Fluidity Parameters of Lipid Regions Determined by Fluorescence Polarization

Trehalose is a nonreducing disaccharide of glucose commonly found at high concentrations in anhydrobiotic organisms. In the presence of trehalose, dry dipalmitoyl phosphatidylcholine (DPPC) had a transition temperature similar to that of the fully hydrated lipid, whereas DPPC dried without trehalose had a transition temperature about 30 degrees Kelvin higher. Results obtained with infrared spectroscopy indicate that trehalose and DPPC interact by hydrogen bonding between the OH groups in the carbohydrate and the polar head groups of DPPC. These and previous results show that this hydrogen bonding alters the spacing of the polar head groups and may thereby decrease van der Waals interactions in the hydrocarbon chains of the DPPC. This interaction between trehalose and DPPC is specific to trehalose. Hence this specificity may be an important factor in the ability of this molecule to stabilize dry membranes in anhydrobiotic organisms.

https://science.sciencemag.org/content/sci/223/4637/701.full.pdf

Preservation of Membranes in Anhydrobiotic Organisms: The Role of Trehalose

http://www.bio21.bas.bg/ibf/PC_review.pdf

Phases and phase transitions of the phosphatidylcholines

Stabilization of dry phospholipid bilayers and proteins by sugars.

Liposomes can be designed to release an entrapped drug preferentially at temperatures attainable by mild local hyperthermia. In a test system in vitro, protein synthesis by Escherichia coli is inhibited and killing of the cells is enhanced by heating neomycin-containing liposomes to their phase transition temperature to maximize drug release. In the presence of serum the ratio of release at 44 degrees C to that at 37 degrees C can be made greater than 100:1, suggesting possible applications in the treatment of tumors or local infection.

http://science.sciencemag.org/content/sci/202/4374/1290.full.pdf

Design of liposomes for enhanced local release of drugs by hyperthermia

The results of a calorimetric and fluorescent probe study of the thermotropic behavior of various types of dispersions of dipalmitolphosphatidylcholine bilayer vesicles are reported. Bangham-type, multilamellar vesicles exhibit tow distinct phase transitions at 34.6 and 41.2 degrees C. On the other hand, single-lamellar spherical vesicles appear to exhibit a single transition at 37 degrees C. The single-lamellar vesicles are thermodynamically unstable below 27 degrees C and slowly transform into a multilamellar structure with a single phase transition of 41.2 degrees C. These transformed structures resemble, but are not identical with, Bangham-type vesicles. An experimentally testable thermodynamic and kinetic model based upon these results is developed.

A calorimetric and fluorescent probe study of the gel-liquid crystalline phase transition in small, single-lamellar dipalmitoylphosphatidylcholine vesicles.

A recently developed differential scanning calorimeter has been used to characterize the thermotropic behavior of aqueous dispersions of liposomes containing sphingomyelin. Liposomes derived from sheep brain sphingomyelin exhibit a broad gel-liquid crystalline phase transition in the temperature range of 20-45 degrees C. The transition is characterized by maxima in the heat capacity function at 31.2 and 37.1 degrees C and a total enthalpy change of 7.2 +/-0.4 kcal/mol. Beef brain sphingomyelin liposomes behave similarly but exhibit heat capacity maxima at 30, 32, and 38 degrees C and a total enthalpy change of 6.9 kcal/mol. The thermotropic behavior of four pure synthetic sphingomyelins is reminiscent of multilamellar lecithin liposomes in that a single, sharp, main transition is observed. Results obtained for liposomes containing mixtures of different sphingomyelins are complex. A colyophilized mixture of N-palmitoylsphingosinephosphorylcholine, N-stearoylsphingosinephosphorylcholine, and N-lignocerylsphingosinephosphorylcholine in a 1 : 1 : 1 mol ratio exhibits a single transition with a Tm below that observed for the individual components. On the other hand a 1 : 1 mixture of N-stearoylsphingosinephosphorylcholine and 1-palmitoyl-2-oleylphosphatidylcholine exhibits three maxima in the heat capacity function. It is clear from these results that the thermotropic behavior of sphingomyelin-containing liposomes is a complex function of the exact composition. Furthermore, it appears that the behavior of the liposomes derived from natural sphingomyelins cannot be explained in terms of phase separation of the individual components.

J. Suurkuusk

Papers

A calorimetric and fluorescent probe study of the gel-liquid crystalline phase transition in small, single-lamellar dipalmitoylphosphatidylcholine vesicles.

A calorimetric study of the thermotropic behavior of aqueous dispersions of natural and synthetic sphingomyelins.