RESUMO
Synthetic cationic lipids have garnered significant attention as promising candidates for gene/DNA transfection in therapeutic applications. The phase behavior of the vesicles formed by these lipids is intriguing, revealing intricate connections to the structure and dynamics of the membrane. These phenomena emerge from the complex interplay between hydrophobic and electrostatic interactions of the lipids. In this study, we explore the impact of an ionic liquid-based surfactant, 1-decyl-3-methylimidazolium bromide (DMIM[Br]), on the structural, dynamical, and phase behavior of cationic dihexadecyldimethylammonium bromide (DHDAB) vesicles. Our investigations indicate that the addition of DMIM[Br] increases the vesicle size while thinning the membrane. Further, DMIM[Br] also induces substantial changes in the membrane phase behavior. At 10 and 25 mol %, DMIM[Br] eliminates the pre-transition from coagel to intermediate crystalline (IC) phase and decreases the onset temperature of the main phase transition to the fluid phase. In the cooling cycle, the addition of DMIM[Br] further induces the formation of an intermediate gel phase. This behavior is reminiscent of the non-synchronous ordering observed in the DODAB membrane, a longer-chain counterpart of DHDAB. Interestingly, at 40 mol % of DMIM[Br], the formation of the intermediate gel phase is largely suppressed. Neutron scattering data provide evidence that the addition of DMIM[Br] enhances lipid mobility in coagel and fluid phases, suggesting that DMIM[Br] acts as a plasticizer, enhancing membrane fluidity across all of the phases. Our findings infer that DMIM[Br] modulates the membrane's phase behavior and fluidity, two essential ingredients for the efficient transport of cargo, by controlling the balance of electrostatic and hydrophobic interactions.
RESUMO
A process in which a disordered system of pre-existing molecules generates an organized structure through specific, local interactions among the molecules themselves is termed molecular self-assembly. Micelles, microemulsions, and vesicles are examples of such self-assembled systems where amphiphilic molecules are involved. As the functional properties of these systems (such as wetting and emulsification, release of solubilized drugs, etc.) are dictated by the dynamic behavior of the surfactants at the molecular level, it is of immense interest to investigate these systems for the same. The dynamics in soft matter systems is quite complex, involving different time and length scales. We used a combination of neutron scattering and molecular dynamics simulation studies in probing the dynamic landscape in various self-assembled surfactant aggregates. Neutron scattering experiments were carried out using several spectrometers covering a wide dynamic range to probe motions on different time scales. The interaction between the surfactants can be varied by changing the molecular architecture, counterion concentration, temperature, and so forth. It is important to study the effect of these parameters on the dynamics of surfactants in these aggregates. We have carried out experiments on various ionic (anionic as well as cationic) micelles with varied counterion concentrations, vesicles, and lipid bilayers to unravel the complex dynamic features present in these systems. In this feature article, we will discuss some important results of our recent work on dynamics in these self-assembled surfactant aggregates.
RESUMO
The maintenance of cell membrane fluidity is of critical importance for various cellular functions. At lower temperatures when membrane fluidity decreases, plants and cyanobacteria react by introducing unsaturation in the lipids, so that the membranes return to a more fluidic state. To probe how introduction of unsaturation leads to reduced membrane fluidity, a model cationic lipid dioctadecyldimethylammonium bromide (DODAB) has been chosen, and the effects of an unsaturated lipid monoolein (MO) on the structural dynamics and phase behavior of DODAB have been monitored by quasielastic neutron scattering and time-resolved fluorescence measurements. In the coagel phase, fluidity of the lipid bilayer increases significantly in the presence of MO relative to pure DODAB vesicles and becomes manifest in significantly enhanced dynamics of the constituent lipids along with faster hydration and orientational relaxation dynamics of a fluorophore. On the contrary, MO restricts both lateral and internal motions of the lipid molecules in the fluid phase (>330 K), which is consistent with relatively slow hydration and orientational relaxation dynamics of the fluorophore embedded in the mixed lipid bilayer. The present study illustrates how incorporation of an unsaturated lipid at lower temperatures (below the phase transition) assists the model lipid (DODAB) in regulating fluidity via enhancement of dynamics of the constituent lipids.
