Abstract
The relaxation kinetics of the gel to liquid-crystalline transition of five phosphatidylcholine (DC14PC to DC18PC) bilayer dispersions have been investigated using volume perturbation calorimetry, a steady-state technique which subjects a sample to sinusoidal changes in volume. Temperature and pressure responses to the volume perturbation are measured to monitor the relaxation to a new equilibrium position. The amplitude demodulation and phase shift of these observables are analyzed with respect to the perturbation frequency to yield relaxation times and amplitudes. In the limit of low perturbation frequency, the temperature and pressure responses are proportional to the equilibrium excess heat capacity and bulk modulus, respectively. At all temperatures, the thermal response data are consistent with a single primary relaxation process of the lipid. The less accurate bulk modulus data exhibit two relaxation times, but it is not clear whether they reflect lipid processes or are characteristic of the instrument. The observed thermal relaxation behavior of all multilamellar vesicles are quantitatively similar. The relaxation times vary from approximately 50 ms to 4 s, with a pronounced maximum at a temperature just greater than Tm, the temperature of the excess heat capacity maximum. Large unilamellar vesicles also exhibit a single relaxation process, but without a pronounced maximum in the relaxation time. Their relaxation time is approximately 80 ms over most of the transition range.
Full text
PDF










Selected References
These references are in PubMed. This may not be the complete list of references from this article.
- Albon N., Sturtevant J. M. Nature of the gel to liquid crystal transition of synthetic phosphatidylcholines. Proc Natl Acad Sci U S A. 1978 May;75(5):2258–2260. doi: 10.1073/pnas.75.5.2258. [DOI] [PMC free article] [PubMed] [Google Scholar]
- Bangham A. D., Standish M. M., Watkins J. C. Diffusion of univalent ions across the lamellae of swollen phospholipids. J Mol Biol. 1965 Aug;13(1):238–252. doi: 10.1016/s0022-2836(65)80093-6. [DOI] [PubMed] [Google Scholar]
- Black S. G., Dixon G. S. AC calorimetry of dimyristoylphosphatidylcholine multilayers: hysteresis and annealing near the gel to liquid-crystal transition. Biochemistry. 1981 Nov 10;20(23):6740–6744. doi: 10.1021/bi00526a033. [DOI] [PubMed] [Google Scholar]
- Caffrey M., Fanger G., Magin R. L., Zhang J. Kinetics of the premelting (L beta'-P beta') and main transition (P beta'-L alpha) in hydrated dipalmitoylphosphatidylcholine. A time-resolved x-ray diffraction study using microwave-induced temperature-jumps. Biophys J. 1990 Sep;58(3):677–686. doi: 10.1016/S0006-3495(90)82410-3. [DOI] [PMC free article] [PubMed] [Google Scholar]
- Caffrey M. Kinetics and mechanism of the lamellar gel/lamellar liquid-crystal and lamellar/inverted hexagonal phase transition in phosphatidylethanolamine: a real-time X-ray diffraction study using synchrotron radiation. Biochemistry. 1985 Aug 27;24(18):4826–4844. doi: 10.1021/bi00339a017. [DOI] [PubMed] [Google Scholar]
- Caffrey M., Magin R. L., Hummel B., Zhang J. Kinetics of the lamellar and hexagonal phase transitions in phosphatidylethanolamine. Time-resolved x-ray diffraction study using a microwave-induced temperature jump. Biophys J. 1990 Jul;58(1):21–29. doi: 10.1016/S0006-3495(90)82350-X. [DOI] [PMC free article] [PubMed] [Google Scholar]
- Caffrey M. The study of lipid phase transition kinetics by time-resolved X-ray diffraction. Annu Rev Biophys Biophys Chem. 1989;18:159–186. doi: 10.1146/annurev.bb.18.060189.001111. [DOI] [PubMed] [Google Scholar]
- Evans E., Kwok R. Mechanical calorimetry of large dimyristoylphosphatidylcholine vesicles in the phase transition region. Biochemistry. 1982 Sep 28;21(20):4874–4879. doi: 10.1021/bi00263a007. [DOI] [PubMed] [Google Scholar]
- Freire E., Biltonen R. Estimation of molecular averages and equilibrium fluctuations in lipid bilayer systems from the excess heat capacity function. Biochim Biophys Acta. 1978 Dec 4;514(1):54–68. doi: 10.1016/0005-2736(78)90076-7. [DOI] [PubMed] [Google Scholar]
- Genz A., Holzwarth J. F. Dynamic fluorescence measurements on the main phase transition of dipalmytoylphosphatidylcholine vesicles. Eur Biophys J. 1986;13(6):323–330. doi: 10.1007/BF00265668. [DOI] [PubMed] [Google Scholar]
- Gruenewald B., Blume A., Watanabe F. Kinetic investigations on the phase transition of phospholipid bilayers. Biochim Biophys Acta. 1980 Mar 27;597(1):41–52. doi: 10.1016/0005-2736(80)90148-0. [DOI] [PubMed] [Google Scholar]
- Halvorson H. R. Relaxation kinetics of glutamate dehydrogenase self-association by pressure perturbation. Biochemistry. 1979 Jun 12;18(12):2480–2487. doi: 10.1021/bi00579a007. [DOI] [PubMed] [Google Scholar]
- Lichtenberg D., Romero G., Menashe M., Biltonen R. L. Hydrolysis of dipalmitoylphosphatidylcholine large unilamellar vesicles by porcine pancreatic phospholipase A2. J Biol Chem. 1986 Apr 25;261(12):5334–5340. [PubMed] [Google Scholar]
- Mayer L. D., Hope M. J., Cullis P. R. Vesicles of variable sizes produced by a rapid extrusion procedure. Biochim Biophys Acta. 1986 Jun 13;858(1):161–168. doi: 10.1016/0005-2736(86)90302-0. [DOI] [PubMed] [Google Scholar]
- Mayorga O. L., van Osdol W. W., Lacomba J. L., Freire E. Frequency spectrum of enthalpy fluctuations associated with macromolecular transitions. Proc Natl Acad Sci U S A. 1988 Dec;85(24):9514–9518. doi: 10.1073/pnas.85.24.9514. [DOI] [PMC free article] [PubMed] [Google Scholar]
- Mcelhaney R. N., de Gier J., van der Neut-Kok E. C. The effect of alterations in fatty acid composition and cholesterol content on the nonelectrolyte permeability of Acholeplasma laidlawii B cells and derived liposomes. Biochim Biophys Acta. 1973 Mar 16;298(2):500–512. doi: 10.1016/0005-2736(73)90376-3. [DOI] [PubMed] [Google Scholar]
- Melchior D. L., Steim J. M. Thermotropic transitions in biomembranes. Annu Rev Biophys Bioeng. 1976;5:205–238. doi: 10.1146/annurev.bb.05.060176.001225. [DOI] [PubMed] [Google Scholar]
- Mitaku S., Jippo T., Kataoka R. Thermodynamic properties of the lipid bilayer transition. Pseudocritical phenomena. Biophys J. 1983 May;42(2):137–144. doi: 10.1016/S0006-3495(83)84379-3. [DOI] [PMC free article] [PubMed] [Google Scholar]
- Mountcastle D. B., Biltonen R. L., Halsey M. J. Effect of anesthetics and pressure on the thermotropic behavior of multilamellar dipalmitoylphosphatidylcholine liposomes. Proc Natl Acad Sci U S A. 1978 Oct;75(10):4906–4910. doi: 10.1073/pnas.75.10.4906. [DOI] [PMC free article] [PubMed] [Google Scholar]
- Nagle J. F., Wilkinson D. A. Lecithin bilayers. Density measurement and molecular interactions. Biophys J. 1978 Aug;23(2):159–175. doi: 10.1016/S0006-3495(78)85441-1. [DOI] [PMC free article] [PubMed] [Google Scholar]
- Romero G., Thompson K., Biltonen R. L. The activation of porcine pancreatic phospholipase A2 by dipalmitoylphosphatidylcholine large unilamellar vesicles. Analysis of the state of aggregation of the activated enzyme. J Biol Chem. 1987 Oct 5;262(28):13476–13482. [PubMed] [Google Scholar]
- Tenchov B. G., Yao H., Hatta I. Time-resolved x-ray diffraction and calorimetric studies at low scan rates: I. Fully hydrated dipalmitoylphosphatidylcholine (DPPC) and DPPC/water/ethanol phases. Biophys J. 1989 Oct;56(4):757–768. doi: 10.1016/S0006-3495(89)82723-7. [DOI] [PMC free article] [PubMed] [Google Scholar]
- Tsong T. Y., Kanehisa M. I. Relaxation phenomena in aqueous dispersions of synthetic lecithins. Biochemistry. 1977 Jun 14;16(12):2674–2680. doi: 10.1021/bi00631a014. [DOI] [PubMed] [Google Scholar]
- Van Osdol W. W., Biltonen R. L., Johnson M. L. Measuring the kinetics of membrane phase transitions. J Biochem Biophys Methods. 1989;20(1):1–46. doi: 10.1016/0165-022x(89)90079-1. [DOI] [PubMed] [Google Scholar]
- Vaz W. L., Clegg R. M., Hallmann D. Translational diffusion of lipids in liquid crystalline phase phosphatidylcholine multibilayers. A comparison of experiment with theory. Biochemistry. 1985 Jan 29;24(3):781–786. doi: 10.1021/bi00324a037. [DOI] [PubMed] [Google Scholar]
- Vaz W. L., Melo E. C., Thompson T. E. Fluid phase connectivity in an isomorphous, two-component, two-phase phosphatidylcholine bilayer. Biophys J. 1990 Jul;58(1):273–275. doi: 10.1016/S0006-3495(90)82373-0. [DOI] [PMC free article] [PubMed] [Google Scholar]
- Yager P., Peticolas W. L. The kinetics of the main phase transition of aqueous dispersions of phospholipids induced by pressure jump and monitored by Raman spectroscopy. Biochim Biophys Acta. 1982 Jun 28;688(3):775–785. doi: 10.1016/0005-2736(82)90291-7. [DOI] [PubMed] [Google Scholar]