Structural Effects on the Langmuir Monolayers of Calix[4]arene Induced by Lower Rim Aromatic Substitution

The Langmuir monolayer properties of lower rim aromatically substituted calix[4]arenes, 5,11,17,23-tetra-tert-butyl-25,27-bis（2-naphth-1＇-ylacetylaminoethoxy）-26,28-dihydroxylcalix[4]arene （BNAEC）, 5,11,17,23-tetra-tert- butyl-25,27-bis（2-benzoylamino ethoxy）-26,28-dihydroxylcalix[4]arene （BBAEC） and 5,11,17,23-tetra-tert-butyl- 25,27-bis（2-cinnamoylaminoethoxy）-26,28-dihydroxylcalix[4]arene （BCAEC）, have been studied. Film balance measurements and Brewster angle microscopy （BAM） observation demonstrate that all the compounds can form Langmuir monolayers with different molecular limiting areas. BNAEC or BBAEC monolayer is able to form condensed domains during compression, while BCAEC monolayer can never form condensed domain. BNAEC monolayer is more readily to form condensed domain than BBAEC monolayer. Moreover, BNAEC monolayer can form the total condensed phase during compression even when T=28℃, while BBAEC monolayer can not when T 〉 10 ℃. The results imply that different lower rim aromatic substitutions affect essentially the intermolecular interaction and molecular packing in the monolayer at air/water interface.

Influence of amphotericin B on liquid crystal state of the Cholesterol/Dipalmitoylphosphatidylcholine monolayer in the presence of different metal cations

Amphotericin B is a very effective antifungal drug,but it has an adverse reaction to the membrane of mammals＇ cells.The interaction between Am B and cholesterol（Chol） causes the formation of pores on the membrane to destroy its integrity.In particular,Am B has a significant effect on the permeability of membrane for K~＋ions.It has been reported that Na＋ions and Ca^（2＋）ions may have some influence on the interaction between amphotericin B and lipid molecules.In this work,the effects of these metal cations on the physical state and intermolecular interaction of the Cholesterol/Dipalmitoylphosphatidylcholine（Chol/DPPC） monolayer with and without Am B have been investigated.The addition of Am B induces the change of physical state of the lipid monolayer from liquid-gel phase to liquid phase.Different metal cations could influence the phase transition of the Am B-lipid monolayer.The K~＋ions and Ca2＋ions make the obvious phase transition disappear.However,the presence of Na＋ions has little influence on the phase transition of the Am B-lipid monolayer.The addition of Am B and the presence of different metal cations weaken the attractive force on the monolayers.After addition of Am B,the force between the molecules is the strongest in the environment of K＋ions,thus is the weakest in the environment of Ca^（2＋）ions,which may be due to the distribution of these metal cations inside and outside of cells.A large number of K＋ions distribute inside of the cells,thus most of Na＋and Ca^（2＋）ions exist out of the cells.Hence,it may be possible that when Am B molecules are out of the cells,the reaction between the drug and lipid molecules is weaker than that inside the cells.These results may have a great reference value for further studying the toxicity mechanism of Am B and the influence of metal cations on the membrane.

Mapping the structure-activity relationship of β-sitosteryl fatty acid esters in condensing phospholipid monolayers

Abstract The phase behavior of twelve synthesized β- sitosteryl fatty acid esters with acyl moieties with different chain lengths （C2：0-C18：0） and different degrees of unsaturation （C18：1-C18：3） were investigated in pure and mixed Langmuir monolayers with phospholipids. The surface-pressure isotherms showed that short chain fl- sitosteryl fatty acid esters gave smaller mean molecular areas and had decreased monolayer stability and the long chain steryl esters did not produce collapsed plateaus. All the steryl esters displayed strong condensing effects, but there was a pronounced structural dependency： medium chain esters （C8 and C 10） were less efficient than short and long chain esters. Atomic force microscopy imaging demonstrated that monolayers mixed with dipalmitoyl phosphatidylcholine （DPPC） displayed both DPPC-rich and steryl lipid-rich domains. However, the height and area differences between the two phases and the roughness and morphologic patterns were very dependent on the steryl lipid concentrations as well as the length, the degree of unsaturation and the molecular conformations of the acyl segments. These findings not only provide a better understanding of the interactions between phytosteryl hydrophobic derivatives and biomembranes, but also may be of general use for the design and engineering of phytosterol structural derivations for specific food and pharmaceutical applications.