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Maria M Santore

Publications and source records attributed to Maria M Santore.

4 recordsLinked to original sources

Fibrinogen adsorption on three silica-based surfaces: conformation and kinetics.

Using AFM (atomic force microscopy) to probe protein conformation and arrangement, and TIRF (total internal reflectance fluorescence) to monitor kinetics, fibrinogen adsorption on three different silica-based surfaces was studied: the native oxide on silicon, acid-etched microscope slides, and acid-etched polished glass. The three are chemically similar, but the microscope slide is rougher and induces AFM tip instabilities that appear as high spots on the bare surface. Fibrinogen's conformation and transport-limited adsorption kinetics are found to be quantitatively similar on all three surfaces. Further, the number of adsorbed proteins in progressive AFM micrographs quantitatively match the coverages measured by TIRF during early adsorption. Surfaces appear full, via AFM, when adsorbed amounts are about an order of magnitude below their true saturation levels (via TIRF) because, above about 0.26 mg/m(2), individual proteins cannot be discerned. The results demonstrate how the appearance of AFM micrographs can be misleading regarding surface saturation. On all three surfaces, fibrinogen is, at most, slightly aggregated, showing limited, if any, surface mobility. The complexities of the microscope slide's surface landscape minimally impact adsorption.

Adsorption↗

Manipulation of micrometer-scale adhesion by tuning nanometer-scale surface features.

This article demonstrates how the adhesion rates of micrometer-scale particles on a planar surface can be manipulated by nanometer-scale features on the latter. Here, approximately 500-nm-diameter spherical silica particles carrying a substantial and relatively uniform negative charge experienced competing attractions and repulsions as they approached and attempted to adhere to a negative planar silica surface carrying flat 11-nm-diameter patches of concentrated positive charge. The average spacing of these patches profoundly influenced the particle adhesion. For dense positive patch spacing on the planar collector, the particle adhesion was rapid, and the fundamental adhesion kinetics were masked by particle transport to the interface. For patch densities corresponding to a planar surface with net zero charge, particle adhesion was still rapid. Adhesion kinetics were observably reduced for patch spacings exceeding 20 nm and become slower with increased patch spacing. Ultimately, above a critical or threshold average patch spacing of 32 nm, no particle adhesion occurred. The presence of the threshold average patch spacing suggests that more than one positive surface patch was needed for particle capture under the particular conditions of this study. Furthermore, at the threshold, the length scales of the patch spacing and of the interactive surface area between the particle and the surface become similar: The concept of adhesion dominated by the matching of length scales is reminiscent of pattern recognition, even though the patch distribution on the collector is random in this work. Indeed, fluctuations play a critical role in these adhesion dynamics, hence the current behavior cannot be predicted by a mean field approach.

Nanotechnology↗

Protein spreading kinetics at liquid-solid interfaces via an adsorption probe method.

We report the areal growth kinetics of fibrinogen adsorbed on model hydrophobic and hydrophilic surfaces measured via an adsorption probe method. This approach exploits the adsorption of probe molecules to determine the evolution of fibrinogen test molecules under conditions where the fibrinogen test molecules adsorb at relatively dilute surface conditions, minimizing interactions between them. It is found that fibrinogen test molecules spread from an average initial footprint of 100 nm2 to a final footprint near 500 nm2 per molecule on the hydrophobic surface, with a single-exponential decay of 1735 s. On a hydrophilic monolayer, the area increases from 100 to 160 nm2 with a characteristic time of 6740 s. These results demonstrate the power of the adsorption probe approach and comprise the first measurements of the averaged area relaxations of adsorbed proteins. The observation of single-exponential dynamics is remarkable, given the extensive relaxation on the hydrophobic surface, which must involve fibrinogen denaturing.

Adsorption↗

The relationship between polymer/substrate charge density and charge overcompensation by adsorbed polyelectrolyte layers.

This work examines polyelectrolyte adsorption (exclusively driven by electrostatic attractions) for a model system (DMAEMA, polydimethylaminoethyl methacrylate, adsorbing onto silica) where the adsorbing polycation is more densely charged than the substrate. Variations in the relative charge densities of the polymer and substrate are accomplished by pH, and the polycation is of sufficiently low molecular weight that the adsorbed conformation is generally flat under all conditions examined. We demonstrate, quantitatively, that the charge overcompensation observed on the isotherm plateau can be attributed to the denser positive charge on the adsorbing polycation and that the ultimate coverage obtained corresponds to the adsorption of one oligomer onto each original negative silica charge, when the silica charge is most sparse, at pH 6. This limiting behavior breaks down at higher pHs where the greater silica charge density accommodates single chains adsorbing onto multiple negative sites. As a result of the greater substrate charge density and reduced polycation charge at higher pHs, the extent of charge overcompensation diminishes while the coverage increases on the plateau of the isotherm. Ultimately at the highest pHs, a regime is approached where the coil's excluded surface area, not surface charge, limits the ultimate coverage. In addition to quantifying the crossover from the charge-limiting to the area-limiting behaviors, this paper quantitatively reports adsorption-induced changes in bound counterion density and ionization at the interface, which were generally found to be independent of coverage for this model system.

Journal Article↗