PubMed · 14404572
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H L KARPMAN. 1960. The Keys equation.. https://doi.org/10.1016/0002-8703(60)90314-8
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Molecularly imprinted cyclodextrins (MI-CDs) are prepared by cross-linking CDs in the presence of a template molecule. The binding ability of MI-CDs to the template molecule is specific; therefore, MI-CDs will prove to be useful materials. In this study, we prepared microspheres of MI-CDs (MSs-MI-CD) in a dimethylsulfoxide/poly(dimethylsiloxane) (PDMS) emulsion, using cholesterol as the template molecule. MSs-MI-CD were prepared under various conditions and were evaluated with respect to their morphology, size, and binding ability. MSs-MI-CD prepared at 65 degrees C were in an aggregated form; however, we could prepare separated and uniform MSs-MI-CD at 95 degrees C. The viscosity of PDMS influenced the size of MSs-MI-CD. The mean particle diameters of MSs-MI-CD prepared with 50 and 1000 mm(2)/s PDMS were 146 and 43 microm, respectively. The binding ability of MSs-MI-CD to cholesterol was higher than that of non-imprinted microspheres. Cholesterol imprinting also promoted the binding ability to other steroids; however, the increase in binding ability was most remarkable in the case of cholesterol, suggesting that we successfully introduced the cholesterol-specific binding ability into MSs-MI-CD. The novel MSs-MI-CD preparation method is useful and simple, and it will provide opportunities for further studies on the specific binding ability of MI-CDs.
Lipid-lipid interactions across cholesterol-rich phospholipid bilayers were investigated by measuring nearest-neighbor preferences of exchangeable phospholipids derived from 1,2-dimyristoyl-sn-glycero-3-phosphoethanolamine (DMPE) and 1,2-distearoyl-sn-glycero-3-phosphoethanolamine (DSPE), in the presence of nonexchangeable dimers (i.e., templates) made from DMPE or DSPE. When homotemplates were present, a significant preference for homophospholipid association was observed. In contrast, when the corresponding heterotemplate was present, heterodimer formation was favored. These results support a model in which the longer phospholipid in one monolayer preferentially associates with the shorter one in the adjoining monolayer. In the absence of cholesterol, transbilayer complementarity was also observed but to a lesser degree. Transbilayer complementarity of phospholipids is likely to play an important role in stabilizing biological membranes and in promoting a compositional interdependence of their two lipid leaflets.
A full description of coexisting phases includes their respective compositions, which are provided by the thermodynamic tie-lines. Fluorescence microscopy enables visualization of coexisting lipid phases in giant unilamellar phases, but the composition information is missing. For cholesterol-containing lipid mixtures, knowledge of the compositions of the coexisting phases is important for understanding the nature of "membrane rafts". We propose and demonstrate a new method, based on ESR spectroscopy, for determining tie-lines in regions of two-phase coexistence in a ternary lipid mixture. Over 100 different lipid compositions containing the spin-labeled phospholipid 16-PC in or near the two-phase coexistence region of the liquid-disordered and the gel phases of dipalmitoyl-PC/dilauroyl-PC/cholesterol (DPPC/DLPC/Chol) were studied to determine five tie-lines, spread over virtually the full range of this coexistence region. The method is based on the facts that (1) along a tie-line the ESR spectrum must be a superposition of the two ESR spectra from the respective single phases at the phase boundaries (connected by the tie-line) in a ratio given by the lever rule; (2) along a tie-line the partition coefficient, K(p), for the spin-label, which is also determined in our method, must be constant. We do find that K(p) for 16-PC is close to unity, but its value depends on the particular tie-line. The coexisting phases in equilibrium are characterized by the K(p) of the spin-label and its respective dynamic parameters obtained from fitting the ESR spectra to dynamical models.