Confocal Raman Microscopy Investigation of the Wetting of Reversed-Phase Liquid Chromatographic Stationary Phase Particles

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

doi:10.1021/ac901037d

Confocal Raman Microscopy Investigation of the Wetting of Reversed-Phase Liquid Chromatographic Stationary Phase Particles

Journal Article · Tue Aug 25 00:00:00 EDT 2009 · Analytical Chemistry

DOI:https://doi.org/10.1021/ac901037d· OSTI ID:2480668

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

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

Wetting phenomena in reversed-phase liquid chromatographic (RPLC) stationary phase particles strongly influence the retention of solutes with high water-content mobile phases. To better understand these phenomena, this work reports the spectroscopic observation of the wetting of the interior of individual C₁₈-silica stationary phase particles with acetonitrile–water mobile phase solutions by confocal Raman microscopy. It was found that the pores of dry C₁₈ silica do not wet when the concentration of acetonitrile is below 0.12 mol fraction (28% by volume). It was also found that there is a wetting hysteresis, where particles that had been previously exposed to acetonitrile solutions above the wetting transition remain filled with solution even at much lower concentrations of acetonitrile in the surrounding solution. Contact angles of acetonitrile–water solutions were measured at a planar C₁₈-modified silica surface and used to predict the capillary wetting of the particles based on the Young–Laplace equation. The solution composition at the wetting transition detected by Raman microscopy is higher in acetonitrile concentration than predicted by the Young–Laplace equation, which may be due to the presence of a vapor or air gap at the interface between the hydrophobic pores and aqueous solution. Further evidence of this behavior is found in water porosimetry results, which show wetting pressures ~5 times greater than predicted by the Young–Laplace equation and are consistent with only 50% of a water interface being in contact with the C₁₈ surface. Furthermore, this fraction increases to 80% at an acetonitrile concentration of 0.12 mol fraction, leading to spontaneous and irreversible wetting of the hydrophobic pores.

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:: 2480668

Journal Information:: Analytical Chemistry, Journal Name: Analytical Chemistry Journal Issue: 18 Vol. 81; ISSN 0003-2700

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (37)

Study of Penetration of Water into Hydrophobized Porous Silicas Fadeev, Alexander Y.; Eroshenko, Valentine A. Journal of Colloid and Interface Science, Vol. 187, Issue 2 https://doi.org/10.1006/jcis.1996.4495	journal	March 1997
Raman spectroscopic study of the conformational order of octadecylsilane stationary phases: effects of electrolyte and pH Orendorff, Christopher J.; Pemberton, Jeanne E. Analytical and Bioanalytical Chemistry, Vol. 382, Issue 3 https://doi.org/10.1007/s00216-005-3133-4	journal	March 2005
Characterization of C18-bonded liquid chromatographic stationary phases by Raman spectroscopy: Doyle, Charles A.; Vickers, Thomas J.; Mann, Charles K. Journal of Chromatography A, Vol. 877, Issue 1-2 https://doi.org/10.1016/S0021-9673(00)00174-6	journal	April 2000
Characterization of C18-bonded liquid chromatographic stationary phases by Raman spectroscopy: Doyle, Charles A.; Vickers, Thomas J.; Mann, Charles K. Journal of Chromatography A, Vol. 877, Issue 1-2 https://doi.org/10.1016/S0021-9673(00)00175-8	journal	April 2000
Raman spectroscopy of octadecylsilane stationary phase conformational order Pemberton, Jeanne E.; Ho, Mankit; Orendorff, Christopher J. Journal of Chromatography A, Vol. 913, Issue 1-2 https://doi.org/10.1016/S0021-9673(01)00569-6	journal	April 2001
Distribution of a solute between two phases Katz, E. D.; Ogan, K.; Scott, R. P. W. Journal of Chromatography A, Vol. 352 https://doi.org/10.1016/S0021-9673(01)83371-9	journal	February 1986
Conformational order of n-alkyl modified silica gels as evaluated by Fourier transform infrared spectroscopy Srinivasan, Gokulakrishnan; Neumann-Singh, Shashikala; Müller, Klaus Journal of Chromatography A, Vol. 1074, Issue 1-2 https://doi.org/10.1016/j.chroma.2005.03.056	journal	May 2005
Mechanism of retention loss when C8 and C18 HPLC columns are used with highly aqueous mobile phases Walter, Thomas H.; Iraneta, Pamela; Capparella, Mark Journal of Chromatography A, Vol. 1075, Issue 1-2 https://doi.org/10.1016/j.chroma.2005.04.039	journal	May 2005
Investigation on conformational order and mobility of DiamondBond-C18 and C18-alkyl modified silica gels by Fourier transform infrared and solid-state NMR spectroscopy Srinivasan, Gokulakrishnan; Kyrlidis, Angelos; McNeff, Clayton Journal of Chromatography A, Vol. 1081, Issue 2 https://doi.org/10.1016/j.chroma.2005.05.034	journal	July 2005
Fourier transform infrared spectrometric determination of alkyl chain conformation on chemically bonded reversed-phase liquid chromatography packings Sander, Lane C.; Callis, James B.; Field, Larry R. Analytical Chemistry, Vol. 55, Issue 7 https://doi.org/10.1021/ac00258a021	journal	June 1983
Confocal Raman Microscopy for Monitoring Chemical Reactions on Single Optically Trapped, Solid-Phase Support Particles Houlne, Michael P.; Sjostrom, Christopher M.; Uibel, Rory H. Analytical Chemistry, Vol. 74, Issue 17 https://doi.org/10.1021/ac020325t	journal	July 2002
Structure−Function Relationships in High-Density Octadecylsilane Stationary Phases by Raman Spectroscopy. 1. Effects of Temperature, Surface Coverage, and Preparation Procedure Ducey,, Michael W.; Orendorff, Christopher J.; Pemberton, Jeanne E. Analytical Chemistry, Vol. 74, Issue 21 https://doi.org/10.1021/ac0203488	journal	October 2002
Structure−Function Relationships in High-Density Octadecylsilane Stationary Phases by Raman Spectroscopy. 2. Effect of Common Mobile-Phase Solvents Ducey,, Michael W.; Orendorff, Christopher J.; Pemberton, Jeanne E. Analytical Chemistry, Vol. 74, Issue 21 https://doi.org/10.1021/ac0203490	journal	October 2002
Structure−Function Relationships in High-Density Octadecylsilane Stationary Phases by Raman Spectroscopy. 3. Effects of Self-Associating Solvents Orendorff, Christopher J.; Ducey,, Michael W.; Pemberton, Jeanne E. Analytical Chemistry, Vol. 75, Issue 14 https://doi.org/10.1021/ac020638o	journal	June 2003
Structure−Function Relationships in High-Density Octadecylsilane Stationary Phases by Raman Spectroscopy. 4. Effects of Neutral and Basic Aromatic Compounds Orendorff, Christopher J.; Ducey,, Michael W.; Pemberton, Jeanne E. Analytical Chemistry, Vol. 75, Issue 14 https://doi.org/10.1021/ac020639g	journal	June 2003
Optical-Trapping Raman Microscopy Detection of Single Unilamellar Lipid Vesicles Cherney, Daniel P.; Conboy, John C.; Harris, Joel M. Analytical Chemistry, Vol. 75, Issue 23 https://doi.org/10.1021/ac034838r	journal	December 2003
Structure−Function Relationships in High-Density Docosylsilane Bonded Stationary Phases by Raman Spectroscopy and Comparison to Octadecylsilane Bonded Stationary Phases Liao, Zhaohui; Orendorff, Christopher J.; Sander, Lane C. Analytical Chemistry, Vol. 78, Issue 16 https://doi.org/10.1021/ac060385p	journal	July 2006
Microscopic Origins of Band Broadening in Chromatography. Polarity Distribution in C₁₈ Stationary Phase Probed by Confocal Ratiometric Imaging of Nile Red Zhong, Zhenming; Geng, M. Lei Analytical Chemistry, Vol. 79, Issue 17 https://doi.org/10.1021/ac071272o	journal	July 2007
Distribution phenomena of mobile-phase components and determination of dead volume in reversed-phase liquid chromatography McCormick, R. M.; Karger, B. L. Analytical Chemistry, Vol. 52, Issue 14 https://doi.org/10.1021/ac50064a005	journal	December 1980
Structure−Function Relationships in High-Density Docosylsilane Bonded Stationary Phases by Raman Spectroscopy and Comparison to Octadecylsilane Bonded Stationary Phases: Effects of Common Solvents Liao, Zhaohui; Pemberton, Jeanne E. Analytical Chemistry, Vol. 80, Issue 8 https://doi.org/10.1021/ac702270b	journal	March 2008
Confocal Raman Microscopy of the Interfacial Regions of Liquid Chromatographic Stationary-Phase Materials Gasser-Ramirez, Jennifer L.; Harris, Joel M. Analytical Chemistry, Vol. 81, Issue 8 https://doi.org/10.1021/ac802541p	journal	March 2009
Wetting of Octadecylsilylated Silica in Methanol−Water Eluents Li, Zengbiao; Rutan, Sarah C.; Dong, Shannian Analytical Chemistry, Vol. 68, Issue 1 https://doi.org/10.1021/ac950666p	journal	January 1996
Characterization of Octadecylsilane Stationary Phases on Commercially Available Silica-Based Packing Materials by Raman Spectroscopy Ho, Mankit; Cai, Mei; Pemberton, Jeanne E. Analytical Chemistry, Vol. 69, Issue 13 https://doi.org/10.1021/ac961118u	journal	July 1997
Alkyl Chain Conformation of Octadecylsilane Stationary Phases by Raman Spectroscopy. 1. Temperature Dependence Ho, Mankit; Pemberton, Jeanne E. Analytical Chemistry, Vol. 70, Issue 23 https://doi.org/10.1021/ac980471s	journal	December 1998
Wetting in Hydrophobic Nanochannels: A Challenge of Classical Capillarity Helmy, Roy; Kazakevich, Yuri; Ni, Chaoying Journal of the American Chemical Society, Vol. 127, Issue 36 https://doi.org/10.1021/ja053267c	journal	August 2005
Observing Capillarity in Hydrophobic Silica Nanotubes Jayaraman, Karthik; Okamoto, Kenji; Son, Sang Jun Journal of the American Chemical Society, Vol. 127, Issue 49 https://doi.org/10.1021/ja055535c	journal	November 2005
The Solvation of Acetonitrile Reimers, Jeffrey R.; Hall, Lachlan E. Journal of the American Chemical Society, Vol. 121, Issue 15 https://doi.org/10.1021/ja983878n	journal	April 1999
Quantitative Correlation of Raman Spectral Indicators in Determining Conformational Order in Alkyl Chains Orendorff, Christopher J.; Ducey, Michael W.; Pemberton, Jeanne E. The Journal of Physical Chemistry A, Vol. 106, Issue 30 https://doi.org/10.1021/jp014311n	journal	July 2002
Activation Barrier Scaling for the Spontaneous Evaporation of Confined Water ^† Luzar, Alenka The Journal of Physical Chemistry B, Vol. 108, Issue 51 https://doi.org/10.1021/jp0470703	journal	December 2004
Hydrophobicity at Small and Large Length Scales Lum, Ka; Chandler, David; Weeks, John D. The Journal of Physical Chemistry B, Vol. 103, Issue 22 https://doi.org/10.1021/jp984327m	journal	June 1999
When Wenzel and Cassie Are Right: Reconciling Local and Global Considerations Marmur, Abraham; Bittoun, Eyal Langmuir, Vol. 25, Issue 3 https://doi.org/10.1021/la802667b	journal	January 2009
Direct Observation of Wetting and Diffusion in the Hydrophobic Interior of Silica Nanotubes Okamoto, Kenji; Shook, Charles J.; Bivona, Louis Nano Letters, Vol. 4, Issue 2 https://doi.org/10.1021/nl034954+	journal	January 2004
Wettability of porous surfaces Cassie, A. B. D.; Baxter, S. Transactions of the Faraday Society, Vol. 40, p. 546-551 https://doi.org/10.1039/tf9444000546	journal	January 1944
Water confined in cylindrical micropores Giaya, Arjan; Thompson, Robert W. The Journal of Chemical Physics, Vol. 117, Issue 7 https://doi.org/10.1063/1.1494419	journal	August 2002
High-resolution in situ x-ray study of the hydrophobic gap at the water-octadecyl-trichlorosilane interface Mezger, M.; Reichert, H.; Schoder, S. Proceedings of the National Academy of Sciences, Vol. 103, Issue 49 https://doi.org/10.1073/pnas.0608827103	journal	November 2006
III. An essay on the cohesion of fluids Young, Thomas Philosophical Transactions of the Royal Society of London, Vol. 95, p. 65-87 https://doi.org/10.1098/rstl.1805.0005	journal	January 1805
Transformation of a Simple Plastic into a Superhydrophobic Surface Erbil, H. Y.; Demirel, A. Levent; Avcl, Yonca Science, Vol. 299, Issue 5611, p. 1377-1380 https://doi.org/10.1126/science.1078365	journal	February 2003

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