement of lipid through the bowel under the conditions of this study. Triether/fat ratios indicated that fat absorption occurred largely from the upper small bowel in control animals and from the lower small bowel in the absence of bile. Bile diversion resulted in more rapid gastric emptying initially, but very slow gastric emptying of the last part of the oil test meal. Intestinal transit of test meal or either marker was not significantly affected by bile diversion. No evidence for a direct effect of bile diversion on gastrointestinal motility was found. (+info)
Identification of selective mechanism-based inactivators of cytochromes P-450 2B4 and 2B5, and determination of the molecular basis for differential susceptibility.
(7/902)
Rabbit cytochromes P-450 (P-450) 2B4 and 2B5 differ by only 12 amino acid residues yet they exhibit unique steroid hydroxylation profiles. Previous studies have led to the identification of active site residues that are determinants of these specificities. In this study, mechanism-based inactivators were identified that discriminate between the closely related 2B4 and 2B5 enzymes. A previously characterized inhibitor, 2-ethynylnaphthalene (2EN), was found to be selective for 2B4 inactivation. As inhibitor metabolism and the partition ratio affect susceptibility, molecular dynamics simulations were performed to assess the stability of the productive binding orientation of 2EN within 2B4 and 2B5 three-dimensional models. Although 2EN was stable within the 2B4 model, it exhibited substantial movement away from the heme moiety in the 2B5 model. However, heterologously expressed 2B5 was found to catalyze the oxidation of 2EN to the stable product 2-naphthylacetic acid. Thus, the increased mobility of 2EN may result in reduced susceptibility of 2B5 by increasing the probability that the reactive ketene intermediate hydrolyzes with water instead of reacting with active site residues. Another compound, 1-adamantyl propargyl ether (1APE), selectively inactivated 2B5. The structural basis for 2EN and 1APE susceptibility was assessed using active site mutants. Interconversion of 2EN susceptibility was observed for 2B4 or 2B5 mutants containing a single alteration at residue 363. Single substitutions in 2B4 also conferred susceptibility to 1APE; however, multiple alterations were required to reduce the susceptibility of 2B5. These alterations may influence inhibitor susceptibility by affecting the stability of the productive binding orientation. (+info)
Carrier-mediated hepatic uptake of peptidic endothelin antagonists in rats.
(8/902)
The endothelin antagonist BQ-123, an anionic cyclopentapeptide, is taken up by rat hepatocytes through active transport systems. Here, we have examined the hepatocellular uptake mechanism for several BQ-123 derivatives with anionic charges using isolated rat hepatocytes. BQ-485, a linear peptide, BQ-518, a cyclic peptide, and compound A, a cyclic peptide with a cationic moiety, were taken up by hepatocytes in a concentration-dependent manner. The uptake of BQ-485 was most efficient, whereas compound A showed comparable uptake with BQ-123. The uptake of these peptides was Na(+)- and energy-dependent, suggesting that active transport mechanisms are involved in their uptake into hepatocytes. BQ-485, BQ-518, and compound A can almost completely inhibit both the Na(+)-dependent and -independent uptake of [(3)H]BQ-123, with inhibition constants (K(i)) that are comparable to the Michaelis-Menten constants (K(m)) for their Na(+)-dependent and -independent uptake, respectively. Inhibition by BQ-485 was competitive, and the uptake of BQ-485 can be inhibited by BQ-123, with K(i) values that are comparable with the K(m) values for BQ-123 uptake. The uptake of BQ-123 by COS-7 cells transfected with either Na(+)-dependent taurocholate-cotransporting polypeptide (Ntcp) or Na(+)-independent basolateral organic anion-transporting polypeptide (oatp1) was minimal. Thus, these three peptides share the transporters that also recognize BQ-123 but appear to differ from Ntcp and oatp1. (+info)