Graphene oxide modified screen-printed electrodes have been tested as amperometric sensors for morphine determination. The results demonstrate that the arising of electrocatalytic processes ascribable to the graphene coating, combined with the use of a suitable cleaning procedure, allow the sensor to achieve higher sensitivity (2.61 nA ppb-1) and lower limit of detection (2.5 ppb) with respect to those reported in the literature for similar devices. Due to very low detection limit found, the device is suitable to detect the presence of morphine in urine samples after a very simple and rapid pre-treatment of the matrix, allowing the removal of interfering species affecting the voltammetric responses. Tests performed in synthetic urine samples demonstrate that the presence of the electrocatalytic coating is mandatory in resolving the peak due to morphine oxidation in respect to uric acid. The sensor proposed is, thus, suitable to detect this drug even at concentration values below the cutoff levels defined by European and American regulations. These results allow us to propose the sensor for screening tests in portable devices, to be applied in systematic controls of drug abuses, e.g. in drivers and in men at work.
We describe a nanocomposite material for the electrochemical detection of β-nicotinamide adenine dinucleotide (NADH), a coenzyme involved in redox reactions of all living cells and in the detection of many organic species by electrochemical biosensors. The composite is made of nanosheets of electrochemically exfoliated graphene oxide (EGO) covalently functionalized with dopamine (DP) molecules. The EGO DP material finally obtained is rich of 1,2-dihydroxyphenyl moieties and is able to detect NADH at a particular low potential value with higher sensitivity with respect to pristine EGO. To study the effectiveness of 1,2-dihydroxyphenyl moieties in inducing electrocatalytic oxidation of NADH, we combined standard voltammetric techniques with UV-Vis absorption spectroelectrochemistry, which allowed us to measure the variations in composition occurring at the electrode|solution interface, i.e. to measure the consumption rate of NADH. Spectroelectrochemical tests performed by polarising the electrode at a fixed potential value were finally used to compare the performance of EGO DP with both EGO and EGO-DP blend (MIX) for the detection of NADH. The covalently functionalized EGO (EGO DP ) shows sensitivity to NADH up to 300 M -1 , around 180 % and 140 % better than either pristine EGO or MIX, respectively.
A flexible electrode system entirely constituted by single-walled carbon nanotubes (SWCNTs) has been proposed as the sensor platform for β-nicotinamide adenine dinucleotide (NADH) detection. The performance of the device, in terms of potential at which the electrochemical process takes place, significantly improves by electrochemical functionalization of the carbon-based material with a molecule possessing an o-hydroquinone residue, namely caffeic acid. Both the processes of SWCNT functionalization and NADH detection have been studied by combining electrochemical and spectroelectrochemical experiments, in order to achieve direct evidence of the electrode modification by the organic residues and to study the electrocatalytic activity of the resulting material in respect to functional groups present at the electrode/solution interface. Electrochemical measurements performed at the fixed potential of +0.30 V let us envision the possible use of the device as an amperometric sensor for NADH detection. Spectroelectrochemistry also demonstrates the effectiveness of the device in acting as a voltabsorptometric sensor for the detection of this same analyte by exploiting this different transduction mechanism, potentially less prone to the possible presence of interfering species.
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