Kinetics of Human Serum Albumin Adsorption on Polycation Functionalized Silica.

The adsorption kinetics of human serum albumin (HSA) on bare and poly-L-arginine (PARG)-modified silica substrates were investigated using reflectometry and atomic force microscopy (AFM). Measurements were carried out at various pHs, flow rates and albumin concentrations in the 10 and 150 mM NaCl solutions. The mass transfer rate constants and the maximum protein coverages were determined for the bare silica at pH 4.0 and theoretically interpreted in terms of the hybrid random sequential adsorption model. These results were used as reference data for the analysis of adsorption kinetics at larger pHs. It was shown that the adsorption on bare silica rapidly decreased with pH and became negligible at pH 7.4. The albumin adsorption on PARG-functionalized silica showed an opposite trend, i.e., it was negligible at pH 4 and attained maximum values at pH 7.4 and 150 mM NaCl, the conditions corresponding to the blood serum environment. These results were interpreted as the evidence of a significant role of electrostatic interactions in the albumin adsorption on the bare and PARG-modified silica. It was also argued that our results can serve as useful reference data enabling a proper interpretation of protein adsorption on substrates functionalized by polyelectrolytes.

Poly-L-Arginine Molecule Properties in Simple Electrolytes: Molecular Dynamic Modeling and Experiments.

Physicochemical properties of poly-L-arginine (P-Arg) molecules in NaCl solutions were determined by molecular dynamics (MD) modeling and various experimental techniques. Primarily, the molecule conformations, the monomer length and the chain diameter were theoretically calculated. These results were used to interpret experimental data, which comprised the molecule secondary structure, the diffusion coefficient, the hydrodynamic diameter and the electrophoretic mobility determined at various ionic strengths and pHs. Using these data, the electrokinetic charge and the effective ionization degree of P-Arg molecules were determined. In addition, the dynamic viscosity measurements for dilute P-Arg solutions enabledto determine the molecule intrinsic viscosity, which was equal to 500 and 90 for ionic strength of 10-5 and 0.15 M, respectively. This confirmed that P-Arg molecules assumed extended conformations and approached the slender body limit at the low range of ionic strength. The experimental data were also used to determine the molecule length and the chain diameter, which agreed with theoretical predictions. Exploiting these results, a robust method for determining the molar mass of P-Arg samples, the hydrodynamic diameter, the radius of gyration and the sedimentation coefficient was proposed.

Thickness of the particle-free layer near charged interfaces in suspensions of like-charged nanoparticles.

When a suspension of charged nanoparticles is in contact with a like-charged water-solid interface, next to this interface a particle-free layer is formed. The present study provides reliable measurements of the thickness of this particle-free layer with three different techniques, namely optical reflectivity, quartz crystal microbalance (QCM), and direct force measurements with atomic force microscopy (AFM). Suspensions of negatively charged nanoparticles of different size and type are investigated. When the measured layer thickness is normalized to the particle size, one finds that this normalized thickness shows universal inverse square root dependence on the particle volume fraction. This universal dependence can be also derived from Poisson-Boltzmann theory for highly asymmetric electrolytes, whereby one has to assume that the nanoparticles represent the multivalent coions.

Structuring of colloidal silica nanoparticle suspensions near water-silica interfaces probed by specular neutron reflectivity.

Structuring of aqueous suspensions of colloidal silica nanoparticles near an isolated planar silica-water interface is studied by specular neutron reflectivity. The reflectivity data clearly show that the suspensions develop a damped, oscillatory concentration profile in the normal direction to the interface. The wavelengths of these oscillations agree well with those independently determined by direct force measurements in the slit-geometry. The reflectivity data further demonstrate that the oscillatory structure persists over several layers and that the first particle layer is separated from the interface by a particle-free region.

Kinetics of Poly-l-lysine Adsorption on Mica and Stability of Formed Monolayers: Theoretical and Experimental Studies.

Various physicochemical parameters of poly-l-lysine (PLL) solutions comprising the diffusion coefficient, the electrophoretic mobility, the density, and the intrinsic viscosity were determined for the pH range 3.0-9.2. This allowed us to calculate derivative parameters characterizing the PLL molecule such as: zeta potential, the number of electrokinetic charges, ionization degree, contour length, and cross section area. These data were exploited in theoretical calculations of PLL adsorption kinetics on solid substrates under diffusion transport. A hybrid approach was used comprising a blocking function derived from the random sequential adsorption (RSA) model. In experiments, the PLL adsorption on mica was studied using the streaming potential measurements and interpreted in terms of a general electrokinetic model. This confirmed a side-on adsorption mechanism of the macroion molecules at the examined pH range. Additionally, using this method, the stability of PLL monolayers was determined performing in situ desorption kinetic experiments. In this way, the equilibrium adsorption constant and the energy minimum depth were determined. It was confirmed that the monolayer stability decreases with pH following the decrease in the number of electrokinetic charges per molecule. This confirmed the electrostatic interaction driven adsorption mechanism of PLL. It is also predicted that at pH 5.7-7.4 the monolayers were stable under diffusion-controlled desorption over the time exceeding 100 h. In addition to their significance for basic science, the results obtained in this work can be exploited for developing procedures for preparing stable PLL monolayers of well controlled coverage and electrokinetic properties.

Hematite/silica nanoparticle bilayers on mica: AFM and electrokinetic characterization.

Quantitative studies on self-assembled hematite/silica nanoparticle (NP) bilayers on mica were performed by applying scanning electron microscopy (SEM), atomic force microscopy (AFM), and streaming potential measurements. The coverage of the supporting hematite layers was adjusted by changing the bulk concentration of the suspension and the deposition time. The coverage was determined by direct enumeration of deposited particles from AFM images and SEM micrographs. Afterward, silica nanoparticle monolayers were assembled under diffusion-controlled transport. A unique functional relationship was derived connecting the silica coverage with the hematite precursor layer coverage. The formation of the hematite monolayer and the hematite/silica bilayer was also monitored in situ by streaming potential measurements. It was confirmed that the zeta potential of the bilayers was independent of the supporting layer coverage, exceeding 0.15. These measurements were theoretically interpreted in terms of the general electrokinetic model that allowed for deriving a formula for calculating nanoparticle coverage in the bilayers. Additionally, from desorption experiments, the interactions among hematite/silica particles in the bilayers were determined using DLVO theory. These results facilitate the development of a robust method of preparing nanoparticle bilayers with controlled properties, with potential applications in catalytic processes.

Initial degree of detaching bubble adsorption coverage and the kinetics of dynamic adsorption layer formation.

The influence of the initial adsorption coverage at the surface of an air bubble (radius 0.74 mm) formed at a capillary orifice on profiles of its rising velocities and shape variations was investigated in n-octanol, n-octyltrimethylammonium bromide (CTAB) and Tween80 solutions of different concentrations. The bubble formation and the degree of adsorption coverage at its surface at the moment of departure were controlled using an elaborated automatic bubble generator (Bubble-on-Demand) coupled with a programmable bubble trap, allowing adsorption time control over the motionless (captured) bubble interface. It was found that the degree of the initial bubble adsorption coverage (whose value was calculated according to the existing adsorption models), has a profound influence on the kinetics of the dynamic adsorption layer (DAL) development.

Influence of n-octanol and α-terpineol on thin film stability and bubble attachment to hydrophobic surface.

We have investigated the influence of concentration of surfactants typically used as flotation frothers (α-terpineol and n-octanol) and roughness of the solid surface on phenomena occurring during rising bubble collisions with a model hydrophobic Teflon surface. The time of three-phase contact (TPC) formation (t(TPC)) and the time of drainage (t(D)) of the film formed between the colliding bubble and Teflon surfaces were determined using a high-speed camera working with a frequency 1040 Hz. The Teflon surface roughness was varied on a microscopic scale, within a roughness ranging between 1 and 100 µm. We have found that the roughness of the Teflon surface is a crucial factor of the kinetics of the TPC formation, both in the absence and in the presence of the surfactants. With the surface roughness increasing from ca. 1 to 80 µm the t(TPC) can be shortened by an order of magnitude, i.e. from 105 ms down to a few milliseconds. We have demonstrated that bouncing of the colliding bubble is responsible for the large differences in the times of TPC formation at the Teflon surfaces of different roughness. Low concentrations of α-terpineol and n-octanol caused a decrease in the t(TPC) with respect to distilled water. However, at high concentrations the t(TPC) was prolonged. The prolongation of the time of the TPC formation was dependent on the Teflon surface roughness and we have attributed this effect to different amounts of air present in the cavities and scratches of hydrophobic surfaces of different roughness. The mechanism of prolongation of the t(TPC) at high concentration of surface-active substances (frother overdosage) is proposed.