Power Law Behavior in Protein Desorption Kinetics Originating from Sequential Binding and Unbinding

Armstrong, Megan J.; Rodríguez, Juan B.; Dahl, Peter; Salamon, Peter; Hess, Henry; Katira, Parag

doi:10.1021/acs.langmuir.0c02260

Cited by 5 publications

(12 citation statements)

References 66 publications

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“…Previous work pointed out a nonzero probability of losing objects could be responsible for the downward deviation . Interestingly, the emergence of an apparent power-law form of CCRTDs at short timescales is consistent with previous work studying the desorption kinetics of plasma proteins at interfaces between aqueous solution and hydrophobic, hydrophilic, and nonfouling surfaces. ,− …”

Section: Resultssupporting

confidence: 89%

“…22,48−50 The complex desorption process can be modeled as an initially adsorbed object that performs random walk over a rugged energy landscape. 37 Protein Desorption Exhibits Aging. To understand the most likely underlying mechanism leading to the broad range of timescales, we designed a specific set of analyses and measurements.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…To test this hypothesis quantitatively, we modeled CCRTDs using kinetic Monte Carlo simulations involving a state-balance model. 37 The simulation details are described in the SI. In short, the desorption energy exploration can be modeled as a biased random walk on a rugged one-dimensional energy landscape possessing a number (N) of wells of various depths, each of which corresponds to specific binding energy (Figure 4C).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Protein Desorption Kinetics Depends on the Timescale of Observation

et al. 2022

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The presence of so-called reversible and irreversible protein adsorption on solid surfaces is well documented in the literature and represents the basis for the development of nanoparticles and implant materials to control interactions in physiological environments. Here, using a series of complementary single-molecule tracking approaches appropriate for different timescales, we show that protein desorption kinetics is much more complex than the traditional reversible–irreversible binary picture. Instead, we find that the surface residence time distribution of adsorbed proteins transitions from power law to exponential behavior when measured over a large range of timescales (10–2–106 s). A comparison with macroscopic results obtained using a quartz crystal microbalance suggested that macroscopic measurements have generally failed to observe such nonequilibrium phenomena because they are obscured by ensemble-averaging effects. These findings provide new insights into the complex phenomena associated with protein adsorption and desorption.

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Section: Resultssupporting

confidence: 89%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

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Protein Desorption Kinetics Depends on the Timescale of Observation

et al. 2022

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“…While our work here focuses on 5 μm chiral stationary phase particles, HILO can be applied to a broad class of real separation materials related to the interests of analytical chemists and chemical engineers, such as cellulose, 39 silica, 16,17 and polymer 40,41 based structures, model ligands, 11,42 and films. 33,43 With future iterations of this imaging approach, we recommend the use of finer axial position controls and index of refraction media to improve localization precision.…”

Section: ■ Resultsmentioning

confidence: 99%

Single-Molecule Imaging in Commercial Stationary Phase Particles Using Highly Inclined and Laminated Optical Sheet Microscopy

Neria

Kisley

2023

Anal. Chem.

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We resolve the three-dimensional, nanoscale locations of single-molecule analytes within commercial stationary phase materials using highly inclined and laminated optical sheet (HILO) microscopy. Single-molecule fluorescence microscopy of chromatography can reveal the molecular heterogeneities that lead to peak broadening, but past work has focused on surfaces designed to mimic stationary phases, which have different physical and chemical properties than the three-dimensional materials used in real columns and membranes. To extend single-molecule measurements to commercial stationary phases, we immobilize individual stationary phase particles and modify our microscope for imaging at further depths with HILO, a method which was originally developed to resolve single molecules in cells of comparable size to column packing materials (∼5–10 μm). We describe and characterize how to change the angle of incidence to achieve HILO so that other researchers can easily incorporate this method onto their existing epi- or total internal reflection fluorescence microscopes. We show improvements up to a 32% in signal-to-background ratio and 118% in the number of single molecules detected within stationary phase particles when using HILO compared to epifluorescence. By controlling the objective position relative to the sample, we produce three-dimensional maps of molecule locations throughout entire stationary phase particles at nanoscale lateral and axial resolutions. The number of localized molecules remains constant axially throughout isolated stationary phase particles and between different particles, indicating that heterogeneity in a separation would not be caused by such affinity differences at microscales but instead kinetic differences at nanoscales on identifiable and distinct adsorption sites.

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“…This would not impact α unless more than one region of the particle can bind stochastically to mucins, increasing the binding time beyond the sampling time, t b ≫Δt eff . This would lead to an effective power-law distribution of binding times with no apparent characteristic binding time [49,50]. The emergence of longtailed attachment time distributions leads to subdiffusion.…”

Section: Discussionmentioning

confidence: 99%

Empirical and Theoretical Analysis of Particle Diffusion in Mucus

et al. 2021

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Mucus is a complex fluid that coats multiple organs in animals. Various physicochemical properties can alter the diffusion of microscopic particles in mucus, impacting drug delivery, virus infection, and disease development. The simultaneous effect of these physicochemical properties in particle diffusion, however, remains elusive. Here, we analyzed 106 published experiments to identify the most dominant factors controlling particle diffusion in mucus. The effective diffusion—defined using a one-second sampling time window across experiments—spanned seven orders of magnitude, from 10–5 to 102 μm2/s. Univariate and multivariate statistical analyses identified the anomalous exponent (the logarithmic slope of the mean-squared displacement) as the strongest predictor of effective diffusion, revealing an exponential relationship that explained 89% of the variance. A theoretical scaling analysis revealed that a stronger correlation of the anomalous exponent over the generalized diffusion constant occurs for sampling times two orders of magnitude larger than the characteristic molecular (or local) displacement time. This result predicts that at these timescales, the molecular properties controlling the anomalous exponent, like particle–mucus unbinding times or the particle to mesh size ratio, would be the most relevant physicochemical factors involved in passive microrheology of particles in mucus. Our findings contrast with the fact that only one-third of the studies measured the anomalous exponent, and most experiments did not report the associated molecular properties predicted to dominate the motion of particles in mucus. The theoretical foundation of our work can be extrapolated to other systems, providing a guide to identify dominant molecular mechanisms regulating the mobility of particles in mucus and other polymeric fluids.

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Power Law Behavior in Protein Desorption Kinetics Originating from Sequential Binding and Unbinding

Cited by 5 publications

References 66 publications

Protein Desorption Kinetics Depends on the Timescale of Observation

Protein Desorption Kinetics Depends on the Timescale of Observation

Single-Molecule Imaging in Commercial Stationary Phase Particles Using Highly Inclined and Laminated Optical Sheet Microscopy

Empirical and Theoretical Analysis of Particle Diffusion in Mucus

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