Compressibility lipid

It is readily apparent that the ( + )-C-15 6,6, C-15 9,9 and C-15 12,12 compounds show a collapse to some three-dimensional state, as has been observed for most over-compressed lipid films (Handa and Nagaki, 1979 Stewart and Arnett, 1982). However, the ensuing plateau region is... 

Lai et al. (1986) studied the compressibility as a measure of flowability of egg lipid and co-dried carbohydrate and salt, as a function of temperature, moisture, and lipid content. Temperature increased compressibility, resulting from the ability of the cohesive powder bed to maintain an open structure supported by the interparticle forces. These softened, plasticized, and extremely weak structures collapsed under very small pressures giving rise to the measured compressibility. Lipid removal neither improved flowability nor yielded reliable results in compressibility. 

Overall membrane compression Lipid-domain interface fluctuations Free volume fluctuations Local depressions and distortions Transient hydrophobic pores Transient hydrophilic pores Foot-in-the-door hydrophilic pores Composite hydrophilic pores Membrane enzyme changes Membrane macromolecule protrusion changes Rupture and REB not actually described (5) Suggested alternative to transient pores (6) Transport of nonpolar species (7) Possible precursors to hydrophilic pores (8, 9) Possible precursor to hydrophilic pores (10) Key to quantitative descriptions (10-16) Candidate metastable pores" Candidate metastable pores Coupling to membrane macromolecules (17) Candidate signaling change mechanism... 

If compression is requited to provide a stick or pan-type of product, the bulk components must be held together with a binder. Common binders ate various Hpids, polymers, polysaccharides, and waxes. Some binder compositions include water, which is removed by drying the compact. The amount of binder must be carefully controlled to yield a soHd, nonfragile compact that is soft enough to pay off. Excessive amounts of or improperly compounded binders glaze during use because of transfer of skin lipids to the compact. 

FIG. 16 Fomation of a Langmuir lipid monolayer at the air/subphase interface and the subsequent crystallization of S-layer protein, (a) Amphiphilic lipid molecules are placed on the air/subphase interface between two barriers. Upon compression between the barriers, increase in surface pressure can be determined by a Wilhelmy plate system, (b) Depending on the final area, a liquid-expanded or liquid-condensed lipid monolayer is formed, (c) S-layer subunits injected in the subphase crystallized into a coherent S-layer lattice beneath the spread lipid monolayer and the adjacent air/subphase interface. 

FIG. 17 Schematic illustration of the setup for a tip-dip experiment. First glycerol dialkyl nonitol tetraether lipid (GDNT) monolayers are compressed to the desired surface pressure (measured by a Wilhehny plate system). Subsequently a small patch of the monolayer is clamped by a glass micropipette and the S-layer protein is recrystallized. The lower picture shows the S-layer/GDNT membrane on the tip of the glass micropipette in more detail. The basic circuit for measurement of the electric features of the membrane and the current mediated by a hypothetical ion carrier is shown in the upper part of the schematic drawing. 

Another observation should be made with respect to the term elastic in describing interfacial capacitors. It was originally introduced by Crowley [1] for membranes and reflects the compressibility of lipid layers which behave in some respects like an elastic film. Its relation to electrochemical interfaces is less obvious. Consider an interface between a metal electrode and an electrolyte. As we will see in Section III, the effective gap of the interfacial capacitor is the distance between the centers of mass of the electronic, e, and ionic, i, charge density distributions... 

Measurements of pressure-area (jc-A) isotherms and transfers of monolayers on a substrate were carried out by using a computer-controlled film balance system (San-Esu Keisoku, Co., Fukuoka, FSD-20). Maximum surface area on the trough was 475 X 150 mm2. The trough surface and the moving barrier were coated with Teflon, and the subphase was temperature-controlled with a thermostat (20 0.5 °C). The concentration of lipid solutions was 1 mg/ml and the spreading amount of lipid solutions was 50 - 150 pi. After solvent evaporation, the monolayer was compressed at the speed of 0.60 cm2 s-i. Measurements of n-A isotherms and transfers of monolayer on a QCM substrate were performed automatically with the usual manner [26,27]. 

In the experiments on the Jt-A characteristics, it has been usually assumed that thermal equilibrium will be attained easily if the experiment is performed using a slow rate of compression of thin film at the interface. Measurements under thermal equilibrium are, of course, the necessary condition to obtain the physico-chemical properties of the individual "phase" of the lipid ensemble. 

Next, we discuss the mechanism of the characteristic features observed in the Jt-A curve. When the PhDA2-8 thin film is compressed with relatively high speed, there will be a non-negligible effect of the special inhomogeneity over the lipid film, i.e., the surface pressure in the region near the blade becomes larger than that in the other region. 

In the above subsection it was demonstrated that the inclusion of electrostatic interactions into the pressure-area-temperature equation of state provides a better fit to the observed equilibrium behavior than the model with two-dimensional neutral gas. Considering this fact, we would like to devote our attention now to the character of the lipid film under the dynamical, nonequilibrium conditions. In the following we shall describe the dynamical behavior of the phospholipid(l,2-dipalmitoyl-3-sn-phosphatidylethanolamines DPPE) thin films in the course of the compression and expansion cycles at air/water interface. 

Figure 20. (a) The (dimensionless) lateral compressibility (dilatational modulus, elastic area expansion modulus) (left ordinate) and the dimensionless area per molecule (right ordinate) as a function of the tail length (t) of the PC lipids in equilibrium bilayer membranes. The conversion to real compressibilities and areas per molecule is discussed in the text, (b) The (dimensionless) surface tension and the (dimensionless) lateral compressibility as a function of the relative expansion for the C PC lipid... 

The lateral compressibility, i.e. the relative area change upon an imposed membrane tension, decreases slightly more than linearly with the chain length. This means that it is more difficult to expand the membrane surface area of a long-chained lipid than a shorter one. In Figure 20 dimensionless units are used, which means that the surface tension is given in units kT/as. 

Again, using a lateral dimension of a site, d = 0.2 nm, and the lattice site area as = 3d2, means that y 1 corresponds with about 33mNm 1 lateral tension. In other words, one needs to apply a lateral tension of order 40mNm 1 to double the membrane area. This prediction seems to be a factor of about six lower than estimates that were recently reported by Evans and co-workers [107], These authors use micropipettes to pressurise giant vesicles and obtain values of the order Ka = 8y/Sinn = 230mNm. There are also some data on the compressibility modulus, as found by MD simulations on primitive surfactants [62] Ka = 400 mN m 1. In a molecular detailed simulation study on DPPC lipids, Feller and Pastor [40] report a KA value of about 140 mNm 1. 

Feller, S. E. and Pastor, R. W. (1999). Constant surface tension simulations of lipid bilayers the sensitivity of surface areas and compressibilities, J. Chem. Phys., Ill, 1281-1287. 

It is found that, even a monolayer of lipid (on water), when compressed can undergo various states. In the following text, the various states of monomolecular films will be described as measured from the surface pressure, n, versus area, A, isotherms, in the case of simple amphiphile molecules. On the other hand, the Il-A isotherms of biopolymers will be described separately since these have a different nature. 

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