Capillary electrophoretic and nuclear magnetic resonance studies of interactions between halophenols and ionic liquid or tetraalkylammonium cations.

Aqueous capillary electrophoretic studies were performed to investigate interactions between halophenols and 1-ethyl-3-methylimidazolium tetrafluoroborate or tetraethylammonium tetrafluoroborate electrolytes. In both cases, increased halogen size correlated with increased affinity for the electrolyte cation. For isomers, the ortho substituted isomer exhibited higher affinity than the para isomer.

Pneumocysterol [(24Z)-ethylidenelanost-8-en-3beta-ol], a rare sterol detected in the opportunistic pathogen Pneumocystis carinii hominis: structural identity and chemical synthesis.

Pneumocystis carinii pneumonia (PcP) remains among the most prevalent opportunistic infections among AIDS patients. Currently, drugs used clinically for deep mycosis act by binding ergosterol or disrupting its biosynthesis. Although classified as a fungus, P.

Identification of C31 and C32 sterols in Pneumocystis carinii hominis-infected human lungs.

Two sterols in autopsied whole lung specimens obtained from Pneumocystis carinii pneumonia patients were detected by gas-liquid chromatography and their structures were elucidated by mass spectrometry and nuclear magnetic resonance spectrometry. Both were in the lanosterol series; the C31 sterol, with a methyl group at C-24, was identified as euphorbol, and the more abundant C32 sterol, with an ethyl group at C-24, is given the trivial name pneumocysterol.

Side reactions in the pyroglutamic acid-7-amino-4-methylcoumarin synthesis.

N-Formylpyroglutamic acid-7-amido-4-methylcoumarine and pyroglutamyl-pyroglutamic acid-7-amido-4-methylcoumarin are the major products in the synthesis of pyroglutamic acid-7-amido-4-methylcoumarin by phosphorus pentachloride in dimethylformamide and dicyclohexylcarbodiimide under pyridine activation.

Characterization of a GM1-dependent surface interaction for alcohol with DPPC membranes.

A unique surface interaction for perdeuterated ethanol and 1-butanol with dipalmitoylphosphatidylcholine (DPPC)/monosialoganglioside (GM1) multilamellar vesicles can be detected from the fast exchange averaging of the nuclear quadrupole coupling constant of the alcohol in the free and bound states using deuterium NMR. At 1.0% perdeuterated ethanol or 0.

Ethanol disordering of GM1-enriched short-sleep synaptosomal plasma membranes.

The Long-Sleep (LS) and Short-Sleep (SS) mouse synaptosomal plasma membranes differ in ethanol sensitivity at superficial membrane regions, which corresponds with the behavioral response of the mice to ethanol hypnosis. The only significant difference between these synaptosomal plasma membranes is the synaptosomal monosialoganglioside (GM1) content, LS > SS. Here, GM1 was examined as a parameter for increasing membrane sensitivity to ethanol effects in the ethanol-resistant SS membranes.

Synaptic plasma membrane structure and polarity of long-sleep and short-sleep mice.

Membrane dielectric as a primary basis for effects of ethanol was examined in synaptic plasma membranes (SPM) of genetically selected ethanol-sensitive long-sleep (LS) and ethanol-resistant short-sleep (SS) mice. Multifrequency phase and modulation of fluorometry of diphenylhexatriene (DPH) was used to resolve structural and dielectric differences in the membrane interior core. Fluorescence spectral peak ratios, fluorescence lifetime analysis, and initial rates of photoreaction of DPH in SPM provided sensitive measures of SPM interior core dielectric properties.

Membranes and the genetics of ethanol response.

A combination of fluorescence polarization (FPZ) and nuclear magnetic resonance (NMR) techniques have revealed that ethanol has diverse and domain dependent effects on membrane order. Under some conditions, in the more superficial membrane domains, ethanol actually orders rather disorders membrane structure. Using 1H-NMR we have examined in synaptic membranes from LS and SS mice the effects of ethanol-d6 on membrane order.

pH homeostasis in Leishmania donovani amastigotes and promastigotes.

Intracellular pH and pH gradients of Leishmania donovani amastigotes and promastigotes were determined over a broad range of extracellular pH values. Intracellular pH was determined by 31P NMR and by equilibrium distribution studies with 5,5-dimethyloxazolidine-2,4-dione or methylamine. Promastigotes maintain intracellular pH values close to neutral between extracellular pH values of 5.

Ethanol-induced changes in neuronal membrane order. An NMR study.

The effects of ethanol-d6 on the lipid matrix of rat brain neuronal membranes were investigated by delayed Fourier transform 1H-NMR techniques. At 24 degrees C, neither 0.1 nor 0.

Cyanogen-induced gamma-glutamyl to imidazole cross-link in carbonic anhydrase. A unique mode of inhibition.

The irreversible inhibition of carbonic anhydrase by cyanogen occurs by a unique mechanism. Cyanogen is an affinity label: it behaves like a carbodiimide and produces an intra-molecular cross-link without being incorporated. The nucleophile-labile cross-link is formed between a gamma-COOH of a Glu and an imidazole of a His with a 1:1:1 stoichiometry with the enzyme.

1H-NMR spectra of rat synaptic plasma membranes: effect of temperature and comparison with fluorescence polarization.

1H-NMR spectra of rat synaptic plasma membranes obtained over the temperature range of 24-46 degrees C are presented. The data illustrate that a transition occurs from a more ordered to less ordered state at approximately 37 degrees C. This phenomenon was not related to using D2O as the solvent and was replicated, although with less sensitivity, using fluorescence polarization methodology.

Determination of ethanol partition coefficients to the interior and the surface of dipalmityl-phosphatidylcholine liposomes using deuterium nuclear magnetic resonance spectroscopy.

The binding of ethanol-d6 to dipalmityl-phosphatidylcholine liposomes (DPPC) can be separated into two processes, namely, ethanol in the bilayer and on the surface of the bilayer. For the deuterons of the methylene group, the T2 of both bound states is shorter than the respective preexchange lifetime (tau beta) and therefore the amount of ethanol bound to both sites can be determined from the decrease in the methylene intensity resonance in the presence of DPPC. For the methyl resonance, however, only the T2 of deuterons on ethanol bound to the surface is less than its tau beta and the amount of surface bound ethanol-d6 can be determined.

Detection of a bulk water structure related conformational change in horse heart cytochrome c in Cl- -H2O solutions utilizing spectrofluoroelectrochemical techniques.

Utilizing the ratio of the fluorescence intensities of the reduced and oxidized forms of horse heart cytochrome c (cyt c), it is possible to monitor conformational changes of the protein upon reduction. The temperature dependence from 25 to 50 degrees C of the ratio is sigmoidal in nature, indicative of a conformational transition with the midpoint being 43 degrees C in 0.10 M NaCl, 0.

Determination of the formal reduction potential, the electron stoichiometry, and the magnitude of the conformational change upon reduction for cytochrome c from potential-dependent fluorescence spectra.

A long-optical-path electrochemical cell was used to determine the formal reduction potential (E0') and the electron stoichiometry (n) for 1 microM horse heart cytochrome c solutions from Nernst plots of the fluorescence spectrum of the tryptophan-59. Various concentration ratios of the oxidized to the reduced forms of the protein were generated by application of different potentials. The fluorescence spectrum was found to decrease with increasing concentrations of reduced cytochrome c.

The salt-induced destacking of purine in aqueous NaCl systems and its implications on life at elevated temperatures.

Aqueous purine solutions in the absence and presence of NaCl have been studied by vapor-pressure osmometry and high-resolution proton-magnetic-resonance spectroscopy. The presence of NaCl causes a marked change in the temperature dependence of the molal osmotic coefficient and the chemical shift of the purine resonances when compared with the corresponding quantities in purine solutions containing no added salt. In the absence of salt, the destacking of the purine is gradual as the temperature is increased, whereas there is a sharp decrease in purine stacking at approximately 42 degrees C in the presence of NaCl.