Transport of ions and biomolecules through asymmetric single nanopores fabricated by heavy ion irradiation and chemical etching

In the framework of the CRP 'Radiation Synthesis of Stimuli-responsive Membranes, Hydrogels and Adsorbents for Separation Purposes', GSI has worked on the production of polymeric single conical nanopores and the study of the ionic transport through these pores. To produce single-pore membranes, polyethylene teraphthalate (PET) and polyimide (PI) foils were first irradiated with GeV single heavy ions. By subsequent one-side etching, asymmetric nanopores were created. The diameter of the conical pores in PET varied between 4-20 nm at the small opening and several hundred nm at the large opening. In the case of PI, due to the higher bulk etching rate, the large aperture reached a few μm. The current-voltage (I-V) characteristics were measured at symmetric electrolyte conditions of KCl at various concentrations and pH values. It was found that conical nanopores with charged surfaces are cation selective, and show preferential cation flow (i.e. rectification) from the narrow entrance to the wide opening of the cone. Concentration and pH influence the rectification properties for both polymers was studied. The experimental results are in agreement with existing models. The transient transport properties of single PET and PI pores were also investigated. The ion current through PET nanopores fluctuates considerably, the fluctuation depending on the voltage, whereas PI nanopores display a stable current signal for KCl concentrations between 0.1 and 3 M, and pH values between 2 and 8. This different behavior has been attributed to the chemical structure of the two polymers influencing surface characteristics of the resulting nanopores. Finally, the application of polyimide conical nanopores as single-molecule-DNA sensors is being investigated. First results demonstrate their ability to detect individual plasmid DNA molecules. The nanopore sensor is also able to discriminate between DNA fragments of different lengths. (author)