In addition to CZE, micellar electrokinetic chromatography (MEKC) is one of the most widely used CE modes. Electrokinetic chromatography separation involving micelles was first described by Terabe et al. (145) to extend application of CE to electrically neutral substances. Today, MEKC is an accepted method for the simultaneous separation of both neutral and ionic solutes. The method requires addition of a surfactant, such as sodium dodecyl sulfate (SDS), to the BGE at a concentration above its critical micelle concentration. Selectivity is based on the differential partitioning of solutes between micellar and aqueous phases and differential electrokinetic migration, including electro-osmotic and electrophoretic mobilities. Recently, Watari developed microemulsion electrokinetic chromatography (MEEKC) as an extension of MEKC (146). However, hyphenation of MEKC with MS is severely hampered by the presence of nonvolatile ionic surfactants, which often leads to a significant loss of electrospray efficiency and ion source contamination. The signal suppression mechanism can best

Table 2

Small Molecules Analyzed by CE-MS

Compounds CE mode Reference

Drugs of abuse CZE-ESI-MS 66-70

(amphetamine and derivatives, CZE-ESI-MS-MS 71-73

LSD, heroin, cocaine) NACE-ESI-MS 57,74

Carnitine, acylcarnitines CZE-ESI-MS-MS 75

Tricyclic antidepressant drugs EKC-ESI-MS 76


ß-Adrenergic blocker drugs EKC-ESI-MS 76

(propranolol, alprenolol)

ß-Agonists (clenbuterol and analogs) ITP-CZE-ESI-MS 77


Venlafaxine and metabolites NACE-ESI-MS 79

Chiral CE-ESI-MS 80

Tramadol and metabolites Chiral CE-ESI-MS 80,81

Methadone and EDDP Chiral CE-ESI-MS 80


Haloperidol and metabolites CZE-ESI-MS 52,83-86

Pyrazolacridines NACE-ESI-MS 86,87

Paracetamol, phenacetine, metabolites CZE-ESI-MS 88

Pseudoephedrine, dextrometorphan CZE-ESI-MS-MS 89 phenylpropanolamine, pyrilamine guaiafenesin, acetaminophen

Benzodiazepines and metabolites CZE-ESI-MS 90,92

CZE-ESI-MS-MS 91,93,144

Nonsteroidal anti-inflammatory drugs CZE-ESI-MS 95


Chiral CE-ESI-MS 96

Morphine CZE-ESI-MS-MS 143

Sulfonamides CZE-API-MS 90


Terbutaline, ketamine, propranolol Chiral CE-ESI-MS 98,99

Ephedrine Chiral CE-ESI-MS 99

Caffeine and metabolites MEKC-ESI-MS 150,155

Local anesthetics Chiral CE-ESI-MS 100

Chiral CE-ESI-MS-MS 101


Camphoresulfonic acid, tropic acid, Chiral CE-ESI-MS 102

arylpropionic acid, warfarin

Mifentidine and metabolites NACE-ESI-MS 52,86,103-105

Paracetamol and metabolites CZE-ESI-MS 106

Nonopioid analgesics and metabolites CZE-ESI-MS 107


CE mode


Diagnostic metabolites

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