Kinetics of the subtransition of asymmetrically substituted phosphatidylcholines

339

256

The thermotropic phase behavior of a series of 1,2-diacylphosphatidylcholines containing linear saturated acyl chains of 10-22 carbons was studied by differential scanning calorimetry. When fully hydrated and thoroughly equilibrated by prolonged incubation at appropriate low temperatures, all of the compounds studied form an apparently stable subgel phase (the Lc phase). The formation of the stable Lc phase is a complex process which apparently proceeds via a number of metastable intermediates after being nucleated by incubation at appropriate low temperatures. The process of Lc phase formation is subject to considerable hysteresis, and our observations indicate that the kinetic limitations become more severe as the length of the acyl chain increases. The kinetics of Lc phase formation also depend upon whether the acyl chains contain an odd or an even number of carbon atoms. The Lc phase is unstable at higher temperatures and upon heating converts to the so-called liquid-crystalline state (the L alpha phase). The conversion from the stable Lc to the L alpha phase can be a direct, albeit a multistage process, as observed with very short chain phosphatidylcholines, or one or more stable gel states may exist between the Lc and L alpha states. For the longer chain compounds, conversions from one stable gel phase to another become separated on the temperature scale, so that discrete subtransition, pretransition, and gel/liquid-crystalline phase transition events are observed.(ABSTRACT TRUNCATED AT 250 WORDS)

Section: Temperature (°C)mentioning

confidence: 99%

A differential scanning calorimetric study of the thermotropic phase behavior of model membranes composed of phosphatidylcholines containing linear saturated fatty acyl chains

Lewis¹,

Mak²,

McElhaney³

1987

339

256

“…McIntosh et al, 1984; Lewis et al, 1984;Tiimmler et al, 1984;Hui et al, 1984;Serrallach et al, 1984). For most PCs, at least two transitions were observed corresponding to the pretransition and main transition.…”

mentioning

confidence: 99%

Mixed-chain phosphatidylcholine bilayers: structure and properties

Mattai¹,

Sripada²,

Shipley³

1987

117

Calorimetric and X-ray diffraction data are reported for two series of saturated mixed-chain phosphatidylcholines (PCs), 18:0/n:0-PC and n:0/18:0-PC, where the sn-1 and sn-2 fatty acyl chains on the glycerol backbone are systematically varied by two methylene groups from 18:0 to 10:0 (n = 18, 16, 14, 12, or 10). Fully hydrated PCs were annealed at -4 degrees C and their multilamellar dispersions characterized by differential scanning calorimetry and X-ray diffraction. All mixed-chain PCs form low-temperature "crystalline" bilayer phases following low-temperature incubation, except 18:0/10:0-PC. The subtransition temperature (Ts) shifts toward the main (chain melting) transition temperature (Tm) as the sn-1 or sn-2 fatty acyl chain is reduced in length; for the shorter chain PCs (18:0/12:0-PC, 12:0/18:0-PC, and 10:0/18:0-PC), Ts is 1-2 degrees C greater than Tm, and the subtransition enthalpy (delta Hs) is much greater than for the longer acyl chain PCs. Tm decreases with acyl chain length for both series of PCs except 18:0/10:0-PC, while for the positional isomers, n:0/18:0-PC and 18:0/n:0-PC, Tm is higher for the isomer with the longer acyl chain in the sn-2 position of the glycerol backbone. The conversion from the crystalline bilayer Lc phase to the liquid-crystalline L alpha phase with melted hydrocarbon chains occurs through a series of phase changes which are chain length dependent. For example, 18:0/18:0-PC undergoes the phase changes Lc----L beta'----P beta'----L alpha, while the shorter chain PC, 10:0/18:0-PC, is directly transformed from the Lc phase to the L alpha phase. However, normalized enthalpy and entropy data suggest that the overall thermodynamic change, Lc----L alpha, is essentially chain length independent. On cooling, the conversion to the Lc phases occurs via bilayer gel phases, L beta', for the longer chain PCs or through triple-chain interdigitated bilayer gel phases, L beta, for the shorter chain PC 18:0/12:0-PC and possibly 10:0/18:0-PC. Molecular models indicate that the bilayer gel phases for the more asymmetric PC series, 18:0/n:0-PC, must undergo progressive interdigitation with chain length reduction to maintain maximum chain-chain interaction. The L beta phase of 18:0/10:0-PC is the most stable structure for this PC below Tm. The formation and stability of the triple-chain structures can be rationalized from molecular models.

“…This property is independent of the preference of the cryptand for the gel states of the membrane. As shown in the accompanying paper (Tümmler et al, 1984), the subtransition of mixed-chain lecithins is detected by the anthracenoyl dye with similar high resolution and sensitivity as the pretransition, and in this case, no fusion of sonicated vesicles takes place. Moreover, control measurements with DPPC dispersions yielded essentially the same results as those described in this paper for DMPC (data not shown).…”

Section: Discussionmentioning

confidence: 61%

Anthracenoyl crown ethers and cryptands as fluorescent probes for solid-phase transitions of phosphatidylcholines: syntheses and phospholipid membrane studies

Herrmann¹,

Tuemmler²,

Maaß³

et al. 1984

Self Cite

Three structurally related crown compounds and cryptands have been synthesized that differ by the number and linkage of coronand units and anthracene moieties. The interaction of the fluorescent dyes with sonicated dimyristoylphosphatidylcholine (DMPC) vesicles is characterized by the relative quantum yields, uptake kinetics, binding curves, lifetimes, fluorescence titrations with water- and lipid-soluble quenching agents, fluorescence anisotropy, and equilibrium cooling curves. The most lipophilic compound II, which displays a similar quantum yield as the parent fluorophore 9,10-dimethylanthracene, shows a nearly equal distribution between solid and fluid lipid and is located at the bilayer surface. The least lipophilic compound IV is excluded from the hydrocarbon phase. The anthracenophane cryptand III preferentially partitions into solid-phase lecithins with the highest affinity for the phases L epsilon and L beta. The binding constant to DMPC amounts to (5.4 +/- 1.3) X 10(2) M-1 at 0 degrees C. From fluorescence quenching titrations it is concluded that the average position of the anthracenoyl dye III discontinuously shifts during the gel to liquid crystalline transition from the glycerol backbone to the choline head group. Electron microscopy and NMR experiments revealed that the anthracenophane induces in the liquid crystalline phase the fusion of small unilamellar DMPC vesicles to unilamellar medium-sized vesicles and macrovesicles, which subsequently fuse at the transition temperature to large multilamellar coacervates. Due to its large change of fluorescence intensity, the anthracenophane cryptand is a very sensitive probe for the detection of the pretransition of symmetrically substituted and of the subtransition of asymmetrically substituted phosphatidylcholines.(ABSTRACT TRUNCATED AT 250 WORDS)