Electrophoretic capture and detection of nanoparticles at the opening of a membrane pore using scanning electrochemical microscopy.

Stochastic electrophoretic capture of individual nanometer-scale particles at the small opening of a conically shaped nanopore in a synthetic membrane is described. Particle capture is sensed using a scanning electrochemical microscope (SECM) to measure the decrease in the transport rate of a redox-active molecule through the pore. The SECM tip is positioned at the larger backside opening of pore and used to amperometrically monitor the transport rate prior, during, and after particle capture. Following capture, the particle is released by electrophoretically driving it out of the pore opening and back into the solution. The capture and release method is demonstrated by detection of charged polystyrene spheres (43-150-nm diameter) using a polycarbonate membrane with conically shaped pores, the small opening of the pore having a diameter of 60 nm. The inverse of the time to capture polystyrene spheres increases with particle concentration over the range 10(8)-10(10) particles/mL. Selective detection based on nanoparticle charge and size is also demonstrated. A quantitative theoretical description of the rate of particle capture is presented, and the physical mechanism of particle capture, based on the balance of electrostatic and entropic forces, is considered.