In cell-matrix adhesions, integrin receptors and associated proteins provide a dynamic coupling of the extracellular matrix (ECM) to the cytoskeleton. This allows bidirectional transmission of... Show moreIn cell-matrix adhesions, integrin receptors and associated proteins provide a dynamic coupling of the extracellular matrix (ECM) to the cytoskeleton. This allows bidirectional transmission of forces between the ECM and the cytoskeleton, which tunes intracellular signaling cascades that control survival, proliferation, differentiation, and motility. The quantitative relationships between recruitment of distinct cell-matrix adhesion proteins and local cellular traction forces are not known. Here, we applied quantitative super-resolution microscopy to cell-matrix adhesions formed on fibronectin-stamped elastomeric pillars and developed an approach to relate the number of talin, vinculin, paxillin, and focal adhesion kinase (FAK) molecules to the local cellular traction force. We find that FAK recruitment does not show an association with traction-force application, whereas a ∼60 pN force increase is associated with the recruitment of one talin, two vinculin, and two paxillin molecules on a substrate with an effective stiffness of 47 kPa. On a substrate with a fourfold lower effective stiffness, the stoichiometry of talin:vinculin:paxillin changes to 2:12:6 for the same ∼60 pN traction force. The relative change in force-related vinculin recruitment indicates a stiffness-dependent switch in vinculin function in cell-matrix adhesions. Our results reveal a substrate-stiffness-dependent modulation of the relationship between cellular traction-force and the molecular stoichiometry of cell-matrix adhesions. Show less
In this work, we present an in-depth study of the role of mass transport conditions in tuning the hydrogen evolution kinetics on gold by means of rotation rate control. Interestingly, we find that... Show moreIn this work, we present an in-depth study of the role of mass transport conditions in tuning the hydrogen evolution kinetics on gold by means of rotation rate control. Interestingly, we find that the hydrogen evolution reaction (HER) activity decreases with the increasing rotation rate of the electrode. As we increase the rotation (mass transport) rate, the locally generated hydroxyl ions (2H(2)O +2e(-) & RARR; H-2 + 2OH(-)) are transported away from the electrode surface at an accelerated rate. This results in decreasing local pH and, because of the need to satisfy local electroneutrality, decreasing near-surface cation concentration. This decrease in the near-surface cation concentration results in the suppression of HER. This is because the cations near the surface play a central role in stabilizing the transition state for the rate determining Volmer step (*H-OH delta--cat(+)). Furthermore, we present a detailed analytical model that qualitatively captures the observed mass transport dependence of HER solely based on the principle of electroneutrality. Finally, we also correlate the cation identity dependence of HER on gold (Li+ < Na+ < K+) to the changes in the effective concentration of the cations in the double layer with the changes in their solvation energy. Show less
Joy, D.; Souvik, M.; Satrajit, A.; Spiering, P.; Meyer, J.; Somers, M.F. 2021
We show how an existing concurrent multi-scale method named hybrid particle field-molecular dynamics (hPF-MD) can be adapted to enable the simulation of structure and/or structural dynamics in... Show moreWe show how an existing concurrent multi-scale method named hybrid particle field-molecular dynamics (hPF-MD) can be adapted to enable the simulation of structure and/or structural dynamics in compressible systems. Implementing such new equations of state (EOS) into hPF-MD, while conserving the efficiency associated with treating intermolecular interactions in a continuum fashion, opens this method up to describe a new class of phenomena in which non-uniform densities play a role, for example, evaporation and crystallization. We carefully consider how compressible hPF-MD compares to its mean-field counterpart for two particular EOS, adopted from the Cell Model for polymers and the Carnahan-Starling expression for hard spheres. Here, we performed a very basic analysis for a single-component system, focusing on the significance of various particle-based parameters and the particle-to-field projection. Our results illustrate the key role of the particle density per field grid cell and show that projection based on a Gaussian kernel is preferred over the standard cloud-in-cell projection. They also suggest that the behavior of hPF-MD close to the critical point is non-classical, i.e., in agreement with a critical exponent for a pure particle description, despite the mean-field origin of the method. Show less
Reactions of molecules on metal surfaces are notoriously difficult to simulate accurately. Density functional theory can be utilized to generate a potential energy surface, but with presently... Show moreReactions of molecules on metal surfaces are notoriously difficult to simulate accurately. Density functional theory can be utilized to generate a potential energy surface, but with presently available functionals, the results are not yet accurate enough. To provide benchmark barrier heights with a high-quality method, diffusion Monte Carlo (DMC) is applied to H-2 + Al(110). Barrier heights have been computed for six geometries. Our present goal is twofold: first, to provide accurate barrier heights for the two lowest lying transition states of the system, and second, to assess whether density functionals are capable of describing the variation of barrier height with molecular orientation and impact site through a comparison with DMC barriers. To this end, barrier heights computed with selected functionals at the generalized gradient approximation (GGA) and meta-GGA levels are compared to the DMC results. The comparison shows that all selected functionals yield a rather accurate description of the variation of barrier heights with impact site and orientation, although their absolute values may not be accurate. RPBE-vdW-DF and BEEF-vdW were found to perform quite well even in terms of absolute numbers. Both functionals provided barrier heights for the energetically lowest lying transition state that are within 1 kcal/mol of the DMC value. Show less
Sevink G.J.A., Liwo J.A., Asinari P., MacKernan D., Milano G., Pagonabarraga I. 2020
Stepped transition metal surfaces, including the reconstructed Pt(110)-(2 × 1) surface, can be used to model the effect of line defects on catalysts. We present a combined experimental and... Show moreStepped transition metal surfaces, including the reconstructed Pt(110)-(2 × 1) surface, can be used to model the effect of line defects on catalysts. We present a combined experimental and theoretical study of CHD3 dissociation on this surface. Theoretical predictions for the initial sticking coefficients, S0, are obtained from ab initio molecular dynamics calculations using the specific reaction parameter (SRP) approach to density functional (DF) theory, while the measured sticking coefficients were obtained using the King and Wells method. The SRP DF used here had been previously derived for methane dissociation on Pt(111) so that the experiments test the transferability of this SRP DF to methane + Pt(110)-(2 × 1). The agreement between the experimental and calculated S0 is poor, with the average energy shift between the theoretical and measured reactivities being 20 kJ/mol. There are two factors which may contribute to this difference, the first of which is that there is a large uncertainty in the calculated sticking coefficients due to a large number of molecules being trapped on the surface at the end of the 1 ps propagation time. The second is that the SRP32-vdW functional may not accurately describe the Pt(110)-(2 × 1) surface. At the lowest incident energies considered here, Pt(110)-(2 × 1) is more reactive than the flat Pt(111) surface, but the situation is reversed at incident energies above 100 kJ/mol. Show less
An important industrial process is methanol steam reforming, which is typically used in conjunction with copper catalysts. However, little agreement exists on the reaction mechanisms involved on a... Show moreAn important industrial process is methanol steam reforming, which is typically used in conjunction with copper catalysts. However, little agreement exists on the reaction mechanisms involved on a copper catalyst. Therefore, we have performed research yielding additional insight into the reaction mechanism for dissociative chemisorption of methanol on Cu(111) using ab initio molecular dynamics, supported by static calculations of the molecule-surface interaction with density functional theory. Our work predicts that after the initial dissociation, formaldehyde is formed through three different mechanisms. Additionally, it is observed that at high energy, CH cleavage is the dominant pathway instead of the formerly presumed OH cleavage pathway. Finally, in order to describe the interaction of methanol with the metal surface, the SRP32-vdW functional is used, which has been previously developed and tested for CHD3 on Ni(111), Pt(111), and Pt(211) using the Specific Reaction Parameter (SRP) approach. In this work, the SRP32-vdW functional is applied to methanol on Cu(111) as well, in the hope that future experiments can validate the transferability of the SRP32-vdW functional to chemically related molecule-metal surface systems. Show less
The curvature dependence of the surface tension can be described by the Tolman length (first-order correction) and the rigidity constants (second-order corrections) through the Helfrich expansion.... Show moreThe curvature dependence of the surface tension can be described by the Tolman length (first-order correction) and the rigidity constants (second-order corrections) through the Helfrich expansion. We present and explain the general theory for this dependence for multicomponent fluids and calculate the Tolman length and rigidity constants for a hexane-heptane mixture by use of square gradient theory. We show that the Tolman length of multicomponent fluids is independent of the choice of dividing surface and present simple formulae that capture the change in the rigidity constants for different choices of dividing surface. For multicomponent fluids, the Tolman length, the rigidity constants, and the accuracy of the Helfrich expansion depend on the choice of path in composition and pressure space along which droplets and bubbles are considered. For the hexane-heptane mixture, we find that the most accurate choice of path is the direction of constant liquid-phase composition. For this path, the Tolman length and rigidity constants are nearly linear in the mole fraction of the liquid phase, and the Helfrich expansion represents the surface tension of hexane-heptane droplets and bubbles within 0.1% down to radii of 3 nm. The presented framework is applicable to a wide range of fluid mixtures and can be used to accurately represent the surface tension of nanoscopic bubbles and droplets Show less
