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81.
The effects of cholesterol, a lipid mostly found in the sarcolemmal membranes, on the interaction of amiodarone with synthetic
models of dimyristoylphosphatidylcholine (DMPC) and with native models of mitochondria and brain microsomes was studied. Alterations
on the structural order of lipids were assessed by fluorescence polarization of 1,6-diphenyl-1,3,5-hexatriene (DPH) probing
the bilayer core, and of the propionic acid derivative 3-(p-(6-phenyl)-1,3,5-hexatrienyl)phenylpropionic acid (DPH-PA) probing the outer regions of the bilayer. As detected by the probes
and according to classic observations, cholesterol progressively increased the molecular order in the fluid phase of DMPC.
Additionally, it modulated the type and extension of amiodarone effects. For low cholesterol concentrations (≤10–15 mol%),
amiodarone (50 μM) ordered DMPC bilayers and the effects were almost identical to those observed in pure DMPC. For higher cholesterol concentrations,
amiodarone ordering effects decreased slightly and faded for cholesterol concentrations as high as 25 and 30 mol%, when detected
by DPH-PA and DPH, respectively. Above these high cholesterol concentrations, a crossover from ordering to disordering effects
of amiodarone was apparent, either in the upper region of the bilayer or the hydrophobic core. The effects of amiodarone in
native membranes of mitochondria and brain microsomes, in which "native" cholesterol accounts for about 0 and 25 mol%, respectively,
correlated reasonably with the results in models of synthetic lipids. There is a close relationship between cholesterol concentration
and amiodarone effects, in either synthetic models or native model membranes. Therefore, it may be predicted that the lipid
physicochemical properties regulated by cholesterol concentration will also modulate the effects of amiodarone in sarcolemma. 相似文献
82.
This review article describes some general comments on micellar electrokinetic chromatography (MEKC) from the viewpoint of pseudo-stationary phases and presents a compiled list of surfactants used for MEKC, prepared from published papers. We tried to give comments on some typical surfactants from the practical point of view. 相似文献
83.
Summary Two new cyclodextrin (CD) derivatives, heptakis{2,6-di-O-pentyl-3-O-[3′-(2″-chloro-4″,5″-dioxylmethene)-phenyl-5′-iso-oxazolylmethyl]}-β-CD
(CD I) and heptakis{2,6-di-O-methyl-3-O-[3′-(2″-chloro)-phenyl-5′-iso-oxazolylmethyl]}-β-CD (CD II) were synthesized and coated
on fused-silica capillary columns. Their chromatographic characteristics, including column efficiency, polarity, selectivity
and phase transition were studied and compared with similar β-CD stationary phases. It was found that the heterocycle group
has a significant effect on the selectivity of the CD stationary phases. Both stationary phases can be successfully used to
separate many di- and trisubstituted benzene positional isomers and show stronger separation ability in separating low-polarity
benzene positional isomers than other β-CD stationary phases. 相似文献
84.
Summary Chirally substituted Si–H-containing polysiloxanes were synthesized, which can be immobilized on small particle silica gel as well as on the smooth surfaces of fused silica capillaries. Immobilization is achieved either by crosslinking or by chemical bonding to the surfaces via silanol groups; both reactions can only be performed by addition of H2PtCl6, which acts as catalyst for hydrosilylation and as stoichiometric reagent for crosslinking. Chiral substituents of systematically varied chemical structure were introduced into the polysiloxanes by hydrosilylation. The mechanism of immobilization was investigated by spectroscopic methods, notably29Si-NMR. Homogenous stationary-phase coatings of variable film thickness and corresponding retentivity can easily be achieved. The enantioselectivity of the phase systems was characterized in dependency on the chemical structure of the chiral selectors attached to the polysiloxane chain of the chiral stationary phases and also in terms of the functional groups introduced into the solutes by derivatisation. 相似文献
85.
Summary The paper discusses the effect of the length and structure of the hydrocarbon chain connecting the nitrile group to the silica gel surface on the chromatographic properties of cyanoalkyl phases.When using non-polar and polar mobile phases, the selectivity of the cyanodecyl phases toward PAHs is higher than of the cyanopropyl phase and of hydroxylated silica gel.Polar additives to the mobile phase drastically decrease the retention on silica gel and on the cyanopropyl phase while affect the properties of cyanodecyl phases only to a considerably less degree. Newly synthesized phases with different structures of the hydrocarbon chain are compared with the commerical cyano-and ODS-phases. The retention mechanism on the cyanoalkyl phases is discussed. 相似文献
86.
Liquid chromatographic comparisons for enantiomer resolution of α-amino acids and chiral primary amino compounds were made using chiral stationary phases (CSPs) prepared by covalently bonding (+)-(18-crown-6)-2,3,11,12-tetracarboxylic acid (18-C-6-TA) of the same chiral selector. The resolution of all α-amino acids on CSP 1 developed in our group was found to be better than that on CSP 2 reported by Machida et al. All α-amino acids examined in this study were well enantioseparated on CSP 1 (α=1.22–2.47), while four analytes were not resolved or all the other analytes were poorly resolved on CSP 2 than on CSP 1. However, in resolving the primary amino compounds without a carbonyl group, CSP 1 was comparable with CSP 2. Although (+)-18-C-6-TA of the same chiral selector was used to prepare CSP 1 and CSP 2, this study showed that different connecting methods for the CSPs might influence their ability to resolve the analytes depending on their structures related to the chiral recognition mechanism. 相似文献
87.
A range of mixed ether-esters of cellulose was prepared from partially substituted ethylcellulose and methylcellulose. The 13C-NMR analysis of ethylcellulose with a DS of 2.5 indicated that the hydroxyl groups at carbon six of anhydroglucose units were completely substituted. Acetylation of the ethylcellulose under different conditions yielded (acetyl) (ethyl) cellulose (AEC) samples with acetyl degree of substitution ranging from 0 to 0.5. Fully substituted (propionyl) (ethyl) cellulose (PEC) and (acetyl) (methyl) cellulose (AMC) were also prepared. Chiral nematic liquid crystals were formed in these mixed ester/ethers of cellulose in concentrated solutions of acidic solvents. The critical concentration for the phase separation of the cellulosic solutions depended on the nature of the substituent, the degree of substitution, and the solvent at a given temperature. Methylcellulose solutions in trifluoroacetic acid and dichloroacetic acid form chiral nematic liquid crystals with a left-handed helicoidal structure. The acetylated methyl cellulose samples did not show the reversal of handedness with increasing acetyl content that was previously observed for the corresponding ethylcellulose samples. © 1994 John Wiley & Sons, Inc. 相似文献
88.
Kevin E. Bassler Kazuo Sasaki Robert B. Griffiths 《Journal of statistical physics》1991,62(1-2):45-88
Certain features in Frenkel-Kontorova and other models of phases with a one-dimensional modulation can be analyzed by assuming parallel interfaces separating sets of lattice planes belonging to two different phases, and treating the free energy to create interfaces, as well as the interaction of two, three, or more interfaces, as phenomenological parameters. A strategy employed by Fisher and Szpilka for interacting defects can be extended to the case of interfaces, allowing a systematic study of the phase diagram by ignoring all interface interactions, and then successively taking into account pair, triple, and higher-order terms. The possible phase diagrams which can occur near the point where =0 include: various sorts of endpoints analogous to critical endpoints, an accumulation point of first-order transitions and triple points, and a self-similar structure which we call an upsilon point, which turns out to be an accumulation point of an infinite number of segments of first-order transition lines, each of which terminates in two upsilon points. 相似文献
89.
New phases which arise from partial substitution of Ti4+ by Cr3+ and Li+ of the compound La2/3TiO3 have been obtained, giving rise to the series La1.33LixCrxTi2−xO6 (x=0.66, 0.55 and 0.44). These phases adopt a perovskite-type structure as deduced from their structural characterization. Rietveld's analyses of neutron diffraction data show that it is orthorhombic (S.G. Pbnm) with ordered domains. Conductivity has been examined by complex impedance spectroscopy and it increases with increasing lithium and chromium content. These materials behave as mixed conductors with low activation energies. Magnetic susceptibility variation with temperature shows antiferromagnetic interactions at the lowest temperatures. 相似文献
90.
Y. Saito K. Jinno J. J. Pesek Y. -L. Chen G. Luehr J. Archer J. C. Fetzer W. R. Biggs 《Chromatographia》1994,38(5-6):295-303
Summary The chromatographic retention behaviour of two liquidcrystal bonded phases have been evaluated using polycyclic aromatic hydrocarbons (PAHs) as the probe samples in reversed-phase high performance liquid chromatography (RP-HPLC). The results clearly indicate that these phases have better planarity and shape recognition capabilities than commercially-avaialble polymeric octadecylsilica (ODS) phases whose strong planarity and shape selectivities were found earlier. It can also be concluded from the chromatographic observations that the shape recognition capability of these phases is dependent on both mobile phase composition and column temperature, but that the effect of mobile phase and temperature on the shape selectivity work independently. The retention behaviour can be explained by changes in the phase structure with changes of eluent composition and temperature. 相似文献