Brownian sieving enhancement of microcapillary hydrodynamic chromatography. Analysis of the separation performance based on Brenner's macro-transport theory.

In a recent article [Analytical Chemistry, 93(17), 6808-6816 (2021)], an unconventional device configuration enforcing a Brownian sieving mechanism was proposed as proof of concept for the efficient implementation of microcapillary hydrodynamic chromatography (MHDC). In this article, we perform a thorough analysis of the device geometry and of operating conditions, in order to single out the optimal configuration maximizing separation resolution. Brenner's macro-transport theory provides the technical picklock to perform the search for the optimum over a wide choice of device geometries and for a range of values of the particle Péclet number covering most conditions encountered in practical implementations of MHDC. Specifically, effective transport coefficients defining the dynamics of the suspended phase are obtained by the solution of a two-dimensional steady-state advection-diffusion equation defined onto the channel cross-section. The eigenvalue/eigenfunction structure of the associated transient problem is exploited in order to quantify the timescale for reaching the macro-transport regime conditions. Based on this timescale and on the effective transport parameters, an estimate of the column length necessary to achieve a prescribed level of separation resolution is obtained. We identify device geometry and operating conditions where the capillary length is shrunk down by a factor above ten compared to the standard MHDC configuration. Lagrangian stochastic statistics of particle ensembles are used to validate the results obtained through Brenner's macro-transport approach. The method proposed can be readily generalized to other classes of device geometries enforcing the same Brownian sieving mechanism.

Brownian Sieving Effect for Boosting the Performance of Microcapillary Hydrodynamic Chromatography. Proof of Concept.

Microcapillary hydrodynamic chromatography (MHDC) is a well-established technique for the size-based separation of suspensions and colloids, where the characteristic size of the dispersed phase ranges from tens of nanometers to micrometers. It is based on hindrance effects which prevent relatively large particles from experiencing the low velocity region near the walls of a pressure-driven laminar flow through an empty microchannel. An improved device design is here proposed, where the relative extent of the low velocity region is made tunable by exploiting a two-channel annular geometry. The geometry is designed so that the core and the annular channel are characterized by different average flow velocities when subject to one and the same pressure drop. The channels communicate through openings of assigned cut-off length, say A. As they move downstream the channel, particles of size bigger than A are confined to the core region, whereas smaller particles can diffuse through the openings and spread throughout the entire cross section, therein attaining a spatially uniform distribution. By using a classical excluded-volume approach for modeling particle transport, we perform Lagrangian-stochastic simulations of particle dynamics and compare the separation performance of the two-channel and the standard (single-channel) MHDC. Results suggest that a quantitative (up to thirtyfold) performance enhancement can be obtained at operating conditions and values of the transport parameters commonly encountered in practical implementations of MHDC. The separation principle can readily be extended to a multistage geometry when the efficient fractionation of an arbitrary size distribution of the suspension is sought.