Molecularly imprinted polymers on graphene oxide surface for EIS sensing of testosterone.

A novel electrochemical biosensor was developed for ultrasensitive determination of testosterone from femtomolar to micromolar levels via electrochemical impedance spectroscopy (EIS) measurements. The sensor features a nanosized molecularly imprinted polymer (MIP) film that was electrochemically grafted on a graphene-oxide sheets modified electrode. The detection mechanism of this senor is explained via the change of the interfacial impedance that derived from the recognition of the target molecule. Due to the nanosheet structure as well as the high surface area of graphene-oxide, the sensitivity of the MIP sensor is enhanced remarkably. Under an optimized condition, a wide linear range from 1fM to 1µm (1×10-15-1×10-6molL-1) and a detection limit of 0.4fM (4.0×10-16molL-1) was obtained. This composite film presented a good selectivity over structurally similar steroid hormones, and a long term stability in room temperature for the detection of testosterone. Considering these advantages, the MIP/GO electrochemical biosensor could be a substitute of testosterone immunosensor, and may be further extended to the detection of other endogenous substances.

[1]  Tianshu Zhou,et al.  A molecularly imprinted polymer based on functionalized multiwalled carbon nanotubes for the electrochemical detection of parathion-methyl. , 2012, The Analyst.

[2]  Rigoberto C. Advincula,et al.  Electropolymerized Molecularly Imprinted Polymer Film: EIS Sensing of Bisphenol A , 2011 .

[3]  Xinxiang Zhang,et al.  Antibody development to testosterone and its application in capillary electrophoresis‐based immunoassay , 2008, Electrophoresis.

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

[5]  J. Coleman,et al.  High-concentration, surfactant-stabilized graphene dispersions. , 2010, ACS nano.

[6]  Mustafa Kemal Sezgintürk,et al.  Electrochemical biosensors for hormone analyses. , 2015, Biosensors & bioelectronics.

[7]  W. Mu,et al.  Biomolecules/gold nanowires-doped sol-gel film for label-free electrochemical immunoassay of testosterone. , 2008, Journal of biochemical and biophysical methods.

[8]  Ashutosh Tiwari,et al.  An ultrasensitive molecularly-imprinted human cardiac troponin sensor. , 2013, Biosensors & bioelectronics.

[9]  J. Schiettecatte,et al.  Multicenter evaluation of a new automated electrochemiluminescence immunoassay for the quantification of testosterone compared to liquid chromatography tandem mass spectrometry. , 2011, Clinical biochemistry.

[10]  Nengqin Jia,et al.  Electrochemical sensing based on graphene oxide/Prussian blue hybrid film modified electrode , 2011 .

[11]  A. Araujo,et al.  Endogenous Testosterone and Mortality in Men: A Systematic Review and Meta-Analysis , 2011 .

[12]  P. Norouzi,et al.  Selective determination of chloramphenicol at trace level in milk samples by the electrode modified with molecularly imprinted polymer , 2012 .

[13]  C. Magi-Galluzzi,et al.  Low testosterone and risk of biochemical recurrence and poorly differentiated prostate cancer at radical prostatectomy. , 2008, Urology.

[14]  Lu Zhang,et al.  Supportless electrochemical sensor based on molecularly imprinted polymer modified nanoporous microrod for determination of dopamine at trace level. , 2016, Biosensors & bioelectronics.

[15]  Susana Campuzano,et al.  An electrochemical immunosensor for testosterone using functionalized magnetic beads and screen-printed carbon electrodes. , 2010, Biosensors & bioelectronics.

[16]  Guobao Xu,et al.  Electrochemical cholesterol sensor based on carbon nanotube@molecularly imprinted polymer modified ceramic carbon electrode. , 2013, Biosensors & bioelectronics.

[17]  Stéphane Berciaud,et al.  Probing the intrinsic properties of exfoliated graphene: Raman spectroscopy of free-standing monolayers. , 2009, Nano letters.

[18]  Bei Wang,et al.  FACILE SYNTHESIS AND CHARACTERIZATION OF GRAPHENE NANOSHEETS , 2008 .

[19]  Saskia S Sterk,et al.  Detection of anabolic androgenic steroid abuse in doping control using mammalian reporter gene bioassays. , 2009, Analytica chimica acta.

[20]  A. Ferrari,et al.  Raman spectroscopy of graphene and graphite: Disorder, electron phonon coupling, doping and nonadiabatic effects , 2007 .

[21]  Yue Gu,et al.  Hierarchical polystyrene@reduced graphene oxide–Pt core–shell microspheres for non-enzymatic detection of hydrogen peroxide , 2015 .

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

[23]  Shenguang Ge,et al.  Molecularly Imprinted Polymer Grafted Porous Au‐Paper Electrode for an Microfluidic Electro‐Analytical Origami Device , 2013 .

[24]  Ashutosh Tiwari,et al.  Detection of p53 gene point mutation using sequence-specific molecularly imprinted PoPD electrode. , 2012, Biosensors & bioelectronics.

[25]  Andre K. Geim,et al.  Electric Field Effect in Atomically Thin Carbon Films , 2004, Science.

[26]  J. Mitchell,et al.  Ultrasensitive detection of testosterone using conjugate linker technology in a nanoparticle-enhanced surface plasmon resonance biosensor. , 2009, Biosensors & bioelectronics.

[27]  Chunhong Zhu,et al.  Magnetic sensing film based on Fe₃O₄@Au-GSH molecularly imprinted polymers for the electrochemical detection of estradiol. , 2016, Biosensors & bioelectronics.

[28]  F. Zhao,et al.  Electrochemical sensor for chloramphenicol based on novel multiwalled carbon nanotubes@molecularly imprinted polymer. , 2015, Biosensors & bioelectronics.

[29]  Jian Ji,et al.  Electrochemical sensor based on molecularly imprinted film at Au nanoparticles-carbon nanotubes modified electrode for determination of cholesterol. , 2015, Biosensors & bioelectronics.