Disclosed herein are automated systems for performing various biochemical and molecular biological procedures, including processor-controlled execution of protocols involving multiple steps performed in, on, or with liquid microdroplets. Example protocols are the various Polymerase Chain Reaction (PCR) protocols, but the subject systems are not limited to performing PCR protocols. Formation of a microdroplet of the sample for use in the described systems is achieved by bringing an amount of the sample into contact with a hydrophobic milieu, such as a superhydrophobic surface or hydrophobic liquid.