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.

Publication: Electrofluorochromic systems: Molecules and materials exhibiting redox-switchable fluorescence

H. Al-Kutubi, H. R. Zafarani, L. Rassaei and K. Mathwig, European Polymer Journal 83 (2016) 478, Special Issue “Redox Active Macromolecules”.
[link, pdf]

europolElectrofluorochromic molecules share the unique property that their fluorescence changes as a function of their oxidation state. This makes them interesting from a fundamental perspective as molecular dyads are designed and synthesized to tune the interplay of electrochemical and luminescent properties of molecules. Electrofluorochromic systems also find applications in sensing because a fluorescent signal can be detected with high sensitivity. Moreover, in the recent years the interest in redox-switchable fluorescent polymers has strongly increased due to their applicability in display devices. Here, we review electrofluorochromic molecules and polymers; we emphasize their structures and functional principles and point to specific applications.


Publication: Single-molecule electrochemistry in nanochannels: probing the time of first passage

S. Kang, A. F. Nieuwenhuis, K. Mathwig, D. Mampallil, Z. A. Kostiuchenko and Serge G. Lemay, Faraday Discussions 193 (2016) 41.

[link, pdf]


The diffusive mass transport of individual redox molecules was probed experimentally in microfabricated nanogap electrodes. The residence times for molecules inside a well-defined detection volume were extracted and the resulting distribution was compared with quantitative analytical predictions from random-walk theory for the time of first passage. The results suggest that a small number of strongly adsorbing sites strongly influence mass transport at trace analyte levels.

Journal Article

G. A. Kalkman, Y. Zhang, E. Monachino, K. Mathwig, M. E. Kamminga, P. Pourhossein, P. E. Oomen, S. A. Stratmann, Z. Zhao, A. M. van Oijen, E. M. J. Verpoorte and R. C. Chiechi Bisecting Microfluidic Channels with Metallic Nanowires Fabricated by Nanoskiving ACS Nano 10 (2016) 2852.

TOCnanowireThis paper describes the fabrication of millimeter-long gold nanowires that bisect the center of microfluidic channels. We fabricated the nanowires by nanoskiving and then suspended them over a trench in a glass structure. The channel was sealed by bonding it to a complementary poly(dimethylsiloxane) structure. The resulting structures place the nanowires in the region of highest flow, as opposed to the walls where it approaches zero, and expose their entire surface area to fluid. We demonstrate active functionality, by constructing a hot-wire anemometer to measure flow through determining the change in resistance of the nanowire as a function of heat dissipation at low voltage (< 5V). Further, passive functionality is demonstrated by visualizing individual, fluorescently labelled DNA molecules attached to the wires. We measure rates of flow and show that, compared to surface-bound DNA strands, elongation saturates at lower rates of flow and background fluorescence from non-specific binding is reduced.