Patterns of non-electrolyte permeability

Reflexion coefficients (σ’s) for epithelial cells of rabbit gall-bladder for 206 non-electrolytes have been measured and analysed. In general, σ’s decrease from 1.0 to 0 with increasing lipid:water partition coefficients, so that the intermolecular forces governing permeation of most non-electrolytes are the same as those governing partition between a bulk lipid phase and water. The two classes of deviations to this pattern are related to the specific structure of cell membranes. First, highly branched molecules have higher σ's (permeate more slowly) than expected from partition coefficients, an effect attributed to anisotropy of membrane lipids. Secondly, the smallest, most lipid-insoluble molecules have lower σ’s (permeate more readily) than expected, and are also anomalous in that: effects of changes in their structure on σ disobey Overton’s rules; the inverse relation between σ and temperature is less steep for them than for other solutes; and their σ’s are little affected by decreases in pH which increase σ’s of other solutes. These anomalies are interpreted to mean that small polar solutes in transit through the membrane interact minimally or not at all with hydrocarbon tails of membrane lipids, but instead follow a route formed by localized concentrations of membrane polar groups associated with ‘frozen’ water molecules, where the coupling phenomena between permeating water, ions, and small polar-electrolytes observed in cell membranes may also occur.

1969 ◽  
Vol 172 (1028) ◽  
pp. 227-271 ◽  

Reflexion coefficients (σ’s) for epithelial cells of rabbit gall-bladder for 206 non-electrolytes have been measured and analysed. In general, σ’s decrease from 1.0 to 0 with increasing lipid :water partition coefficients, so that the intermolecular forces governing permeation of most non-electrolytes are the same as those governing partition between a bulk lipid phase and water. The two classes of deviations to this pattern are related to the specific structure of cell membranes. First, highly branched molecules have higher σ’s (permeate more slowly) than expected from partition coefficients, an effect attributed to an isotropy of membrane lipids. Secondly, the smallest, most lipid-insoluble molecules have lower σ’s (permeate more readily) than expected, and are also anomalous in that: effects of changes in their structure on or disobey Overton’s rules; the inverse relation between or and temperature is less steep for them than for other so lutes; and their σ’s are little affected by decreases in pH which increase σ’s of other solutes. These anomalies are interpreted to mean that small polar solutes in transit through the membrane interact minimally or not at all with hydrocarbon tails of membrane lipids, but in stead follow a route formed by localized concentrations of membrane polar groups associated with ‘frozen’ water molecules, where the coupling phenomena between permeating water, ions, and small polar-electrolytes observed in cell membranes may also occur.


Membranes ◽  
2021 ◽  
Vol 11 (1) ◽  
pp. 53
Author(s):  
Anna Chachaj-Brekiesz ◽  
Jan Kobierski ◽  
Anita Wnętrzak ◽  
Patrycja Dynarowicz-Latka

Experimental surface pressure (π) and electric surface potential (ΔV) isotherms were measured for membrane lipids, including the following phosphatidylcholines (PCs)—1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC); 1,2-distearoyl-sn-glycero-3-phosphocholine (DSPC); 1,2-diarachidoyl-sn-glycero-3-phosphocholine (DAPC); and 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC). In addition, other phospholipids, such as phosphatidylethanolamines (represented by 1,2-dipalmitoyl-sn-glycero-3-phosphoethanolamine (DPPE)) and sphingolipids (represented by N-(hexadecanoyl)-sphing-4-enine-1-phosphocholine (SM)) were also studied. The experimental apparent dipole moments (μAexp) of the abovementioned lipids were determined using the Helmholtz equation. The particular contributions to the apparent dipole moments of the investigated molecules connected with their polar (μ⊥p) and apolar parts (μ⊥a) were theoretically calculated for geometrically optimized systems. Using a three-layer capacitor model, introducing the group’s apparent dipole moments (calculated herein) and adopting values from other papers to account for the reorientation of water molecules (μ⊥w/εw), as well as the for the local dielectric permittivity in the vicinity of the polar (εp) and apolar (εa) groups, the apparent dipole moments of the investigated molecules were calculated (μAcalc). Since the comparison of the two values (experimental and calculated) resulted in large discrepancies, we developed a new methodology that correlates the results from density functional theory (DFT) molecular modeling with experimentally determined values using multiple linear regression. From the fitted model, the following contributions to the apparent dipole moments were determined: μ⊥w/εw=−1.8±1.4 D; εp=10.2±7.0 and εa=0.95±0.52). Local dielectric permittivity in the vicinity of apolar groups (εa) is much lower compared to that in the vicinity of polar moieties (εp), which is in line with the tendency observed by other authors studying simple molecules with small polar groups. A much higher value for the contributions from the reorientation of water molecules (μ⊥w/εw) has been interpreted as resulting from bulky and strongly hydrated polar groups of phospholipids.


2019 ◽  
Vol 12 ◽  
pp. 117863531882092 ◽  
Author(s):  
Andrea C Cutro ◽  
E Anibal Disalvo ◽  
María A Frías

Background: Phenylalanine (Phe) is involved in physiological and pathological processes in cell membranes in which expanded and condensed states coexist. In this direction, it was reported that surface hydration is important for the binding affinity of the amino acid which significantly perturbs 1,2-dipalmitoyl- sn-glycero-3-phosphocholine (DPPC) monolayer structure and morphology. A deeper insight showed that Phe inserts in DPPC monolayer defects as a monomer at pH 5 and forms aggregates that adsorb to the membrane surface generating a reconfiguration of the lipid arrangement in areas of higher packing. This new arrangement in the monolayer causes the reorientation of dipoles of lipid and water molecules which is congruent with the dehydration and surface tension changes reported above. With this background, this article studies the affinity of Phe in liquid-expanded 1,2-dimyristoyl- sn-glycero-3 phosphocholine (LE DMPC) and liquid-condensed 1,2-dipalmitoyl- sn-glycero-3-phosphocholine (LC DPPC) monolayers and their effects on membrane properties. Results: The adsorption of Phe can be described by a cooperative process in non-independent sites suggesting that Phe/lipid systems reorganize to form new structures at a high degree of coverage. Compressibility modulus and Brewster angle microscopy (BAM) images allow to propose that Phe causes a new phase in 1,2-dimyristoyl- sn-glycero-3 phosphocholine (DMPC) and DPPC. Conclusions: Phe imposes new arrangements in the lipid phase to form new structures with different compressibility behavior than lipid binary mixtures of DMPC and DPPC. Phe interaction with the LC and LE phases gives place to a process in which a synergistic effect between non-independent sites can be produced. These features of Phe/lipid interaction would be of great importance to understand the multiple effects of Phe on cell membranes.


Nanomaterials ◽  
2019 ◽  
Vol 9 (1) ◽  
pp. 64 ◽  
Author(s):  
Qin Wang ◽  
Hui Xie ◽  
Zhiming Hu ◽  
Chao Liu

In this study, molecular dynamics simulations were carried out to study the coupling effect of electric field strength and surface wettability on the condensation process of water vapor. Our results show that an electric field can rotate water molecules upward and restrict condensation. Formed clusters are stretched to become columns above the threshold strength of the field, causing the condensation rate to drop quickly. The enhancement of surface attraction force boosts the rearrangement of water molecules adjacent to the surface and exaggerates the threshold value for shape transformation. In addition, the contact area between clusters and the surface increases with increasing amounts of surface attraction force, which raises the condensation efficiency. Thus, the condensation rate of water vapor on a surface under an electric field is determined by competition between intermolecular forces from the electric field and the surface.


2021 ◽  
Author(s):  
Isaac D. Falk ◽  
Bálint Gál ◽  
Ahanjit Bhattacharya ◽  
Jeremy H. Wei ◽  
Paula V. Welander ◽  
...  

Archaeal glycerol dibiphytanyl glycerol tetraethers (GDGT) are some of the most unusual membrane lipids identified in nature. These amphiphiles are the major constituents of the membranes of numerous <i>Archaea</i>, some of which are extremophilic organisms. Due to their unique structures, there has been significant interest in studying both the biophysical properties and the biosynthesis of these molecules. However, these studies have thus far been hampered by limited access to chemically pure samples. Herein, we report a concise and stereoselective synthesis of the archaeal tetraether lipid GDGT-0 and the synthesis and self-assembly of derivatives bearing different polar groups.


1973 ◽  
Vol 51 (6) ◽  
pp. 1213-1219 ◽  
Author(s):  
Elizabeth S. Swanson ◽  
William W. Thomson ◽  
J. Brian Mudd

The objective of this study was to determine the effects of ozone on membrane lipids and on the electron-density patterns of cell membranes in electron micrographs. Analysis of fatty acids from tobacco leaves fumigated with ozone indicated that there was no significant difference between the ozone-treated and the control plants in the relative amounts of the fatty acids. This suggests that if the primary site of ozone action is unsaturated lipids in membranes then the amounts of affected unsaturated fatty acids are too small to be detected by gas chromatography. In support of this, characteristic electron-microscopic images of membranes are observed in cells of fumigated leaves. However, measurements of the length and width of the chloroplasts and the determination of axial ratios indicated that the ozone treatment resulted in a shrinkage of the chloroplasts. In contrast, mitochondrial changes are apparently explained in terms of ozone-induced swelling.


1980 ◽  
Vol 58 (10) ◽  
pp. 755-770 ◽  
Author(s):  
Joan M. Boggs

Biological membranes have unique lipid compositions suggesting a specific role for many lipids. Evidence is reviewed concerning the intermolecular forces between glycero- and sphingolipids and cholesterol, the dependence of many of these interactions on the state of ionization of lipids, pH, ionic strength, and divalent cation concentration. The effect of intermolecular interactions between certain lipids on lipid clustering, interaction with cholesterol, on the conformation of proteins, and on transitions to the hexagonal phase is considered. Other forces which cause lipid phase separation or clustering are discussed. It is concluded that lipids are in dynamic equilibrium with their environment and can act as receptors for certain intra- or extracellular stimuli, which they can translate into a response by undergoing changes in fluidity, phase transitions, or phase separation.


1968 ◽  
Vol 52 (1) ◽  
pp. 191-208 ◽  
Author(s):  
Martin Blank

Transport across physical-chemical interfaces is considered in connection with three particular problems of biological interfaces: the structure and properties of cell membranes, the properties of the lung surfactant, and the effects of ionic currents across excitable membranes. With regard to cell membranes, studies of monolayer permeation suggest that permselectivity on the basis of size is a property of bilayer structure and probably gives rise to the observed dependence of the permeability on partition coefficients. The permeabilities of lipid and protein monolayers are consistent with the bimolecular leaflet (BML) model of the membrane and not with mosaic models. Experiments with the lung surfactant indicate that, in addition to its surface tension-lowering properties, it is unusual in its ability to form a strong two-dimensional network, which probably contributes to alveolar stability. Finally, the results of studies of interfacial ionic transference suggest a new way of accounting for the ionic fluxes in excitable membranes during an action potential without assuming ion-selective pores or carriers. In the suggested mechanism, it is possible to account for the change in ionic selectivity and the proper phasing of the fluxes, as well as other aspects of excitation in natural membranes.


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