Solvent and pH effects on fast and ultrasensitive 1,1'-oxalyldi(4-methyl)imidazole chemiluminescence

Solvent and pH effects on fast and ultrasensitive 1,1'-oxalyldi(4-methyl)imidazole chemiluminescence (OD4MI-CL) were studied. The influences of these two factors on the complex OD4MI-CL reaction are discussed within a conceptual prototype for developing aqueous and non-aqueous capillary electrophoresis (ACE and NACE) devices with OD4MI-CL detection. The reaction channel length and OD4MI yield from the reaction between bis(2,4,6-trichlorophenyl) oxalate (TCPO) and 4-methylimidazole in the channel will be influenced by pH, water volume fraction, and cosolvent properties of the solution. Optimum OD4MI-CL efficiency is observed at pH 6.5 when 1-propanol, which has a low dielectric constant (epsilon = 20.8), is used as the NACE solvent in the separation channel. Water (epsilon = 80.1), the solvent in the ACE separation channel, acts similarly to a high dielectric constant organic solvent in NACE because the disadvantages normally associated with TCPO-CL reactions in water disappear due to the faster OD4MI-CL reaction versus OD4MI decomposition in aqueous solution. Therefore, it is expected that the OD4MI-CL detection system can be used in both NACE and ACE devices without requiring detector modifications. We also conclude that OD4MI-CL detection in NACE and ACE devices will be much more sensitive than the TCPO-CL detection used in current NACE devices.