Nihan Aydemir

Intrinsically Conducting Polymer Nanowires for Biosensing

Nanomaterials are commonly exploited to increase the sensitivity of sensors. Conductive polymers are emerging as promising sensing materials as they are easy to functionalize with the appropriate sensing probes, and also act as signal transducers. By constraining the material into one dimensional nanowires, extraordinary sensitivity is achieved. This review deals with the fabrication of these electrically conductive polymer nanowire (ECPNW) sensors and their use for detecting nucleic acid sequences, proteins and pathogens.

A Label-Free, Sensitive, Real-Time, Semiquantitative Electrochemical Measurement Method for DNA Polymerase Amplification (ePCR)

Oligonucleotide hybridization to a complementary sequence that is covalently attached to an electrochemically active conducting polymer (ECP) coating the working electrode of an electrochemical cell causes an increase in reaction impedance for the ferro-ferricyanide redox couple. We demonstrate the use of this effect to measure, in real time, the progress of DNA polymerase chain reaction (PCR) amplification of a minor component of a DNA extract. The forward primer is attached to the ECP. The solution contains other PCR components and the redox couple. Each cycle of amplification gives an easily measurable impedance increase. Target concentration can be estimated by cycle count to reach a threshold impedance. As proof of principle, we demonstrate an electrochemical real-time quantitative PCR (e-PCR) measurement in the total DNA extracted from chicken blood of an 844 base pair region of the mitochondrial Cytochrome c oxidase gene, present at ∼1 ppm of total DNA. We show that the detection and semiquantitation of as few as 2 copies/μL of target can be achieved within less than 10 PCR cycles.

New immobilisation method for oligonucleotides on electrodes enables highly-sensitive, electrochemical label-free gene sensing

We present a versatile and facile procedure for the immobilisation of bioprobe molecules to an electrochemical sensing element. We eliminate lengthy preparation procedures for direct functionalisation of electrode surfaces by pre-attaching probe molecules to carboxylic acid bearing termonomers of pyrrole phenylenes or thiophene phenylenes. We demonstrate that these conjugates can be electrodeposited at low potentials to form nano-scale porous, electroactive conducting polymer films, exposing the bioprobe and retaining activity and specificity for binding, exemplified here with DNA sensors. The electrochemical reaction impedance for Fe(CN)63-/4- on oligonucleotide-modified electrodes showed remarkable (down to aM) detection sensitivity for target DNA sequences present in solution. Cross-sensitivity to non-complementary target sequences is small and multi-target arrays are easily made. There is no need for labelling of either probe or target oligonucleotide.

Electrochemomechanical deformation (ECMD) of PPyDBS in free standing film formation and trilayer designs

An investigation is reported into the electrochemomechanical deformation (ECMD) of polypyrrole (PPy) doped with dodecylbenzenesulfonate (DBS) in the form of freestanding films and deposited onto conductive substrates (chemically fixed poly-3,4-(ethylenedioxythiophene, PEDOT) based on PVdF (poly(vinylidenefluoride)). Linear actuation has been achieved starting from a trilayer bending actuator design with a stretchable middle layer. To allow evaluation of the proposed design, commercially available PVdF membranes were chosen as model material. For bending trilayer functionality, electronic separation of both electrode layers is essential, but in order to obtain linear actuation, the CP layers on either side are connected to form a single working electrode. The PPyDBS free standing films and PPyDBS deposited on PEDOT-PVdF-PEDOT were investigated by electrochemical methods (cyclic voltammetry, square wave potentials) in a 4-methyl-1,3-dioxolan-2-one (propylene carbonate, PC) solution of tetrabutylammonium trifluoromethanesulfonate (TBACF3SO3). This study also presents a novel method of utilizing scanning ion-conductance microscopy (SICM) to accurately examine the electrochemical redox behavior of the surface layer of the linear actuator using a micropipette tip.

Polymer electronic composites that heal by solvent vapour

Recent advances in organic electronic devices have reached new milestones in performance and function, and they are used in applications ranging from displays to sensory devices. However, they still present limitations in mechanical flexibility and electrical durability following the damage caused during their lifetime. Herein, we present a simple route to prepare conducting polymer composites that can address some of these issues through solvent vapour-induced healing of cracks formed within conducting polymer composites. Conducting polymer composites were prepared by solution blending of poly(3-hexylthiophene) (P3HT) and poly(dimethylsiloxane) (PDMS)-containing urea segmented copolymer. The bicomponent composites with various weight fractions of neutral P3HT were used to demonstrate their electroactivity whereas the electrical conductivity, mechanical and solvent vapour-induced self-healing studies were carried out with composites with various weight fractions of FeCl3-doped P3HT. A mechanically bisected free-standing film with 30 wt% of doped P3HT was observed to be readily healed through exposure to solvent vapour at room temperature, with a mechanical healing efficiency of 55 ± 24% and restoration of electrical conductivity up to 82 ± 1%.

Conducting electrospun fibres with polyanionic grafts as highly selective, label-free, electrochemical biosensor with a low detection limit for non-Hodgkin lymphoma gene.

A highly selective, label-free sensor for the non-Hodgkin lymphoma gene, with an aM detection limit, utilizing electrochemical impedance spectroscopy (EIS) is presented. The sensor consists of a conducting electrospun fibre mat, surface-grafted with poly(acrylic acid) (PAA) brushes and a conducting polymer sensing element with covalently attached oligonucleotide probes. The sensor was fabricated from electrospun NBR rubber, embedded with poly(3,4-ethylenedioxythiophene) (PEDOT), followed by grafting poly(acrylic acid) brushes and then electrochemically polymerizing a conducting polymer monomer with ssDNA probe sequence pre-attached. The resulting non-Hodgkin lymphoma gene sensor showed a detection limit of 1aM (1 × 10-18mol/L), more than 400 folds lower compared to a thin-film analogue. The sensor presented extraordinary selectivity, with only 1%, 2.7% and 4.6% of the signal recorded for the fully non-complimentary, T-A and G-C base mismatch oligonucleotide sequences, respectively. We suggest that such greatly enhanced selectivity is due to the presence of negatively charged carboxylic acid moieties from PAA grafts that electrostatically repel the non-complementary and mismatch DNA sequences, overcoming the non-specific binding.

Carbide-derived carbon (CDC) linear actuator properties in combination with conducting polymers

Carbide–derived Carbon (CDC) material is applied for super capacitors due to their nanoporous structure and their high charging/discharging capability. In this work we report for the first time CDC linear actuators and CDC combined with polypyrrole (CDC-PPy) in ECMD (Electrochemomechanical deformation) under isotonic (constant force) and isometric (constant length) measurements in aqueous electrolyte. CDC-PPy actuators showing nearly double strain under cyclic voltammetric and square wave potential measurements in comparison to CDC linear actuators. The new material is investigated by SEM (scanning electron microscopy) and EDX (energy dispersive X-ray analysis) to reveal how the conducting polymer layer and the CDC layer interfere together.

An Ultrasensitive Electrochemical Impedance-Based Biosensor Using Insect Odorant Receptors to Detect Odorants

Herein, we present that insect odorant receptors reconstituted into the lipid bilayers of liposomes can be successfully immobilized onto a gold surface and selectively and sensitively detect odorant molecules. The odorant receptors (OrXs) Or10a, Or22a, and Or71a from the common fruit fly, Drosophila melanogaster, were recombinantly expressed, purified and integrated into nano-liposomes (100-200 nm). These liposomes were covalently attached to the self-assembled monolayers (SAMs) of a 6-mercaptohexanoic acid (MHA)-modified gold surface. X-ray Photo Electron Spectroscopy (XPS) and Quartz Crystal Microbalance with Dissipation (QCM-D) measurements confirmed the successful modification of the gold surface and immobilization of liposomes. Atomic Force Microscopy (AFM) revealed that the liposomes were covalently attached to the surface without any disruption of vesicles. The liposomes tethered to the gold sensor surface were then treated with a range of known ligands of various concentrations. We demonstrated by Electrochemical Impedance Spectroscopy (EIS) that an OrX/liposome EIS sensor can sensitively and selectively detect its known ligand to femtomolar concentrations by detecting a change in electrical signal upon binding. Our study is the first step towards using purified insect odorant receptors alone in biosensors to enable the development of novel ultrasensitive volatile sensors for medical diagnostic, air quality, food safety and border security applications.

Direct Writing and Characterization of Three-Dimensional Conducting Polymer PEDOT Arrays

Direct writing is an effective and versatile technique for three-dimensional (3D) fabrication of conducting polymer (CP) structures. It is precisely localized and highly controllable, thus providing great opportunities for incorporating CPs into microelectronic array devices. Herein we demonstrate 3D writing and characterization of poly(3,4-ethylenedioxythiophene)-polystyrenesulfonate (PEDOT:PSS) pillars in an array format, by using an in-house-constructed variant of scanning ion conductance microscopy (SICM). CP pillars with different aspect ratios were successfully fabricated by optimizing the writing parameters: pulling speed, pulling time, concentration of the polymer solution, and the micropipette tip diameter. Especially, super high aspect ratio pillars of around 7 μm in diameter and 5000 μm in height were fabricated, indicating a good capability of this direct writing technique. Additions of an organic solvent and a cross-linking agent contribute to a significantly enhanced water stability of the pillars, critical if the arrays were to be used in biologically relevant applications. Surface morphologies and structural analysis of CP pillars were characterized by scanning electron microscopy and Raman spectroscopy, respectively. Electrochemical properties of the individual pillars of different heights were examined by cyclic voltammetry using a double-barrel micropipette as an electrochemical cell. Exceptional mechanical properties of the pillars, such as high flexibility and robustness, were observed when bent by applying a force. The 3D pillar arrays are expected to provide versatile substrates for functionalized and integrated biological sensing and electrically addressable array devices.