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Lipids at the air–water interface

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Abstract

Lipids are important natural chemical compounds, as they comprise the major component in biological membranes. Biological membranes are composed of lipids in a bilayer structure and proteins incorporated into the bilayers or bound to the bilayer surface. Due to the amphiphilic nature of lipids, they self-assemble in aqueous solution into a variety of lyotropic phases, the most important one being the lamellar phase made up of stacks of lipid bilayers separated by water layers. The bilayer structure can be easily produced by dispersing lipids in water. Lipids are amphiphilic structures built up of a polar headgroup and one or two hydrophobic alkyl chains. They are, therefore, surface active and form the so-called insoluble monolayers or Langmuir films at the air–water interface. These monolayers resemble half of a lipid bilayer and are, therefore, widely used as model systems for bilayer membranes. In this review, the properties and the phase behavior of phospholipid monolayers, as well as the techniques used for studying these monolayers will be described. In addition, examples for the information gained using different techniques will be shown.

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Notes

  1. Irving Langmuir was born in 1881 in New York and died in 1957 in Woods Hole, USA. In 1932 he was awarded with the Nobel-Prize in Chemistry for his “discoveries and investigations in surface chemistry”. He worked together with Katherine Blodgett on surface adsorption phenomena and on thin films. They developed the concept of a “monolayer”, i.e. a single layer of molecules on a surface. In honor of Langmuir, monolayers of sparingly soluble molecules at the air–water interface were named after him.

  2. Ludwig Ferdinand Wilhelmy was born in 1812 in Stargard, Germany and died in 1864 in Berlin, Germany. From 1849 till 1854 he was academic lecturer at the University of Heidelberg, Germany. In 1863, he published his article on the use of the “Wilhelmy plate” for measuring the surface tension of liquids in the famous journal “Annalen der Physik”.

  3. The surface tension γ is a property of a fluid interface to acquire the least surface area possible. This property arises from the fact that the attractive forces between the molecules in the liquid are higher (cohesion) than the force between molecules in the gas phase and the liquid surface (adsorption). This leads to a net force being directed inward into the liquid and the appearance of the surface as if it were covered by an elastic membrane under tension. Therefore, the term “surface tension” was coined. The surface tension has the dimension of a force per unit length (N m−1), which is equivalent to an energy per unit area (J m−2). Therefore, in many cases the term surface energy is also used. Attractive forces between water molecules in liquid water are very high, because of the occurrence of hydrogen bonds between molecules. Therefore, the surface tension of pure water is also very high with 72 mN m−1, much higher than for other ordinary organic liquids. If the surface is covered by amphiphilic substances, the surface tension decreases, because the attractive forces between these molecules are much lower.

  4. Phase transitions in three dimensions are classified according to Paul Ehrenfest [45, 46]. The classification is based on the properties of the derivatives of the thermodynamic free energy, for instance, the Gibbs free energy with respect to other thermodynamic variables. If the first derivative is discontinuous, then the phase transition is of first order. If the first derivative is continuous and the second derivative discontinuous, then the transition is of second order, etc. Solid–liquid, liquid–gas, and solid–gas transitions of bulk materials are of first order. The terminology was taken over to the classification of two-dimensional transition, i.e., Langmuir monolayers at the air–water interface.

  5. Many fluorescence microscopes used in biophysical studies are of the epifluorescence design (see Fig. 8). The light coming from the excitation light source first passes through an optic filter, where the appropriate wave length for excitation of the fluorescent molecule is selected. The excitation light then passes through a dichroic mirror where it is reflected and focused onto the sample by the objective lens. Light with the wave length of the excitation light reflected from the sample is reflected by the dichroic mirror into the light source. The fluorescence light with a longer wave length emitted from the sample passes through the same objective lens and then is not reflected by the dichroic mirror but passes through the dichroic mirror and through the emission filter which prevents residual excitation light reaching the detector. The emitted light is then focused onto the detector, in this case a high sensitivity CCD camera.

  6. In a GIXD experiment, the incident beam is a monochromatic X-ray beam with a defined wavelength. The beam is adjusted so that it strikes the water surface at an angle just below the critical angle αc for total external reflection at the chosen wavelength. This critical angle αc for total reflection is ~ 0.13° for a wavelength of 0.138 nm (= 9000 eV photon energy). When the beam is totally reflected a so-called evanescent wave travels along the surface of the air–water interface. The penetration depth of this wave is ca. 8 nm, i.e. somewhat larger than the thickness of a typical lipid monolayer. If the monolayer covering the surface has an ordered structure with crystallites, Bragg scattering can occur. The crystallites should be oriented such that lattice planes have an angle Θhk relative to the evanescent beam so that the condition λ = 2dhk sin Θhk for Bragg scattering is fulfilled.

  7. In infrared spectroscopy (IR) the sample is irradiated with radiation covering the infrared region of the electromagnetic spectrum. The so-called mid-IR is the wavelength region between 2.5 and 25 µm, which is equivalent to the wavenumber region between 4000 and 400 cm−1. This type of radiation excites vibrational modes of the molecules under investigation. Organic molecules have a number of vibrational modes which are characteristic for certain “group vibrations”, for instance, the C=O group or the CH2-groups in aliphatic chains of lipids. The IR spectrum shows typical absorption bands which can be analyzed with respect to their frequency (wavenumber) and intensity.

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Acknowledgements

This work was supported by Grants from the Deutsche Forschungsgemeinschaſt (DFG), the state of Saxonia-Anhalt, the Phospholipid Research Center, Heidelberg, Germany, and Boehringer Ingelheim GmbH and Co, Ingelheim, Germany. I want to express my gratitude to all members of my group for their contributions to the research results presented here in this review.

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  1. Institute of Chemistry–Physical Chemistry, Martin-Luther-University Halle-Wittenberg, von-Danckelmann-Platz 4, 06120, Halle(Saale), Germany

    Alfred Blume

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Blume, A. Lipids at the air–water interface. ChemTexts 4, 3 (2018). https://doi.org/10.1007/s40828-018-0058-z

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