In a quartz crystal microbalance, particles adhering to a sensor crystal are perturbed around their equilibrium positions via thickness-shear vibrations at the crystal's fundamental frequency and overtones. The amount of adsorbed molecular mass is measured as a shift in resonance frequency. In inertial loading, frequency shifts are negative and proportional to the adsorbed mass, in contrast with "elastic loading", where particles adhere via small contact points. Elastic loading in air yields positive frequency shifts according to a coupled resonance model. We explore here the novel application of a coupled resonance model for colloidal particle adhesion in a liquid phase theoretically and demonstrate its applicability experimentally. Particles with different radii and in the absence and presence of ligand-receptor binding showed evidence of coupled resonance. By plotting the frequency shifts versus the quartz crystal microbalance with dissipation overtone number, frequencies of zero-crossing could be inferred, indicative of adhesive bond stiffness. As a novelty of the model, it points to a circular relation between bandwidth versus frequency shift, with radii indicative of bond stiffness. The model indicates that bond stiffness for bare silica particles adhering on a crystal surface is determined by attractive Lifshitz-van der Waals and ionic-strength-dependent, repulsive electrostatic forces. In the presence of ligand-receptor interactions, softer interfaces develop that yield stiffer bonds due to increased contact areas. In analogy with molecular vibrations, the radii of adhering particles strongly affect the resonance frequencies, while bond stiffness depends on environmental parameters to a larger degree than for molecular adsorption.
Triblock copolymers of polyethylene oxide (PEO) and polypropylene oxide (PPO), that is, PEOn-PPOm-PEOn, better known as Pluronic can adsorb to surfaces in either a pancake or a brushlike configuration. The brushlike configuration is advantageous in numerous applications, since it constitutes a surface repellent to proteins and microorganisms. The conformation of the adsorbed Pluronic layer depends on the hydrophobicity of the substratum surface, but the hydrophobicity threshold above which a brushlike conformation is adopted is unknown. Therefore, the aim of this study is to investigate Pluronic F-127 adsorption on surfaces with different hydrophobicities using a quartz crystal microbalance with dissipation. Adsorption in a brushlike conformation occurred on surfaces with a water contact angle above 80 degrees , as inferred from the thickness, viscosity, and elasticity of the adsorbed layer. The concentration of Pluronic F-127 in solution affected only the kinetics of adsorption and not the final layer thickness or conformation of adsorbed Pluronic molecules.
A quartz crystal microbalance with dissipation (QCM-D) monitoring can be an alternative tool to characterize nanoparticle size by virtue of its acoustic principle to sense adsorbed mass. In this study, sizes obtained by QCM-D for polymer-coated metallic nanoparticles and polydisperse polystyrene latex particle suspensions were compared with those obtained by transmission electron microscopy (TEM) and dynamic light scattering (DLS). We describe the obtained "QCM-D mass", which is weighted over surface area, by a general particle height distribution equation that can be used to determine the average particle diameter of a distribution of particles deposited on the QCM-D surface. Because the particle height distribution equation can be used for any particle geometry and surface packing geometry, it is described how the QCM-D can also be used to study the orientation of deposited nonspherical particles. Herein, the mean nanoparticle sizes obtained by QCM-D were generally in closer agreement with the primary particle size determined by TEM than with the sizes obtained by DLS, suggesting that primarily smaller particles within the particle population deposited on the sensor surface. Overall, the results from this study demonstrate that QCM-D could serve as an alternative and/or complementary means to characterize the size of nanoparticles deposited on a surface from suspensions of varying complexity.
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