Atrazine-based self-assembled monolayers and their interaction with anti-atrazine antibody: building of an immunosensor.

As a part of our objective to build an immunosensor for the detection of the pesticide atrazine (ATZ) in environmental samples, we studied the self-assembling process of the disulfide derivative of the pesticide atrazine on a gold substrate. Atrazine-based self-assembled monolayers were characterized by ellipsometry, scanning tunneling microscopy, polarization-modulation infrared reflection-absorption spectroscopy (PM IRRAS), X-ray photoelectron spectroscopy and quartz crystal microbalance (QCM) measurements. Two different time constants for the adsorption process were observed, depending on the experimental method used. The QCM data reflect adsorption kinetics of the original disulfide compound, whereas ellipsometry and ex situ PM IRRAS refer to the formation of thiolate (ATZS) monolayers. In situ QCM data demonstrated the suitability of such monolayers for the detection of atrazine in aqueous samples. Exposure of the ATZS sensing surface to an anti-atrazine antibody (anti-ATZ IgG) resulted in complete coverage of the surface by antibody, whereas approximately half of the antibody molecules were displaced from the QCM sensor surface by further addition of atrazine into the solution.

[1]  Hubert Perrot,et al.  Building of an immunosensor: how can the composition and structure of the thiol attachment layer affect the immunosensor efficiency? , 2006, Biosensors & bioelectronics.

[2]  K. Cammann,et al.  A new non-enzymatic tracer for time-resolved fluoroimmunoassay of triazine herbicides , 1994 .

[3]  Lauro T Kubota,et al.  Determination of thickness, dielectric constant of thiol films, and kinetics of adsorption using surface plasmon resonance. , 2005, Langmuir : the ACS journal of surfaces and colloids.

[4]  L. Wackett,et al.  Biodegradation of atrazine and related s-triazine compounds: from enzymes to field studies , 2001, Applied Microbiology and Biotechnology.

[5]  V. Lakshminarayanan,et al.  Cyclic voltammetric and electrochemical impedance studies on the structure, adsorption kinetics, and barrier properties of some organic dithiol self-assembled monolayers on gold. , 2003, Journal of colloid and interface science.

[6]  G. Blanchard,et al.  An Undergraduate Laboratory Experiment for the Direct Measurement of Monolayer-Formation Kinetics , 1995 .

[7]  C. Bala,et al.  Magnetic beads-based immunoassay as a sensitive alternative for atrazine analysis , 2008 .

[8]  S. Zanna,et al.  Self‐Assembling of Redox‐Active Atrazine Poly(ethylenimine) Conjugates – Interfacial Electrochemical and Spectroscopic Characterization , 2006 .

[9]  Gary J. Blanchard,et al.  Direct Measurement of the Adsorption Kinetics of Alkanethiolate Self-Assembled Monolayers on a Microcrystalline Gold Surface , 1994 .

[10]  K. Uosaki,et al.  Effects of concentration and temperature on the formation process of decanethiol self-assembled monolayer on Au(111) followed by electrochemical reductive desorption , 2008 .

[11]  A. Brolo,et al.  Adsorption/desorption behaviour of cysteine and cystine in neutral and basic media: electrochemical evidence for differing thiol and disulfide adsorption to a Au(1 1 1) single crystal electrode , 2003 .

[12]  Guoli Shen,et al.  A Piezoelectric Immunosensor Using Hybrid Self-Assembled Monolayers for Detection of Schistosoma japonicum , 2012, PloS one.

[13]  E. Fuerst,et al.  Interactions of Herbicides with Photosynthetic Electron Transport , 1991, Weed Science.

[14]  Damià Barceló,et al.  Strengths and limitations of immunoassays for effective and efficient use for pesticide analysis in water samples: A review , 1998 .

[15]  G G Guilbault,et al.  A piezoelectric immunobiosensor for atrazine in drinking water. , 1992, Biosensors & bioelectronics.

[16]  Jan Přibyl,et al.  Development of piezoelectric immunosensors for competitive and direct determination of atrazine , 2003 .

[17]  George M. Whitesides,et al.  Comparison of the Structures and Wetting Properties of Self-Assembled Monolayers of n- Alkanethiols on the Coinage Metal Surfaces, Cu, Ag, Au' , 1991 .

[18]  K. Hsiung,et al.  Comparison of different protein immobilization methods on quartz crystal microbalance surface in flow injection immunoassay. , 2001, Analytical biochemistry.

[19]  F. Ackerman The Economics of Atrazine , 2007, International journal of occupational and environmental health.

[20]  Michael D. Ward,et al.  Measurement of interfacial processes at electrode surfaces with the electrochemical quartz crystal microbalance , 1992 .

[21]  C. Silien,et al.  Self-assembly of a pyridine-terminated thiol monolayer on Au(111). , 2009, Langmuir : the ACS journal of surfaces and colloids.

[22]  V. Pedrosa,et al.  Studies on the electrochemical behavior of a cystine self-assembled monolayer modified electrode using ferrocyanide as a probe , 2007 .

[23]  J. Kaur,et al.  Direct hapten coated immunoassay format for the detection of atrazine and 2,4-dichlorophenoxyacetic acid herbicides. , 2008, Analytica chimica acta.

[24]  C. Pradier,et al.  Immobilization of atrazine on gold, a first step towards the elaboration of an indirect immunosensor: characterization by XPS and PM‐IRRAS , 2006 .

[25]  Krishna M. Vattipalli,et al.  Nanoporous impedemetric biosensor for detection of trace atrazine from water samples. , 2012, Biosensors & bioelectronics.

[26]  A. Brolo,et al.  Protonation and deprotonation of cysteine and cystine monolayers probed by impedance spectroscopy , 2009 .

[27]  M. Colombini,et al.  Electrochemistry of s-triazine herbicides: Reduction of atrazine and terbutylazine in aqueous solutions , 1995 .

[28]  C. Pradier,et al.  Immobilization of Protein A on SAMs for the elaboration of immunosensors. , 2006, Colloids and surfaces. B, Biointerfaces.

[29]  Ralph G. Nuzzo,et al.  Spontaneously organized molecular assemblies. 3. Preparation and properties of solution adsorbed monolayers of organic disulfides on gold surfaces , 1987 .

[30]  T. Ohsaka,et al.  Molecular-level design of binary self-assembled monolayers on polycrystalline gold electrodes , 2004 .

[31]  M. Ward,et al.  In Situ Interfacial Mass Detection with Piezoelectric Transducers , 1990, Science.

[32]  V. Macagno,et al.  Reactivity of 1,8-octanedithiol monolayers on Au(111): Experimental and theoretical investigation , 2005 .

[33]  D. K. Schwartz,et al.  Mechanisms and kinetics of self-assembled monolayer formation. , 2001, Annual review of physical chemistry.

[34]  Nicole Jaffrezic-Renault,et al.  A disposable immunomagnetic electrochemical sensor based on functionalised magnetic beads on gold surface for the detection of atrazine , 2006 .

[35]  Yukari Sato,et al.  In situ and dynamic monitoring of the self-assembling and redox processes of a ferrocenylundecanethiol monolayer by electrochemical quartz crystal microbalance , 1992 .

[36]  Nicole Jaffrezic-Renault,et al.  Impedance spectroscopy and affinity measurement of specific antibody–antigen interaction , 2006 .

[37]  G. Whitesides,et al.  Formation of monolayer films by the spontaneous assembly of organic thiols from solution onto gold , 1989 .

[38]  C. Pradier,et al.  Functionalisation of gold surfaces with thiolate SAMs: Topography/bioactivity relationship – A combined FT-RAIRS, AFM and QCM investigation , 2007 .

[39]  Angel Rodriguez,et al.  Impedimetric immunosensor for atrazine detection using interdigitated μ-electrodes (IDμE's) , 2007 .

[40]  Jan-Martin Heldt,et al.  Evaluation of the carbonyl metallo immunoassay (CMIA) for the determination of traces of the herbicide atrazine , 2003 .

[41]  R. Sokolová,et al.  Adsorption of s-triazine pesticides, terbutylazine and atrazine: environmental risk parallels differences in compact film formation , 2003 .

[42]  Yu-Ling Cheng,et al.  A quartz crystal microbalance study of β-cyclodextrin self assembly on gold and complexation of immobilized β-cyclodextrin with adamantane derivatives , 2008 .

[43]  T. Colborn,et al.  Pesticide use in the U.S. and policy implications: A focus on herbicides , 1999, Toxicology and industrial health.

[44]  S. Dübel,et al.  Determination of phage antibody affinities to antigen by a microbalance sensor system. , 1999, BioTechniques.