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.

Rapid and portable electrochemical quantification of phosphorus.

Phosphorus is one of the key indicators of eutrophication levels in natural waters where it exists mainly as dissolved phosphorus. Various analytical protocols exist to provide an offsite analysis, and a point of site analysis is required. The current standard method recommended by the Environmental Protection Agency (EPA) for the detection of total phosphorus is colorimetric and based upon the color of a phosphomolybdate complex formed as a result of the reaction between orthophosphates and molybdates ions where ascorbic acid and antimony potassium tartrate are added and serve as reducing agents. Prior to the measurements, all forms of phosphorus are converted into orthophosphates via sample digestion (heating and acidifying). The work presented here details an electrochemical adaptation of this EPA recommended colorimetric approach for the measurement of dissolved phosphorus in water samples using screen-printed graphite macroelectrodes for the first time. This novel indirect electrochemical sensing protocol allows the determination of orthophosphates over the range from 0.5 to 20 µg L(-1) in ideal pH 1 solutions utilizing cyclic voltammetry with a limit of detection (3σ) found to correspond to 0.3 µg L(-1) of phosphorus. The reaction time and influence of foreign ions (potential interferents) upon this electroanalytical protocol was also investigated, where it was found that a reaction time of 5 min, which is essential in the standard colorimetric approach, is not required in the new proposed electrochemically adapted protocol. The proposed electrochemical method was independently validated through the quantification of orthophosphates and total dissolved phosphorus in polluted water samples (canal water samples) with ion chromatography and ICP-OES, respectively. This novel electrochemical protocol exhibits advantages over the established EPA recommended colorimetric determination for total phosphorus with lower detection limits and shorter experimental times. Additionally this electrochemical adaptation allows the determination of dissolved phosphorus without the use of ascorbic acid and antimony potassium tartrate as reducing agents (as used in the colorimetric method). The potential portability of this protocol is demonstrated in the development of the PhosQuant electrochemical device and provides a portable device for the rapid electrochemical detection of dissolved phosphorus using screen-printed electrodes.

Indirect electroanalytical detection of phenols.

A novel indirect electrochemical protocol for the electroanalytical detection of phenols is presented for the first time. This methodology is demonstrated with the indirect determination of the target analytes phenol, 2-chlorophenol, 4-chlorophenol and 2,4-dichlorophenol through an electrochemically adapted optical protocol. This electrochemical adaptation allows the determination of the above mentioned phenols without the use of any oxidising agents, as is the case in the optical method, where pyrazoline compounds (mediators) chemically react with the target phenols forming a quinoneimine product which is electrochemically active providing an indirect analytical signal to measure the target phenol(s). A range of commercially available pyrazoline substitution products, namely 4-dimethylaminoantipyrine, antipyrine, 3-methyl-1-(2-phenylethyl)-2-pyrazolin-5-one, 3-amino-1-(1-naphthylmethyl)-2-Pyrazolin-5-one, 4-amino-1,2-dimethyl-3-pentadecyl-3-pyrazolin-5-one hydrochloride, 3-amino-1-(2-amino-4-methylsulfonylphenyl)-2-pyrazolin-5-one hydrochloride and 4-aminoantipyrine are evaluated as mediators for the indirect detection of phenols. The indirect electrochemical detection of phenol, 2-chlorophenol, 4-chlorophenol and 2,4-dichlorophenol through the use of 4-aminoantipyrine as a mediator are successfully determined in drinking water samples at analytically useful levels. Finally, the comparison of the direct (no mediator) and the proposed indirect determination (with 4-aminoantipyrine) towards the analytical detection of the target phenols in drinking water is presented. The limitation of the proposed electroanalytical protocol is quantified for all the four target phenols.

Electrochemistry provides a point-of-care approach for the marker indicative of Pseudomonas aeruginosa infection of cystic fibrosis patients.

It has recently been demonstrated that 2-aminoacetophenone (2-AA) is a chemical indicator in exhaled air/breath of Pseudomonas aeruginosa infection associated with progressive life threatening decline of lung function in cystic fibrosis sufferers [Scott-Thomas et al., BMC Pulm. Med., 2010, 10, 56]. Currently the detection of 2-AA involves laboratory based instrumentation such as mass spectrometry and a hand-held point-of-care type breath device would be ideal in providing real-time results within seconds to accelerate patient care decision-making processes. To this end, we demonstrate proof-of-concept that the chemical marker 2-AA, indicative of Pseudomonas aeruginosa infection, can be measured using electrochemical based sensing strategies. A range of commercially available electrode substrates are explored demonstrating for the first time that 2-AA is electrochemically active within aqueous based solutions providing an (electro)analytical signal. Glassy carbon, boron-doped diamond and platinum electrodes have been explored towards the electrochemical oxidation of 2-AA. Electrode fouling is observed requiring pre-treatment in the form of mechanical polishing between voltammetric scans and measurements. To alleviate this, screen-printed graphite electrodes are shown to be a more viable option for implementation into breath sensing devices and overcome the fouling problem since due to their low cost and disposable nature, a new electrode can be used for each measurement. The analytical utility of the platinum, screen-printed and boron-doped diamond electrodes were found to correspond to 6.85, 7.66 and 4.86 mM respectively. The challenges associated with the electrochemical sensing of 2-AA in breath that need to be overcome are discussed. This generic approach where electrochemical based technology is used to provide measurements for chemical markers in exhaled air/breath for medical diagnostics termed electrochemical breathprints (ec-breathprints), has the potential to be developed into a hand-held point-of-care breath diagnostic tool for identifying Pseudomonas aeruginosa infection in exhaled air/breath.

An improved electrochemical creatinine detection method via a Jaffe-based procedure.

The detection of creatinine via an enzymeless electrochemical method is reported through an indirect electrochemical system in which the picrate anion consumed upon the reaction with creatinine is electrochemically measured. After careful optimisation it is found that in pH 13 two linear analytical ranges are possible utilising an Edge Plane Pyrolytic Graphite (EPPG) electrode: 0-6 mM and 7.5-11.5 mM, with a limit of detection (3σ) corresponding to 0.27 mM; all measurements were taken after a five minute reaction time. Furthermore, screen printed carbon electrodes were applied to the same system and yielded remarkably similar linear ranges to the case of the EPPG electrode: 0-6 mM and 6-11 mM, with a limit of detection (3σ) of 0.72 mM. These results are critically analysed and contrasted with the previous literature. This electrochemical protocol is applied to the detection of urinary creatinine where we find creatinine content of three samples falling well within our reported linear ranges and more importantly indicating correct kidney function. Additionally our electrochemical results are 'benchmarked' against UV/Vis spectrometry. The devised electroanalytical protocols have the potential to serve as a more solid foundation for electrochemical creatinine testing and have potential to be applied as a point-of-care diagnostics system through the use of screen printing technology, especially considering urinary creatinine concentrations fall within our reported linear ranges for both healthy adults and adults with deficient glomerular filtration.

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'.

Electrochemistry of Q-graphene.

A newly synthesised type of graphene, Q-Graphene, has been physically and electrochemically characterised with Scanning and Transmission Electron Microscopy (SEM, TEM), X-ray Photoelectron Spectroscopy (XPS) and Cyclic Voltammetry (CV). Interpretation of SEM, TEM and XPS data reveal the material to consist of hollow carbon nanospheres of multi-layer graphene (viz. graphite), which exhibit a total oxygen content of ca. 36.0% (atomic weight via XPS). In addition to the carbon structures present, spherical magnesium oxide particles of ≤50 nm in diameter are abundantly present in the sample (ca. 16.2%). Interestingly, although the TEM/SEM images show macroporous carbon structures, Raman spectroscopy shows peaks typically characteristic of graphene, which suggests the material is highly heterogeneous and consists of many types of carbon allotropes. Q-Graphene is electrochemically characterised using both inner-sphere and outer-sphere electrochemical redox probes, namely potassium ferrocyanide(II), hexaammine-ruthenium(III) chloride and hexachloroiridate(III), in addition to the biologically relevant and electroactive analytes, norepinephrine, ß-nicotinamide adenine dinucleotide (NADH) and l-ascorbic acid. The electrochemical response of Q-Graphene is benchmarked against edge plane- and basal plane-pyrolytic graphite (EPPG and BPPG respectively), pristine graphene and graphite alternatives. Q-Graphene is found to exhibit fast electron transfer kinetics, likely due to its high proportion of folded edges and surface defects, exhibiting a response similar to that of EPPG - which exhibits fast electron transfer rates due to the high proportion of edge plane sites it possesses. Furthermore, we demonstrate that the specific oxygen content plays a pivotal role in dictating the observed electrochemical response, which is analyte dependant. Consequently there is potential for this new member of the graphene family to be beneficially utilised in various electrochemical applications.

Graphene electrochemistry: fundamental concepts through to prominent applications.

The use of graphene, a one atom thick individual planar carbon layer, has exploded in a plethora of scientific disciplines since it was reported to possess a range of unique and exclusive properties. Despite graphene being explored theoretically since the 1940s and known to exist since the 1960s, the recent burst of interest from a large proportion of scientists globally can be correlated with work by Geim and Novoselov in 2004/5, who reported the so-called "scotch tape method" for the production of graphene in addition to identifying its unique electronic properties which has escalated into graphene being reported to be superior in a superfluity of areas. Consequently, many are involved in the pursuit of producing new methodologies to fabricate pristine graphene on an industrial scale in order to meet the current world-wide appetite for graphene. One area which receives considerable interest is the field of electrochemistry, where graphene has been reported to be beneficial in various applications ranging from sensing through to energy storage and generation and carbon based molecular electronics. Electrochemistry is an interfacial technique which is dominated by processes that occur at the solid-liquid interface and thus with the correct understanding can be beneficially utilised to characterise the surface under investigation. In this tutorial review we overview fundamental concepts of Graphene Electrochemistry, making electrochemical characterisation accessible to those who are working on new methodologies to fabricate graphene, bridging the gap between materials scientists and electrochemists and also assisting those exploring graphene in electrochemical areas, or that wish to start to. An overview of the recent understanding of graphene modified electrodes is also provided, highlighting prominent applications reported in the current literature.

Graphene electroanalysis: inhibitory effects in the stripping voltammetry of cadmium with surfactant free graphene.

We explore the use of surfactant free graphene towards the electroanalytical sensing of cadmium(II) ions via anodic stripping voltammetry. In line with literature methodologies, we modify an electrode substrate which exhibits relatively fast electron transfer with commercially available graphene which is free from surfactants. Surprisingly, we find that graphene reduces the analytical performance and hence inhibits the electrochemical detection of cadmium(II) ions, with calibration plots in model aqueous solutions revealing no advantages of employing graphene in this analytical context.

Exploring the physicoelectrochemical properties of graphene.

Convincing evidence is presented demonstrating that the electro-catalytic nature of graphene resides in electron transfer from the edge of graphene which structurally resembles the behaviour of edge plane (rather than basal plane) of highly ordered pyrolytic graphite. The impact of surfactants intrinsic to graphene on the electrochemical response is highlighted.

Graphite screen printed electrodes for the electrochemical sensing of chromium(VI).

We demonstrate that graphite screen printed macroelectrodes allow the low ppb sensing of chromium(VI) in aqueous solutions over the range 100 to 1000 microg L(-1) with a limit of detection of 19 microg L(-1). The underlying electrochemical mechanism is explored indicating an indirect process involving surface oxygenated species. The drawbacks of using hydrochloric acid as a model solution to evaluate the electrochemical detection of chromium(VI) are also pointed out. The analytical protocol is shown to be applicable for the sensing of chromium(VI) in canal water samples at levels set by the World Health Organisation. The protocol is simplified over existing analytical methodologies and given its analytical performance and economical nature, holds promise for the de-centralised screening of chromium(VI).

Gold nanoparticle ensembles allow mechanistic insights into electrochemical processes.

Gold-nanoparticle-modified electrodes find wide and diverse applications in the area of electrochemistry. We demonstrate for the first time that gold-nanoparticle-modified electrodes can provide mechanistic information and we exemplify this with the electrochemical deposition of arsenic(III). Our approach of using nanoparticle ensembles is a facile and economical methodology that provides an alternative to using expensive gold single-crystal electrodes that require careful surface preparation before each measurement.

High throughput screening of lead utilising disposable screen printed shallow recessed microelectrode arrays.

The cathodic stripping voltammetry of lead at disposable screen printed shallow recessed microelectrode arrays has been developed for the first time. The array comprises 6 microdiscs which have radii of 116 (+/-6) microns which are recessed by 4 microns and are separated by 2500 microns from their nearest neighbour in a hexagonal arrangement. The electroanalytical determination of lead was explored in 0.1 M nitric acid and found that using a 120 s deposition time, a detection limit of 3 microM is feasible which is not possible utilising a screen printed graphite macro-electrode. The sensitivity of this analytical protocol can be tailored by varying the deposition time and it is found that increasing this to 320 s facilitates a limit of detection of 39 nM. This methodology is shown to be feasible for the portable and economical screening of lead in river water samples at the levels indicated by the EC Dangerous Substances Directive (76/464/EEC).

Why 'the bigger the better' is not always the case when utilising microelectrode arrays: high density vs. low density arrays for the electroanalytical sensing of chromium(VI).

We demonstrate, with the example of the electroanalytical sensing of chromium(vi) using ultra-microelectrode arrays, that a larger number of microelectrodes comprising an array do not necessarily provide improved electroanalytical performance. Using a low density array, which consists of 256 microdiscs where each microdisc comprising the array has a radius of 10 microns in a cubic arrangement separated from their nearest neighbour by 100 microns, the electroanalytical sensing of chromium(vi) is shown to be possible over the range 13-428 microM with a limit of detection of 3.4 microM readily achievable. Using a high density microelectrode, consisting of 2597 microdiscs where each microdisc has a radius of 2.5 microns in a hexagonal pattern which are separated from their nearest neighbour by 55 microns, the electroanalytical performance, in terms of linear range and sensitivity, is considerably lower going against the misconception that a high density array should produce a superior analytical response. The reason for this disparity is discussed and it is shown that the arrangement of the microelectrodes on the array is critical due to the interaction of diffusion zones between neighbouring electrodes allowing analysts to make informed decisions on the conscientious choice of microelectrode arrays.

Next generation screen printed electrochemical platforms: Non-enzymatic sensing of carbohydrates using screen printed electrodes.

The first example of a copper(ii) oxide screen printed electrode is reported which is characterised with microscopy and explored towards the electrochemical sensing of glucose, maltose, sucrose and fructose. It is shown that the non-enzymatic electrochemical sensing of glucose with cyclic voltammetry and amperometry is possible with low micro-molar up to milli-molar glucose readily detectable which compares competitively with nano-catalyst modified electrodes. The sensing of glucose shows a modest selectivity over maltose and sucrose while fructose is not detectable. An additional benefit of this approach is that metal oxides with known oxidation states can be incorporated into the screen printed electrodes allowing one to identify exactly the origin of the observed electro-catalytic response which is difficult when utilising metal oxide modified electrodes formed via electro-deposition techniques which result in a mixture of metal oxides/oxidation states. These next generation screen printed electrochemical sensing platforms provide a simplification over previous copper oxide systems offering a novel fabrication route for the mass production of electro-catalytic sensors for analytical and forensic applications.

Screen printed electrochemical platforms for pH sensing.

We explore the possible use of screen printing technology for fabricating disposable electrochemical platforms for the sensing of pH. These screen printed pH sensors incorporate the pH sensitive phenanthraquinone moiety which undergoes a Nernstian potential shift with pH, and the pH insensitive dimethylferrocene which acts as an internal reference. This generic approach offers a calibration-less and reproducible approach for portable pH measurements with the possibility of miniaturisation allowing incorporation into existing sensing devices. The advantages, limitations and future prospects of this fabrication approach for producing electrochemical platforms for pH sensing are also discussed.