Electrochemiluminescence at 3D Printed Titanium Electrodes.

The fabrication and electrochemical properties of a 3D printed titanium electrode array are described. The array comprises 25 round cylinders (0.015 cm radius, 0.3 cm high) that are evenly separated on a 0.48 × 0.48 cm square porous base (total geometric area of 1.32 cm2). The electrochemically active surface area consists of fused titanium particles and exhibits a large roughness factor ≈17. In acidic, oxygenated solution, the available potential window is from ~-0.3 to +1.2 V. The voltammetric response of ferrocyanide is quasi-reversible arising from slow heterogeneous electron transfer due to the presence of a native/oxidatively formed oxide. Unlike other metal electrodes, both [Ru(bpy)3]1+ and [Ru(bpy)3]3+ can be created in aqueous solutions which enables electrochemiluminescence to be generated by an annihilation mechanism. Depositing a thin gold layer significantly increases the standard heterogeneous electron transfer rate constant, ko, by a factor of ~80 to a value of 8.0 ± 0.4 × 10-3 cm s-1 and the voltammetry of ferrocyanide becomes reversible. The titanium and gold coated arrays generate electrochemiluminescence using tri-propyl amine as a co-reactant. However, the intensity of the gold-coated array is between 30 (high scan rate) and 100-fold (slow scan rates) higher at the gold coated arrays. Moreover, while the voltammetry of the luminophore is dominated by semi-infinite linear diffusion, the ECL response is significantly influenced by radial diffusion to the individual microcylinders of the array.

Wireless electrochemiluminescence at functionalised gold microparticles using 3D titanium electrode arrays.

Wireless electrochemiluminescence is generated using interdigitated, 3D printed, titanium arrays as feeder electrodes to shape the electric field. Gold microparticles (45 µm diameter), functionalised with 11-mercaptoundecanoic acid, act as micro-emitters to generate electrochemiluminescence from [Ru(bpy)3]2+, (bpy is 2,2'-bipyridine) where the co-reactant is tripropylamine. The oxide coated titanium allows intense electric fields, whose distribution depends on the geometry of the array, to be created in the absence of deliberately added electrolyte. COMSOL modelling and long exposure ECL imaging have been used to map the electric field distribution. Significantly, we demonstrate that by controlling the surface charge of the gold microparticles through the solution pH, the light intensity can be increased by a factor of more than 10.

Electrochemical Properties of Screen-Printed Carbon Nano-Onion Electrodes.

The properties of carbon nano-onions (CNOs) make them attractive electrode materials/additives for the development of low-cost, simple to use and highly sensitive Screen Printed Electrodes (SPEs). Here, we report the development of the first CNO-based ink for the fabrication of low-cost and disposable electrodes, leading to high-performance sensors. Achieving a true dispersion of CNOs is intrinsically challenging and a key aspect of the ink formulation. The screen-printing ink formulation is achieved by carefully selecting and optimising the conductive materials (graphite (GRT) and CNOs), the polymer binder, the organic solvent and the plasticiser. Our CNO/GRT-based screen-printed electrodes consist of an interconnected network of conducting carbon particles with a uniform distribution. Electrochemical studies show a heterogeneous electron transfer rate constant of 1.3 ± 0.7 × 10-3 cm·s-1 and a higher current density than the ferrocene/ferrocenium coupled to a commercial graphite SPEs. In addition, the CNO/GRT SPE can detect dopamine in the concentration range of 10.0-99.9 µM with a limit of detection of 0.92 µM (N = 3). They exhibit a higher analytical sensitivity than the commercial graphite-based SPE, with a 4-fold improvement observed. These results open up the possibility of using high-performing CNO-based SPEs for electrochemical applications including sensors, battery electrodes and electrocatalysis.

Electrochemical detection of viruses and antibodies: A mini review.

Near patient detection of viral infection represents a powerful approach for the control of emerging threats to global health. Moreover, the ability to identify individuals who have contracted the disease and developed antibodies that confer immunity is central to a return to normal daily activities. This review presents some of the recent advances in electrochemical sensors for the detection of viruses and their associated antibody profiles. Given the speed, portability, sensitivity and selectivity achieved using electrochemical detection, these sensor systems hold the promise of transformative change in clinical practice.

Can solvent induced surface modifications applied to screen-printed platforms enhance their electroanalytical performance?

In this paper the effect of solvent induced chemical surface enhancements upon graphitic screen-printed electrodes (SPEs) is explored. Previous literature has indicated that treating the working electrode of a SPE with the solvent N,N-dimethylformamide (DMF) offers improvements within the electroanalytical response, resulting in a 57-fold increment in the electrode surface area compared to their unmodified counterparts. The protocol involves two steps: (i) the SPE is placed into DMF for a selected time, and (ii) it is cured in an oven at a selected time and temperature. Beneficial electroanalytical outputs are reported to be due to the increased surface area attributed to the binder within the bulk surface of the SPEs dissolving out during the immersion step (step i). We revisit this exciting concept and explore these solvent induced chemical surface enhancements using edge- and basal-plane like SPEs and a new bespoke SPE, utilising the solvent DMF and explore, in detail, the parameters utilised in steps (i) and (ii). The electrochemical performance following steps (i) and (ii) is evaluated using the outer-sphere redox probe hexaammineruthenium(iii) chloride/0.1 M KCl, where it is found that the largest improvement is obtained using DMF with an immersion time of 10 minutes and a curing time of 30 minutes at 100 °C. Solvent induced chemical surface enhancement upon the electrochemical performance of SPEs is also benchmarked in terms of their electroanalytical sensing of NADH (dihydronicotinamide adenine dinucleotide reduced form) and capsaicin both of which are compared to their unmodified SPE counterparts. In both cases, it is apparent that a marginal improvement in the electroanalytical sensitivity (i.e. gradient of calibration plots) of 1.08-fold and 1.38-fold are found respectively. Returning to the original exciting concept, interestingly it was found that when a poor experimental technique was employed, only then significant increases within the working electrode area are evident. In this case, the insulating layer that defines the working electrode surface, which was not protected from the solvent (step (i)) creates cracks within the insulating layer exposing the underlying carbon connections and thus increasing the electrode area by an unknown quantity. We infer that the origin of the response reported within the literature, where an extreme increase in the electrochemical surface area (57-fold) was reported, is unlikely to be solely due to the binder dissolving but rather poor experimental control over step (i).

Can the mechanical activation (polishing) of screen-printed electrodes enhance their electroanalytical response?

The mechanical activation (polishing) of screen-printed electrodes (SPEs) is explored and shown to exhibit an improved voltammetric response (in specific cases) when polished with either commonly available alumina slurry or diamond spray. Proof-of-concept is demonstrated for the electrochemical sensing of nitrite where an increase in the voltammetric current is found using both polishing protocols, exhibiting an improved limit of detection (3σ) and a two-fold increase in the electroanalytical sensitivity compared to the respective un-polished counterpart. It is found that mechanical activation/polishing increases the C/O ratio which significantly affects inner-sphere electrochemical probes only (whereas outer-sphere systems remain unaffected). Mechanical activation/polishing has the potential to be a simple pre-treatment technique that can be extended and routinely applied towards other analytes for an observable improvement in the electroanalytical response.

Silsesquioxane organofunctionalized with 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole: Preparation and subsequent reaction with silver and potassium hexacyanoferrate(III) for detection of L-cysteine.

The octakis(3-chloropropyl)octasilsesquioxane (SS) was organofunctionalized with 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole (Purpald). The functionalized silsesquioxane with Purpald (SP) was characterized by Fourier transform infrared spectroscopy (FT-IR), and nuclear magnetic resonance (NMR). After functionalized, silsesquioxane can interact with silver nitrate and subsequently with potassium hexacyanoferrate (III) (AgHSP). The novel hybrid composite formed (AgHSP) was characterized by Fourier transform infrared spectra, scanning electron microscopy (SEM), and energy dispersive X-ray spectroscopy (EDX). AgHSP was electrochemically characterized by cyclic voltammetry (CV) using graphite paste electrode. The AgHSP incorporated into a graphite paste electrode (20% w/w) was tested for detection of l-cysteine. The modified electrode showed a linear response from 9.0 × 10(-5) to 5.0 × 10(-3)mol L(-1) with the corresponding equation Y(A)=0.01315+1.865 [l-cysteine], and a correlation coefficient of r(2)=0.9995. The method showed a detection limit of 1.76×10(-4)mol L(-1) with a relative standard deviation of ± 2% (n=3) and amperometric sensitivity of 1.865 A/mol L(-1).

Forensic electrochemistry: indirect electrochemical sensing of the components of the new psychoactive substance "Synthacaine".

"Synthacaine" is a New Psychoactive Substance which is, due to its inherent psychoactive properties, reported to imitate the effects of cocaine and is therefore consequently branded as "legal cocaine". The only analytical approach reported to date for the sensing of "Synthacaine" is mass spectrometry. In this paper, we explore and evaluate a range of potential analytical techniques for its quantification and potential use in the field screening "Synthacaine" using Raman spectroscopy, presumptive (colour) testing, High Performance Liquid Chromatography (HPLC) and electrochemistry. HPLC analysis of street samples reveals that "Synthacaine" comprises a mixture of methiopropamine (MPA) and 2-aminoindane (2-AI). Raman spectroscopy and presumptive (colour) tests, the Marquis, Mandelin, Simon's and Robadope test, are evaluated towards a potential in-the-field screening approach but are found to not be able to discriminate between the two when they are both present in the same sample, as is the case in the real street samples. We report for the first time a novel indirect electrochemical protocol for the sensing of MPA and 2-AI which is independently validated in street samples with HPLC. This novel electrochemical approach based upon one-shot disposable cost effective screen-printed graphite macroelectrodes holds potential for in-the-field screening for "Synthacaine".

Electroanalytical detection of pindolol: comparison of unmodified and reduced graphene oxide modified screen-printed graphite electrodes.

Recent work has reported the first electroanalytical detection of pindolol using reduced graphene oxide (RGO) modified glassy carbon electrodes [S. Smarzewska and W. Ciesielski, Anal. Methods, 2014, 6, 5038] where it was reported that the use of RGO provided significant improvements in the electroanalytical signal in comparison to a bare (unmodified) glassy carbon electrode. We demonstrate, for the first time, that the electroanalytical quantification of pindolol is actually possible using bare (unmodified) screen-printed graphite electrodes (SPEs). This paper addresses the electroanalytical determination of pindolol utilising RGO modified SPEs. Surprisingly, it is found that bare (unmodified) SPEs provide superior electrochemical signatures over that of RGO modified SPEs. Consequently the electroanalytical sensing of pindolol is explored at bare unmodified SPEs where a linear range between 0.1 µM-10.0 µM is found to be possible whilst offering a limit of detection (3σ) corresponding to 0.097 µM. This provides a convenient yet analytically sensitive method for sensing pindolol. The optimised electroanalytical protocol using the unmodified SPEs, which requires no pre-treatment (electrode polishing) or electrode modification step (such as with the use of RGO), was then further applied to the determination of pindolol in urine samples. This work demonstrates that the use of RGO modified SPEs have no significant benefits when compared to the bare (unmodified) alternative and that the RGO free electrode surface can provide electro-analytically useful performances.