A Multiwalled‐Carbon‐Nanotube‐Based Biosensor for Monitoring Microcystin‐LR in Sources of Drinking Water Supplies

A multiwalled carbon nanotube (MWCNT)‐based electrochemical biosensor is developed for monitoring microcystin‐LR (MC‐LR), a toxic cyanobacterial toxin, in sources of drinking water supplies. The biosensor electrodes are fabricated using vertically well‐aligned, dense, millimeter‐long MWCNT arrays with a narrow size distribution, grown on patterned Si substrates by water‐assisted chemical vapor deposition. High temperature thermal treatment (2500 °C) in an Ar atmosphere is used to enhance the crystallinity of the pristine materials, followed by electrochemical functionalization in alkaline solution to produce oxygen‐containing functional groups on the MWCNT surface, thus providing the anchoring sites for linking molecules that allow the immobilization of MC‐LR onto the MWCNT array electrodes. Addition of the monoclonal antibodies specific to MC‐LR in the incubation solutions offers the required sensor specificity for toxin detection. The performance of the MWCNT array biosensor is evaluated using micro‐Raman spectroscopy, including polarized Raman measurements, X‐ray photoelectron spectroscopy, cyclic voltammetry, optical microscopy, and Faradaic electrochemical impedance spectroscopy. A linear dependence of the electron‐transfer resistance on the MC‐LR concentration is observed in the range of 0.05 to 20 μg L−1, which enables cyanotoxin monitoring well below the World Health Organization (WHO) provisional concentration limit of 1 μg L−1 for MC‐LR in drinking water.

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

[2]  V. Shanov,et al.  Analysis of the Electrochemical Oxidation of Multiwalled Carbon Nanotube Tower Electrodes in Sodium Hydroxide , 2012 .

[3]  J. Domínguez,et al.  Multi-scale strategies for the monitoring of freshwater cyanobacteria: reducing the sources of uncertainty. , 2012, Water research.

[4]  Bin Du,et al.  Nanoporous PtRu Alloy Enhanced Nonenzymatic Immunosensor for Ultrasensitive Detection of Microcystin‐LR , 2011 .

[5]  Young Hee Lee,et al.  Graphene Versus Carbon Nanotubes in Electronic Devices , 2011 .

[6]  Booncharoen Wongkittisuksa,et al.  Label-free capacitive immunosensors for ultra-trace detection based on the increase of immobilized antibodies on silver nanoparticles. , 2011, Analytica chimica acta.

[7]  Feng Yan,et al.  Streptavidin‐Functionalized Silver‐Nanoparticle‐Enriched Carbon Nanotube Tag for Ultrasensitive Multiplexed Detection of Tumor Markers , 2011 .

[8]  J. Figueiredo,et al.  Controlling and Quantifying Oxygen Functionalities on Hydrothermally and Thermally Treated Single-Wall Carbon Nanotubes , 2011 .

[9]  Xiaoyi Liang,et al.  Effect of oxygen-containing functional groups on the impedance behavior of activated carbon-based electric double-layer capacitors , 2011 .

[10]  D. Su,et al.  Facile Removal of Amorphous Carbon from Carbon Nanotubes by Sonication , 2011 .

[11]  J. Humbert,et al.  Influence of sampling strategies on the monitoring of cyanobacteria in shallow lakes: lessons from a case study in France. , 2011, Water research.

[12]  Eugene M. Terentjev,et al.  Tailoring the Electrical Properties of Carbon Nanotube–Polymer Composites , 2010 .

[13]  A. C. Ziegler,et al.  Cyanotoxin mixtures and taste-and-odor compounds in cyanobacterial blooms from the Midwestern United States. , 2010, Environmental science & technology.

[14]  A. Ramanavičius,et al.  Electrochemical impedance spectroscopy of polypyrrole based electrochemical immunosensor. , 2010, Bioelectrochemistry.

[15]  Jie Zhang,et al.  Glass Fibers with Carbon Nanotube Networks as Multifunctional Sensors , 2010 .

[16]  Christine Edwards,et al.  Rapid detection of microcystins in cells and water. , 2010, Toxicon : official journal of the International Society on Toxinology.

[17]  Long Jiang,et al.  Simple and highly sensitive detection of hepatotoxin microcystin-LR via colorimetric variation based on polydiacetylene vesicles , 2010 .

[18]  Jing Zhang,et al.  Carbon nanohorn sensitized electrochemical immunosensor for rapid detection of microcystin-LR. , 2010, Analytical chemistry.

[19]  K. Gademann,et al.  Occurrence of microcystin‐producing cyanobacteria in Ugandan freshwater habitats , 2009, Environmental toxicology.

[20]  Jin-Young Park,et al.  DNA Hybridization Sensors Based on Electrochemical Impedance Spectroscopy as a Detection Tool , 2009, Sensors.

[21]  John Robertson,et al.  State of Transition Metal Catalysts During Carbon Nanotube Growth , 2009 .

[22]  M. Strano,et al.  Two-Phonon Combination Raman Modes in Covalently Functionalized Single-Wall Carbon Nanotubes , 2008 .

[23]  P. Schmuki,et al.  Phase Composition, Size, Orientation, and Antenna Effects of Self-Assembled Anodized Titania Nanotube Arrays : A Polarized Micro-Raman Investigation , 2008 .

[24]  V. Shanov,et al.  Fabrication and characterization of carbon nanotube array electrodes with gold nanoparticle tips , 2008 .

[25]  John Robertson,et al.  In-situ X-ray Photoelectron Spectroscopy Study of Catalyst−Support Interactions and Growth of Carbon Nanotube Forests , 2008 .

[26]  F. Shinjo,et al.  A protein phosphatase 2A (PP2A) inhibition assay using a recombinant enzyme for rapid detection of microcystins. , 2008, Toxicon : official journal of the International Society on Toxinology.

[27]  Rashid Bashir,et al.  Electrical/electrochemical impedance for rapid detection of foodborne pathogenic bacteria. , 2008, Biotechnology advances.

[28]  Y. Gogotsi,et al.  Monitoring oxidation of multiwalled carbon nanotubes by Raman spectroscopy , 2007 .

[29]  M. Dresselhaus,et al.  Studying disorder in graphite-based systems by Raman spectroscopy. , 2007, Physical chemistry chemical physics : PCCP.

[30]  Y. Kim,et al.  The structural evolution of thin multi-walled carbon nanotubes during isothermal annealing , 2007 .

[31]  Tapan Chakrabarti,et al.  Methods for determining microcystins (peptide hepatotoxins) and microcystin-producing cyanobacteria. , 2006, Water research.

[32]  Min Liu,et al.  Single-walled carbon nanotubes modified by electrochemical treatment for application in electrochemical capacitors , 2006 .

[33]  Lianmao Peng,et al.  Shaping Carbon Nanotubes and the Effects on Their Electrical and Mechanical Properties , 2006 .

[34]  Y. Gogotsi,et al.  Effect of graphitization on the wettability and electrical conductivity of CVD-carbon nanotubes and films. , 2006, The journal of physical chemistry. B.

[35]  L. Lawton,et al.  Detection of the cyanobacterial hepatotoxins microcystins. , 2005, Toxicology and applied pharmacology.

[36]  T. Lim,et al.  Electrochemical oxidation of multi-walled carbon nanotubes and its application to electrochemical double layer capacitors , 2005 .

[37]  James Alastair McLaughlin,et al.  High resolution XPS characterization of chemical functionalised MWCNTs and SWCNTs , 2005 .

[38]  M. Sanjuán,et al.  Single-Walled Carbon Nanotubes as Electrodes in Supercapacitors , 2004 .

[39]  M. Dresselhaus,et al.  Annealing effect on disordered multi-wall carbon nanotubes , 2003 .

[40]  H. Oh,et al.  Rapid Bioassay for Microcystin Toxicity Based on Feeding Activity of Daphnia , 2003, Bulletin of environmental contamination and toxicology.

[41]  K. Sivonen,et al.  Detection of microcystins with protein phosphatase inhibition assay, high-performance liquid chromatography–UV detection and enzyme-linked immunosorbent assay , 2002 .

[42]  Y. Lévi,et al.  Seasonal variation of microcystin concentrations in the Saint-Caprais reservoir (France) and their removal in a small full-scale treatment plant. , 2002, Water Research.

[43]  R. Niessner,et al.  Multidimensional biochemical detection of microcystins in liquid chromatography. , 2001, Analytical chemistry.

[44]  Young Hee Lee,et al.  Electrochemical Properties of High-Power Supercapacitors Using Single-Walled Carbon Nanotube Electrodes , 2001 .

[45]  P. J. Reucroft,et al.  X-ray photoelectron spectroscopic studies of surface modified single-walled carbon nanotube material , 2001 .

[46]  Elizabeth C. Dickey,et al.  PURIFICATION AND STRUCTURAL ANNEALING OF MULTIWALLED CARBON NANOTUBES AT GRAPHITIZATION TEMPERATURES , 2001 .

[47]  Seong Chu Lim,et al.  Supercapacitors Using Single‐Walled Carbon Nanotube Electrodes , 2001 .

[48]  J. Robertson,et al.  Interpretation of Raman spectra of disordered and amorphous carbon , 2000 .

[49]  Rao,et al.  Polarized raman study of aligned multiwalled carbon nanotubes , 2000, Physical review letters.

[50]  Jussi Meriluoto,et al.  Chromatography of microcystins , 1997 .

[51]  Katsumi Tanigaki,et al.  Opening and purification of carbon nanotubes in high yields , 1995 .

[52]  K. Sivonen,et al.  Detection of toxicity of cyanobacteria by Artemia salina bioassay , 1991 .

[53]  J. Gergely,et al.  Zero-length crosslinking procedure with the use of active esters. , 1990, Analytical biochemistry.

[54]  F. Tuinstra,et al.  Raman Spectrum of Graphite , 1970 .