Enhanced Raman spectroscopy coupled to chemometrics for identification and quantification of acetylcholinesterase inhibitors

Abstract In this work, we present a new complete method using Surface Enhanced Raman Spectroscopy (SERS) and chemometrics for the qualitative and quantitative detection of pesticides by measuring the acetylcholinesterase (ACHE) activity. The Raman SERS is not only used for measuring the ACHE activity, but also for the direct detection of pesticides individually and for their identification. Gold nanoparticles (AuNPs) were used as dynamic SERS substrates for sensitive monitoring of ACHE activity in the presence of very low levels of organophosphate and carbamate pesticides, chemical warfare agents that are known to be ACHE inhibitors. The lowest detectable level for paraoxon was determined at 4.0 × 10−14 M and 1.9 × 10−9 M for carbaryl. The use of the enzyme allowed limits of detection for both pesticides that were much lower than the limits obtained by direct SERS analysis of the pesticides. The system shows a linear relationship between the intensity band at 639 cm−1 and pesticide concentration. These results suggest that this biosensor could be used in the future for the non-selective detection of all ACHE inhibitors at very low concentrations with possible identification of the inhibitor.

[1]  William E Brewer,et al.  Disposable pipette extraction for the analysis of pesticides in fruit and vegetables using gas chromatography/mass spectrometry. , 2010, Journal of chromatography. A.

[2]  Abdullah Mohamed Asiri,et al.  Acetylcholinesterase biosensor based on a gold nanoparticle-polypyrrole-reduced graphene oxide nanocomposite modified electrode for the amperometric detection of organophosphorus pesticides. , 2014, The Analyst.

[3]  Lingtao Kong,et al.  Polystyrene/Ag nanoparticles as dynamic surface-enhanced Raman spectroscopy substrates for sensitive detection of organophosphorus pesticides. , 2014, Talanta.

[4]  I. Boyaci,et al.  A high sensitive assay platform based on surface-enhanced Raman scattering for quantification of protease activity. , 2010, Talanta.

[5]  J. Kumar,et al.  Reusable SERS active substrates for ultrasensitive molecular detection , 2015 .

[6]  D. Reinhoudt,et al.  Fluorescence quenching of dye molecules near gold nanoparticles: radiative and nonradiative effects. , 2002, Physical review letters.

[7]  Fernando P. Carvalho,et al.  Agriculture, pesticides, food security and food safety , 2006 .

[8]  Guangxia Yu,et al.  Efficient immobilization of acetylcholinesterase onto amino functionalized carbon nanotubes for the fabrication of high sensitive organophosphorus pesticides biosensors. , 2015, Biosensors & bioelectronics.

[9]  F. Fonnum,et al.  Radiochemical micro assays for the determination of choline acetyltransferase and acetylcholinesterase activities. , 1969, The Biochemical journal.

[10]  Roman Ashauer,et al.  Toxicokinetic and toxicodynamic model for diazinon toxicity—mechanistic explanation of differences in the sensitivity of Daphnia magna and Gammarus pulex , 2012, Environmental toxicology and chemistry.

[11]  Haitao Li,et al.  Silver nanoparticles on cotton swabs for improved surface-enhanced Raman scattering, and its application to the detection of carbaryl , 2016, Microchimica Acta.

[12]  Takaaki Satake,et al.  Coulometric microdevice for organophosphate pesticide detection , 2014 .

[13]  K. Dhanalakshmi,et al.  Non-enzymatic organophosphorus pesticide detection using gold atomic cluster modified electrode , 2014 .

[14]  Z. Liron,et al.  Surface-enhanced Raman scattering detection of cholinesterase inhibitors. , 2011, Analytica chimica acta.

[15]  T. Satake,et al.  A micro IrOx potentiometric sensor for direct determination of organophosphate pesticides , 2015 .

[16]  Barbara Rasco,et al.  Determination of carbaryl pesticide in Fuji apples using surface-enhanced Raman spectroscopy coupled with multivariate analysis , 2015 .

[17]  D. Aslanian.  Vibrational spectroscopic approach to the study of acetylcholine and related compounds. , 1983, Life sciences.

[18]  Young Ho Kim,et al.  Mutation and duplication of arthropod acetylcholinesterase: Implications for pesticide resistance and tolerance. , 2015, Pesticide biochemistry and physiology.

[19]  John G. Voeller,et al.  Food Safety and food security , 2014 .

[20]  I. Boyaci,et al.  Surface enhanced Raman spectroscopy as a new spectral technique for quantitative detection of metal ions. , 2013, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[21]  Pawan Kumar,et al.  Recent advancements in sensing techniques based on functional materials for organophosphate pesticides. , 2015, Biosensors & bioelectronics.

[22]  Joanna Niedziółka-Jönsson,et al.  Electrodeposition for preparation of efficient surface-enhanced Raman scattering-active silver nanoparticle substrates for neurotransmitter detection , 2013 .

[23]  J. Hollender,et al.  Characterization of acetylcholinesterase inhibition and energy allocation in Daphnia magna exposed to carbaryl. , 2013, Ecotoxicology and environmental safety.

[24]  Li Zhang,et al.  Synthesis of silver nanocubes as a SERS substrate for the determination of pesticide paraoxon and thiram. , 2014, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[25]  S. Ai,et al.  Innovative approach for the electrochemical detection of non-electroactive organophosphorus pesticides using oxime as electroactive probe. , 2015, Analytica chimica acta.

[26]  C. Nilsson,et al.  Direct derivatization and rapid GC-MS screening of nerve agent markers in aqueous samples. , 2010, Analytical chemistry.

[27]  Sanjay Gupta,et al.  A review of antioxidants and Alzheimer's disease. , 2005, Annals of clinical psychiatry : official journal of the American Academy of Clinical Psychiatrists.

[28]  Sarit S. Agasti,et al.  Gold nanoparticles in chemical and biological sensing. , 2012, Chemical reviews.

[29]  A. Mulchandani,et al.  Ferrocene-conjugated m-phenylenediamine conducting polymer-incorporated peroxidase biosensors. , 1999, Analytical biochemistry.

[30]  Weiping Liu,et al.  Enantioselective separation and analysis of chiral pesticides by high-performance liquid chromatography , 2009 .

[31]  Yingying Zheng,et al.  An acetylcholinesterase biosensor based on ionic liquid functionalized graphene–gelatin-modified electrode for sensitive detection of pesticides , 2015 .

[32]  D. B. Pedersen,et al.  Studies of the interaction of two organophosphonates with nanostructured silver surfaces. , 2012, The Analyst.

[33]  Vincenza Andrisano,et al.  Characterization of reversible and pseudo-irreversible acetylcholinesterase inhibitors by means of an immobilized enzyme reactor. , 2007, Journal of chromatography. A.

[34]  P. Eyer,et al.  Kinetic analysis of the protection afforded by reversible inhibitors against irreversible inhibition of acetylcholinesterase by highly toxic organophosphorus compounds. , 2006, Biochemical pharmacology.

[35]  J. Boussey,et al.  Large-area, cost-effective Surface-Enhanced Raman Scattering (SERS) substrates fabrication , 2015 .

[36]  Yaodong Zhang,et al.  In situ induced metal-enhanced fluorescence: a new strategy for biosensing the total acetylcholinesterase activity in sub-microliter human whole blood. , 2015, Biosensors & bioelectronics.

[37]  S. de Cheveigné,et al.  Interaction of acetylcholine and beta-methylacetylcholine with aluminum oxide surface studied by inelastic electron tunneling spectrometry. , 1980, Biochemical and biophysical research communications.

[38]  Qinghua He,et al.  Organophosphorus pesticides detection using broad-specific single-stranded DNA based fluorescence polarization aptamer assay. , 2014, Biosensors & bioelectronics.