Self-assembly of biomembranes results from the intricate interactions between water and the lipids’ hydrophilic head groups. Therefore, the lipid–water interplay strongly contributes to modulating membrane architecture, lipid diffusion, and chemical activity. Here, we introduce a new method of obtaining dehydrated, phase-separated, supported lipid bilayers (SLBs) solely by controlling the decrease of their environment’s relative humidity. This facilitates the study of the structure and dynamics of SLBs over a wide range of hydration states. We show that the lipid domain structure of phase-separated SLBs is largely insensitive to the presence of the hydration layer. In stark contrast, lipid mobility is drastically affected by dehydration, showing a 6-fold decrease in lateral diffusion. At the same time, the diffusion activation energy increases approximately 2-fold for the dehydrated membrane. The obtained results, correlated with the hydration structure of a lipid molecule, revealed that about six to seven water molecules directly hydrating the phosphocholine moiety play a pivotal role in modulating lipid diffusion. These findings could provide deeper insights into the fundamental reactions where local dehydration occurs, for instance during cell–cell fusion, and help us better understand the survivability of anhydrobiotic organisms. Finally, the strong dependence of lipid mobility on the number of hydrating water molecules opens up an application potential for SLBs as very precise, nanoscale hydration sensors.
6 April 2023 in The Journal of Physical Chemistry B
Single-component azobenzene-based phototropic liquid crystals (PtLC) are promising materials that have started to be explored for photonic applications. One of the essential factors determining the applicability of these materials is the rate of the thermally driven cis–trans isomerization. In this paper, the kinetics of the thermal back cis-to-trans reaction in a pure 4-hexyl-4′-methoxyazobenzene (6-AB-O1) compound in its isotropic liquid and nematic phases is studied (the undoped LC). The reaction rate constants, activation energies and thermal activation parameters were determined based on spectroscopic studies. The reaction kinetics is compared to that measured for the compound dissolved in chloroform. The results demonstrate that the thermal back reaction depends on the phase and molecular environment of the cis-isomer. Moreover, the effect of temperature on the absorption spectra of 6-AB-O1 in its isotropic, nematic and crystalline phases is examined. The changes in the compound's absorption spectra in the respective phases have been correlated to the positional order parameter S.
In the report we demonstrate how, using laser light, effectively trap gas bubbles and transport them through a liquid phase to a desired destination by shifting the laser beam position. The physics underlying the effect is complex but quite general as it comes from the limited to two-dimension, well-known, Marangoni effect. The experimental microscope-based system consists of a thin layer of liquid placed between two glass plates containing a dye dissolved in a solvent and a laser light beam that is strongly absorbed by the dye. This point-like heat source locally changes surface tension of nearby liquid-air interface. Because of temperature gradients a photo-triggered Marangoni flows are induced leading to self-amplification of the effect and formation of large-scale whirls. The interface is bending toward beam position allowing formation of a gas bubble upon suitable beam steering. Using various techniques (employing luminescent particles or liquid crystals), we visualize liquid flows propelled by the tangential to interface forces. This helped us to understand the physics of the phenomenon and analyze accompanying effects leading to gas bubble trapping. The manipulation of sessile droplets moving on the glass surface induced via controlled with laser light interface bending (i.e. “droplet catapult”) is demonstrated as well.
30 April 2024 in Journal of the American Chemical Society
The nanoscopic layer of water that directly hydrates biological membranes plays a critical role in maintaining the cell structure, regulating biochemical processes, and managing intermolecular interactions at the membrane interface. Therefore, comprehending the membrane structure, including its hydration, is essential for understanding the chemistry of life. While cholesterol is a fundamental lipid molecule in mammalian cells, influencing both the structure and dynamics of cell membranes, its impact on the structure of interfacial water has remained unknown. We used surface-specific vibrational sum-frequency generation spectroscopy to study the effect of cholesterol on the structure and hydration of monolayers of the lipids 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC), 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC), and egg sphingomyelin (SM). We found that for the unsaturated lipid DOPC, cholesterol intercalates in the membrane without significantly changing the orientation of the lipid tails and the orientation of the water molecules hydrating the headgroups of DOPC. In contrast, for the saturated lipids DPPC and SM, the addition of cholesterol leads to clearly enhanced packing and ordering of the hydrophobic tails. It is also observed that the orientation of the water hydrating the lipid headgroups is enhanced upon the addition of cholesterol. These results are important because the orientation of interfacial water molecules influences the cell membranes' dipole potential and the strength and specificity of interactions between cell membranes and peripheral proteins and other biomolecules. The lipid nature-dependent role of cholesterol in altering the arrangement of interfacial water molecules offers a fresh perspective on domain-selective cellular processes, such as protein binding.