Skip to main content
NCBI home page
Biophysical Journal logoLink to Biophysical Journal
. 1990 Sep;58(3):677–686. doi: 10.1016/S0006-3495(90)82410-3

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.

M Caffrey 1, G Fanger 1, R L Magin 1, J Zhang 1
PMCID: PMC1281008  PMID: 2207258

Abstract

The dynamics and mechanism of the premelting (L beta'-P beta') and main transitions (P beta'-L alpha) in fully hydrated dipalmitoylphosphatidylcholine were examined by low-angle time-resolved x-ray diffraction (TRXRD) using microwave radiation to effect uniform, internal sample heating. Equilibrium and dynamic aspects of the transitions were investigated. The dynamic studies involved applying a temperature jump of sufficient amplitude to effect the two transitions sequentially. Our findings are as follows. (a) Microwave radiation has proven useful as a means for implementing rapid and uniform internal heating in temperature-jump studies of lipid-phase transition kinetics. (b) Heating rate can be controlled by adjusting microwave power setting. (c) The thermal expansion coefficient of the three lyotropic phases follows the sequence L beta' not equal to O greater than P beta' much greater than L alpha. (d) Regardless of temperature-jump amplitude and sample heating rate the P beta' phase was always in evidence as an intermediate between the L beta' and L alpha phases. (e) The degree of development of the P beta' phase was inversely proportional to temperature-jump amplitude and heating rate. (f) The shortest transit time recorded for the combined L beta'-P beta', and P beta'-L alpha transitions was less than 1 s. (g) Upon cooling from the L alpha phase the onset of the chain disorder/order transition was apparent as a dramatic change of slope in the scattering angle vs. time plot which is interpreted as arising from sample heating by the latent heat of the transition. (h) Based on the shape of the low-angle diffraction pattern of the P beta' phase the P beta'-L alpha transition appears to be reversible with no evidence of metastability as was observed in the slow scan TRXRD measurements of Tenchov et al. (1989. Biophys. J. 56:757-768).

Full text

PDF
677

Images in this article

679FIGURE 1
on p.679

Selected References

These references are in PubMed. This may not be the complete list of references from this article.

  1. Blume A., Hillmann M. Dimyristoylphosphatidic acid/cholesterol bilayers. Thermodynamic properties and kinetics of the phase transition as studied by the pressure jump relaxation technique. Eur Biophys J. 1986;13(6):343–353. doi: 10.1007/BF00265670. [DOI] [PubMed] [Google Scholar]
  2. Caffrey M., Bilderback D. H. Kinetics of the main phase transition of hydrated lecithin monitored by real-time X-ray diffraction. Biophys J. 1984 Mar;45(3):627–631. doi: 10.1016/S0006-3495(84)84201-0. [DOI] [PMC free article] [PubMed] [Google Scholar]
  3. Caffrey M., Feigenson G. W. Fluorescence quenching in model membranes. 3. Relationship between calcium adenosinetriphosphatase enzyme activity and the affinity of the protein for phosphatidylcholines with different acyl chain characteristics. Biochemistry. 1981 Mar 31;20(7):1949–1961. doi: 10.1021/bi00510a034. [DOI] [PubMed] [Google Scholar]
  4. Caffrey M., Feigenson G. W. Influence of metal ions on the phase properties of phosphatidic acid in combination with natural and synthetic phosphatidylcholines: an X-ray diffraction study using synchrotron radiation. Biochemistry. 1984 Jan 17;23(2):323–331. doi: 10.1021/bi00297a023. [DOI] [PubMed] [Google Scholar]
  5. 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]
  6. Caffrey M. Kinetics and mechanism of transitions involving the lamellar, cubic, inverted hexagonal, and fluid isotropic phases of hydrated monoacylglycerides monitored by time-resolved X-ray diffraction. Biochemistry. 1987 Oct 6;26(20):6349–6363. doi: 10.1021/bi00394a008. [DOI] [PubMed] [Google Scholar]
  7. 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]
  8. 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]
  9. Cho K. C., Choy C. L., Young K. Kinetics of the pretransition of synthetic phospholipids. A calorimetric study. Biochim Biophys Acta. 1981 Jan 26;663(1):14–21. doi: 10.1016/0005-2760(81)90190-9. [DOI] [PubMed] [Google Scholar]
  10. 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]
  11. Genz A., Holzwarth J. F., Tsong T. Y. The influence of cholesterol on the main phase transition of unilamellar dipalmytoylphosphatidylcholine vesicles. A differential scanning calorimetry and iodine laser T-jump study. Biophys J. 1986 Dec;50(6):1043–1051. doi: 10.1016/S0006-3495(86)83548-2. [DOI] [PMC free article] [PubMed] [Google Scholar]
  12. Inoue T., Ohshima H., Kamaya H., Ueda I. Stopped-flow rapid kinetics of anesthetic-induced phase transition in phospholipid vesicle membranes: nonlocalized fluctuation. Biochim Biophys Acta. 1985 Aug 27;818(2):117–122. doi: 10.1016/0005-2736(85)90554-1. [DOI] [PubMed] [Google Scholar]
  13. Janiak M. J., Small D. M., Shipley G. G. Nature of the Thermal pretransition of synthetic phospholipids: dimyristolyl- and dipalmitoyllecithin. Biochemistry. 1976 Oct 19;15(21):4575–4580. doi: 10.1021/bi00666a005. [DOI] [PubMed] [Google Scholar]
  14. Johnson M. L., Winter T. C., Biltonen R. L. The measurement of the kinetics of lipid phase transitions: a volume-perturbation kinetic calorimeter. Anal Biochem. 1983 Jan;128(1):1–6. doi: 10.1016/0003-2697(83)90335-4. [DOI] [PubMed] [Google Scholar]
  15. Lentz B. R., Freire E., Biltonen R. L. Fluorescence and calorimetric studies of phase transitions in phosphatidylcholine multilayers: kinetics of the pretransition. Biochemistry. 1978 Oct 17;17(21):4475–4480. doi: 10.1021/bi00614a018. [DOI] [PubMed] [Google Scholar]
  16. Mabrey S., Sturtevant J. M. Investigation of phase transitions of lipids and lipid mixtures by sensitivity differential scanning calorimetry. Proc Natl Acad Sci U S A. 1976 Nov;73(11):3862–3866. doi: 10.1073/pnas.73.11.3862. [DOI] [PMC free article] [PubMed] [Google Scholar]
  17. Subczynski W. K., Kusumi A. Effects of very small amounts of cholesterol on gel-phase phosphatidylcholine membranes. Biochim Biophys Acta. 1986 Jan 29;854(2):318–320. doi: 10.1016/0005-2736(86)90125-2. [DOI] [PubMed] [Google Scholar]
  18. Teissie J. Fluorescence temperature jump relaxations of dansylphosphatidylethanolamine in aqueous dispersions of dipalmitoylphosphatidylcholine during the gel to liquid-crystal transition. Biochim Biophys Acta. 1979 Aug 23;555(3):553–557. doi: 10.1016/0005-2736(79)90409-7. [DOI] [PubMed] [Google Scholar]
  19. 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]
  20. 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]
  21. Tsong T. Y. Kinetics of the crystalline-liquid crystalline phase transition of dimyristoyl L-alpha-lecithin bilayers. Proc Natl Acad Sci U S A. 1974 Jul;71(7):2684–2688. doi: 10.1073/pnas.71.7.2684. [DOI] [PMC free article] [PubMed] [Google Scholar]
  22. Wack DC, Webb WW. Synchrotron x-ray study of the modulated lamellar phase P beta ' in the lecithin-water system. Phys Rev A Gen Phys. 1989 Sep 1;40(5):2712–2730. doi: 10.1103/physreva.40.2712. [DOI] [PubMed] [Google Scholar]

Articles from Biophysical Journal are provided here courtesy of The Biophysical Society

RESOURCES