Publication: Electroanalysis with a single microbead of phosphate binding resin (FerrIX™) mounted in epoxy film

A. K. Thompson, K. Mathwig, P. J. Fletcher, R. Castaing and F. Marken, J. Solid State Electrochem., published online. [link]

Commercial resin microbeads are widely applied in ion exchange and extraction. Here, a single anion-selective and phosphate binding resin microbead (FerrIX™) is mounted into an epoxy membrane and investigated by 4-electrode membrane voltammetry and membrane impedance spectroscopy. Anion transport properties are observed to dominate associated with three distinct potential domains: (I) a low bias ohmic potential domain (dominant at high electrolyte concentration), (II) a concentration polarisation potential domain, and (III) an over-limiting potential domain. Voltammetric responses show transient diffusion-migration features at higher scan rates and quasi-steady state features at lower scan rates. Inherent microbead conductivity is shown to be linked to two resistive elements, electrolyte concentration dependent and independent, in series. The effects of phosphate binding are revealed as transient pattern in impedance spectroscopy data. Preliminary data suggest phosphate concentration-dependent peak features in the imaginary impedance versus frequency plot due to phosphate binding into the microbead.

Publication: Ionic Diode and Molecular Pump Phenomena Associated with Caffeic Acid Accumulated into an Intrinsically Microporous Polyamine (PIM‐EA‐TB)

Z. Li, L. Wang, R. Malpass-Evans, M. Carta, N. B. McKeown, K. Mathwig, P. J. Fletcher and F. Marken, ChemElectroChem 8 (2021) 2044. Invited contribution to the Marcin Opałło Festschrift. [link, pdf]

The polymer of intrinsic microporosity PIM‐EA‐TB provides a molecularly rigid micropore structure containing tertiary amine sites and is shown here to interact with hydrogen bonding guest molecules such as caffeic acid. Voltammetric data with a PIM‐EA‐TB film on glassy carbon electrodes show that in both acidic solution (pH 2; PIM‐EA‐TB is protonated) and in neutral solution (pH 6; PIM‐EA‐TB is not protonated) caffeic acid is slowly accumulated into the microporous host. Binding constants are estimated and suggested to be linked to hydrogen bonding causing accumulation of caffeic acid. When employing PIM‐EA‐TB as an asymmetric membrane coated onto a 5 mm thick Teflon support film with 10 mm diameter microholes (using either a single microhole or a 10 × 10 array of microholes), binding of caffeic acid is shown to cause a modulation of the ionic current without affecting the pH‐dependent ionic diode behaviour. Two complementary types of effects of caffeic acid guests are discussed based on blocking anion diffusion pathways and based on removal of positive charges. The caffeic acid transport mechanism/efficiency is investigated in view of selective molecular pumping.

Publication: Microscale Ionic Diodes: An Overview

B. R. Putra, L. Tshwenya, M. A. Buckingham, J. Chen, K. J. Aoki, K. Mathwig, O. A. Arotiba, A. K. Thompson and F. Marken, Electroanalysis 33 (2021) 1398. [link, pdf]

Ionic rectifier membranes or devices generate uni‐directional ion transport to convert an alternating current (AC) ion current input into stored energy or direct current (DC) in the form of ion/salt gradients. Electrochemical experiments 80 years ago were conducted on biological membrane rectifier systems, but today a plethora of artificial ionic rectifier types has been developed and electroanalytical tools are employed to explore mechanisms and performance. This overview focuses on microscale ionic rectifiers with a comparison to nano‐ and macroscale ionic rectifiers. The potential is surveyed for applications in electrochemical analysis, desalination, energy harvesting, electrochemical synthesis, and in selective ion extraction.

Publication: Electrochemiluminescence reaction pathways in nanofluidic devices

S. Voci, H. Al-Kutubi, L. Rassaei, K. Mathwig and N. Sojic Anal. Bioanal. Chem. 41, (2020) 4067. [link, pdf]

Nanofluidic electrochemical devices confine the volume of chemical reactions to femtoliters. When employed for light generation by electrochemiluminescence (ECL), nanofluidic confinement yields enhanced intensity and robust luminescence. Here, we investigate different ECL pathways, namely coreactant and annihilation ECL in a single nanochannel and compare light emission profiles. By high-resolution imaging of electrode areas, we show that different reaction schemes produce very different emission profiles in the unique confined geometry of a nanochannel. The confrontation of experimental results with finite element simulation gives further insight into the exact reaction ECL pathways. We find that emission strongly depends on depletion, geometric exclusion, and recycling of reactants in the nanofluidic device.

Publication: Switching Anionic and Cationic Semi-Permeability in Partially Hydrolyzed Polyacrylonitrile: A pH-Tunable Ionic Rectifier

L. Tshwenya, F. Marken, K. Mathwig and O. A. Arotiba, ACS Applied Materials and Interfaces 12 (2020) 3214. [link, pdf]

TOC_phPan2Membrane materials with semi-permeability for anions or for cations are of interest in electrochemical and nanofluidic separation and purification technologies. In this study, partially hydrolyzed poly-acrylonitrile (phPAN) is investigated as a pH-switchable anion/cation conductor. When switching from anionic to cationic semi-permeability, also the ionic current rectification effect switches for phPAN materials deposited asymmetrically onto a 5, 10, 20, or 40 µm diameter microhole in a 6 µm thick polyethylene-terephthalate (PET) film substrate. Therefore, ionic rectifier behavior can be tuned and used to monitor and characterize semi-permeability. Effects of electrolyte type and concentration, and pH (relative to the zeta potential at approximately 3.1) are investigated by voltammetry, chronoamperometry, and impedance spectroscopy. A computational model provides good qualitative agreement with observed electrolyte concentration data. High rectification effects are observed for both cations (pH > 3.1) and anions (pH < 3.1), but only at relatively low ionic strengths.

Publication: Towards Determining Kinetics of Annihilation Electrogenerated Chemiluminescence by Concentration-Dependent Luminescent Intensity

K. Mathwig and N. Sojic, Journal of Analysis and Testing 3 (2019) 160. [link, pdf]

toc_joatIn ion-annihilation electrochemiluminescence (ECL), luminophore ions are generated by oxidation as well as reduction at electrodes surfaces, and subsequently recombine into an electronically excited state, which emits light. The intensity of the emitted light is often limited by the kinetic rate of recombination of the luminophore ion species. Recombination or annihilation rates are high ranging up to approximately 1010 M−1 s−1 and can be difficult to determine using scanning electrochemical microscopy or high-frequency oscillations of an electrode potential. Here, we propose determining annihilation kinetics by measuring the relative change of the emitted light intensity as a function of luminophore concentration. Using finite element simulations of annihilation ECL in a geometry of two closely spaced electrodes biased at constant potentials, we show that, with increasing concentrations, luminescence intensity crosses over from a quadratic dependence on concentration to a linear regime—depending on the rate of annihilation. Our numerical results are applicable to scanning electrochemical microscopy as well as nanofluidic electrochemical devices to determine fast ion-annihilation kinetics.

Publication: Digestion-on-a-chip: a continuous-flow modular microsystem recreating enzymatic digestion in the gastrointestinal tract

P. de Haan, M. A. Ianovska, K. Mathwig, G. A. A. van Lieshout, V. Triantis, H. Bouwmeester and E. Verpoorte, Lab on a Chip 19 (2019) 1599. [link, pdf]

toc_gut.gifIn vitro digestions are essential for determining the bioavailability of compounds, such as nutrients. We have developed a cell-free, miniaturized enzymatic digestive system, employing three micromixers connected in series to mimic the digestive functions of the mouth, stomach and small intestine. This system continuously processes samples, e.g. containing nutrients, to provide a constant flow of digested materials which may be presented to a subsequent gut-on-a-chip absorption module, containing living human intestinal cells. Our system incorporates three-compartment enzymatic digestion, one of the key functions of the gastrointestinal tract. In each of these compartments, we modify the chemical environment, including pH, buffer, and mineral composition, to closely mimic the local physiological environment and create optimal conditions for digestive processes to take place. It will therefore provide an excellent addition to existing gut-on-a-chip systems, providing the next step in determining the bio-availability of orally administered compounds in a fast and continuous-flow ex vivo system. In this paper, we demonstrate enzymatic digestion in each separate compartment using compounds, starch and casein, as model nutrients. The use of transparent, microfluidic micromixers based on chaotic advection, which can be probed directly with a microscope, enabled enzyme kinetics to be monitored from the very start of a reaction. Furthermore, we have digested lactoferrin in our system, demonstrating complete digestion of this milk protein in much shorter times than achievable with standard in vitro digestions using batch reactors.

Publication: High-throughput, non-equilibrium studies of single biomolecules using glass made nanofluidic devices

M. Fontana, C. Fijen, S. G. Lemay, K. Mathwig and J. Hohlbein, Lab on a Chip 19 (2019) 79. [link, pdf]

TOC2Single-molecule detection schemes offer powerful means to overcome static and dynamic heterogeneity inherent to complex samples. However, probing biomolecular interactions and reactions with high throughput and time resolution remains challenging, often requiring surface-immobilized entities. Here, we introduce glass-made nanofluidic devices for the high-throughput detection of freely-diffusing single biomolecules by camera-based fluorescence microscopy. Nanochannels of 200 nm height confine the movement of biomolecules. Using pressure-driven flow through an array of parallel nanochannels and by tracking the movement of fluorescently labelled DNA oligonucleotides, we observe conformational changes with high throughput. In a device geometry featuring a T-shaped junction of nanochannels, we drive steady-state non-equilibrium conditions by continuously mixing reactants and triggering chemical reactions. We use the device to probe the conformational equilibrium of a DNA hairpin as well as to continuously observing DNA synthesis in real time. Our platform offers a straightforward and robust method for studying reaction kinetics at the single-molecule level.

Publication: Enhanced annihilation electrochemiluminescence by nanofluidic confinement

H. Al-Kutubi, S. Voci, L. Rassaei, N. Sojic and K. Mathwig, Chemical Science 9 (2018) 8946. [link, pdf]

toc_eclMicrofabricated nanofluidic electrochemical devices offer a highly controlled nanochannel geometry; they confine the volume of chemical reactions to the nanoscale and enable greatly amplified electrochemical detection. Here, the generation of stable light emission by electrochemiluminescence (ECL) in transparent nanofluidic devices is demonstrated for the first time by exploiting nanogap amplification. Through continuous oxidation and reduction of [Ru(bpy)3]2+ luminophores at electrodes positioned at opposite walls of a 100-nm nanochannel, we compare classic redox cycling and ECL annihilation. Enhanced ECL light emission of attomole luminophore quantities is evidenced under ambient conditions due to the spatial confinement in a 10-femtoliter volume, resulting in a short diffusion timescale and highly efficient ECL reaction pathways at the nanoscale.

Electrochemistry Symposium in Groningen

The Annual Symposium of the Working Group on Electrochemistry of the Royal Netherland Chemical Society will take place in Groningen this November:

Hyphenated Electrochemistry – Combining Electrochemical Methods with Complementary Techniques for Sensing Applications

The capability of electrochemistry is greatly enhanced when used in combination with other methods. The meeting focusses on such hyphenated techniques, which have recently gained more importance in a variety of fields, for example in analytics. Topics include single-molecule detection, electrochemiluminescence, electrochemical transistors, micro- and nanofluidic lab-on-a-chip detection, and diverse
applications such as fuel cells and protein analysis.

Date: Friday 23 November 2018
Location: NH Hotel Groningen, Hanzeplein 132, 9713 GW Groningen

See here for the program, and here for the registration.