Confocal Raman Microscopy of the Interfacial Regions of Liquid Chromatographic Stationary-Phase Materials

Gasser-Ramirez, Jennifer L.; Harris, Joel M.

doi:10.1021/ac802541p

Confocal Raman Microscopy of the Interfacial Regions of Liquid Chromatographic Stationary-Phase Materials

Journal Article · Mon Mar 16 00:00:00 EDT 2009 · Analytical Chemistry

DOI:https://doi.org/10.1021/ac802541p· OSTI ID:2480669

Gasser-Ramirez, Jennifer L. ^[1]; Harris, Joel M. ^[1]

University of Utah, Salt Lake City, UT (United States)

The influence of organic modifiers on the structure of reversed-phase liquid chromatographic (RPLC) stationary phases has been a topic of considerable investigation. Retention of organic modifiers in the stationary phase has previously been determined by chromatographic measurements, and the polarity and heterogeneity of the resulting solvation environment has been studied using solvatochromic, fluorescent, and spin probes. In the present work, the composition and solvation environment of a stationary phase is investigated using confocal Raman microscopy, which allows the in situ examination of the solvation environment within individual chromatographic stationary phase particles without the use of probe molecules. The accumulation of organic modifiers in the stationary phase can be quantified, and the environment of the modifier in the stationary phase can be determined. Specifically, we have investigated the interactions of acetonitrile with C₁₈-functionalized silica particles using confocal Raman microscopy, which enables the sampling of small (~1 fL) volumes within individual 10 μm particles. Bare chromatographic silica was also studied in order to investigate the interactions of acetonitrile with surface silanols. The nitrile-stretching (ν_CN) frequency of acetonitrile responds sensitively to the dipolarity of its local microenvironment. The populations of solution-phase and interfacial acetonitrile are thus spectroscopically distinguishable. Scattering from ν_CN shows contributions from three different environments within a single RPLC chromatographic particle: acetonitrile in the interparticle mobile phase, C₁₈-chain associated acetonitrile, and acetonitrile that is interacting with residual surface silanols. Here, data are presented quantifying these populations and characterizing their environments within single stationary phase particles.

View Accepted Manuscript (DOE)

Research Organization:: University of Utah, Salt Lake City, UT (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: FG03-93ER14333

OSTI ID:: 2480669

Journal Information:: Analytical Chemistry, Journal Name: Analytical Chemistry Journal Issue: 8 Vol. 81; ISSN 0003-2700

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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