Separations at the Speed of Sensors.

Abstract

The virtue of chemical sensors is speed and analyte specificity. The response time to generate an analytical signal typically varies from ∼1 to 20 s, and they are generally limited to a single analyte. Chemical sensors are significantly affected by multiple interferents, matrix effects, temperature, and can vary widely in sensitivity depending on the sensor format. Separation-based analyses remove matrix effects and interferents and are compatible with multiple analytes. However, the speed of such analyses has not been commensurate with traditional sensors until now. Beds of very small size with optimal geometry, containing core-shell particles of judicious immobilized selectors, can be used in an ultrahigh-flow regime, thereby providing subsecond separations of up to 10 analytes. Short polyether ether ketone lined stainless steel columns of various geometries were evaluated to determine the optimal bed geometry for subsecond analysis. Coupling these approaches provides subsecond-based detection and quantitation of multiple chiral and achiral species, including nucleotides, plant hormones, acids, amino acid derivatives, and sedatives among a variety of other compounds. The subsecond separations were reproducible with 0.9% RSD on retention times and showed consistent performance with 0.9% RSD on reduced plate height in van Deemter curves. A new powerful signal processing algorithm is proposed that can further enhance separation outputs and optical spectra without altering band areas on more complex separations such as 10 peaks under a second.