Recycling old screen-printed electrodes with newly designed plastic antibodies on the wall of carbon nanotubes as sensory element for in situ detection of bacterial toxins in water

Abstract Using low cost portable devices that enable a single analytical step for screening environmental contaminants is today a demanding issue. This concept is here tried out by recycling screen-printed electrodes that were to be disposed of and by choosing as sensory element a low cost material offering specific response for an environmental contaminant. Microcystins (MCs) were used as target analyte, for being dangerous toxins produced by cyanobacteria released into water bodies. The sensory element was a plastic antibody designed by surface imprinting with carefully selected monomers to ensure a specific response. These were designed on the wall of carbon nanotubes, taking advantage of their exceptional electrical properties. The stereochemical ability of the sensory material to detect MCs was checked by preparing blank materials where the imprinting stage was made without the template molecule. The novel sensory material for MCs was introduced in a polymeric matrix and evaluated against potentiometric measurements. Nernstian response was observed from 7.24 × 10 −10 to 1.28 × 10 −9  M in buffer solution (10 mM HEPES, 150 mM NaCl, pH 6.6), with average slopes of −62 mV decade −1 and detection capabilities below 1 nM. The blank materials were unable to provide a linear response against log(concentration), showing only a slight potential change towards more positive potentials with increasing concentrations (while that of the plastic antibodies moved to more negative values), with a maximum rate of +33 mV decade −1 . The sensors presented good selectivity towards sulphate, iron and ammonium ions, and also chloroform and tetrachloroethylene (TCE) and fast response ( in situ ” analysis.

[1]  Wei Yang,et al.  Induction of Apoptosis in Mouse Liver by Microcystin-LR , 2005, Molecular & Cellular Proteomics.

[2]  R. Li,et al.  Aligned synthesis of multi-walled carbon nanotubes with high purity by aerosol assisted chemical vapor deposition: Effect of water vapor , 2010 .

[3]  Jinghong Li,et al.  Carbon nanofiber-based composites for the construction of mediator-free biosensors. , 2008, Biosensors & bioelectronics.

[4]  Jun Li,et al.  Inlaid Multi-Walled Carbon Nanotube Nanoelectrode Arrays for Electroanalysis , 2005 .

[5]  W. Carmichael,et al.  Human Fatalities from Cyanobacteria: Chemical and Biological Evidence for Cyanotoxins , 2001 .

[6]  Sandro Carrara,et al.  Screen-printed electrodes based on carbon nanotubes and cytochrome P450scc for highly sensitive cholesterol biosensors. , 2008, Biosensors & bioelectronics.

[7]  Steve F. A. Acquah,et al.  Polyurea-functionalized multiwalled carbon nanotubes: synthesis, morphology, and Raman spectroscopy. , 2005, The journal of physical chemistry. B.

[8]  John H. T. Luong,et al.  Solubilization of Multiwall Carbon Nanotubes by 3‐Aminopropyltriethoxysilane Towards the Fabrication of Electrochemical Biosensors with Promoted Electron Transfer , 2004 .

[9]  A. Lobo,et al.  Influence of diameter in the Raman spectra of aligned multi-walled carbon nanotubes , 2007 .

[10]  Damià Barceló,et al.  Biosensors as useful tools for environmental analysis and monitoring , 2006, Analytical and bioanalytical chemistry.

[11]  Olof Ramström,et al.  The Emerging Technique of Molecular Imprinting and Its Future Impact on Biotechnology , 1996, Bio/Technology.

[12]  Kurt Straif,et al.  Carcinogenicity of nitrate, nitrite, and cyanobacterial peptide toxins. , 2006, The Lancet. Oncology.

[13]  M. Goreti F. Sales,et al.  Novel Potentiometric Sensors of Molecular Imprinted Polymers for Specific Binding of Chlormequat , 2008 .

[14]  Maogen Zhang,et al.  Carbon nanotube-chitosan system for electrochemical sensing based on dehydrogenase enzymes. , 2004, Analytical chemistry.

[15]  Dusan Losic,et al.  Protein electrochemistry using aligned carbon nanotube arrays. , 2003, Journal of the American Chemical Society.

[16]  W. Preiser,et al.  Fatal microcystin intoxication in haemodialysis unit in Caruaru, Brazil , 1998, The Lancet.

[17]  Sara Tombelli,et al.  New trends in affinity sensing: aptamers for ligand binding , 2003 .

[18]  D. Caron,et al.  Rapid and Label-Free Cell Detection by Metal-Cluster-Decorated Carbon Nanotube Biosensors , 2008, 2008 Device Research Conference.

[19]  M. Smyth,et al.  Electrochemical detection of microcystins, cyanobacterial peptide hepatotoxins, following high-performance liquid chromatography. , 1998, Journal of chromatography. A.

[20]  Mingfei Pan,et al.  Electrochemical sensor using methimazole imprinted polymer sensitized with MWCNTs and Salen-Co(III) as recognition element. , 2012, Biosensors & bioelectronics.

[21]  K. Mosbach,et al.  Molecularly imprinted polymers and their use in biomimetic sensors. , 2000, Chemical reviews.

[22]  Observation of bias-dependent low field positive magneto-resistance in Co-doped amorphous carbon films , 2010 .

[23]  R. Buck,et al.  Recommended procedures for calibration of ion-selective electrodes (Technical Report) , 1993 .

[24]  Y. Umezawa,et al.  Selectivity coefficients for ion-selective electrodes: Recommended methods for reporting KA,Bpot values (Technical Report) , 1995 .

[25]  T. Downing,et al.  Comparison of the structure of key variants of microcystin to vasopressin. , 2005, Environmental toxicology and pharmacology.

[26]  Peter Dubruel,et al.  Recent advances in recognition elements of food and environmental biosensors: a review. , 2010, Biosensors & bioelectronics.

[27]  G. Wulff Molecular Imprinting in Cross‐Linked Materials with the Aid of Molecular Templates— A Way towards Artificial Antibodies , 1995 .

[28]  Jonathan M. Cooper,et al.  Biosensors : a practical approach , 2004 .

[29]  F. T. Moreira,et al.  Sulfadiazine-Potentiometric Sensors for Flow and Batch Determinations of Sulfadiazine in Drugs and Biological Fluids , 2009, Analytical sciences : the international journal of the Japan Society for Analytical Chemistry.

[30]  J. V. Bannister Biosensors: Fundamentals and applications , 1987 .

[31]  Kiyoshi Toko,et al.  Fabrication of a novel immunosensor using functionalized self-assembled monolayer for trace level detection of TNT by surface plasmon resonance. , 2007, Talanta.

[32]  Hiroyuki Koide,et al.  Recognition, neutralization, and clearance of target peptides in the bloodstream of living mice by molecularly imprinted polymer nanoparticles: a plastic antibody. , 2010, Journal of the American Chemical Society.

[33]  K. Balasubramanian,et al.  Biosensors based on carbon nanotubes , 2006, Analytical and bioanalytical chemistry.

[34]  Gil U. Lee,et al.  Scanning probe microscopy. , 2010, Current opinion in chemical biology.

[35]  Sergey A. Piletsky,et al.  Electrochemical Sensors Based on Molecularly Imprinted Polymers , 2002 .

[36]  M. Pumera,et al.  New materials for electrochemical sensing VI: Carbon nanotubes , 2005 .

[37]  Filip Braet,et al.  Carbon nanotubes for biological and biomedical applications , 2007 .

[38]  F. T. Moreira,et al.  Artificial antibodies for troponin T by its imprinting on the surface of multiwalled carbon nanotubes: its use as sensory surfaces. , 2011, Biosensors & bioelectronics.

[39]  R. Seeber,et al.  Optimization of the DPV potential waveform for determination of ascorbic acid on PEDOT-modified electrodes , 2007 .

[40]  Ernö Pretsch,et al.  Potentiometric sensors for trace-level analysis. , 2005, Trends in analytical chemistry : TRAC.

[41]  Shweta Singh,et al.  Recent trends in development of biosensors for detection of microcystin. , 2012, Toxicon : official journal of the International Society on Toxinology.

[42]  Ryne P. Raffaelle,et al.  Purity assessment of multiwalled carbon nanotubes by Raman spectroscopy , 2007 .

[43]  A. Martin,et al.  Comparative study of first- and second-order Raman spectra of MWCNT at visible and infrared laser excitation , 2006 .

[44]  K. Rhee,et al.  Surface modification of multi-walled carbon nanotubes using 3-aminopropyltriethoxysilane , 2008 .

[45]  Y. Okahata,et al.  Peptide imprinted polymer nanoparticles: a plastic antibody. , 2008, Journal of the American Chemical Society.

[46]  Chwee-Lin Choong,et al.  Carbon nanotube array: a new MIP platform. , 2009, Biosensors & bioelectronics.

[47]  Antje J Baeumner,et al.  Biosensors for environmental pollutants and food contaminants , 2003, Analytical and bioanalytical chemistry.

[48]  P. Ajayan,et al.  Spectral fingerprinting of structural defects in plasma-treated carbon nanotubes , 2003 .

[49]  Li Niu,et al.  Electrochemical sensor for dopamine based on a novel graphene-molecular imprinted polymers composite recognition element. , 2011, Biosensors & bioelectronics.

[50]  J. Robertson,et al.  Raman spectroscopy of hydrogenated amorphous carbons , 2005 .

[51]  A. Huczko,et al.  Studies of Multiwall Carbon Nanotubes Using Raman Spectroscopy and Atomic Force Microscopy , 2004 .

[52]  Xiaoling Yang,et al.  Self-assembled CNTs/CdS/dehydrogenase hybrid-based amperometric biosensor triggered by photovoltaic effect. , 2008, Biosensors & bioelectronics.

[53]  E. Borowiak‐Palen,et al.  Oxidation and reduction of multiwalled carbon nanotubes — preparation and characterization , 2010 .