This invention provides methods for using liquid junction potentials to control the transport of charged particles in fluid streams that are in laminar flow within microfluidic channels. Applications of the methods of this invention include sample preconditioning (removal of interfering substances), electrophoretic separation (fractionation) of charged particles, enhanced or delayed mixing of charged particles across a fluid interface relative to diffusion only, focusing charged particles in a fluid stream in one or two dimensions, and concentration of charged reactants at a fluid interface.