Monitoring phases and phase transitions in phosphatidylethanolamine monolayers using active interfacial microrheology

This is the published version. Copyright 2015 Royal Society of ChemistryActive interfacial microrheology is a sensitive tool to detect phase transitions and headgroup order in phospholipid monolayers. The re-orientation of a magnetic nickel nanorod is used to explore changes in the surface rheology of 1,2-dilauroyl-sn-glycero-3-phosphoethanolamine (DLPE) and 1,2-dimyristoyl-sn-glycero-3-phosphoethanolamine (DMPE), which differ by two CH2 groups in their alkyl chains. Phosphatidylethanolamines such as DLPE and DMPE are a major component of cell membranes in bacteria and in the nervous system. At room temperature, DLPE has a liquid expanded (LE) phase for surface pressure, Π < ∼38 mN m−1; DMPE has an LE phase for Π < ∼7 mN m−1. In their respective LE phases, DLPE and DMPE show no measurable change in surface viscosity with Π, consistent with a surface viscosity <10−9 N s m−1, the resolution of our technique. However, there is a measurable, discontinuous change in the surface viscosity at the LE to liquid condensed (LC) transition for both DLPE and DMPE. This discontinuous change is correlated with a significant increase in the surface compressibility modulus (or isothermal two-dimensional bulk modulus). In the LC phase of DMPE there is an exponential increase in surface viscosity with Π consistent with a two-dimensional free area model. The second-order LC to solid (S) transition in DMPE is marked by an abrupt onset of surface elasticity; there is no measurable elasticity in the LC phase. A measurable surface elasticity in the S phase suggests a change in the molecular ordering or interactions of the DMPE headgroups that is not reflected in isotherms or in grazing incidence X-ray diffraction. This onset of measurable elasticity is also seen in DLPE, even though no indication of a LC–S transition is visible in the isotherms

Active Interfacial Shear Microrheology of Aging Protein Films

This is the published version. Copyright 2010 The American Physical SocietyThe magnetically driven rotation of 300 nm diameter rods shows the surface viscosity of albumin at an air-water interface increases from 10−9 to 10−5  N s/m over 2 h while the surface pressure saturates in minutes. The increase in surface viscosity is not accompanied by a corresponding increase in elasticity, suggesting that the protein film anneals with time, resulting in a more densely packed film leading to increased resistance to shear. The nanometer dimensions of the rods provide the same sensitivity as passive microrheology with an improved ability to measure more viscous films

A phase of liposomes with entangled tubular vesicles

An equilibrium phase belonging to the family of bilayer liposomes in ternary mixtures of dimyristoylphosphatidylcholine (DMPC), water, and geraniol (a biological alcohol derived from oil-soluble vitamins that acts as a cosurfactant) has been identified. Electron and optical microscopy reveal the phase, labeled Ltv, to be composed of highly entangled tubular vesicles. In situ x-ray diffraction confirms that the tubule walls are multilamellar with the lipids in the chain-melted state. Macroscopic observations show that the Ltv phase coexists with the well-known L4 phase of spherical vesicles and a bulk L alpha phase. However, the defining characteristic of the Ltv phase is the Weissenberg rod climbing effect under shear, which results from its polymer-like entangled microstructure

Direct observations of dislocations in thermotropic smectics using freeze-fracture replication

Modern rapid-freezing methods followed by freeze-fracture replication techniques are ideally suited to allow the direct visualization of the three-dimensional structure and defects of thermotropic smectic and cholesteric liquid crystalline phases with resolution approaching molecular dimensions. Cholesterol nonanoate was quench frozen from near the smectic-cholesteric transition to reveal extensive, well defined smectic layers distorted by a high density of screw and edge dislocations. The screw dislocations typically had Burgers vectors of a single layer and commonly organized as twist walls. This is suggestive that the twist present in the cholesteric phase induces a residual twist in the smectic phase incompatible with perfect layering. Screw-edge dislocation loops were also commonly observed, also organized into twist walls. These twist walls have been suggested as being responsible for the breakdown of smectic ordering leading to the cholesteric phase.Les méthodes modernes de trempe suivie de réplication par fracture sont idéales pour la visualisation directe de la structure tridimensionnelle et des défauts dans les phases cristal liquide smectique et cholestérique. La résolution y est proche des distances moléculaires. On a trempé le nonanoate de cholestérol à partir du voisinage de la transition smectique-cholestérique pour mettre en évidence des couches smectiques étendues et bien définies, distordues par des dislocations coins et vis ayant une densité très élevée. Les dislocations vis ont des vecteurs de Burgers de couche unique organisée comme des parois twistées. Il est tentant de penser que le twist présent dans la phase cholestérique induit un twist résiduel dans la phase smectique qui est incompatible avec la mise en forme de couches. On a observé aussi des boucles de dislocations viscoin organisées également en parois twistées. On a suggéré que ces parois soient responsables de la disparition de l'ordre smectique amenant la phase cholestérique

Interfacial rheology and direct imaging reveal domain-templated network formation in phospholipid monolayers penetrated by fibrinogen

Phospholipids are found throughout the natural world, including the lung surfactant (LS) layer that reduces pulmonary surface tension and enables breathing. Fibrinogen, a protein involved in the blood clotting process, is implicated in LS inactivation and the progression of disorders such as acute respiratory distress syndrome. However, the interaction between fibrinogen and LS at the air-water interface is poorly understood. Through a combined microrheological, confocal and epifluorescence microscopy approach we quantify the interfacial shear response and directly image the morphological evolution when a model LS monolayer is penetrated by fibrinogen. When injected into the subphase beneath a monolayer of the phospholipid dipalmitoylphosphatidylcholine (DPPC, the majority component of LS), fibrinogen preferentially penetrates disordered liquid expanded (LE) regions and accumulates on the boundaries between LE DPPC and liquid condensed (LC) DPPC domains. Thus, fibrinogen is line active. Aggregates grow from the LC domain boundaries, ultimately forming a percolating network. This network stiffens the interface compared to pure DPPC and imparts the penetrated monolayer with a viscoelastic character reminiscent of a weak gel. When the DPPC monolayer is initially compressed beyond LE-LC coexistence, stiffening is significantly more modest and the penetrated monolayer retains a viscous-dominated, DPPC-like character