Quantitative Analysis in Capillary Electrophoresis: Transformation of Raw Electropherograms into Continuous Distributions

Quantitative analysis in capillary electrophoresis based on time-scale electropherograms generally uses time-corrected peak areas to account for the differences in apparent velocities between solutes. However, it could be convenient and much more relevant to change the time-scale electropherograms into mass relative distribution of the effective mobility or any other characteristic parameter (molar mass, chemical composition, charge density, ...). In this study, the theoretical background required to perform the variable change on the electropherogram was developed with an emphasis on the fact that both <i>x</i> and <i>y</i> axes should be changed when the time scale electropherograms are modified to get the distributions. Applications to the characterization of polymers and copolymers by different modes of capillary electrophoresis (CE) are presented, including the molar mass distribution of poly-l-lysine oligomers by capillary gel electrophoresis (CGE), molar mass distribution of end-charged poly-l-alanine by free solution CE, molar mass distribution of evenly charged polyelectrolytes by CGE, and charge density distribution of variously charged polyelectrolytes by free solution CE

Acoustophoretic Mobility and Its Role in Optimizing Acoustofluidic Separations

In the separation sciences, sample species are separated according to their physicochemical properties, the nature of the selective field, and, if present, the properties of the medium in which they are dissolved or suspended. Separations may be carried out on a continuous basis in microfluidic devices or split-flow thin channel (SPLITT) devices by selectively transporting species in a direction transverse to the direction of flow of the suspending fluid. Separation is achieved in the so-called transport mode according to relative differences in mobility of the species under the influence of the applied field. Gravitational, centrifugal, thermal gradient, magnetic, electric, and dielectric fields may all be used for continuous SPLITT fractionation. We present here the theory for optimizing the operation of the relatively new technique of acoustic SPLITT fractionation for the continuous separation of non-Brownian materials. The theory is based on a quantitatively defined acoustophoretic mobility that is consistent with the generalized concept of mobility proposed by Giddings. Until now, acoustophoretic mobility has almost exclusively been used as a qualitative descriptor for velocity induced by an acoustic field. The quantitative definition presented here will contribute to the advancement of all forms of acoustofluidic separations

Measuring Arbitrary Diffusion Coefficient Distributions of Nano-Objects by Taylor Dispersion Analysis

Taylor dispersion analysis is an absolute and straightforward characterization method that allows determining the diffusion coefficient, or equivalently the hydrodynamic radius, from angstroms to submicron size range. In this work, we investigated the use of the Constrained Regularized Linear Inversion approach as a new data processing method to extract the probability density functions of the diffusion coefficient (or hydrodynamic radius) from experimental taylorgrams. This new approach can be applied to arbitrary polydisperse samples and gives access to the whole diffusion coefficient distributions, thereby significantly enhancing the potentiality of Taylor dispersion analysis. The method was successfully applied to both simulated and real experimental data for solutions of moderately polydisperse polymers and their binary and ternary mixtures. Distributions of diffusion coefficients obtained by this method were favorably compared with those derived from size exclusion chromatography. The influence of the noise of the simulated taylorgrams on the data processing is discussed. Finally, we discuss the ability of the method to correctly resolve bimodal distributions as a function of the relative separation between the two constituent species

Polydispersity Analysis of Taylor Dispersion Data: The Cumulant Method

Taylor dispersion analysis is an increasingly popular characterization method that measures the diffusion coefficient, and hence the hydrodynamic radius, of (bio)­polymers, nanoparticles, or even small molecules. In this work, we describe an extension to current data analysis schemes that allows size polydispersity to be quantified for an arbitrary sample, thereby significantly enhancing the potentiality of Taylor dispersion analysis. The method is based on a cumulant development similar to that used for the analysis of dynamic light scattering data. Specific challenges posed by the cumulant analysis of Taylor dispersion data are discussed, and practical ways to address them are proposed. We successfully test this new method by analyzing both simulated and experimental data for solutions of moderately polydisperse polymers and polymer mixtures

Limits in Size of Taylor Dispersion Analysis: Representation of the Different Hydrodynamic Regimes and Application to the Size-Characterization of Cubosomes

Taylor dispersion analysis (TDA) is an absolute method (no calibration needed) for the determination of the molecular diffusion coefficient (<i>D</i>) based on the band broadening of a solute in a laminar flow. TDA is virtually applicable to any solute with size ranging from angstrom to sub-micrometer. The higher sizing limit is restricted by the occurrence of possibly two regimes: convective and hydrodynamic chromatography (HDC) regimes, which have different physical origins that should not be confused. This work aims at clearly defining the experimental conditions for which these two regimes can play a role, alone or concomitantly. It also calculates the relative error on <i>D</i> due to the HDC regime according to the solute to capillary size ratio. It is demonstrated in this work that HDC does not significantly affect the TDA measurement as long as the hydrodynamic radius of the solute is lower than 0.0051 times the capillary radius. Experimental illustrations of the occurrence of the two regimes are given taking polystyrene nanoparticles as model solutes. Finally, application of TDA to the sizing of large real-life solutes is proposed, taking cubosomes as new drug nanocarriers of potential interest for drug delivery purposes