CE with multi-walled carbon nanotubes (MWCNTs). Part I. Functionalized and SDS coated MWCNTs as pseudo-stationary phases in nanoparticle EKC - Studies on retention energetics.


Department of Chemistry, Oklahoma State University, Stillwater, OK 74078-3071, United States. Electronic address: [Email]


In this study, multi-walled carbon nanotubes (MWCNTs) in either unmodified, hydroxylated (MWCNT-OH), carboxylated (MWCNT-COOH) or sulfonated (MWCNT-SO3H) forms were incorporated into the running electrolytes in capillary electrophoresis (CE) to play the role of pseudo-stationary phases (PSPs) and perform nanoparticle electrokinetic capillary chromatography (NPEKC). MWCNT-COOH and MWCNT-SO3H were derived from MWCNTs via their treatment with concentrated strong acids. These functionalized MWCNTs were characterized by Raman and FTIR spectroscopies to demonstrate their covalent functionalization. The study of MWCNT-SO3H and MWCNT-OH as PSPs were introduced in this research report for the first time in NPEKC. The results obtained with functionalized MWCNTs were compared to those obtained using unmodified MWCNTs for better understanding the electrophoretic behavior of these functionalized MWCNTs. While only MWCNT-COOH allowed the separation of some nucleic acid bases and nucleosides, neutral solutes such as alkylbenzenes (ABs), phenyl alkyl alcohols (PAAs) and aniline derivatives in neutral forms (i.e., at basic pH) were not resolved in the presence of neither MWCNT-COOH nor MWCNT-SO3H in the running electrolytes, indicating that these functionalized MWCNTs do not have enough surface charge density to function as effective PSPs in NPEKC. This necessitated the coating of the functionalized MWCNTs under investigation with sodium dodecyl sulfate (SDS) to bring about the separation of neutral solutes by NPEKC. The SDS coated MWCNTs whether unmodified or functionalized were characterized with two homologous series namely ABs and PAAs in order to evaluate their relative retention energetics under the same electrolyte composition. The results showed that the systems pairs SDS-MWCNT-COOH/SDS-MWCNTs and SDS-MWCNT-OH/SDS-MWCNTs were homoenergetics (i.e., same energetics) while the system pair SDS-MWCNT-SO3H/SDS-MWCNTs was homeoenergetics (i.e., similar energetics). On the other hand, all the systems pairs SDS coated MWCNTs/SDS were homeoenergetics. Homoenergetics means that the solute retention has an identical physico-chemical basis and the differences observed in the magnitude of solute retention on the various PSPs are attributed to differences in the nonpolar phase ratios of the PSPs under otherwise the same electrolyte composition. Conversely, homeoenergetics signifies that the solute retention has a similar physico-chemical basis in the PSPs systems under investigation, which also differ in their phase ratios.


MWCNTs, Functionalized MWCNTs,Nanoparticle electrokinetic capillary chromatography,Pseudo-stationary phase,Retention energetics,