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1.
Studies of the ethanol-induced interdigitated gel phase in phosphatidylcholines using the fluorophore 1,6-diphenyl-1,3,5-hexatriene 总被引:4,自引:0,他引:4
It is now well established that a number of amphiphilic molecules such as ethanol can induce the formation of the fully interdigitated gel phase in phosphatidylcholines. We have shown earlier that alcohols such as ethanol induce biphasic melting behavior in phosphatidylcholines [Rowe, E. S. (1983) Biochemistry 22, 3299-3305] but not in phosphatidylethanolamines [Rowe, E. S. (1985) Biochim. Biophys. Acta 813, 321-330]. Simon and McIntosh [(1984) Biochim. Biophys. Acta 773, 169-172] showed that the alcohol-induced biphasic melting behavior in phosphatidylcholines is a consequence of acyl chain interdigitation. In the present study we demonstrate the detection of the transition of DPPC and DSPC to the interdigitated phase in the presence of ethanol using the fluorescence properties of the commonly used fluorophore 1,6-diphenyl-1,3,5-hexatriene (DPH). By correlating fluorescence and X-ray diffraction results, we have demonstrated the use of fluorescence to study the phase transition from the noninterdigitated to the interdigitated phase. Using this method, we have investigated the temperature and ethanol concentration dependence of the induction of the interdigitated phase in DSPC and DPPC and shown that the induction of interdigitation by ethanol is temperature dependent, with higher temperature favoring interdigitation. The temperature-ethanol phase diagrams have been determined for DPPC and DSPC. 相似文献
2.
Differential scanning calorimetry (DSC) and fluorescence spectroscopy are useful techniques for investigating the phase transitions of phospholipid bilayers. In this study, these methods have been extended to determine the effects of ethanol on DSPC and DSPC/2 mol.% cholesterol bilayers. The biphasic effect of the main transition was observed on the DSC heating scans above 0.60 M ethanol. In addition, the concentration at which the biphasic effect occurs is not significantly changed in the presence of 2 mol.% cholesterol. For the fluorescence studies, 1,6-diphenyl-1,3,5-hexatriene (DPH) has been incorporated into the bilayer to monitor the phase transitions through the displacement of DPH. This fluorescent probe is used to directly determine the onset of interdigitation in the bilayer systems as indicated by a large decrease in the DPH fluorescence intensity. The addition of cholesterol lowered and broadened the transition temperatures of the phosphatidylcholine (PC) system. However, 2 mol.% cholesterol did not have a significant effect on the induction of the interdigitated phase in DSPC as observed from the small difference in ethanol threshold concentration for the two systems. This suggests that DSPC forms a more stable interdigitated gel phase than other PCs with shorter acyl chains. 相似文献
3.
In this study we introduce a mesoscopic lipid-water-alcohol model. Dissipative particle dynamics (DPD) simulations have been used to investigate the induced interdigitation of bilayers consisting of double-tail lipids by adding alcohol molecules to the bilayer. Our simulations nicely reproduce the experimental phase diagrams. We find that alcohol can induce an interdigitated structure where the common bilayer structure changes into monolayer in which the alcohol molecules screen the hydrophobic tails from the water phase. At low concentrations of alcohol the membrane has domains of the interdigitated phase that are in coexistence with the common membrane phase. We compute the effect of the chain length of the alcohol on the phase behavior of the membrane and show that the stability of the interdigitated phase depends on the length of the alcohol. We show that we can reproduce the experimental hydrophobic thickness of the bilayer for various combinations of lipids and alcohols. We use our model to clarify some of the experimental questions related to the structure of the interdigitated phase and put forward a simple model that explains the alcohol chain length dependence of the stability of this interdigitated phase. 相似文献
4.
Long chain spin labels with the nitroxide group located near the terminal methyl of the chain were used to determine the percentage interdigitated lipid in complexes of polymyxin B (PMB) and polymyxin B nonapeptide (PMBN) with the acidic lipids dipalmitoylphosphatidylglycerol (DPPG) and dipalmitoylphosphatidic acid (DPPA) at varying mole ratios of drug to lipid and at different pH values. These spin labels are more motionally restricted in the interdigitated than in the non-interdigitated gel phase bilayer. This allows determination of the percentage interdigitated lipid by resolution of the spectrum into motionally restricted and more mobile components. At nonsaturating concentrations of PMB, significantly more DPPG than that which can be maximally PMB-bound, becomes interdigitated. As the temperature approaches the gel to liquid crystalline phase transition temperature, the bilayer becomes progressively non-interdigitated. The ESR spectrum indicates that PMB also causes interdigitation of DPPA. However, in contrast to DPPG, the amount of DPPA which is interdigitated at pH 6, is less than the amount which is expected to be PMB-bound. This is attributed to the ability of DPPA to participate in lateral interlipid hydrogen bonding interactions. Such lateral interactions would be abolished in the interdigitated bilayer and thus they are expected to inhibit its formation. At pH 9, where the interlipid interactions of DPPA are weakened, PMB induces even more lipid than that which is PMB-bound to become interdigitated. Indeed, the percentage interdigitated lipid is even greater than found for DPPG. This may be partly a result of the greater negative charge of DPPA at this pH. A greater repulsive negative charge is expected to favor interdigitation. PMBN is less effective than PMB at inducing interdigitation of DPPG and causes little or no interdigitation of DPPA at pH 6, even at saturating concentrations. PMBN also does not lower the phase transition temperature of DPPA at pH 6 as much as PMB. At pH 9, the effect of PMBN on DPPA is more similar to the effect of PMB. However, even for DPPG, and DPPA at pH 9, PMBN does not maintain interdigitation of the lipids at higher temperatures as effectively as PMB. PMBN's smaller perturbing effect and greatly decreased ability to cause interdigitation of DPPA at pH values below 9 may be related to a decreased ability to cause lateral separation of the lipid molecules, which is necessary in order to weaken the interlipid interactions.(ABSTRACT TRUNCATED AT 400 WORDS) 相似文献
5.
Adsorption of alcohol molecules or other small amphiphilic molecules in the cell membrane can induce significant changes in the structure of the membrane. To understand the molecular mechanisms underlying these structural changes, we developed a mesoscopic membrane model. Molecular simulations on this model nicely reproduce the experimental phase diagrams. We find that alcohol can induce an interdigitated structure in which the normal bilayer structure changes into a monolayer in which the alcohol molecules screen the hydrophobic tails from the water phase. We compute the effect of the chain length of the alcohol on the phase behaviour of the membrane. At low concentrations of alcohol, the membrane has domains of the interdigitated phase that are in coexistence with the normal membrane phase. We use our model to clarify some of the experimental questions related to the structure of the interdigitated phase and put forward a simple model that explains the alcohol chain length dependence of the stability of this interdigitated phase. 相似文献
6.
Differential scanning calorimetric studies of ethanol interactions with distearoylphosphatidylcholine: transition to the interdigitated phase 总被引:1,自引:0,他引:1
It is well established that ethanol and other amphipathic molecules induce the formation of a fully interdigitated gel phase in saturated like-chain phosphatidylcholines (PC's). We have previously shown that the induction of interdigitation in PC's by ethanol is dependent upon the alcohol concentration, the lipid chain length, and the temperature [Nambi, P., Rowe, E. S. & McIntosh, T. J. (1988) Biochemistry 27, 9175-9182]. In the present study, we have used high-sensitivity differential scanning calorimetry to investigate the transitions of distearoylphosphatidylcholine between the noninterdigitated and the interdigitated phases. The enthalpy of the L beta' to L beta I transition is approximately half that of the L beta' to P beta' transition which occurs in the absence of ethanol. The reversibility of these transitions has also been investigated by employing both heating and cooling scans in order to establish the most stable phases as a function of temperature and ethanol concentration. It has been demonstrated that the transition to the interdigitated phase is reversible as a function of temperature. Kinetic studies on the reverse transition (L beta I to L beta') demonstrate that this transition can be very slow, requiring weeks to reach completion. The rate depends upon temperature and ethanol concentration. The slow phase changes mean that the lipid can exist for long periods of time in a phase structure which is not the most stable state. The biological significance of this type of lipid behavior is the implication that the phase structure of biological membranes may depend not only on the most stable phase structure of the lipids present but also on the synthetic pathway or other kinetic variables. 相似文献
7.
Effects of alcohol-induced lipid interdigitation on proton permeability in L-alpha-dipalmitoylphosphatidylcholine vesicles.
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6-Carboxyfluorescein was employed to examine the effect of alcohol-induced lipid interdigitation on proton permeability in L-alpha-dipalmitoylphosphatidylcholine (DPPC) large unilamellar vesicles. Proton permeability was measured by monitoring the decrease of 6-carboxyfluorescein fluorescence after a pH gradient from 3.5 (outside the vesicle) to 8.0 (inside the vesicle) was established. At 20 degrees C and below 1.2 M ethanol, the fluorescence decrease is best described by a single exponential function. Above 1.2 M ethanol, the intensity decrease is better described by a two-exponential decay law. Using the fitted rate constants and the vesicle radii determined from light-scattering measurements, the proton permeability coefficient, P, in DPPC vesicles was calculated as a function of ethanol concentration. At 20 degrees C, P increases monotonically with increasing ethanol content up to 1.0 M, followed by an abrupt increase at 1.2 M. The vesicle size also exhibits a sudden increase at around 1.2 M ethanol, which has been shown to result from vesicle aggregation rather than vesicle fusion. The abrupt increases in P and in vesicle size occur at the concentration region close to the critical ethanol concentration for the formation of the fully interdigitated gel state of DPPC. At 14 degrees C, the abrupt change in P shifts to 1.9-2.0 M ethanol, completely in accordance with the ethanol-temperature phase diagram of interdigitated DPPC. Effects of methanol and benzyl alcohol on lipid interdigitation have also been examined. At 20 degrees C, DPPC large unilamellar vesicles exhibit a dramatic change in P at 3 M methanol and at 40 mM benzyl alcohol. These concentrations come close to the critical methanol and benzyl alcohol concentrations for the formation of fully interdigitated DPPC structures determined previously by others. It can be concluded that proton permeability increases dramatically as DPPC is transformed from the noninterdigitated gel to the fully interdigitated gel state by high concentrations of alcohol. This marked increase in proton permeability can be attributed to the combined effect of the changes in membrane thickness and surface charge density, due to the ethanol-induced lipid interdigitation. The possible effects of the increased proton permeability caused by ingested ethanol on gastric mucosal membranes are discussed. 相似文献
8.
The effect of bath application of several short chain N-alcohols on voltage-dependent potassium conductance has been studied in intact giant axons of Loligo forbesi under voltage-clamp conditions. All tested alcohols (methanol, ethanol, propanol, butanol, heptanol and octanol) were found to depress potassium conductance only at concentrations much larger than those necessary to reduce sodium conductance. The efficacy of the different molecules was correlated with the carbon-chain length. In all cases the effects were found to be at least partly reversible. Low concentrations of propanol (100 mM) or heptanol (1 mM) were found to increase potassium conductance whereas higher concentrations had the usual depressing effect. The two alcohols were found to induce a slow inactivation of the potassium conductance. A detailed analysis of the time course of the turning-on of the potassium current for various pulse potentials in the presence of TTX revealed that, for membrane potential values more positive than -20 mV, the time constant of activation was reduced in the presence of propanol or heptanol. The delay which separates the change in potential and the turning-on of the potassium current, which was systematically analysed for different pulse and prepulse potential values, was increased by the two alcohols, the curve relating this delay to prepulse potential being shifted towards larger (positive) delays. This high degree of complexity in the effects on potassium conductance suggests that the alcohol molecules modify several more or less independent mechanisms associated with the turning-on of the potassium current. 相似文献
9.
Effects of alcohols on the phase transition temperatures of mixed-chain phosphatidylcholines. 总被引:2,自引:2,他引:0
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The biphasic effect of ethanol on the main phase transition temperature (Tm) of identical-chain phosphatidyl-cholines (PCs) in excess H2O is now well known. This biphasic effect can be attributed to the transformation of the lipid bilayer, induced by high concentrations of ethanol, from the partially interdigitated L beta, phase to the fully interdigitated L beta I phase at T < Tm. The basic packing unit of the L beta I phase has been identified recently as a binary mixture of PC/ethanol at the molar ratio of 1:2. The ethanol effect on mixed-chain PCs, however, is not known. We have thus in this study investigated the alcohol effects on the Tm of mixed-chain PCs with different delta C values, where delta C is the effective acyl chain length difference between the sn-1 and sn-2 acyl chains. Initially, molecular mechanics (MM) simulations are employed to calculate the steric energies associated with a homologous series of mixed-chain PCs packed in the partially and the fully interdigitated L beta I motifs. Based on the energetics, the preference of each mixed-chain PC for packing between these two different motifs can be estimated. Guided by MM results, high-resolution differential scanning calorimetry is subsequently employed to determine the Tm values for aqueous lipid dispersions prepared individually from a series of mixed-chain PCs (delta C = 0.5-6.5 C-C bond lengths) in the presence of various concentrations of ethanol. Results indicate that aqueous dispersions prepared from mixed-chain PCs with a delta C value of less than 4 exhibit a biphasic profile in the plot of Tm versus ethanol concentration. In contrast, highly asymmetric PCs (delta C > 4) do not exhibit such biphasic behavior. In the presence of a longer chain n-alcohol, however, aqueous dispersions of highly asymmetric C(12):C(20)PC (delta C = 6.5) do show such biphasic behavior against ethanol. Our results suggest that the delta C region in a highly asymmetric PC packed in the L beta I phase is most likely the binding site for n-alcohol. 相似文献
10.
Thermodynamic reversibility of phase transitions. Specific effects of alcohols on phosphatidylcholines 总被引:6,自引:0,他引:6
E S Rowe 《Biochimica et biophysica acta》1985,813(2):321-330
The gel-to-fluid phase transitions of several phosphatidylethanolamines (PE's) and phosphatidylcholines (PC's) have been investigated in the presence of three short-chain alcohols. The effects of the alcohols on the thermodynamic reversibility of these transitions was studied and it was found that the transitions for PC's are not thermodynamically reversible at relatively high alcohol concentrations. The PE transitions are thermodynamically reversible for all alcohol concentrations, and the PE's do not exhibit the biphasic effects of alcohol on the transition temperature previously reported for the PC's (Rowe, E.S. (1983) Biochemistry 22, 3299-3305). The biphasic transition temperature effects and the thermodynamic irreversibility of PC transitions at high alcohol concentrations appear to be correlated with the induction of a fully interdigitated gel phase recently reported in the literature (Simon, S.A. and McIntosh, T.J. (1984) Biochim. Biophys. Acta 773, 169-172). The biological significance of these findings is discussed. 相似文献
11.
It is now recognized that many amphiphilic molecules such as ethanol can induce the formation of the fully interdigitated gel phase (L beta I) in phosphatidylcholines (PC's). In the present study, we have developed a simple detection method for the L beta I phase using pyrene-labeled PC (PyrPC), which is a PC analogue with covalently coupled pyrene moiety at the end of one of its acyl chains. The intensity ratio of its fluorescence vibrational bands is a reflection of the polarity of the environment of the fluorophore. We have tested this fluorophore in several established interdigitated lipid systems, including 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (1,2-DPPC) in the presence of high concentrations of ethanol and 1,2-di-O-hexadecyl-sn-glycero-3-phosphocholine (DHPC) and 1,3-dipalmitoyl-sn-glycero-2-phosphocholine (1,3-DPPC) in the absence of any additives. We have found in each of these systems that the ratio of the intensities of band III (387.5 nm) to band I (376.5 nm) is sensitive to the lipid phase change from the noninterdigitated L beta' phase to the interdigitated L beta I phase. By comparison of the III/I ratios for PyrPC in the lipid systems with the III/I ratios for methylpyrene in organic solvents, it was shown that the polarity of the PyrPC environment in the L beta I phase is similar to that of pentanol or ethanol. Using this method, we investigated the effect of cholesterol on the ethanol induction of the interdigitated gel phase in 1,2-DPPC. We found that the ethanol induction of the interdigitated gel phase is prevented by the presence of 20 mol % cholesterol. 相似文献
12.
The influence of low amounts of cholesterol on the interdigitated gel phase of hydrated dihexadecylphosphatidylcholine. 总被引:3,自引:0,他引:3
Dihexadecylphosphatidylcholine (DHPC)/cholesterol binary mixtures in excess of water have been characterized by small-angle X-ray diffraction and differential scanning calorimetry and a temperature-composition phase diagram for this binary has been constructed. The property of cholesterol to perturb the hydrocarbon chain interdigitation in the lamellar gel phase of DHPC and to convert it into a non-interdigitated state has been observed by small- angle X-ray diffraction at cholesterol concentrations as low as 0.1 mol%. The interdigitated and non-interdigitated lamellar gel phases coexist in the range up to 5 mol% cholesterol. At this and higher cholesterol concentrations only non-interdigitated phases have been found in the phase diagram of the mixture. It is suggested that the ability of cholesterol in low concentration to eliminate the hydrocarbon chain interdigitation is related to the free energy increase due to unfavourable line boundaries between the interdigitated and non-interdigitated lipid domains. 相似文献
13.
山莨菪碱诱导DPPG/DPPC混合物形成交插凝胶相──荧光偏振研究 总被引:2,自引:0,他引:2
山莨菪碱诱导DPPG脂质体交插结构,其脂酰链末端插到对面分子层脂酰链第五个碳原子的位置,而生物膜中普遍存在的DPPC不能被山莨菪碱诱导形成交插相,但DPPG/DPPC混合物则能形成交插相,即伴随DPPG的交插,DPPC分子也发生交插。当DPPG/DPPC摩尔比为2:1或1:1时,其脂酰链末端插到对面分子层第八个碳原子的位置。当DPPG/DPPC摩尔比为1:2时,就不能发生交插而呈完全的非交插状态。同时,发现当体系中钠离子浓度达到400mmol/L时,山莨菪碱就不能再诱导DPPG形成交插凝胶相。 相似文献
14.
We have systematically investigated the effect of short chain alcohols (methanol to n-propanol) on the phase transitions of 1,2-dihexadecylphosphatidylcholine (DHPC), a lipid that forms a stable interdigitated gel phase (L beta I) in aqueous solution. The temperature of the low-temperature L beta I to P beta' phase transition of DHPC was found to increase with alcohol concentration, showing that alcohol interacts preferentially with the interdigitated phase relative to the non-interdigitated gel. The main transition of DHPC exhibited a biphasic effect of alcohol concentration similar to that previously observed with DPPC (Rowe, E.S. (1983) Biochemistry 22,3299-3305). As alcohol concentration is increased the lower L beta I to P beta' and main P beta' to L alpha transitions of DHPC merge at the threshold concentration of the biphasic effect, so that above this concentration there is one phase transition from L beta I directly to L alpha. This is analogous to DPPC above its biphasic threshold. Similar to DPPC, the transition between L beta I and L alpha exhibits marked hysteresis. 相似文献
15.
Hydrostatic pressure induces hydrocarbon chain interdigitation in single-component phospholipid bilayers 总被引:11,自引:0,他引:11
By use of neutron diffraction for structural analysis, the temperature-pressure phase diagrams of several fully hydrated single-component phospholipid bilayers have been explored up to hydrostatic pressures of 2 kbars. The gel to liquid-crystalline phase transition temperature Tm increases linearly with pressure over a 10(-3)-2 kbar range in accordance with the Clausius-Clapeyron relationship giving dTm/dP values of 23.0 degrees C/kbar for 1,2-dimyristoyl-sn-glycero-3-phosphatidylcholine (DMPC) and 1,2-dipalmitoyl-sn-glycero-3-phosphatidylcholine (DPPC) and 28.0 degrees C/kbar for 1,2-distearoyl-sn-glycero-3-phosphatidylcholine (DSPC). The so-called pretransition was not observed in the isothermal pressure experiments, suggesting that no appreciable volume change occurs at this transition. These results are in good agreement with those reported using other techniques. In addition, at pressures higher than the isothermal liquid-crystalline to gel transition pressure, a new pressure-induced phase transition was observed for DPPC and DSPC in which the hydrocarbon chains from apposing monolayers become interdigitated with the chains occupying a cross-sectional area approximately equal to 5% less than in the gel phase. The temperature-pressure phase diagrams show the gel-interdigitated phase boundaries to be highly curved and the minimum pressure at which interdigitation occurs to decrease with increasing hydrocarbon chain length. 相似文献
16.
Effect of n-alcohols and glycerol on the pretransition of dipalmitoylphosphatidylcholine 总被引:2,自引:0,他引:2
We have systematically investigated the effect of short-chain n-alcohols and glycerol on the pretransition of 1,2-dipalmitoylphosphatidylcholine (DPPC) by spectrophotometry. It is found that the n-alcohols and glycerol remove the pretransition above a critical concentration for each ligand. In addition, the short-chain n-alcohols below the critical concentration decrease the pretransition temperature. The longer the aliphatic chain length of the n-alcohol (up to butanol) the greater the decrease in the pretransition temperature, and the lower the concentration necessary to remove the pretransition. However, glycerol differs from the short-chain n-alcohols in that it has no significant effect on either the pretransition or the main transition, but it is also capable of removing the pretransition above a critical concentration. It has previously been shown that alcohols have a biphasic effect on the main transition temperature of phosphatidylcholines (Rowe, E.S. (1983) Biochemistry 22, 3299-3305). At high alcohol concentrations, the main transition is not thermodynamically reversible (Rowe, E.S. (1985) Biochim. Biophys. Acta 813, 321-330). Recently, Simon and McIntosh (Biochim. Biophys. Acta (1984) 773, 169-172) have identified that at high ethanol concentration DPPC exists in the interdigitated phase. The critical ligand concentration at which the pretransition disappears coincides with the induction of main transition hysteresis and the biphasic alcohol effect in the main transition. These three effects appear to correlate with the induction of the interdigitated gel state by alcohols and glycerol. 相似文献
17.
Maswadeh H Demetzos C Daliani I Kyrikou I Mavromoustakos T Tsortos A Nounesis G 《Biochimica et biophysica acta》2002,1567(1-2):49-55
Differential scanning calorimetry has been employed to study the thermal effects of vinblastine sulfate upon aqueous, single and multiple bilayer dispersions of 1,2-dipalmitoyl-3-sn-phosphatidylcholine (DPPC). The calorimetric results summarized to an increase in the gel to liquid-crystalline phase transition enthalpy and the abolishment of the L(beta)' (gel phase) to P(beta)' (ripple phase) pretransition for the uni- and multilamellar dispersions, as well as an increase in the transition temperature T(m) and the transition cooperativity for single bilayer DPPC/vinblastine mixed vesicles, are consistent with an induced, partially interdigitated, gel phase. Computational analysis has been successfully applied to clarify the intermolecular effects and verify the feasibility of the proposed interdigitation for the vinblastine sulfate molecules and also for the ursodeoxycholic acid (UDCAH) and bromocylated taxanes, which have been shown to induce an interdigitated gel phase in DPPC bilayers. 相似文献
18.
Jeffrey A. Veiro Parthasarathy Nambi Lourdes L. Herold Elizabeth S. Rowe 《生物化学与生物物理学报:生物膜》1987,900(2)
We have systematically investigated the effect of short-chain n-alcohols and glycerol on the pretransition of 1,2-dipalmitoylphosphatidylcholine (DPPC) by spectrophotometry. It is found that the n-alcohols and glycerol remove the pretransition above a critical concentration for each ligand. In addition, the short-chain n-alcohols below the critical concentration decrease the pretransition temperature. The longer the aliphatic chain length of the n-alcohol (up to butanol) (a) the greater the decrease in the pretransition temperature, and (b) the lower the concentration necessary to remove the pretransition. However, glycerol differs from the short-chain n-alcohols in that it has no significant effect on either the pretransition or the main transition, but it is also capable of removing the pretransition above a critical concentration. It has previously been shown that alcohols have a biphasic effect on the main transition temperature of phosphatidylcholines (Rowe, E.S. (1983) Biochemistry 22, 3299–3305). At high alcohol concentrations, the main transition is not thermodynamically reversible (Rowe, E.S. (1985) Biochim. Biophys. Acta 813, 321–330). Recently, Simon and McIntosh (Biochim. Biophys. Acta (1984) 773, 169–172) have identified that at high ethanol concentration DPPC exists in the interdigitated phase. The critical ligand concentration at which the pretransition disappears coincides with the induction of main transition hysteresis and the biphasic alcohol effect in the main transition. These three effects appear to correlate with the induction of the interdigitated gel state by alcohols and glycerol. 相似文献
19.
Adachi T 《Chemistry and physics of lipids》2000,107(1):93-97
A new method based on a sampling theorem is proposed for determining the phase in the X-ray diffraction analysis of the structure of phospholipid systems. The thickness of a lipid layer is changed by changing the length of hydrocarbon chains in order to rebuild the continuous transform from the scattering amplitudes. By employing this method, the phases were accurately determined in a structure analysis of nine phospholipid/alcohol systems at the interdigitated gel phase. The nine systems are dimyristoylphosphatidylcholine(DMPC)/propanol, DPPC/methanol, DPPC/ethanol, DPPC/propanol, DPPC/butanol, distearoylphosphatidylcholine(DSPC)/methanol, DSPC/ethanol, DSPC/propanol and DSPC butanol systems. 相似文献
20.
Solute effects on the colloidal and phase behavior of lipid bilayer membranes: ethanol-dipalmitoylphosphatidylcholine mixtures. 总被引:1,自引:1,他引:0
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By means of the scanning differential calorimetry, x-ray diffractometry, and the dynamic light scattering, we have systematically studied the phase and packing properties of dipalmitoylphosphatidylcholine vesicles or multibilayers in the presence of ethanol. We have also determined the partial ternary phase diagram of such dipalmitoylphosphatidylcholine/water/ethanol mixtures. The directly measured variability of the structural bilayer parameters implies that ethanol binding to the phospholipid bilayers increases the lateral as well as the transverse repulsion between the lipid molecules. This enlarges the hydrocarbon tilt (by up to 23 degrees) and molecular area (by < or = 40%). Ethanol-phospholid association also broadens the interface and, thus, promotes lipid headgroup solvation. This results in excessive swelling (by 130%) of the phosphatidylcholine bilayers in aqueous ethanol solutions. Lateral bilayer expansion, moreover, provokes a successive interdigitation of the hydrocarbon chains in the systems with bulk ethanol concentrations of 0.4-1.2 M. The hydrocarbon packing density as well as the propensity for the formation of lamellar gel phases simultaneously increase. The pretransition temperature of phosphatidylcholine bilayers is more sensitive to the addition of alcohol (initial shift: delta Tp = 22 degrees C/mol) than the subtransition temperature (delta Ts reversible 5 degrees C/mol), whereas the chain-melting phase transition temperature is even less affected (delta Tm = 1.8 degrees C/mol). After an initial decrease of 3 degrees for the bulk ethanol concentrations below 1.2 M, the Tm value increases by 2.5 degrees above this limiting concentration. The gel-phase phosphatidylcholine membranes below Tm are fully interdigitated above this limiting concentration. The chain tilt on the fringe of full chain interdigitation is zero and increases with higher ethanol concentrations. Above Tm, some of the lipid molecules are solubilized by the bound ethanol molecules. More highly concentrated ethanol solutions (> 7 M) solubilize the phosphatidylcholine bilayers with fluid chains fully and result in the formation of mixed lipid-alcohol micelles. 相似文献