The Stokes-Einstein-Sutherland Equation at the Nanoscale Revisited.

The Stokes-Einstein-Sutherland (SES) equation is at the foundation of statistical physics, relating a particle's diffusion coefficient and size with the fluid viscosity, temperature, and the boundary condition for the particle-solvent interface. It is assumed that it relies on the separation of scales between the particle and the solvent, hence it is expected to break down for diffusive transport on the molecular scale. This assumption is however challenged by a number of experimental studies showing a remarkably small, if any, violation, while simulations systematically report the opposite. To understand these discrepancies, analytical ultracentrifugation experiments are combined with molecular simulations, both performed at unprecedented accuracies, to study the transport of buckminsterfullerene C60 in toluene at infinite dilution. This system is demonstrated to clearly violate the conditions of slow momentum relaxation. Yet, through a linear response to a constant force, the SES equation can be recovered in the long time limit with no more than 4% uncertainty both in experiments and in simulations. This nonetheless requires partial slip on the particle interface, extracted consistently from all the data. These results, thus, resolve a long-standing discussion on the validity and limits of the SES equation at the molecular scale.

Measurement of length distribution of beta-lactoglobulin fibrils by multiwavelength analytical ultracentrifugation.

The whey protein beta-lactoglobulin is the building block of amyloid fibrils which exhibit a great potential in various applications. These include stabilization of gels or emulsions. During biotechnological processing, high shear forces lead to fragmentation of fibrils and therefore to smaller fibril lengths. To provide insight into such processes, pure straight amyloid fibril dispersions (prepared at pH 2) were produced and sheared using the rotor stator setup of an Ultra Turrax. In the first part of this work, the sedimentation properties of fragmented amyloid fibrils sheared at different stress levels were analyzed with mulitwavelength analytical ultracentrifugation (AUC). Sedimentation data analysis was carried out with the boundary condition that fragmented fibrils were of cylindrical shape, for which frictional properties are known. These results were compared with complementary atomic force microscopy (AFM) measurements. We demonstrate how the sedimentation coefficient distribution from AUC experiments is influenced by the underlying length and diameter distribution of amyloid fibrils.In the second part of this work, we show how to correlate the fibril size reduction kinetics with the applied rotor revolution and the resulting energy density, respectively, using modal values of the sedimentation coefficients obtained from AUC. Remarkably, the determined scaling laws for the size reduction are in agreement with the results for other material systems, such as emulsification processes or the size reduction of graphene oxide sheets.

Probing particle heteroaggregation using analytical centrifugation.

The controlled aggregation of colloidal particles is not only a widespread natural phenomenon but also serves as a tool to design complex building blocks with tailored shape and functionalities. However, the quantitative characterization of such heteroaggregation processes remains challenging. Here, we demonstrate the use of analytical centrifugation to characterize the heteroaggregation of silica particles and soft microgels bearing similar surface charges. We investigate the attachment as well as the stability of the formed heteroaggregates as a function of particle to microgel surface ratio, microgel size and the influence of temperature. The attachment of microgels onto the colloidal particles induces a change in the sedimentation coefficient, which is used to quantitatively identify the number of attached microgels. We corroborate the shift in sedimentation coefficient by computer simulations of the frictional properties of heteroaggregates via a modified Brownian dynamic algorithm. The comparison between theoretical investigations and experiments suggest that the microgels deform and flatten upon attachment.

A Comprehensive Brownian Dynamics Approach for the Determination of Non-ideality Parameters from Analytical Ultracentrifugation.

Brownian dynamics (BD) has been applied as a comprehensive tool to model sedimentation and diffusion of nanoparticles in analytical ultracentrifugation (AUC) experiments. In this article, we extend the BD algorithm by considering space-dependent diffusion and solvent compressibility. With this, the changes in the sedimentation and diffusion coefficient from altered solvent properties at increased pressures are accurately taken into account. Moreover, it is demonstrated how the concept of space-dependent diffusion is employed to describe concentration-dependent sedimentation and diffusion coefficients, in particular, through the Gralen coefficient and the second virial coefficient. The influence of thermodynamic nonideality on diffusional properties can be accurately simulated and agree with well-known evaluation tools. BD simulations for sedimentation equilibrium and sedimentation velocity (SV) AUC experiments including effects of hydrodynamic and thermodynamic nonideality are validated by global evaluation in SEDANAL. The interplay of solvent compressibility and retrieved nonideality parameters can be studied utilizing BD. Finally, the second virial coefficient is determined for lysozyme from SV AUC experiments and BD simulations and compared to membrane osmometry. These results are in line with DLVO theory. In summary, BD simulations are established for the validation of nonideal sedimentation in AUC providing a sound basis for the evaluation of complex interactions even in polydisperse systems.

Effect of protein adsorption on the dissolution kinetics of silica nanoparticles.

Nanoparticulate systems in the presence of proteins are highly relevant for various biomedical applications such as photo-thermal therapy and targeted drug delivery. These involve a complex interplay between the charge state of nanoparticles and protein, the resulting protein conformation, adsorption equilibrium and adsorption kinetics, as well as particle dissolution. SiO2 is a common constituent of bioactive glasses used in biomedical applications. In this context, the dissolution behavior of silica particles in the presence of a model protein, bovine serum albumin (BSA), at physiologically relevant pH conditions was studied. Sedimentation analysis using an analytical ultracentrifuge showed that BSA in the supernatant solution is not affected by the presence of silica nanoparticles. However, zeta potential measurements revealed that the presence of the protein alters the particles' charge state. Adsorption and dissolution studies demonstrated that the presence of the protein significantly enhances the dissolution kinetics via interactions of positively charged amino acids in the protein with the negative silica surface and interaction of BSA with dissolved silicate species. Our study provides comprehensive insights into the complex interactions between proteins and oxide nanoparticles and establishes a reliable protocol paving the way for future investigations in more complex systems involving biological solutions as well as bioactive materials.

Versatile strategy for homogeneous drying patterns of dispersed particles.

After spilling coffee, a tell-tale stain is left by the drying droplet. This universal phenomenon, known as the coffee ring effect, is observed independent of the dispersed material. However, for many technological processes such as coating techniques and ink-jet printing a uniform particle deposition is required and the coffee ring effect is a major drawback. Here, we present a simple and versatile strategy to achieve homogeneous drying patterns using surface-modified particle dispersions. High-molecular weight surface-active polymers that physisorb onto the particle surfaces provide enhanced steric stabilization and prevent accumulation and pinning at the droplet edge. In addition, in the absence of free polymer in the dispersion, the surface modification strongly enhances the particle adsorption to the air/liquid interface, where they experience a thermal Marangoni backflow towards the apex of the drop, leading to uniform particle deposition after drying. The method is independent of particle shape and applicable to a variety of commercial pigment particles and different dispersion media, demonstrating the practicality of this work for everyday processes.

Determination of the yield, mass and structure of silver patches on colloidal silica using multiwavelength analytical ultracentrifugation.

Anisotropic nanoparticles offer considerable promise for applications but also present significant challenges in terms of their characterization. Recent developments in the electroless deposition of silver patches directly onto colloidal silica particles have opened up a simple and scalable synthesis method for patchy particles with tunable optical properties. Due to the reliance on patch nucleation and growth, however, the resulting coatings are distributed in coverage and thickness and some core particles remain uncoated. To support process optimization, new methods are required to rapidly determine patch yield, thickness and coverage. Here we present a novel approach based on multiwavelength analytical ultracentrifugation (MWL-AUC) which permits simultaneous hydrodynamic and spectroscopic characterization. The patchy particle colloids are produced in a continuous flow mixing process that makes use of a KM-type micromixer. By varying the process flow rate or metal precursor concentration we show how the silver to silica mass ratio distribution derived from the AUC-measured sedimentation coefficient distribution can be influenced. Moreover, through reasoned assumptions we arrive at an estimation of the patch yield that is close to that determined by arduous analysis of scanning electron microscopy (SEM) images. Finally, combining MWL-AUC, electrodynamic simulations and SEM image analysis we establish a procedure to estimate the patch thickness and coverage.

Structure and adsorption behavior of high hydrostatic pressure-treated ß-lactoglobulin.

HYPOTHESIS: High hydrostatic pressure treatment causes structural changes in interfacial-active ß-lactoglobulin (ß-lg). We hypothesized that the pressure-induced structural changes affect the intra- and intermolecular interactions which determine the interfacial activity of ß-lg. The conducted experimental and numerical investigations could contribute to the mechanistic understanding of the adsorption behavior of proteins in food-related emulsions. EXPERIMENTS: We treated ß-lg in water at pH 7 with high hydrostatic pressures up to 600 MPa for 10 min at 20 °C. The secondary structure was characterized with Fourier-transform infrared spectroscopy (FTIR) and circular dichroism (CD), the surface hydrophobicity and charge with fluorescence-spectroscopy and ζ-potential, and the quaternary structure with membrane-osmometry, analytical ultracentrifugation (AUC) and mass spectrometry (MS). Experimental analyses were supported through molecular dynamic (MD) simulations. The adsorption behavior was investigated with pendant drop analysis. FINDINGS: MD simulation revealed a pressure-induced molten globule state of ß-lg, confirmed by an unfolding of ß-sheets with FTIR, a stabilization of α-helices with CD and loss in tertiary structure induced by an increase in surface hydrophobicity. Membrane-osmometry, AUC and MS indicated the formation of non-covalently linked dimers that migrated slower through the water phase, adsorbed more quickly due to hydrophobic interactions with the oil, and lowered the interfacial tension more strongly than reference ß-lg.