Wolfgang Ensinger

A pH-Tunable Nanofluidic Diode with a Broad Range of Rectifying Properties

The use of fixed charge nanopores in practical applications requires tuning externally the electrostatic interaction between the charged groups and the ionic permeants in order to allow integrating a variety of functions on the same nanostructure. We design, produce, and characterize, theoretically and experimentally, a single-track amphoteric nanopore functionalized with lysine and histidine chains whose positive and negative charges are very sensitive to the external pH. This nanofluidic diode with amphoteric chains attached to the pore surface allows for a broad set of rectification properties supported by a single nanodevice. A definite plus is to functionalize these groups on a conical nanopore with well-defined, controlled structural asymmetry which gives virtually every rectification characteristic that may be required in practical applications. Nanometerscaled amphoteric pores are of general interest because of the potential applications in drug delivery systems, ion-exchange membranes for separation of biomacromolecules, antifouling materials with reduced molecular adsorption, and biochemical sensors.

Morphological evolution of au nanowires controlled by rayleigh instability

A sound knowledge and understanding of the thermal stability of nanowires is a prerequisite for the reliable implementation of nanowire-based devices. We investigate the morphology of Au nanowires annealed isothermally at different temperatures. During the processes, triggered by heating, the wires undergo various configurational changes to finally break up into chains of nanospheres at much lower than bulk melting temperatures due to capillary or so-called Rayleigh instability. The role of three parameters, namely, wire diameter, temperature, and annealing time, on the final morphology is investigated. Both the average sphere diameter and the mean spacing between adjacent spheres are larger than the values predicted for materials with isotropic surface energy. Possible reasons are discussed in the paper.

Ionic Transport Through Single Solid-State Nanopores Controlled with Thermally Nanoactuated Macromolecular Gates

Single solid-state nanopores modified with poly-N-isopropylacrylamide (NIPAM) brushes display thermally controlled gating properties. Below the lower critical solubility temperature (LCST) NIPAM brushes are swollen and, consequently, dramatically reduce the effective cross section of the nanopores (see image). Conversely, above the LCST the brushes dehydrate and suffer a transition into a collapsed state, which promotes the widening of the nanopore and enables a substantial flow of ions.

Highly-Ordered Supportless Three-Dimensional Nanowire Networks with Tunable Complexity and Interwire Connectivity for Device Integration

The fabrication of three-dimensional assemblies consisting of large quantities of nanowires is of great technological importance for various applications including (electro-)catalysis, sensitive sensing, and improvement of electronic devices. Because the spatial distribution of the nanostructured material can strongly influence the properties, architectural design is required in order to use assembled nanowires to their full potential. In addition, special effort has to be dedicated to the development of efficient methods that allow precise control over structural parameters of the nanoscale building blocks as a means of tuning their characteristics. This paper reports the direct synthesis of highly ordered large-area nanowire networks by a method based on hard templates using electrodeposition within nanochannels of ion track-etched polymer membranes. Control over the complexity of the networks and the dimensions of the integrated nanostructures are achieved by a modified template fabrication. The networks possess high surface area and excellent transport properties, turning them into a promising electrocatalyst material as demonstrated by cyclic voltammetry studies on platinum nanowire networks catalyzing methanol oxidation. Our method opens up a new general route for interconnecting nanowires to stable macroscopic network structures of very high integration level that allow easy handling of nanowires while maintaining their connectivity.

Sequence-Specific Recognition of DNA Oligomer Using Peptide Nucleic Acid (PNA)-Modified Synthetic Ion Channels: PNA/DNA Hybridization in Nanoconfined Environment

Here we demonstrate the design and construction of a simple, highly sensitive and selective nanofluidic sensing device, based on a single synthetic conical nanochannel for the sequence specific detection of single-stranded DNA oligonucleotides. The biosensing performance of the device depends sensitively on the surface charge and chemical groups incorporated on the inner channel wall that act as binding sites for different analytes. Uncharged peptide nucleic acid (PNA) probes are covalently immobilized on the channel surface through carbodiimide coupling chemistry. This diminishes the channel surface charge, leading to a significant decrease in the rectified ion current flowing through the channel. The PNA-modified channel acts as a highly specific and selective device for the detection of a complementary single-stranded DNA sequence. Upon PNA/DNA hybridization, the channel surface charge density increased due to the presence of the negatively charged DNA strand. The changes in the surface charge-dependent current-voltage (I-V) curves and rectification ratio of the channel confirm the success of immobilization and PNA/DNA hybridization within a confined space at the nanoscale. In addition, a control experiment indicated that the biosensor exhibits remarkable specificity toward a cDNA strand and also has the ability to discriminate single-base mismatch DNA sequences on the basis of rectified ion flux through the nanochannel. In this context, we envision that the single conical nanochannels functionalized with a PNA probe will provide a biosensing platform for the detection and discrimination of short single-stranded DNA oligomer of unknown sequence.

Logic gates using nanofluidic diodes based on conical nanopores functionalized with polyprotic acid chains.

Single-track conical nanopores functionalized with polyprotic acid chains have pH-sensitive fixed charge groups and show three levels of conductance that allow integrating several functions on a single nanofluidic diode. Nanometer-scaled pores have previously been employed in separation and sensing but not in logic devices, despite the fact that biological ion channels with pH-dependent fixed charges are known to be responsible for information processing in biophysical structures. As a preliminary application, we propose a logic gate scheme where binary and multivalued logical functions are implemented.

Metal Ion Affinity-based Biomolecular Recognition and Conjugation inside Synthetic Polymer Nanopores Modified with Iron–Terpyridine Complexes

Here we demonstrate a novel biosensing platform for the detection of lactoferrin (LFN) via metal-organic frameworks, in which the metal ions have accessible free coordination sites for binding, inside the single conical nanopores fabricated in polymeric membrane. First, monolayer of amine-terminated terpyridine (metal-chelating ligand) is covalently immobilized on the inner walls of the nanopore via carbodiimide coupling chemistry. Second, iron-terpyridine (iron-terPy) complexes are obtained by treating the terpyridine modified-nanopores with ferrous sulfate solution. The immobilized iron-terPy complexes can be used as recognition elements to fabricate biosensing nanodevice. The working principle of the proposed biosensor is based on specific noncovalent interactions between LFN and chelated metal ions in the immobilized terpyridine monolayer, leading to the selective detection of analyte protein. In addition, control experiments proved that the designed biosensor exhibits excellent biospecificity and nonfouling properties. Furthermore, complementary experiments are conducted with multipore membranes containing an array of cylindrical nanopores. We demonstrate that in the presence of LFN in the feed solution, permeation of methyl viologen (MV(2+)) and 1,5-naphthalenedisulphate (NDS(2-)) is drastically suppressed across the iron-terPy modified membranes. On the basis of these findings, we envision that apart from conventional ligand-receptor interactions, the designing and immobilization of alternative functional ligands inside the synthetic nanopores would extend this method for the construction of new metal ion affinity-based biomimetic systems for the specific binding and recognition of other biomolecules.

Single Cigar-Shaped Nanopores Functionalized with Amphoteric Amino Acid Chains: Experimental and Theoretical Characterization

We present an experimental and theoretical characterization of single cigar-shaped nanopores with pH-responsive carboxylic acid and lysine chains functionalized on the pore surface. The nanopore characterization includes (i) optical images of the nanostructure obtained by FESEM; (ii) different chemical procedures for the nanopore preparation (etching time and functionalizations; pH and electrolyte concentration of the external solution) allowing externally tunable nanopore responses monitored by the current-voltage (I-V) curves; and (iii) transport simulations obtained with a multilayer nanopore model. We show that a single, approximately symmetric nanopore can be operated as a reconfigurable diode showing different rectifying behaviors by applying chemical and electrical signals. The remarkable characteristics of the new nanopore are the sharp response observed in the I-V curves, the improved tunability (with respect to previous designs of symmetric nanopores) which is achieved because of the direct external access to the nanostructure mouths, and the broad range of rectifying properties. The results concern both fundamental concepts useful for the understanding of transport processes in biological systems (ion channels) and applications relevant for tunable nanopore technology (information processing and drug controlled release).

Proton-regulated rectified ionic transport through solid-state conical nanopores modified with phosphate-bearing polymer brushes

We describe the use of polyprotic polymer brushes to construct robust signal-responsive chemical devices mimicking the transport properties of proton regulated biological channels.

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.