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At least 721 records · Page 40Linked to original sources
PubMed2001

New halogenated marine prostanoids with cytotoxic activity from the Okinawan soft coral Clavularia viridis.

Five new halogenated prostanoids 1-4 and 6 were isolated from the Okinawan soft coral Clavularia viridis. The gross structure of 1 was elucidated mainly on the basis of NMR spectral data. The relative and absolute configurations were determined by analysis of NOESY and CD data, chemical conversion, and the modified Mosher's method. The structures of 2-4 and 6 were deduced by comparison of their spectral data with those of 1. Compound 1 demonstrated cytotoxic activity.

Algorithms↗
PubMed2003

Isolation of halogenated monoterpenes from bioreactor-cultured microplantlets of the macrophytic red algae Ochtodes secundiramea and Portieria hornemannii.

Field collections of the red macroalgae Ochtodes secundiramea and Portieria hornemannii exhibit site-to-site variations in halogenated monoterpene (HMT) content. In contrast, microplantlets of O. secundiramea and P. hornemannii established through cell and tissue culture techniques had remarkably similar HMT profiles when cultivated in a photobioreactor under identical, controlled conditions. Both algae shared Apakaochtodene B (6) as the only cyclic HMT, 10E-bromomyrcene (3) and 10E-bromo-3-chloro-alpha-myrcene (4) as the dominant acyclic HMTs, and myrcene (1) as their common precursor. Furthermore, HMT yields were comparable between organisms (0.9-1.3 micromol/g dry mass of 6; 3.4-4.4 micromol/g of 3). P. hornemannii microplantlets also contained 7-chloromyrcene (9) as the dominant compound (37-73 micromol/g), suggesting additional chlorination capacity. Proposed pathways for HMT biosynthesis shared by P. hornemannii and O. secundiramea microplantlets possessed two common manifolds: (a) bromonium ion (Br(+))-catalyzed cyclization of 1, followed by chlorination to yield 6; (b) Markovnikov addition of Br(+) at Delta(6,10) of 1 to yield 3 with a marked selectivity (>50:1) for the E isomer, followed by chlorination of 3 to 4. This study demonstrated that bioreactor tissue culture is a new venue for bioprospecting and production of natural compounds from marine macroalgae under a controlled environment.

Catalysis↗
PubMed2003

Isolation and structures of new halogenated prostanoids from the Okinawan soft coral Clavularia viridis.

Fifteen new halogenated prostanoids 9-23 were isolated as minor constituents from the Okinawan soft coral Clavularia viridis. Compounds 9-11 were new members of iodovulone, and compounds 12-18 were 12-O-acetyliodovulones, 12-O-acetylbromovulones, and 12-O-acetylchlorovulones. Compounds 19-23 were 10,11-epoxy congeners of iodovulone, bromovulone, and chlorovulone. The structures of these compounds were determined on the basis of spectroscopic analysis and chemical conversion.

Animals↗
PubMed2006

DNA methyl transferase inhibiting halogenated monoterpenes from the Madagascar red marine alga Portieria hornemannii.

Three new halogenated monoterpenes, 2, 3, and 4, along with the known compounds halomon (1) and two analogues, 5 and 6, were isolated from the Madagascar red marine alga Portieria hornemannii. The structures of all three new compounds were determined by NMR spectroscopy in combination with mass spectrometric data analysis. Two of these monoterpenes (1 and 2) were low micromolar inhibitors of DNA methyl transferase-1.

DNA Modification Methylases↗
PubMed2001

Mesityllithium as a reagent for chemoselective halogen-lithium exchange reaction.

[figure: see text] Mesityllithium was found to be an excellent selective lithiating agent to prepare aryllithium compounds having alkoxycarbonyl groups. To extend our studies on chemoselective lithiation, an important precursor for the synthesis of camptothecin was prepared using a halogen-lithium exchange reaction followed by an intramolecular 1,2-addition.

Camptothecin↗
PubMed2006

Atom transfer cyclization catalyzed by InCl3 via halogen activation.

[reaction: see text] Indium trichloride was found to be an efficient catalyst for the cyclization of allylic halides and alkynes with atom transfer in methylene chloride. Mechanistic evidence supports a cationic reaction pathway with Lewis acid activation of the allylic halogen. Concomitant nucleophilic attack by the alkyne and trapping with halide led to atom transfer cyclization products. Depending on alkyne substitution, a bromine atom was transferred from the substrate or a chlorine atom was transferred from the solvent.

Alkynes↗
PubMed1999

Effect of 2,6-diisopropylphenol and halogenated anesthetics on tetraphenylphosphonium uptake by rat brain synaptosomes: determination of membrane potential.

The effect of 2,6-diisopropylphenol (propofol) in comparison to that of the halogenated anesthetics enflurane, isoflurane, and halothane on tetrapenylphosphonium uptake by rat brain synaptosomes was studied. A direct method to separately measure the synaptosomal and the mitochondrial transmembrane potential by using the tetraphenylphosphonium cation (TPP+) was utilized. The latter is a lipophylic charged molecule which distributes between two compartments according to the transmembrane electrical potential in the presence or absence of 60 mM KCl as a synaptosomal membrane depolarizing agent. After previously reporting the damages induced by general anesthetics on isolated mitochondria, the aim of this paper was to study their possible action on the synaptosomal membrane potential and whether or not drugs concentrations damaging isolated mitochondria are also effective on synaptosomal mitochondria. The results indicated that, in the presence of glucose, mitochondria included in synaptosomes were able to maintain a transmembrane potential of 202+/-8 mV (mean +/- SD) while the synaptosomal membrane showed a potential of 78+/-8 mV (mean +/- SD). When anesthetic concentrations (0.6-1 mM propofol, 10-40 microM enflurane, 30-50 microM isoflurane, 8-15 microM halothane) that impair mitochondrial energy metabolism were used, the synaptosomal transmembrane potential was maintained and, in addition, a slight increase of the TPP+ taken up was observed as the anesthetic concentration was increased.

Anesthetics, Inhalation↗
PubMed1992

The Purkinje vascular entoptic test: a halogen light gives better results.

The Purkinje vascular entoptic test is a test of macular function which employs a light directed through the sclera illuminating the fundus. This light casts shadows of retinal blood vessels on to posterior pole photoreceptors. When the light source is moved, a patient with a good macular function should be able to see a negative image of his or her retinal blood vessels. We evaluated the Purkinje test in eyes with clear ocular media. A bright 3.5 watt halogen rechargeable transilluminator was used instead of a pen torch as previously described. Sixty-eight patients (129 eyes) attending a diabetic eye clinic, were tested. The test correctly identified 91% of eyes with good macular function and 77% of eyes with poor macular function (visual acuity 6/24 or poorer). If a vascular pattern was seen, it was probable (0.89) that good macular function was present. If no vascular pattern was seen, it was probable (0.80) that the eye had poor macular function (chi 2 = 60.14, P = < 0.001). Our results were superior to those previously reported. We attribute the increased accuracy of our test to the brighter light source used.

Adult↗
PubMed2005

Stem cell proliferative history in tissue revealed by temporal halogenated thymidine analog discrimination.

Detection of proliferating cells based on bromodeoxyuridine (BrdU) incorporation and determination of phenotype by immunofluorescence labeling are standard approaches for studying stem and progenitor cell populations in developing and adult tissue as well as in histopathology studies. We describe incorporation of different halogenated thymidine analogs for temporal discrimination of cell cycle in the rat. With equimolar delivery, these analogs are suitable for quantitative histological studies including assessment of the regulation of proliferation, clonal analysis and simultaneous profiling of cell phenotype relative to proliferative history.

Animals↗
PubMed2002

Optical power outputs, spectra and dental composite depths of cure, obtained with blue light emitting diode (LED) and halogen light curing units (LCUs).

OBJECTIVE: To test the hypothesis that a prototype LED light curing unit, (LCU), a commercial LED LCU and a halogen LCU achieve similar cure depths, using two shades of a camphorquinone photoinitiated dental composite. To measure the LCUs' outputs and the frequency of the LED LCU's pulsed light, using a blue LED array as a photodetector. DESIGN: Cure depth and light output characterisation to compare the LCUs. SETTING: An in vitro laboratory study conducted in the UK. MATERIALS AND METHODS: The LCUs cured A2 and A4 composite shades. A penetrometer measured the depth of cure. Analysis was by one-way ANOVA, two-way univariate ANOVA and Fisher's LSD test with a 95% confidence interval. A power meter and spectrograph characterised the LCUs' emissions. A blue LED array measured the pulsed light frequency from an LED LCU. RESULTS: Statistically significant different LCU irradiances (119 mW/cm2 to 851 mW/cm2) and cure depths (3.90 mm SD +/- 0.08 to 6.68 mm SD +/- 0.07) were achieved. Composite shade affected cure depth. A blue LED array detected pulsed light at 12 Hz from the commercial LED LCU. CONCLUSIONS: The prototype LED LCU achieved a greater or equal depth of cure when compared with the commercial LCUs. LEDs may have a potential in dentistry for light detection as well as emission.

Composite Resins↗
PubMed2005

The heterogeneous interaction of HOCl with solid KBr substrates: the catalytic role of adsorbed halogens.

The heterogeneous reactivity of HOCl on solid KBr at ambient temperature has been studied using a Knudsen flow reactor. On solid KBr steady-state uptake experiments reveal the formation of Br- and Cl-containing reaction products formed in secondary reactions such as Br(2), BrCl, HOBr, BrOCl, Cl(2) and Cl(2)O with the latter two predominating in the late stages of the reaction. The uptake coefficient gamma spanning a range between 0.15 and 1 x 10(-3) and product yields of HOCl strongly depend on the nature of the solid sample, whether grain, ground grain or thin sprayed film, as well as on sample processing such as pumping and/or heating. Furthermore, the presence of adsorbed halogen species such as Br(2)(a) are crucial for the kinetics of the reaction of HOCl with solid KBr substrates. The presence of surface-adsorbed water (SAW) leads to deactivation of KBr whereas mechanical stress such as grinding leads to the formation of surface defects that become reaction centers. Desorption of SAW at T > 620 K induces high reactivity of the KBr sample at ambient temperature. A reaction mechanism encompassing all significant observations including unusual autocatalytic activity is given as there is no direct reaction of HOCl with solid KBr. It stresses the importance of adsorbed Br-containing species such as Br(2)(a) and HBr(a) that initiate the heterogeneous chemistry of HOCl on solid KBr in the presence of SAW. The role of surface acidity and SAW for the extent of reaction is emphasized.

Adsorption↗
PubMed1965

THE METABOLISM OF HALOGEN-SUBSTITUTED BENZOIC ACIDS BY PSEUDOMONAS FLUORESCENS.

1. Washed suspensions of Pseudomonas fluorescens, grown with benzoate as sole carbon source, oxidize monohalogenobenzoates in the following descending order of effectiveness: benzoate, fluorobenzoates, chlorobenzoates, bromobenzoates, iodobenzoates. 2. Cells grown on asparagine oxidize benzoate after an adaptive period of 90-120min. This adaptive period is increased by halogenobenzoates in the following approximate descending order of effectiveness: chlorobenzoates, fluorobenzoates (=bromobenzoates), iodobenzoates. This inhibition of adaptation by halogeno analogues depends on the concentration of benzoate and is thus apparently competitive. 3. Cells do not adapt to oxidize the halobenzoates when the halogeno analogues are inducers. However, the fluorobenzoates reduce the lag period taken to form the benzoate-oxidizing system. 4. The halogenobenzoates inhibit adaptation to citrate and nicotinate but not so effectively as benzoate itself. This is presumably a ;diauxic' effect. The analogues do not inhibit adaptation to catechol. 5. The halogenobenzoates are not used as sole carbon source for growth nor do they increase growth when cells grow with asparagine as the main carbon source. 6. It is suggested that this inability to use the analogues for growth is due partly to inability of the cells to liberate the halogen and to carry the oxidation to a stage at which carbon may be assimilated and partly to the inhibition of the induction of the oxidizing enzymes.

Benzoates↗
PubMed1995

Designing safer chemicals: predicting the rates of metabolism of halogenated alkanes.

A computational model is presented that can be used as a tool in the design of safer chemicals. This model predicts the rate of hydrogen-atom abstraction by cytochrome P450 enzymes. Excellent correlations between biotransformation rates and the calculated activation energies (delta Hact) of the cytochrome P450-mediated hydrogen-atom abstractions were obtained for the in vitro biotransformation of six halogenated alkanes (1-fluoro-1,1,2,2-tetrachloroethane, 1,1-difluoro-1,2,2-trichloroethane, 1,1,1-trifluro-2,2-dichloroethane, 1,1,1,2-tetrafluoro-2-chloroethane, 1,1,1,2,2,-pentafluoroethane, and 2-bromo-2-chloro-1,1,1-trifluoroethane) with both rat and human enzyme preparations: In(rate, rat liver microsomes) = 44.99 - 1.79(delta Hact), r2 = 0.86; In(rate, human CYP2E1) = 46.99 - 1.77(delta Hact), r2 = 0.97 (rates are in nmol of product per min per nmol of cytochrome P450 and energies are in kcal/mol). Correlations were also obtained for five inhalation anesthetics (enflurane, sevoflurane, desflurane, methoxyflurane, and isoflurane) for both in vivo and in vitro metabolism by humans: In[F(-)]peak plasma = 42.87 - 1.57(delta Hact), r2 = 0.86. To our knowledge, these are the first in vivo human metabolic rates to be quantitatively predicted. Furthermore, this is one of the first examples where computational predictions and in vivo and in vitro data have been shown to agree in any species. The model presented herein provides an archetype for the methodology that may be used in the future design of safer chemicals, particularly hydrochlorofluorocarbons and inhalation anesthetics.

Animals↗
PubMed2002

Protein oxidation of cytochrome C by reactive halogen species enhances its peroxidase activity.

Reactive halogen species (RHS; X(2) and HOX, where X represents Cl, Br, or I) are metabolites mediated by neutrophil activation and its accompanying respiratory burst. We have investigated the interaction between RHS and mitochondrial cytochrome c (cyt c) by using electrospray mass spectrometry and electron spin resonance (ESR). When the purified cyt c was reacted with an excess amount of hypochlorous acid (HOCl) at pH 7.4, the peroxidase activity of cyt c was increased by 4.5-, 6.9-, and 8.6-fold at molar ratios (HOCl/cyt c) of 2, 4, and 8, respectively. In comparison with native cyt c, the mass spectra obtained from the HOCl-treated cyt c revealed that oxygen is covalently incorporated into the protein as indicated by molecular ions of m/z = 12,360 (cyt c), 12,376 (cyt c + O), and 12,392 (cyt c + 2O). Using tandem mass spectrometry, a peptide (obtained from the tryptic digests of HOCl-treated cyt c) corresponding to the amino acid sequence MIFAGIK, which contains the methionine that binds to the heme, was identified to be involved in the oxygen incorporation. The location of the oxygen incorporation was unequivocally determined to be the methionine residue, suggesting that the oxidation of heme ligand (Met-80) by HOCl results in the enhancement of peroxidase activity of cyt c. ESR spectroscopy of HOCl-oxidized cyt c, when reacted with H(2)O(2) in the presence of the nitroso spin trap 2-methyl-2-nitrosopropane (MNP), yielded more immobilized MNP/tyrosyl adduct than native cyt c. In the presence of H(2)O(2), the peroxidase activity of HOCl-oxidized cyt c exhibited an increasing ability to oxidize tyrosine to tyrosyl radical as measured directly by fast flow ESR. Titration of both native cyt c and HOCl-oxidized cyt c with various amounts of H(2)O(2) indicated that the latter has a decreased apparent K(m) for H(2)O(2), implicating that protein oxidation of cyt c increases its accessibility to H(2)O(2). HOCl-oxidized cyt c also displayed an impaired ability to support oxygen consumption by the purified mitochondrial cytochrome c oxidase, suggesting that protein oxidation of cyt c may break the electron transport chain and inhibit energy transduction in mitochondria.

Cytochrome c Group↗
PubMedDate not supplied

Volatile halogenated hydrocarbons in urban atmosphere and in human blood.

Atmospheric concentrations of volatile, halogenated hydrocarbons (VHH) can be correlated with intensity of industrial or commercial activities and with demographic density. Measurements of VHHs were performed in Turin, Italy. The VHH indoor/outdoor contamination ratio was calculated, and VHH blood concentrations were measured during 1 yr in Turin, Italy. The results showed a typical primary pollutant trend: 18.1 micrograms/m3 during winter and 12.02 micrograms/m3 during summer. During the winter, the VHH indoor/outdoor contamination ratio showed a greater indoor presence (p = .0006) and a higher VHH blood concentration (0.71 vs. 0.22 micrograms/l). The indoor and outdoor atmospheric VHH concentrations provide the major sources of human daily intake, especially during winter.

Air Pollutants↗