Unexpected surface chemistry in capillaries for electrophoresis

Good and reproducible capillary quality is needed to develop robust methods and to facilitate method transfer in CE. Physical surface defects no longer play a major role in variability of fused-silica capillaries. Nevertheless, problems are frequently being reported when buffers in the pH range between 4 and 7 are used. Thus the surface chemistry has been studied by X-ray photoelectron spectroscopy. Silicon–carbon bindings have been found on inner capillary surfaces for electrophoresis. This binding type is not completely removed by pre-conditioning with 1 M NaOH for 30 min. This corresponds to the result, that capillaries provide more stable migration times, especially in the pH range 4–7, when they are pre-conditioned for longer than 1 h. The origin of this Si–C bond is still not quite clear. They could be caused by graphite which is used during the fabrication of the raw cylinders prior to capillary drawing. Further investigations are intended in order to understand if there are any differences in surface carbon content from batch to batch and if this can influence experimental results in CE. A better understanding of the surface chemistry should not only improve robustness in CE, but also help to facilitate and accelerate capillary pre-conditioning and rinsing procedures to remove strongly adsorbed analytes or matrices.