Enhanced Electrochemical Response of Diclofenac at a Fullerene–Carbon Nanofiber Paste Electrode

The requirements of the Water Framework Directive to monitor diclofenac (DCF) concentration in surface water impose the need to find advanced fast and simple analysis methods. Direct voltammetric/amperometric methods could represent efficient and practical solutions. Fullerene–carbon nanofibers in paraffin oil as a paste electrode (F–CNF) was easily obtained by simple mixing and tested for DCF detection using voltammetric and amperometric techniques. The lowest limit of detection of 0.9 nM was achieved by applying square-wave voltammetry operated under step potential (SP) of 2 mV, modulation amplitude (MA) of 10 mV, and frequency of 25 Hz, and the best sensitivity was achieved by four-level multiple pulsed amperometry (MPA) that allowed in situ reactivation of the F–CNF electrode. The selection of the method must take into account the environmental quality standard (EQS), imposed through the “watchlist” of the Water Framework Directive as 0.1 µg·L−1 DCF. A good improvement of the electroanalytical parameters for DCF detection on the F–CNF electrode was achieved by applying the preconcentration step for 30 min before the detection step, which assured about 30 times better sensitivity, recommending its application for the monitoring of trace levels of DCF. The electrochemical behavior of F–CNF as a pseudomicroelectrode array makes it suitable for practical application in the in situ and real-time monitoring of DCF concentrations in water.

[1]  I. Kim,et al.  Reusable carbon nanofibers for efficient removal of methylene blue from aqueous solution , 2018, Chemical Engineering Research and Design.

[2]  J. Schoonman,et al.  Electrochemical Determination of Diclofenac Sodium in Aqueous Solution on Cu-Doped Zeolite-Expanded Graphite-Epoxy Electrode , 2010 .

[3]  M. Ganjali,et al.  Determination of diclofenac using electromembrane extraction coupled with stripping FFT continuous cyclic voltammetry. , 2017, Analytica chimica acta.

[4]  S. Pilehvar,et al.  Recent Advances in Electrochemical Biosensors Based on Fullerene-C60 Nano-Structured Platforms , 2015, Biosensors.

[5]  G. Rounaghi,et al.  Fabrication of a new electrochemical sensor based on Au Pt bimetallic nanoparticles decorated multi-walled carbon nanotubes for determination of diclofenac , 2019, Microchemical Journal.

[6]  Shen-ming Chen,et al.  A new type of terbium diselenide nano octagon integrated oxidized carbon nanofiber: An efficient electrode material for electrochemical detection of morin in the food sample , 2018, Sensors and Actuators B: Chemical.

[7]  A. Afkhami,et al.  Gold nanoparticle/multi-walled carbon nanotube modified glassy carbon electrode as a sensitive voltammetric sensor for the determination of diclofenac sodium. , 2016, Materials science & engineering. C, Materials for biological applications.

[8]  K. Jiao,et al.  Voltammetric study of fullerene C60 and fullerene C60 nanotubes with sandwich method , 2009 .

[9]  Wlodzimierz Kutner,et al.  Electrocatalytic Properties and Sensor Applications of Fullerenes and Carbon Nanotubes , 2003 .

[10]  Shihe Yang,et al.  Highly Selective and Sensitive Detection of Dopamine in the Presence of Excessive Ascorbic Acid Using Electrodes Modified with C60-Functionalized Multiwalled Carbon Nanotube Films , 2009 .

[11]  Loos Robert,et al.  Water Framework Directive. Watch List Method. Analysis of diclofenac in water , 2014 .

[12]  Karolien De Wael,et al.  Fullerene-C60 sensor for ultra-high sensitive detection of bisphenol-A and its treatment by green technology , 2013 .

[13]  M. Elbasri,et al.  Electrochemical behaviorof carbon paste electrode modified with Carbon Nanofibers : Application to detection of Bisphenol A , 2016 .

[14]  Shihe Yang,et al.  Significantly accelerated direct electron-transfer kinetics of hemoglobin in a C(60)-MWCNT nanocomposite film. , 2006, Chemistry.

[15]  Q. Xue,et al.  Comparative tribological and corrosion resistance properties of epoxy composite coatings reinforced with functionalized fullerene C60 and graphene , 2016 .

[16]  R. Risebrough Conservation biology: Fatal medicine for vultures , 2004, Nature.

[17]  G. Álvarez-Romero,et al.  New insights on diclofenac electrochemistry using graphite as working electrode , 2017 .

[18]  Aniela Pop,et al.  Simultaneous Voltammetric Detection of Carbaryl and Paraquat Pesticides on Graphene-Modified Boron-Doped Diamond Electrode , 2017, Sensors.

[19]  Aleem Ahmed Khan,et al.  Diclofenac residues as the cause of vulture population decline in Pakistan , 2004, Nature.

[20]  B. McDuffie,et al.  Diffusion coefficients of ferri- and ferrocyanide ions in aqueous media, using twin-electrode thin-layer electrochemistry , 1970 .

[21]  M. Nimlos,et al.  Porous carbon nanofiber derived from a waste biomass as anode material in lithium-ion batteries , 2019, Journal of the Taiwan Institute of Chemical Engineers.

[22]  K. Wael,et al.  C60-functionalized MWCNT based sensor for sensitive detection of endocrine disruptor vinclozolin in solubilized system and wastewater , 2012 .

[23]  N. A. Kadri,et al.  Immobilized copper ions on MWCNTS-Chitosan thin film: Enhanced amperometric sensor for electrochemical determination of diclofenac sodium in aqueous solution , 2017 .

[24]  R. Schneider,et al.  Liquid chromatography-tandem mass spectrometry detection of diclofenac and related compounds in water samples. , 2018, Journal of chromatography. A.

[25]  M. Sajid,et al.  Recent trends in nanomaterial-modified electrodes for electroanalytical applications , 2019, TrAC Trends in Analytical Chemistry.

[26]  W. LaCourse,et al.  Pulsed electrochemical detection at noble metal electrodes in liquid chromatography , 1992 .

[27]  P. Malchev,et al.  Voltammetric Detection of Urea on an Ag-Modified Zeolite-Expanded Graphite-Epoxy Composite Electrode , 2008, Sensors.

[28]  Jorge Gascón,et al.  Electrochemical Selective and Simultaneous Detection of Diclofenac and Ibuprofen in Aqueous Solution Using HKUST-1 Metal-Organic Framework-Carbon Nanofiber Composite Electrode , 2016, Sensors.