Relationships between equilibrium spreading pressure and phase equilibria of phospholipid bilayers and monolayers at the air-water interface

Heidi - Mansour, George Zografi

Research output: Contribution to journalArticle

36 Citations (Scopus)

Abstract

The intricate interplay between the bilayer and monolayer properties of phosphatidylcholine (PC), phosphatidylglycerol (PG), and phosphatidylethanolamine (PE) phospholipids, in relation to their polar headgroup properties, and the effects of chain permutations on those polar headgroup properties have been demonstrated for the first time with a set of time-independent bilayer-monolayer equilibria studies. Bilayer and monolayer phase behavior for PE is quite different than that observed for PC and PG. This difference is attributed to the characteristic biophysical PE polar headgroup property of favorable intermolecular hydrogen-bonding and electrostatic interactions in both the bilayer and monolayer states, This characteristic hydrogen-bonding ability of the PE polar headgroup is reflected in the condensed nature of PE monolayers and a decrease in equilibrium monolayer collapse pressure at temperatures below the monolayer critical temperature, Tc (whether above or below the monolayer triple point temperature, Tc. This interesting phenomena is compared to equilibrated PC and PG monolayers which collapse to form bilayers at 45 mN/m at temperatures both above and below monolayer Tc. Additionally, it has been demonstrated by measurements of the equilibrium spreading pressure, πe, that at temperatures above the bilayer main gel-to-liquid-crystalline phase-transition temperature, Tm, all liquid-crystalline phospholipid bilayers spread to form monolayers with πe, around 45 mN/m, and spread liquid-expanded equilibrated monolayers collapse at 45 mN/m to form their respective thermodynamically stable liquidcrystalline bilayers. At temperatures below bilayer Tm, PC and PG gel bilayers exhibit a drop in bilayer πe values ≤0.2 mN/m forming gaseous monolayers, whereas the value of ≤c of spread monolayers remains around 45 mN/m. This suggests that spread equilibrated PC and PG monolayers collapse to a metastable liquid-crystalline bilayer structure at temperatures below bilayer Tm (where the thermodynamically stable bilayer liquid-crystalline phase does not exist) and with a surface pressure of 45 mN/m, a surface chemical property characteristically observed at temperatures above bilayer Tm (monolayer Tc). In contrast, PE gel bilayers, which exist at temperatures below bilayer Tm but above bilayer Ts, (bilayer crystal-to-gel phase-transition temperature), exhibit gel bilayer spreading to form equilibrated monolayers with intermediate ≤e, values in the range of 30-40 mN/m; however, bilayer ne and monolayer ≤c values remain equal in value to one another. Contrastingly, at temperatures below bilayer Ts, PE crystalline bilayers exhibit bilayer ≤e, values ≤0.2 mN/m forming equilibrated gaseous monolayers, whereas spread monolayers collapse at a value of ≤c remaining around 30 mN/m, indicative of metastable gel bilayer formation.

Original languageEnglish (US)
Pages (from-to)3809-3819
Number of pages11
JournalLangmuir
Volume23
Issue number7
DOIs
StatePublished - Mar 27 2007
Externally publishedYes

Fingerprint

Phospholipids
Phase equilibria
Monolayers
Water
air
Air
gels
water
Phosphatidylglycerols
temperature
liquids
Phosphatidylcholines
Gels
Crystalline materials
transition temperature
Temperature
Liquids
permutations
hydrogen
chemical properties

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Colloid and Surface Chemistry

Cite this

Relationships between equilibrium spreading pressure and phase equilibria of phospholipid bilayers and monolayers at the air-water interface. / Mansour, Heidi -; Zografi, George.

In: Langmuir, Vol. 23, No. 7, 27.03.2007, p. 3809-3819.

Research output: Contribution to journalArticle

@article{dd52cc457a0f4d3c977420bc7974bd44,
title = "Relationships between equilibrium spreading pressure and phase equilibria of phospholipid bilayers and monolayers at the air-water interface",
abstract = "The intricate interplay between the bilayer and monolayer properties of phosphatidylcholine (PC), phosphatidylglycerol (PG), and phosphatidylethanolamine (PE) phospholipids, in relation to their polar headgroup properties, and the effects of chain permutations on those polar headgroup properties have been demonstrated for the first time with a set of time-independent bilayer-monolayer equilibria studies. Bilayer and monolayer phase behavior for PE is quite different than that observed for PC and PG. This difference is attributed to the characteristic biophysical PE polar headgroup property of favorable intermolecular hydrogen-bonding and electrostatic interactions in both the bilayer and monolayer states, This characteristic hydrogen-bonding ability of the PE polar headgroup is reflected in the condensed nature of PE monolayers and a decrease in equilibrium monolayer collapse pressure at temperatures below the monolayer critical temperature, Tc (whether above or below the monolayer triple point temperature, Tc. This interesting phenomena is compared to equilibrated PC and PG monolayers which collapse to form bilayers at 45 mN/m at temperatures both above and below monolayer Tc. Additionally, it has been demonstrated by measurements of the equilibrium spreading pressure, πe, that at temperatures above the bilayer main gel-to-liquid-crystalline phase-transition temperature, Tm, all liquid-crystalline phospholipid bilayers spread to form monolayers with πe, around 45 mN/m, and spread liquid-expanded equilibrated monolayers collapse at 45 mN/m to form their respective thermodynamically stable liquidcrystalline bilayers. At temperatures below bilayer Tm, PC and PG gel bilayers exhibit a drop in bilayer πe values ≤0.2 mN/m forming gaseous monolayers, whereas the value of ≤c of spread monolayers remains around 45 mN/m. This suggests that spread equilibrated PC and PG monolayers collapse to a metastable liquid-crystalline bilayer structure at temperatures below bilayer Tm (where the thermodynamically stable bilayer liquid-crystalline phase does not exist) and with a surface pressure of 45 mN/m, a surface chemical property characteristically observed at temperatures above bilayer Tm (monolayer Tc). In contrast, PE gel bilayers, which exist at temperatures below bilayer Tm but above bilayer Ts, (bilayer crystal-to-gel phase-transition temperature), exhibit gel bilayer spreading to form equilibrated monolayers with intermediate ≤e, values in the range of 30-40 mN/m; however, bilayer ne and monolayer ≤c values remain equal in value to one another. Contrastingly, at temperatures below bilayer Ts, PE crystalline bilayers exhibit bilayer ≤e, values ≤0.2 mN/m forming equilibrated gaseous monolayers, whereas spread monolayers collapse at a value of ≤c remaining around 30 mN/m, indicative of metastable gel bilayer formation.",
author = "Mansour, {Heidi -} and George Zografi",
year = "2007",
month = "3",
day = "27",
doi = "10.1021/la063053o",
language = "English (US)",
volume = "23",
pages = "3809--3819",
journal = "Langmuir",
issn = "0743-7463",
publisher = "American Chemical Society",
number = "7",

}

TY - JOUR

T1 - Relationships between equilibrium spreading pressure and phase equilibria of phospholipid bilayers and monolayers at the air-water interface

AU - Mansour, Heidi -

AU - Zografi, George

PY - 2007/3/27

Y1 - 2007/3/27

N2 - The intricate interplay between the bilayer and monolayer properties of phosphatidylcholine (PC), phosphatidylglycerol (PG), and phosphatidylethanolamine (PE) phospholipids, in relation to their polar headgroup properties, and the effects of chain permutations on those polar headgroup properties have been demonstrated for the first time with a set of time-independent bilayer-monolayer equilibria studies. Bilayer and monolayer phase behavior for PE is quite different than that observed for PC and PG. This difference is attributed to the characteristic biophysical PE polar headgroup property of favorable intermolecular hydrogen-bonding and electrostatic interactions in both the bilayer and monolayer states, This characteristic hydrogen-bonding ability of the PE polar headgroup is reflected in the condensed nature of PE monolayers and a decrease in equilibrium monolayer collapse pressure at temperatures below the monolayer critical temperature, Tc (whether above or below the monolayer triple point temperature, Tc. This interesting phenomena is compared to equilibrated PC and PG monolayers which collapse to form bilayers at 45 mN/m at temperatures both above and below monolayer Tc. Additionally, it has been demonstrated by measurements of the equilibrium spreading pressure, πe, that at temperatures above the bilayer main gel-to-liquid-crystalline phase-transition temperature, Tm, all liquid-crystalline phospholipid bilayers spread to form monolayers with πe, around 45 mN/m, and spread liquid-expanded equilibrated monolayers collapse at 45 mN/m to form their respective thermodynamically stable liquidcrystalline bilayers. At temperatures below bilayer Tm, PC and PG gel bilayers exhibit a drop in bilayer πe values ≤0.2 mN/m forming gaseous monolayers, whereas the value of ≤c of spread monolayers remains around 45 mN/m. This suggests that spread equilibrated PC and PG monolayers collapse to a metastable liquid-crystalline bilayer structure at temperatures below bilayer Tm (where the thermodynamically stable bilayer liquid-crystalline phase does not exist) and with a surface pressure of 45 mN/m, a surface chemical property characteristically observed at temperatures above bilayer Tm (monolayer Tc). In contrast, PE gel bilayers, which exist at temperatures below bilayer Tm but above bilayer Ts, (bilayer crystal-to-gel phase-transition temperature), exhibit gel bilayer spreading to form equilibrated monolayers with intermediate ≤e, values in the range of 30-40 mN/m; however, bilayer ne and monolayer ≤c values remain equal in value to one another. Contrastingly, at temperatures below bilayer Ts, PE crystalline bilayers exhibit bilayer ≤e, values ≤0.2 mN/m forming equilibrated gaseous monolayers, whereas spread monolayers collapse at a value of ≤c remaining around 30 mN/m, indicative of metastable gel bilayer formation.

AB - The intricate interplay between the bilayer and monolayer properties of phosphatidylcholine (PC), phosphatidylglycerol (PG), and phosphatidylethanolamine (PE) phospholipids, in relation to their polar headgroup properties, and the effects of chain permutations on those polar headgroup properties have been demonstrated for the first time with a set of time-independent bilayer-monolayer equilibria studies. Bilayer and monolayer phase behavior for PE is quite different than that observed for PC and PG. This difference is attributed to the characteristic biophysical PE polar headgroup property of favorable intermolecular hydrogen-bonding and electrostatic interactions in both the bilayer and monolayer states, This characteristic hydrogen-bonding ability of the PE polar headgroup is reflected in the condensed nature of PE monolayers and a decrease in equilibrium monolayer collapse pressure at temperatures below the monolayer critical temperature, Tc (whether above or below the monolayer triple point temperature, Tc. This interesting phenomena is compared to equilibrated PC and PG monolayers which collapse to form bilayers at 45 mN/m at temperatures both above and below monolayer Tc. Additionally, it has been demonstrated by measurements of the equilibrium spreading pressure, πe, that at temperatures above the bilayer main gel-to-liquid-crystalline phase-transition temperature, Tm, all liquid-crystalline phospholipid bilayers spread to form monolayers with πe, around 45 mN/m, and spread liquid-expanded equilibrated monolayers collapse at 45 mN/m to form their respective thermodynamically stable liquidcrystalline bilayers. At temperatures below bilayer Tm, PC and PG gel bilayers exhibit a drop in bilayer πe values ≤0.2 mN/m forming gaseous monolayers, whereas the value of ≤c of spread monolayers remains around 45 mN/m. This suggests that spread equilibrated PC and PG monolayers collapse to a metastable liquid-crystalline bilayer structure at temperatures below bilayer Tm (where the thermodynamically stable bilayer liquid-crystalline phase does not exist) and with a surface pressure of 45 mN/m, a surface chemical property characteristically observed at temperatures above bilayer Tm (monolayer Tc). In contrast, PE gel bilayers, which exist at temperatures below bilayer Tm but above bilayer Ts, (bilayer crystal-to-gel phase-transition temperature), exhibit gel bilayer spreading to form equilibrated monolayers with intermediate ≤e, values in the range of 30-40 mN/m; however, bilayer ne and monolayer ≤c values remain equal in value to one another. Contrastingly, at temperatures below bilayer Ts, PE crystalline bilayers exhibit bilayer ≤e, values ≤0.2 mN/m forming equilibrated gaseous monolayers, whereas spread monolayers collapse at a value of ≤c remaining around 30 mN/m, indicative of metastable gel bilayer formation.

UR - http://www.scopus.com/inward/record.url?scp=34147214040&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=34147214040&partnerID=8YFLogxK

U2 - 10.1021/la063053o

DO - 10.1021/la063053o

M3 - Article

VL - 23

SP - 3809

EP - 3819

JO - Langmuir

JF - Langmuir

SN - 0743-7463

IS - 7

ER -