Publication: Ionic Transport in Microhole Fluidic Diodes Based on Asymmetric Ionomer Film Deposits

K. Mathwig, B. D. B. Aaronson and F. Marken, ChemElectroChem 5 (2018) 897, Alan Bond Festschrift Special Issue (invited contribution).
[link, pdf]

Toc.pngMicrohole fluidic ionic diodes based on asymmetric deposits of charged ionomer membranes (e.g., Nafion or polymers of intrinsic microporosity) on microhole supports yield high rectification ratios for ionic transport. They are fabricated without the need for complex micro- or nano-structuring, and show potential for future applications in desalination and biosensing. Here, we propose an explanation for the functional principle for this type of materials-based ionic diode. A predictive computational model for ionic diode switching is based on finite element analysis. It is employed to determine the influence of diode geometry as well as type and concentration of aqueous electrolyte on the rectification behavior.

Publication: A Nanofluidic Mixing Device for High-Throughput Fluorescence Sensing of Single Molecules

K. Mathwig, C. Fijen, M. Fontana, S. G. Lemay and J. Hohlbein, Procedia Technology 27 (2017) 141.
[link, pdf]

procediatechnol_toc.pngWe introduce a nanofluidic mixing device entirely fabricated in glass for the fluorescence detection of single molecules. The design consists of a nanochannel T-junction and allows the continuous monitoring of chemical or enzymatic reactions of analytes as they arrive from two independent inlets. The fluorescently labeled molecules are tracked before, during and after they enter the mixing region, and their reactions with each other are observed by means of optical readout such as Förster Resonance Energy Transfer (FRET). Our method can be used for analyzing the kinetics of DNA annealing in a high-parallelized fashion.

Publication: Ionic Diode Characteristics at a Polymer of Intrinsic Microporosity (PIM) | Nafion “Heterojunction” Deposit on a Microhole Poly(ethylene-terephthalate) Substrate

B. R. Putra, B. D. B. Aaronson, E. Madrid, K. Mathwig, M. Carta, R. Malpass-Evans, N. B. McKeown and F. Marken, Electroanalysis 29 (2017) 2217.
[link, pdf]

toc_electroanalysisIonic diode phenomena occur at asymmetric ionomer | aqueous electrolyte microhole interfaces. Depending on the applied potential, either an “open” or a “closed” diode state is observed switching between a high ion flow rate and a low ion flow rate. Physically, the “open” state is associated mainly with conductivity towards the microhole within the ionomer layer and the “closed” state is dominated by restricted diffusion-migration access to the microhole interface opposite to the ionomer. In this report we explore a “heterojunction” based on an asymmetric polymer of intrinsic microporosity (PIM) | Nafion ionomer microhole interface. Improved diode characteristics and current rectification are observed in aqueous NaCl. The effects of creating the PIM | Nafion micro-interface are investigated and suggested to lead to novel sensor architectures.

Editorial: Special Issue on Electrochemiluminescence: Fundamentals to Applications

L. Rassaei, G. Xu, Z. Ding and K. Mathwig, ChemElectroChem 4 (2017) 1571.
[link, pdf]

Electrochemiluminescence or electrogenerated chemiluminescence (ECL) is a phenomenon in which an excited state—formed by an electron-transfer reaction between electrogenerated species in the vicinity of a working electrode—emits light. Although the first detailed studies of ECL were reported in the 1960s, ECL publications have revealed an exponential growth worldwide thanks to advances in nanotechnology, photoelectrochemistry, and spectroscopy.

Publication: Electrochemical Amplification in Side-by-Side Attoliter Nanogap Transducers

H. R. Zafarani, K. Mathwig, E. J. R. Sudhölter and L. Rassaei, ACS Sensors 2 (2017) 724.
[link, pdf]

toc_side.pngWe report a strategy for the fabrication of a new type of electrochemical nanogap transducer. These nanogap devices are based on signal amplification by redox cycling. Using two steps of electron-beam lithography, vertical gold electrodes are fabricated side by side at a 70 nm distance encompassing a 20 attoliter open nanogap volume. We demonstrate a current amplification factor of 2.5 as well as the possibility to detect the signal of only 60 analyte molecules occupying the detection volume. Experimental voltammetry results are compared to calculations from finite element analysis.

Publication: A Cationic Diode Based on Asymmetric Nafion® Film Deposits

D. He, E. Madrid, B. D. B. Aaronson, L. Fan, J. Doughty, K. Mathwig, A. M. Bond, N. B. McKeown and F. Marken, ACS Applied Materials and Interfaces 9 (2017) 11272.
[link, pdf]

aamickA thin film of Nafion®, of approximately 5 µm thickness, asymmetrically deposited onto a 6 µm thick film of poly(ethylene terephthalate) (PET) fabricated with a 5, 10, 20, or 40 µm microhole, is shown to exhibit prominent ionic diode behaviour involving cation charge carrier (“cationic diode”). The phenomenon is characterized via voltammetric, chronoamperometric, and impedance methods. Phenomenologically, current rectification effects are comparable to those observed in nano-cone devices where space-charge layer effects dominate. However, for microhole diodes a resistive, a limiting, and an over-limiting potential domain can be identified and concentration polarization in solution is shown to dominate in the closed state

Publication: Modulating Selectivity in Nanogap Sensors

H. R. Zafarani, K. Mathwig, S. G. Lemay, E. J. R. Sudhölter and L. Rassaei, ACS Sensors 1 (2016) 1439.
[link, pdf]

flower_tocInterference or crosstalk of coexisting redox species results in overlapping of electrochemical signals, and it is a major hurdle in sensor development. In nanogap sensors, redox cycling between two independently biased working electrodes results in an amplified electrochemical signal and an enhanced sensitivity. Here, we report new strategies for selective sensing of three different redox species in a nanogap sensor of a two femtoliter volume. Our approach relies on modulating the electrode potentials to define specific potential windows between the two working electrodes; consequently, specific detection of each redox species is achieved. Finite element modelling is employed to simulate the electrochemical processes in the nanogap sensor, and the results are in good agreement with those of experiments.

Proceedings: Electrochemical Sensing with a Single Suspended Nanowire

P. E. Oomen, Y. Zhang, R. C. Chiechi, E. Verpoorte, and K. Mathwig, 20th International Conference on Miniaturized Systems for Chemistry and Life Sciences, Dublin, Ireland, Oct.  9-13 (2016) 102.
[link, pdf]

microtas_tocThe use of nanoscale electrodes is beneficial in microfluidic sensing applications, as a high sensitivity and efficient mass transport can be achieved. Facile preparation of millimeter-long gold nanowires is possible using nanoskiving. Single nanowires were suspended over a glass microchannel, which was closed with a complementary PDMS microchannel. Using the nanowire as an electrode, cyclic voltammograms of ferrocene were recorded, with the electroactive solution flowing through the channel at different rates. Nanowires suspended in the center of the flow profile exhibit higher current responses than nanowires on the bottom of microchannels, due to efficient analyte transport towards the electrode surface.

Publication: Potential-Dependent Stochastic Amperometry of Multiferrocenylthiophenes in an Electrochemical Nanogap Transducer

K. Mathwig, H. R. Zafarani, J. M. Speck, S. Sarkar, H. Lang, S. G. Lemay, L. Rassaei, O. G. Schmidt, The Journal of Physical Chemistry C 120 (2016) 23262.

[link, pdf]


In nanofluidic electrochemical sensors based on redox cycling, zeptomole quantities of analyte molecules can be detected as redox-active molecules travel diffusively between two electrodes separated by a nanoscale gap. These sensors are employed to study the properties of multiferrocenylic compounds in nonpolar media, 2,3,4-triferrocenylthiophene and 2,5-diferrocenylthiophene, which display well-resolved electrochemically reversible one-electron transfer processes. Using stochastic analysis, we are able to determine – as a function of the oxidation states of a specific redox couple – the effective diffusion coefficient as well as the faradaic current generated per molecule; all in a straightforward experiment requiring only a mesoscopic amount of molecules in a femtoliter compartment. It was found that diffusive transport is reduced for higher oxidation states and that analytes yield very high currents per molecule of 15 fA.

Publication: pH-Induced Reversal of Ionic Diode Polarity in 300 nm Thin Membranes Based on a Polymer of Intrinsic Microporosity

Y. Rong, Q. Song, K. Mathwig, E. Madrid, D. He, R. G. Niemann, P. J. Cameron, S. E.C. Dale, S. Bending, M. Carta, R. Malpass-Evans, N. B. McKeown, F. Marken, Electrochemistry Communications 69 (2016) 41.
[link, pdf]

diode“Ionic diode” (or current rectification) effects are potentially important for a range of applications including water purification. In this preliminary report, we observe novel ionic diode behaviour of thin (300 nm) membranes based on a polymer of intrinsic microporosity (PIM-EA-TB) supported on a poly-ethylene-terephthalate (PET) film with a 20 μm diameter microhole, and immersed in aqueous electrolyte media. Current rectification effects are observed for half-cells with the same electrolyte solution on both sides of the membrane for cases where cation and anion mobility differ (HCl, other acids, NaOH, etc.) but not for cases where cation and anion mobility are more alike (LiCl, NaCl, KCl, etc.). A pH-dependent reversal of the ionic diode effect is observed and discussed in terms of tentatively assigned mechanisms based on both (i) ion mobility within the PIM-EA-TB nano-membrane and (ii) a possible “mechanical valve effect” linked to membrane potential and electrokinetic movement of the membrane as well as hydrostatic pressure effects.