Direct in-line injection is successfully demonstrated for capillary electro
phoresis using a commercially available injection valve designed for liquid
chromatographic applications. The internal, fluid-contacting materials in
this valve injector are composed of ceramics and PEEK (polyetheretherketone
). In studies up to 20 kV, this materials design provides a sufficient diel
ectric interface to insulate the high-voltage buffer from the metal valve b
ody. Partial-loop injections from 6 to > 60 nL are shown to be highly repro
ducible and generally consistent with direct electrokinetic injections unde
r the same experimental conditions. The small extracolumn variance contribu
ted hy the valve injection system is symmetrical, and the measured theoreti
cal plates for 75-mum- and 100-mum-i.d., separation capillaries are 1.6 x 1
0(5) and 2.5 x 10(5), respectively, As a result, the separation performance
is quite good, demonstrating the viability of in-line valve injection for
capillary electrophoresis. This development in capillary electrophoretic in
strumentation has important implications for the advancement of electrophor
etic applications as well as for the design of completely integrated analys
is systems.