Fabrication of electrochemical theophylline sensor based on manganese oxide nanoparticles/ionic liquid/chitosan nanocomposite modified glassy carbon electrode

Abstract In this study, the preparation of a glassy carbon (GC) electrode modified with chitosan/NH 2 -ionic liquid/manganese oxide nanoparticles (Chit/NH 2 -IL/MnO x ) was described for electrocatalytic detection of theophylline (TP). First, chitosan hydrogel (Chit) was electrodeposited on the GC electrode surface at a constant potential (−1.5 V) in acidic solution. Then, the previously synthesized amine-terminated 1-(3-Aminopropyl)-3-methylimidazolium bromide ionic liquid (NH 2 -IL) was covalently attached to the modified electrode via glutaraldehyde (GA) as linking agent. Finally, manganese oxide (MnO x ) nanoparticles were electrodeposited onto the Chit/NH 2 -IL film by potential cycling between −1.0 and 1.7 V in Mn(CH 3 COO) 2 ·4H 2 O neutral aqueous solution. Electrochemical behavior of the modified electrode was evaluated by cyclic voltammetry (CV) technique. The charge transfer coefficient ( α ) and electron transfer rate constant ( k s ) for MnOOH/MnO 2 redox couple were calculated to be 0.35 and 1.62 s −1 , respectively. The resulting system brings new capabilities for electrochemical sensing through combining the advantages of IL and MnO x nanoparticles. The differential pulse voltammetric (DPV) results indicated the high ability of GC/Chit/NH 2 -IL/MnO x modified electrode to catalyze the oxidation of TP. DPV determination of TP in acetate buffer solution (pH 5) gave linear responses over the concentration range up to 120 μM with the detection limit of 50 nM and sensitivity of 804 nA μM −1 . Furthermore, the applicability of the sensor for TP analysis in pharmaceutical samples has been successfully demonstrated.

[1]  D. Lincot,et al.  Voltammetric and electrogravimetric study of manganese dioxide thin film electrodes. Part 1. Electrodeposited films , 1997 .

[2]  E. Plattner,et al.  Oxydation Du MnSO4 en dioxyde de manganese dans H2SO4 30 , 1990 .

[3]  Ruo Yuan,et al.  Preparation of a composite film electrochemically deposited with chitosan and gold nanoparticles for the determination of α-1-fetoprotein , 2010, Bioprocess and biosystems engineering.

[4]  F. Palmisano,et al.  Simultaneous determination of caffeine, theobromine, theophylline, paraxanthine and nicotine in human milk by liquid chromatography with diode array UV detection , 2005 .

[5]  Guangchao Zhao,et al.  A label-free electrochemical RNA aptamer for selective detection of theophylline , 2010 .

[6]  R. L. Paul,et al.  The mechanism of the deposition of manganese dioxide: Part III. Rotating ring-disc studies , 1986 .

[7]  N. Shetti,et al.  Voltammetric behavior of theophylline and its determination at multi-wall carbon nanotube paste electrode. , 2012, Colloids and surfaces. B, Biointerfaces.

[8]  A. Ivaska,et al.  Applications of ionic liquids in electrochemical sensors. , 2008, Analytica chimica acta.

[9]  E. N. Fuller,et al.  A Simple Fluorescent Biosensor for Theophylline Based on its RNA Aptamer , 2006, Nucleosides, nucleotides & nucleic acids.

[10]  X. Lou,et al.  Shape-controlled synthesis of MnO2 nanostructures with enhanced electrocatalytic activity for oxygen reduction , 2010 .

[11]  D. Grant,et al.  Metal complexation of chitosan and its glutaraldehyde cross-linked derivative. , 2007, Carbohydrate research.

[12]  A. Salimi,et al.  Highly sensitive immunosensing of prostate-specific antigen based on ionic liquid-carbon nanotubes modified electrode: application as cancer biomarker for prostate biopsies. , 2013, Biosensors & bioelectronics.

[13]  I. Paleska,et al.  Electrochemical behavior of manganese dioxide on a gold electrode , 2003 .

[14]  E. Laviron,et al.  Adsorption, autoinhibition and autocatalysis in polarography and in linear potential sweep voltammetry , 1974 .

[15]  Hui Xu,et al.  Direct electrochemistry and electrocatalysis of heme proteins immobilized in single-wall carbon nanotubes-surfactant films in room temperature ionic liquids , 2009 .

[16]  S. Donne,et al.  An RDE and RRDE study into the electrodeposition of manganese dioxide , 2006 .

[17]  X. Zhao,et al.  Synthesis, characterization and capacitive performance of hydrous manganese dioxide nanostructures , 2011, Nanotechnology.

[18]  E. Ferapontova,et al.  Bioelectrocatalytic detection of theophylline at theophylline oxidase electrodes. , 2007, Biosensors & bioelectronics.

[19]  A. Salimi,et al.  Carbon Nanotubes‐Ionic Liquid and Chloropromazine Modified Electrode for Determination of NADH and Fabrication of Ethanol Biosensor , 2010 .

[20]  Jun Chen,et al.  MnO2-Based Nanostructures as Catalysts for Electrochemical Oxygen Reduction in Alkaline Media† , 2010 .

[21]  S. Martha,et al.  Electrochemical power sources , 2001 .

[22]  H. Takenouti,et al.  Reactivity of nanostructured MnO(2) in alkaline medium studied with a micro-cavity electrode: effect of synthesizing temperature. , 2009, ACS applied materials & interfaces.

[23]  Jing-Juan Xu,et al.  Application of MnO2 nanoparticles as an eliminator of ascorbate interference to amperometric glucose biosensors , 2004 .

[24]  W. Lyon,et al.  Theophylline detection using an aptamer and DNA-gold nanoparticle conjugates. , 2010, Biosensors & bioelectronics.

[25]  Y. Chai,et al.  Study on immunosensor based on gold nanoparticles/chitosan and MnO2 nanoparticles composite membrane/Prussian blue modified gold electrode , 2009, Bioprocess and biosystems engineering.

[26]  R. Challiss,et al.  Differential modulation of tissue function and therapeutic potential of selective inhibitors of cyclic nucleotide phosphodiesterase isoenzymes. , 1991, TIPS - Trends in Pharmacological Sciences.

[27]  R. Gupta,et al.  Estimation of theophylline in plasma by thin-layer chromatography. , 1978, Clinical biochemistry.

[28]  M. Shamsipur,et al.  A novel potentiometric sensor for selective determination of theophylline: Theoretical and practical investigations , 2005 .

[29]  Allen J. Bard,et al.  Encyclopedia of Electrochemistry of the Elements , 1978 .

[30]  Rigoberto C. Advincula,et al.  Surface Plasmon Resonance (SPR) Detection of Theophylline via Electropolymerized Molecularly Imprinted Polythiophenes , 2010 .

[31]  Hazhir Teymourian,et al.  Label-free electrochemical IgE aptasensor based on covalent attachment of aptamer onto multiwalled carbon nanotubes/ionic liquid/chitosan nanocomposite modified electrode. , 2013, Biosensors & bioelectronics.

[32]  Jing-Juan Xu,et al.  A novel glucose ENFET based on the special reactivity of MnO2 nanoparticles. , 2004, Biosensors & bioelectronics.

[33]  Allen J. Bard,et al.  Electrochemical Methods: Fundamentals and Applications , 1980 .

[34]  G. Wittstock,et al.  Localized Deposition of Chitosan as Matrix for Enzyme Immobilization , 2009 .

[35]  S. Minteer,et al.  Poly(methylene green) employed as molecularly imprinted polymer matrix for electrochemical sensing. , 2006, The Analyst.

[36]  A. Chaussé,et al.  Studies of electrodeposition from Mn(II) species of thin layers of birnessite onto transparent semiconductor , 2008 .

[37]  B. Rezaei,et al.  A new method based on electrospray ionisation ion mobility spectrometry (ESI-IMS) for simultaneous determination of caffeine and theophylline. , 2011, Food chemistry.

[38]  Hyunmin Yi,et al.  Voltage-Dependent Assembly of the Polysaccharide Chitosan onto an Electrode Surface , 2002 .

[39]  H. Mishima,et al.  The electrochemical response of manganese hydroxide—oxide films in slightly alkaline solutions—I. The redox couple , 1991 .

[40]  D. Pang,et al.  Electrochemical oxidation of theophylline at multi-wall carbon nanotube modified glassy carbon electrodes , 2005 .

[41]  R. Nirogi,et al.  A simple and rapid HPLC/UV method for the simultaneous quantification of theophylline and etofylline in human plasma. , 2007, Journal of chromatography. B, Analytical technologies in the biomedical and life sciences.

[42]  I. Watson,et al.  The Clinical Use and Measurement of Theophylline , 1988, Annals of clinical biochemistry.

[43]  Hongyuan Chen,et al.  Biocomposite of cobalt phthalocyanine and lactate oxidase for lactate biosensing with MnO2 nanoparticles as an eliminator of ascorbic acid interference , 2006 .

[44]  Wei Sun,et al.  Electrochemistry and electrocatalysis of hemoglobin in Nafion/nano-CaCO3 film on a new ionic liquid BPPF6 modified carbon paste electrode. , 2007, The journal of physical chemistry. B.

[45]  J. Zen,et al.  Determination of theophylline in tea and drug formulation using a Nafion(R)/lead-ruthenium oxide pyrochlore chemically modified electrode. , 1999, Talanta.

[46]  Hazhir Teymourian,et al.  Low potential detection of NADH based on Fe₃O₄ nanoparticles/multiwalled carbon nanotubes composite: fabrication of integrated dehydrogenase-based lactate biosensor. , 2012, Biosensors & bioelectronics.

[47]  D. Graham,et al.  Caffeine--its identity, dietary sources, intake and biological effects. , 2009, Nutrition reviews.

[48]  A. Salimi,et al.  Layer by layer assembly of catalase and amine-terminated ionic liquid onto titanium nitride nanoparticles modified glassy carbon electrode: study of direct voltammetry and bioelectrocatalytic activity. , 2012, Analytica chimica acta.

[49]  T. Ohsaka,et al.  Non-platinum electrocatalysts: Manganese oxide nanoparticle-cobaltporphyrin binary catalysts for oxygen reduction , 2008 .

[50]  E. Ferapontova,et al.  An RNA aptamer-based electrochemical biosensor for detection of theophylline in serum. , 2008, Journal of the American Chemical Society.

[51]  S. Ai,et al.  Electrochemical determination of theophylline in foodstuff, tea and soft drinks based on urchin-like CdSe microparticles modified glassy carbon electrode. , 2012, Food chemistry.

[52]  Ling-bo Qu,et al.  Voltammetric determination of theophylline at a Nafion/multi-wall carbon nanotubes composite film-modified glassy carbon electrode , 2010 .

[53]  Li Niu,et al.  Electrochemical functionalization of single-walled carbon nanotubes in large quantities at a room-temperature ionic liquid supported three-dimensional network electrode. , 2005, Langmuir : the ACS journal of surfaces and colloids.