1859-09-2Relevant articles and documents
n-Caprylammonium Chloride: A Solid Membrane Model
Schenk, K. J.,Ogle, C. A.,Schwarzenbach, D.,Chapuis, G.,Cornut, J.-C.,Rey-Lafon, M.
, p. 5530 - 5536 (1992)
n-Caprylammonium chloride (C8Cl) undergoes three thermotropic phase transitions between 304 and 311 K.Its high-temperature phases (β, γ, and α) are very disordered and resemble smectic mesophases found in biomembranes.The δ-phase (stable between 278 and 304 K) of C8Cl is studied by means of single-crystal X-ray diffraction.Chlorine and nitrogen atoms form a 3-periodic arrangement, but the carbon atoms oscillate about the long axes of the n-caprylammonium chains.These exist as several conformers which can be approximated as a single, entirely extended chain.The cell of the δ-phase allowed us to index powder X-ray photographs of the other phases of C8Cl and to deduce a structural description for them.Percentages of conformers, G forms, and GTG'/GTG sequences in the various phases are estimated from the analysis of characteristic IR and Raman bands, especially of the ω-bideuterated derivative.By a combination of our conclusions with previous NQR and NMR results, a rather complete picture of the phase transitions is deduced: they are brought about by the disordering of the aliphatic chains on one hand and of the hydrogen bonding scheme at the Cl-N interface on the other hand.The dynamics of these two subsystems behave quite differently indeed: changes in the chains occur very gradually, whereas variations in the interface happen quite abruptly.C8Cl successfully mimics the temperature dependence of the bilayer thickness, chain cross section, and order as well as the chain separation/interdigitation transition in biological membranes.
-
Shiner
, (1958)
-
Gas-Phase Chemistry of CH3SOH, (-)CH2(+)SHOH, CH3SO(.), and (.)CH2SOH by Neutralization-Reionization Mass Spectrometry
Turecek, Frantisek,Drinkwater, Donald E.,McLafferty, Fred W.
, p. 7696 - 7701 (1989)
The kinetically unstable molecules methanesulfenic acid (CH3SOH, 1) and its ylide isomer ((-)CH2(+)SHOH, 2) and the isomeric radicals CH3SO(.) and (.)CH2SOH exist as distinct species in the gas phase.CH3SOH was generated by flash-vacuum pyrolysis of methyl tert-butyl sulfoxide and by neutralization of the corresponding cation radical.The ylide (-)CH2(+)SHOH was prepared by neutralizaton of the distonic ion, (.)CH2(+)SHOH, generated from di-n-butyl sulfoxide by double hydrogen rearrangement.Upon collisional activation CH3SOH decomposes to CH3(.) and (.)SOH, while(-)CH2(+)SHOH affords mainly (.)CH2SH and (.)OH.Collisionally activated dissociation (CAD) spectra of the corresponding ions also distinguish these (C,H4,O,S)(.+) isomers.The isomeric radicals CH3SO(.) and (.)CH2SOH and ions CH3SO(+) and CH2SOH(+) were characterized through their neutralization-reionization and CAD mass spectra, respectively.Decomposition mechanisms consistent with deuterium labeling are proposed, and the relative stabilities of the (C,H4,O,S) isomers are estimated by MNDO calculations.
Kwart,Stanulonis
, p. 5249 (1976)
Raman spectroscopy of n-pentyl methyl ether and deuterium labelledanalogues
Bowen, Richard D.,Edwards, Howell G. M.,Farwell, Dennis W.,Morgan, Sara E
experimental part, p. 1725 - 1734 (2012/04/04)
The Raman spectra of n-pentyl methyl ether, C5H 11OCH3, and six selectively deuteriated analogues arereported and discussed. Correlations between the observed ν(sp 3CH)stretching and bending bands and the position of the deuterium atoms in thealkyl chain are developed and refined. Similar progress is possible inassociating specific skeletal vibrations with bands in the Raman spectra. Therelevance of this study to improving the assignment of bands in the Ramanspectra of larger systems of biological interest is highlighted. Copyright
Stereospecificity of hydride transfer during the dismutation of aldehydes catalyzed by alcohol dehydrogenases
Velonia,Smonou
, p. 3119 - 3123 (2007/10/03)
The stereochemistry of the oxidation of aldehydes to acids with alcohol dehydrogenases was studied with respect to the selectivity towards the cofactor.