Carbohydrate-Based Polymeric Surfactants for Chiral Micellar Electrokinetic Chromatography (CMEKC) Coupled to Mass...

Polymeric surfactants (molecular micelles, M_oM_s) with a variety of chiral head groups and chain lengths may be the most promising chiral selectors when used for sensitive detection of chiral compounds in micellar electrokinetic chromatography-mass spectrometry (MEKC-MS). Various carbohydrate-based MS compatible surfactants with phosphate and sulfate head groups have been recently synthesized in our laboratory for its application in CMEKC-MS. In this chapter, we illustrate that the synthesized glucopyranoside-based M_oMs are fully compatible with electrospray ionization MS and can be successfully used as a chiral selector for high-throughput screening of multiple chiral compounds using MRM mode in CMEKC-MS/MS experiments. This chapter describes in detail synthesis and utility of α- and β-glucopyranoside-based polymeric surfactant with two different chain lengths and head groups. The presented examples optimize the effect of appropriate millimolar concentration of monomer sugar surfactants required for polymerization as it affects the separations of acidic and basic compounds. Under the optimized concentration of the monomer needed for polymerization (i.e., an equivalent monomer concentration of M_oM_s), the superiority of MEKC-MS over MEKC-UV is evident. Structurally similar basic drugs with the difference in hydrophobicity are first tested in MEKC-MS to find the optimum head group and optimum chain length with the aim for developing a widely applicable polymeric glucopyranoside-based surfactant. The partial enantioresolution of several structurally similar basic compounds is significantly improved when switching from one head group to another head group of the glucopyranoside M_oM_s. Thus, complementary separations using poly-N-β-D-SUGP versus poly-N-β-D-SUGS were seen. This phenomenon also exists when comparing the M_oM_s, which differ in an anomeric configuration such as poly-N-α-D-SUGP and poly-N-β-D-SUGP.