María Tirado-Miranda

arXiv2024

Measuring Absolute Velocities from Non-Equilibrium Oscillations via Single-Detector 3D Dynamic Light Scattering

Single-detector 3D dynamic light scattering (3D-DLS) emerges as a reliable technique to determine the drift velocity of out-of-equilibrium colloidal particles. In particular, our investigation reveals the appearance of oscillations of a well-defined frequency in the autocorrelation function of the scattered intensity when particles are immersed in a medium exposed to thermally induced convection. These oscillations arise as a consequence of the directed motion of particles due to the convective motion of the fluid. The experimental results obtained for different colloidal systems are corroborated by a theoretical model and thoroughly validated with fluid dynamics and Brownian dynamics simulations. The excellent agreement between experimental, theoretical and simulation data allows us to provide a solid and comprehensive explanation of the observed physical phenomena. This study via advanced dynamic light scattering (DLS) technique offers insights into the field of non-equilibrium particle dynamics, applicable not only to colloidal suspension affected by steady-state diffusion-convection but also to other non-equilibrium situations, such as systems driven by external fields (gravitational, electric or magnetic fields, among others).

cond-mat.soft↗

arXiv2023

Diffusion and interaction effects on molecular release from collapsed microgels

The transport of biomolecules, drugs, or reactants encapsulated inside stimuli-responsive polymer networks in aqueous media is fundamental for many material and environmental science applications, including drug delivery, biosensing, catalysis, nanofiltration, water purification, and desalination. The transport is particularly complex in dense polymer media, such as collapsed hydrogels, where the molecules strongly interact with the polymer network and diffuse via a hopping mechanism. In this study, we employ Dynamical Density Functional Theory (DDFT) to investigate the non-equilibrium release kinetics of non-ionic subnanometer-sized molecules initially uploaded inside collapsed microgel particles. The theory is consistent with previous molecular dynamics simulations of collapsed poly($N$-isopropylacrylamide) (PNIPAM) polymer matrices, accommodating molecules of varying shapes and sizes. We found that, despite the intricate physico-chemical properties involved in the released process, the kinetics is predominantly dictated by two material parameters: the diffusion coefficient of the molecules inside the microgel ($D^*$) and the interaction free energy of the molecules with the microgel ($ΔG$). Our results reveal two distinct limiting regimes: For large, slowly diffusing molecules weakly attracted to the polymer network, the release is primarily driven by diffusion, with a release time that scales as $τ_{1/2} \sim 1/D^*$. Conversely, for small molecules strongly attracted to the polymer network, the release time is dominated by the interaction, scaling as $τ_{1/2} \sim \exp(-ΔG/k_{\textrm{B}} T)$. Our DDFT calculations are directly compared with an analytical equation for the half-release time, demonstrating excellent quantitative agreement. This equation represents a valuable tool for predicting release kinetics of non-ionic molecules from collapsed microgels.

cond-mat.soft↗