Lithographically fabricated templates have been used to imprint picoli
ter to femtoliter microvials in polystyrene. The clear microvials prod
uced in conjunction with a transmission optical microscope and microma
nipulators make it possible to handle volumes as small as 1 pt. Voltam
metry has been carried out in these well-defined microenvironments wit
h restriction of reagents near the electrode surface. Ferrocenecarboxy
lic acid has been utilized to characterize the electrochemical respons
e in these ultrasmall volumes. Sigmoidal voltammograms (0.4-2 V/s) are
obtained for vial sizes down to 1 pL.