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.

Utilising copper screen-printed electrodes (CuSPE) for the electroanalytical sensing of sulfide.

A mediatorless sulfide electrochemical sensing platform utilising a novel nanocopper-oxide screen-printed electrodes (CuSPE) is reported for the first time. The state-of-the-art screen-printed electrochemical sensors demonstrate their capability to quantify sulfide within both the presence and absence of an array of interferents with good levels of sensitivity and repeatability. The direct sensing (using linear sweep voltammetry) of sulfide utilising the CuSPEs provides a mediatorless approach for the detection of sulfide, yielding useful analytical signatures that can be successfully quantified. The proposed novel protocol using the CuSPEs is successfully applied to the sensing of sulfide within drinking water exhibiting a high level of recovery.

Graphite Screen-Printed Electrodes Applied for the Accurate and Reagentless Sensing of pH.

A reagentless pH sensor based upon disposable and economical graphite screen-printed electrodes (GSPEs) is demonstrated for the first time. The voltammetric pH sensor utilizes GSPEs which are chemically pretreated to form surface immobilized oxygenated species that, when their redox behavior is monitored, give a Nernstian response over a large pH range (1-13). An excellent experimental correlation is observed between the voltammetric potential and pH over the entire pH range of 1-13 providing a simple approach with which to monitor solution pH. Such a linear response over this dynamic pH range is not usually expected but rather deviation from linearity is encountered at alkaline pH values; absence of this has previously been attributed to a change in the pKa value of surface immobilized groups from that of solution phase species. This non-deviation, which is observed here in the case of our facile produced reagentless pH sensor and also reported in the literature for pH sensitive compounds immobilized upon carbon electrodes/surfaces, where a linear response is observed over the entire pH range, is explained alternatively for the first time. The performance of the GSPE pH sensor is also directly compared with a glass pH probe and applied to the measurement of pH in "real" unbuffered samples where an excellent correlation between the two protocols is observed validating the proposed GSPE pH sensor.

Regal electrochemistry: British 5 pence coins provide useful metallic macroelectrode substrates.

The utilisation of British Currency (GBP) as an electrode substrate is demonstrated for the first time. Termed Regal electrochemistry, a 5 pence (5p) coin (GBP) is electrically wired using a bespoke electrochemical cell and is electrochemically characterised using the outer-sphere redox probe hexaammineruthenium(III) chloride. The electroanalytical utility of the 5p coin electrode is demonstrated towards the novel, proof-of-concept sensing of lead(II) ions using square-wave voltammetry in model buffer solutions over the linear range 5-2000 nM exhibiting a limit of detection (3σ) of 1.97 nM. Interestingly, the actual cost of the electrode is 2.5 pence (GBP) since both sides of the coins can be utilised and provide a cheap yet reproducible and disposable metallic electrode substrate that is electrochemically useful.

Detection and quantification of new psychoactive substances (NPSs) within the evolved "legal high" product, NRG-2, using high performance liquid chromatography-amperometric detection (HPLC-AD).

The global increase in the production and abuse of cathinone-derived New Psychoactive Substances (NPSs) has developed the requirement for rapid, selective and sensitive protocols for their separation and detection. Electrochemical sensing of these compounds has been demonstrated to be an effective method for the in-field detection of these substances, either in their pure form or in the presence of common adulterants, however, the technique is limited in its ability to discriminate between structurally related cathinone-derivatives (for example: (±)-4'-methylmethcathinone (4-MMC, 2a) and (±)-4'-methyl-N-ethylmethcathinone (4-MEC, 2b) when they are both present in a mixture. In this paper we demonstrate, for the first time, the combination of HPLC-UV with amperometric detection (HPLC-AD) for the qualitative and quantitative analysis of 4-MMC and 4-MEC using either a commercially available impinging jet (LC-FC-A) or custom-made iCell channel (LC-FC-B) flow-cell system incorporating embedded graphite screen-printed macroelectrodes. The protocol offers a cost-effective, reproducible and reliable sensor platform for the simultaneous HPLC-UV and amperometric detection of the target analytes. The two systems have similar limits of detection, in terms of amperometric detection [LC-FC-A: 14.66 µg mL(-1) (2a) and 9.35 µg mL(-1) (2b); LC-FC-B: 57.92 µg mL(-1) (2a) and 26.91 µg mL(-1) (2b)], to the previously reported oxidative electrochemical protocol [39.8 µg mL(-1) (2a) and 84.2 µg mL(-1) (2b)], for two synthetic cathinones, prevalent on the recreational drugs market. Though not as sensitive as standard HPLC-UV detection, both flow cells show a good agreement, between the quantitative electroanalytical data, thereby making them suitable for the detection and quantification of 4-MMC and 4-MEC, either in their pure form or within complex mixtures. Additionally, the simultaneous HPLC-UV and amperometric detection protocol detailed herein shows a marked improvement and advantage over previously reported electroanalytical methods, which were either unable to selectively discriminate between structurally related synthetic cathinones (e.g. 4-MMC and 4-MEC) or utilised harmful and restrictive materials in their design.

An overview of recent developments in the analytical detection of new psychoactive substances (NPSs).

New psychoactive substances (NPSs), sometimes referred to as "legal highs" in more colloquial environments/the media, are a class of compounds that have been recently made available for abuse (not necessarily recently discovered) which provide similar effects to the traditional well studied illegal drugs but are not always controlled under existing local, regional or international drug legislation. Following an unprecedented increase in the number of NPSs in the last 5 years (with 101 substances discovered for the first time in 2014 alone) its, occasionally fatal, consequences have been extensively reported in the media. Such NPSs are typically marketed as 'not for human consumption' and are instead labelled and sold as plant food, bath salts as well as a whole host of other equally nondescript aliases in order to bypass legislative controls. NPSs are a new multi-disciplinary research field with the main emphasis in terms of forensic identification due to their adverse health effects, which can range from minimal to life threatening and even fatalities. In this mini-review we overview this recent emerging research area of NPSs and the analytical approaches reported to provide detection strategies as well as detailing recent reports towards providing point-of-care/in-the-field NPS ("legal high") sensors.

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.

Forensic electrochemistry applied to the sensing of new psychoactive substances: electroanalytical sensing of synthetic cathinones and analytical validation in the quantification of seized street samples.

The electrochemical sensing of new psychoactive substance(s) (NPSs), synthetic cathinone derivatives also termed "legal highs", are explored with the use of metallic modified screen-printed electrochemical sensors (SPES). It is found that no significant electrochemical enhancement is evident with the use of either in situ bismuth or mercury film modified SPES compared to the bare underlying electrode substrate. In fact, the direct electrochemical reduction of the cathinone derivatives mephedrone (4-methylmethcathinone; 4-MMC) and 4'-methyl-N-ethylcathinone (4-methylethcathinone; 4-MEC) is found to be possible for the first time, without heavy metal catalysis, giving rise to useful voltammetric electroanalytical signatures in model aqueous buffer solutions. This novel electroanalytical methodology is validated toward the determination of cathinone derivatives (4-MMC and 4-MEC) in three seized street samples that are independently analyzed with high-performance liquid chromatography (HPLC) wherein excellent agreement between the two analytical protocols is found. Such an approach provides a validated laboratory tool for the quantification of synthetic cathinone derivatives and holds potential for the basis of a portable analytical sensor for the determination of synthetic cathinone derivatives in seized street samples.

Forensic electrochemistry: the electroanalytical sensing of synthetic cathinone-derivatives and their accompanying adulterants in "legal high" products.

The production and abuse of new psychoactive substances, known as "legal highs" which mimic traditional drugs of abuse is becoming a global epidemic. Traditional analytical methodologies exist which can provide confirmatory analysis but there is a requirement for an on-the-spot analytical screening tool that could be used to determine whether a substance, or sample matrix contains such legal, or formally "legal highs". In this paper the electrochemical sensing of (±)-methcathinone and related compounds at a range of commercially available electrode substrates is explored. We demonstrate for the first time that this class of "legal highs" are electrochemically active providing a novel sensing protocol based upon their electrochemical oxidation. Screen-printed graphite sensing platforms are favoured due to their proven ability to be mass-produced providing large numbers of reliable and reproducible electrode sensing platforms that preclude the requirement of surface pre-treatment such as mechanical polishing as is the case in the use of solid/re-usable electrode substrates. Additionally they hold potential to be used on-site potentially being the basis of an on-site legal high screening device. Consequently the electroanalytical sensing of (±)-methcathinone (3a), (±)-4'-methylmethcathinone [3b, 4-MMC, (±)-mephedrone] and (±)-4'-methyl-N-ethylcathinone (3c, 4-MEC) is explored using screen-printed sensing platforms with the effect of pH explored upon the analytical response with their analytical efficiency evaluated towards the target legal highs. Interesting at pH values below 6 the voltammetric response quantitatively changes from that of an electrochemically irreversible response to that of a quasi-reversible signature which can be used analytically. It is demonstrated for the first time that the electroanalytical sensing of (±)-methcathinone (3a), (±)-mephedrone (3b) and 4-MEC (3c) are possible with accessible linear ranges found to correspond to 16­200 µg mL(−1) for 3a (at pH 12) and 16­350 µg mL(−1) for both 3b and 3c in pH 2, with limits of detection (3σ) found to correspond to 44.5, 39.8 and 84.2 µg mL(−1) respectively. Additionally adulterants that are commonly incorporated into cathinone legal highs are electrochemically explored at both pH 2 and 12.

Forensic electrochemistry: the electroanalytical sensing of Rohypnol® (flunitrazepam) using screen-printed graphite electrodes without recourse for electrode or sample pre-treatment.

The electroanalytical sensing of Rohypnol® (flunitrazepam) is reported for the first time utilising screen-printed graphite electrodes without the requirement for any additional pre-treatment or modification. The methodology is shown to be useful for quantifying low levels (µg mL(-1)) of Rohypnol® in not only buffered solutions but also two internationally favoured drinks: Coca Cola™ and the alcopop WKD™ without any sample pre-treatment. The current analytical approaches for the sensing of Rohypnol® are also summarised within this paper. The niche of this electroanalytical protocol is the lack of the requirement of any pre-treatment of the sample/beverage or electrode modification (cleaning, pre-treatment etc.) for the determination of Rohypnol® in beverages and offers a potential rapid, cost-effective, yet suitably sensitive and accurate screening solution to the problem posed by coloured drinks to products such as the colour changing 'Smart Cup'.