Characterization and application of ion track-etched nanopores

This thesis investigates the ionic transport properties of single, conical nanopores in polymers, as well as their applicability as single-molecule sensors. The pores were produced by selective etching of the damaged zones of energetic heavy ions (track-etching technique). More basic investigations of the shape of track-etched pores (by small-angle X-ray scattering, electron microscopy and conductometry) are also included, revealing smaller pore sizes on top of a membrane than inside the pore. Conical track-etched nanopores are cation selective and show asymmetric I-V characteristics, depending on pH value and concentration of the electrolyte. These properties result from their negative surface charges created during the etching process, which lead to an intrinsic asymmetric electric potential long the pore axis. Experiments show a maximum for the rectification at about 0.1 M KCl, in accordance with theoretical calculations. The selectivity of the pores depends on the direction of an applied concentration gradient, being higher for the lower concentration facing the small opening of the pore, again in agreement with calculations. The pores transport properties are strongly influenced by small concentrations of divalent cations. Conical polyimide pores have been found suitable to detect single DNA molecules passing through them via changes in the ionic current

Ion transport and selectivity in nanopores with spatially inhomogeneous fixed charge distributions

Polymeric nanopores with fixed charges show ionic selectivity when immersed in aqueous electrolyte solutions. The understanding of the electrical interaction between these charges and the mobile ions confined in the inside nanopore solution is the key issue in the design of potential applications. The authors have theoretically described the effects that spatially inhomogeneous fixed charge distributions exert on the ionic transport and selectivity properties of the nanopore. A comprehensive set of one-dimensional distributions including the skin, core, cluster, and asymmetric cases are analyzed on the basis of the Nernst-Planck equations. Current-voltage curves, nanopore potentials, and transport numbers are calculated for the above distributions and compared with those obtained for a homogeneously charged nanopore with the same average fixed charge concentration. The authors have discussed if an appropriate design of the spatial fixed charge inhomogeneity can lead to an enhancement of the transport and selectivity with respect to the homogeneous nanopore case. Finally, they have compared the theoretical predictions with relevant experimental [email protected] [email protected]

Ionic conduction, rectification, and selectivity in single conical nanopores

Modern track-etching methods allow the preparation of membranes containing a single charged conical nanopore that shows high ionic permselectivity due to the electrical interactions of the surface pore charges with the mobile ions in the aqueous solution. The nanopore has potential applications in electrically assisted single-particle detection, analysis, and separation of biomolecules. We present a detailed theoretical and experimental account of the effects of pore radii and electrolyte concentration on the current-voltage and current-concentration curves. The physical model used is based on the Nernst-Planck and Poisson equations. Since the validity of continuum models for the description of ion transport under different voltages and concentrations is recognized as one of the main issues in the modeling of future applications, special attention is paid to the fundamental understanding of the electrical interactions between the nanopore fixed charges and the mobile charges confined in the reduced volume of the inside [email protected]

Biosensing with Functionalized Single Asymmetric Polymer Nanochannels

In this work, we describe the direct covalent attachment of protein recognition elements (biotin) with the carboxyl groups present on the walls of polyimide nanochannels. Subsequently, these biotinylated channels were used for the bio-specific sensing of protein analytes. Moreover, surface charge of these asymmetric nanochannels was reversed from negative to positive via the conversion of carboxyl groups into terminated amino groups. The negatively charge (carboxylated) and positively charged (aminated) channels were further used for the electrochemical sensing of bovine serum albumin (BSA, pI = 4.7). These biorecognition events were assessed from the changes in the ionic current flowing through the nanochannel

Fabrication and functionalization of single asymmetric nanochannels for electrostatic/hydrophobic association of protein molecules

We have developed a facile and reproducible method for surfactant-controlled track-etching and chemical functionalization of single asymmetric nanochannels in PET (polyethylene terephthalate) membranes. Carboxyl groups present on the channel surface were converted into pentafluorophenyl esters using EDC/PFP (N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride/pentafluorophenol) coupling chemistry. The resulting amine-reactive esters were further covalently coupled with ethylenediamine or propylamine in order to manipulate the charge polarity and hydrophilicity of the nanochannels, respectively. Characterization of the modified channels was done by measuring their current-voltage (I-V) curves as well as their permselectivity before and after the chemical modification. The electrostatic/hydrophobic association of bovine serum albumin on the channel surface was observed through the change in rectification behaviour upon the variation of pH values

Direct FIB fabrication and integration of “single nanopore devices” for the manipulation of macromolecules

Symposium OO – Materials and Strategies for Lab-on-a-Chip–Biological Analysis, Cell-Material Interfaces and Fluidic Assembly of Nanostructures)International audienceHere we propose to detail an innovative FIB instrumental approach and processing methodologies we have developed for sub-10 nm nanopore fabrication. The main advantage of our method is first to allow direct fabrication of nanopores in relatively large quantities with an excellent reproducibility. Second our approach offers the possibility to further process or functionalize the vicinity of each pore on the same scale keeping the required deep sub-10 nm scale positioning and patterning accuracy. We will summarise the optimisation efforts we have conducted aiming at fabricating thin (10-100 nm thick) and high quality dielectric films to be used as a template for the nanopore fabrication, and at performing efficient and controlled FIB nanoengraving of such a delicate media. Finally, we will describe the method we have developed for integrating these “single nanopore devices” in electrophoresis experiments and our preliminary measurements