Quartz Crystal Microbalance Application and In Silico Studies to Characterize the Interaction of Bovine Serum Albumin with Plasma Polymerized Pyrrole Surfaces: Implications for the Development of Biomaterials.

Plasma polymerized pyrrole/iodine (PPPy/I) microparticles and bovine serum albumin (BSA) protein have shown interesting results in experimental models for the treatment of traumatic spinal cord injury. By studying the interaction between BSA and PPPy/I by a quartz crystal microbalance (QCM) and docking, we obtained important results to elucidate possible cellular interactions and promote the use of these polymers as biomaterials. These measurements were also used to characterize the adsorption process using an equilibrium constant. In addition, atomic force microscopy (AFM) was used to obtain images of the QCM surface sensors before and after BSA adsorption. Furthermore, we carried out molecular dynamics simulations and molecular docking to characterize the molecular recognition between BSA and the previously reported PPPy/I structure. For this study, we used two combinatorial models that have not been tested. Thus, we could determine the electrostatic (ΔGele) and nonelectrostatic (ΔGnonelec) components of the free binding energy (ΔGb). We demonstrated that BSA is adsorbed on PPPy/I with an adsorption constant of K = 24.35 µ-1 indicating high affinity. This observation combined with molecular docking and binding free energy calculations showed that the interaction between BSA and both combinatorial models of the PPPy structure is spontaneous.

High Interfacial Viscoelasticity of Aqueous Mixed Dodecyltrimethylammonium Bromide-Sodium Dodecyl Sulfate Surfactants Forming Inclusion Complexes with α-Cyclodextrin.

Mixtures of anionic-cationic surfactants have shown high synergistic effects in the bulk solution and at the liquid/air interface. These studies have been limited to a reduced concentration range, where there is no formation of aggregates or precipitates. The addition of host molecules, such as cyclodextrins, to these systems reduces the effects of precipitation by forming inclusion complexes and also modifies the values of other surfactant properties, like the Krafft temperature and the critical aggregation concentration (CAC). We studied the interfacial synergistic effects promoted by electrostatic interactions, using the Rosen model to calculate an interaction parameter for mixtures of sodium dodecyl sulfate (SDS) and dodecyltrimethylammonium bromide (DTAB) in the presence of α-cyclodextrin (αCD), in aqueous solutions. We measured the CAC of SDS-DTAB-αCD mixtures using a pendant drop tensiometer, with the αCD concentration fixed at 10 mM and at 283.15 K. We performed rheological measurements on the mixtures where the surfactant total concentration is fixed below the measured CAC, varying the αCD concentration and temperature. We found that the dilatational modulus shows a clear correlation with the interaction parameter. It appears that the attractive interactions within the film are those due to the inclusion complexes formed by two αCD and one surfactant molecule, which according to the previous studies, is the dominant species in both the bulk and liquid/air interface. The synergistic effect observed here for SDS-DTAB surfactant mixtures with αCD can be applied to systems and processes (drop emission, drug delivery methods, stabilization of viral capsids and bacterial membranes, and emulsification) where interfacial processes require specific viscoelastic properties.

Dynamical shapes of droplets of cyclodextrin-surfactant solutions.

We present a series of experiments with droplets of aqueous cyclodextrin-surfactant solutions, in which the volume is reduced after the equilibrium spherical shape is reached. The final shape of the drop after this perturbation is found to be dependent on the concentration of inclusion complexes in the bulk of the solution. These inclusion complexes are formed by two cyclodextrin molecules and one surfactat molecule. We propose a model to describe these dynamical processes. Dipole-dipole interactions on the surface of the drop trigger a competition between water surface tension and dipole-dipole interaction energies. The results of the model reproduce the spherical and rod-like shapes found in the experiments.

Highly viscoelastic films at the water/air interface: α-Cyclodextrin with anionic surfactants.

This work showcases the remarkable viscoelasticity of films consisting of α-cyclodextrin (α-CD) and anionic surfactants (S) at the water/air interface, the magnitude of which has not been observed in similar systems. The anionic surfactants employed are sodium salts of a homologous series of n-alkylsulfates (n = 8-14) and of dodecylsulfonate. Our hypothesis was that the very high viscoelasticity can be systematically related to the bulk and interfacial properties of the system. Through resolution of the bulk distribution of species using isothermal titration calorimetry, the high dilatational modulus is related to (α-CD)2:S1 inclusion complexes in the bulk with respect to both the bulk composition and temperature. Direct interfacial characterization of α-CD and sodium dodecylsulfate films at 283.15 K using ellipsometry and neutron reflectometry reveals that the most viscoelastic films consist of a highly ordered monolayer of 2:1 complexes with a minimum amount of any other component. The orientation of the complexes in the films and their driving force for adsorption are discussed in the context of results from molecular dynamics simulations. These findings open up clear potential for the design of new functional materials or molecular sensors based on films with specific mechanical, electrical, thermal, chemical, optical or even magnetic properties.

Mechanical Properties of DPPC-POPE Mixed Langmuir Monolayers.

The mechanical properties of lipid monolayers and their responses to shear and compression stresses play an important role in processes such as breathing and eye blinking. We studied the mechanical properties of Langmuir monolayers of a model mixture, composed of an unsaturated lipid, 1-palmitoyl-2-oleoyl-sn-glycero-phosphoethanolamine (POPE), and a saturated lipid, 1,2-dipalmitoyl-sn-glycero-phosphocholine (DPPC). We performed isothermal compressions and sinusoidal shear deformations of these mixed monolayers. Also, the different phases were observed with Brewster angle microscopy. We found that the mechanical behavior is affected by the miscibility of both lipids. In the two-phase region, the compression elastic modulus increases with the amount of the LC phase but does not follow the predictions of a simple effective medium model. The discrepancies arise from the fact that, upon compression, the domains grow at a rate faster than the compression rate but not fast enough to reach thermodynamic equilibrium. Before reaching the LC phase, domain percolation is observed and compression and shear moduli become equal to those of the pure LC phase. Most of the monolayers behave as viscoelastic fluids at the frequencies investigated. A minimum in the compression modulus and shear viscosity was observed for mixtures close to equimolar composition, with the minimum being accompanied by a change in domain shapes.