Vertically aligned carbon nanotube-sheathed carbon fibers as pristine microelectrodes for selective monitoring of ascorbate in vivo.

Using as-synthesized vertically aligned carbon nanotube-sheathed carbon fibers (VACNT-CFs) as microelectrodes without any postsynthesis functionalization, we have developed in this study a new method for in vivo monitoring of ascorbate with high selectivity and reproducibility. The VACNT-CFs are formed via pyrolysis of iron phthalocyanine (FePc) on the carbon fiber support. After electrochemical pretreatment in 1.0 M NaOH solution, the pristine VACNT-CF microelectrodes exhibit typical microelectrode behavior with fast electron transfer kinetics for electrochemical oxidation of ascorbate and are useful for selective ascorbate monitoring even with other electroactive species (e.g., dopamine, uric acid, and 5-hydroxytryptamine) coexisting in rat brain. Pristine VACNT-CFs are further demonstrated to be a reliable and stable microelectrode for in vivo recording of the dynamic increase of ascorbate evoked by intracerebral infusion of glutamate. Use of a pristine VACNT-CF microelectrode can effectively avoid any manual electrode modification and is free from person-to-person and/or electrode-to-electrode deviations intrinsically associated with conventional CF electrode fabrication, which often involves electrode surface modification with randomly distributed CNTs or other pretreatments, and hence allows easy fabrication of highly selective, reproducible, and stable microelectrodes even by nonelectrochemists. Thus, this study offers a new and reliable platform for in vivo monitoring of neurochemicals (e.g., ascorbate) to largely facilitate future studies on the neurochemical processes involved in various physiological events.

[1]  T. Ohsaka,et al.  Microfluidic chip-based online electrochemical detecting system for continuous and simultaneous monitoring of ascorbate and Mg2+ in rat brain. , 2013, Analytical chemistry.

[2]  T. Kuwana,et al.  Activation and deactivation of glassy carbon electrodes , 1985 .

[3]  G. Rebec,et al.  Effects of long-term haloperidol treatment on glutamate-evoked ascorbate release in rat striatum. , 2001, European journal of pharmacology.

[4]  R. Kasser,et al.  Electrochemical pretreatment of carbon fibers for in vivo electrochemistry: effects on sensitivity and response time. , 1987, Analytical chemistry.

[5]  Ping Yu,et al.  Dynamic regional changes of extracellular ascorbic acid during global cerebral ischemia: Studied with in vivo microdialysis coupled with on-line electrochemical detection , 2009, Brain Research.

[6]  R. Grünewald Ascorbic acid in the brain , 1993, Brain Research Reviews.

[7]  Andrew G. Ewing,et al.  Carbon nanotube fiber microelectrodes show a higher resistance to dopamine fouling. , 2013, Analytical chemistry.

[8]  R. Adams,et al.  Electrochemical assay for brain ascorbate with ascorbate oxidase. , 1982, Analytical chemistry.

[9]  Kun Liu,et al.  Carbon nanotube-modified carbon fiber microelectrodes for in vivo voltammetric measurement of ascorbic acid in rat brain. , 2007, Analytical chemistry.

[10]  F. Gallagher,et al.  Hyperpolarized [1-13C]-Ascorbic and Dehydroascorbic Acid: Vitamin C as a Probe for Imaging Redox Status in Vivo , 2011, Journal of the American Chemical Society.

[11]  L. Qu,et al.  Carbon microfibers sheathed with aligned carbon nanotubes: towards multidimensional, multicomponent, and multifunctional nanomaterials. , 2006, Small.

[12]  Restricted diffusion of dopamine in the rat dorsal striatum. , 2013, ACS chemical neuroscience.

[13]  Lei Su,et al.  Electrochemistry and Electroanalytical Applications of Carbon Nanotubes: A Review , 2005, Analytical sciences : the international journal of the Japan Society for Analytical Chemistry.

[14]  G. S. Wilson,et al.  In-vivo electrochemistry: what can we learn about living systems? , 2008, Chemical reviews.

[15]  Pavel Takmakov,et al.  Carbon microelectrodes with a renewable surface. , 2010, Analytical chemistry.

[16]  Giammario Calia,et al.  Simultaneous telemetric monitoring of brain glucose and lactate and motion in freely moving rats. , 2013, Analytical chemistry.

[17]  A. Andrews,et al.  Chemistry and the BRAIN Initiative. , 2014, Journal of the American Chemical Society.

[18]  R. Wightman Probing Cellular Chemistry in Biological Systems with Microelectrodes , 2006, Science.

[19]  Ling Xiang,et al.  Comparative study of change in extracellular ascorbic acid in different brain ischemia/reperfusion models with in vivo microdialysis combined with on-line electrochemical detection , 2008, Neurochemistry International.

[20]  D. Anjo,et al.  Electrochemical activation of carbon electrodes in base: minimization of dopamine adsorption and electrode capacitance , 1989 .

[21]  G. Rebec,et al.  A vitamin as neuromodulator: Ascorbate release into the extracellular fluid of the brain regulates dopaminergic and glutamatergic transmission , 1994, Progress in Neurobiology.

[22]  Kendra D Bunner,et al.  Up‐regulation of GLT1 reverses the deficit in cortically evoked striatal ascorbate efflux in the R6/2 mouse model of Huntington’s disease , 2012, Journal of neurochemistry.

[23]  R. Compton,et al.  Mechanistic Determination Using Arrays of Variable-Sized Channel Microband Electrodes: The Oxidation of Ascorbic Acid in Aqueous Solution , 1998 .

[24]  J. Stamford,et al.  Ascorbic acid is neuroprotective against global ischaemia in striatum but not hippocampus: histological and voltammetric data , 1999, Brain Research.

[25]  Pier Giorgio Zambonin,et al.  Ascorbic acid interferences in hydrogen peroxide detecting biosensors based on electrochemically immobilized enzymes , 1993 .

[26]  Greg M. Swain,et al.  Electrochemical and Surface Structural Characterization of Hydrogen Plasma Treated Glassy Carbon Electrodes , 1996 .

[27]  Robert D. O'Neill,et al.  Designing sensitive and selective polymer/enzyme composite biosensors for brain monitoring in vivo , 2008 .

[28]  Wei Zheng,et al.  Carbon‐Nanotube‐Based Glucose/O2 Biofuel Cells , 2006 .

[29]  T. Ohsaka,et al.  Electroanalytical applications of cationic self-assembled monolayers: square-wave voltammetric determination of dopamine and ascorbate. , 2001, Bioelectrochemistry.

[30]  J. Rawlins,et al.  Voltammetrically monitored brain ascorbate as an index of excitatory amino acid release in the unrestrained rat , 1984, Neuroscience Letters.

[31]  A. Aldaz,et al.  Mechanism of L-ascorbic acid oxidation on a mercury electrode. II. Basic medium , 1978 .

[32]  Ling Xie,et al.  Alzheimer's β-Amyloid Peptides Compete for Insulin Binding to the Insulin Receptor , 2002, The Journal of Neuroscience.

[33]  N. Kulagina,et al.  Monitoring glutamate and ascorbate in the extracellular space of brain tissue with electrochemical microsensors. , 1999, Analytical chemistry.

[34]  M. Rice Ascorbate regulation and its neuroprotective role in the brain , 2000, Trends in Neurosciences.

[35]  T. Meyer,et al.  Electrocatalysis of proton-coupled electron-transfer reactions at glassy carbon electrodes , 1985 .

[36]  T. Ohsaka,et al.  Electroanalysis of ascorbate and dopamine at a gold electrode modified with a positively charged self-assembled monolayer , 2001 .

[37]  Itamar Willner,et al.  Biomolecule-functionalized carbon nanotubes: applications in nanobioelectronics. , 2004, Chemphyschem : a European journal of chemical physics and physical chemistry.

[38]  G. Rebec,et al.  γ-Aminobutyric acid infusion in substantia nigra pars reticulata in rats inhibits ascorbate release in ipsilateral striatum , 2000, Neuroscience Letters.

[39]  W. Zhang,et al.  Fabrication, characterization, and potential application of carbon fiber cone nanometer-size electrodes. , 1996, Analytical chemistry.

[40]  R. Adams,et al.  The pharmacological profile of glutamate-evoked ascorbic acid efflux measured by in vivo electrochemistry , 1991, Brain Research.

[41]  T. Kuwana,et al.  Oxidative mechanism of ascorbic acid at glassy carbon electrodes , 1986 .

[42]  F. Gonon,et al.  Voltammetry in the striatum of chronic freely moving rats: Detection of catechols and ascorbic acid , 1981, Brain Research.

[43]  Ping Yu,et al.  Rational design of surface/interface chemistry for quantitative in vivo monitoring of brain chemistry. , 2012, Accounts of chemical research.

[44]  R. Wightman,et al.  Effect of pH and surface functionalities on the cyclic voltammetric responses of carbon-fiber microelectrodes. , 1999, Analytical chemistry.

[45]  Joseph Wang,et al.  Activation of carbon fiber microelectrodes by alternating current electrochemical treatment , 1987 .

[46]  M. Fillenz,et al.  The physiologically induced release of ascorbate in rat brain is dependent on impulse traffic, calcium influx and glutamate uptake , 1994, Neuroscience.

[47]  Protiva Rani Roy,et al.  Simultaneous electrochemical detection of uric acid and ascorbic acid at a poly(N,N-dimethylaniline) film-coated GC electrode , 2004 .

[48]  T. Kuwana,et al.  Radiofrequency oxygen plasma treatment of pyrolytic graphite electrode surfaces , 1977 .

[49]  R. McCreery,et al.  Facile Preparation of Active Glassy Carbon Electrodes with Activated Carbon and Organic Solvents , 1999 .

[50]  J. Obeso,et al.  Ascorbate prevents cell death from prolonged exposure to glutamate in an in vitro model of human dopaminergic neurons , 2013, Journal of neuroscience research.

[51]  A. Andrews,et al.  Head-to-head comparisons of carbon fiber microelectrode coatings for sensitive and selective neurotransmitter detection by voltammetry. , 2011, Analytical chemistry.

[52]  G. S. Wilson,et al.  Enzyme-based biosensors for in vivo measurements. , 2000, Chemical reviews.

[53]  M. A. Johnson,et al.  In vivo electrochemical measurements: past, present and future. , 2013, Bioanalysis.

[54]  R. Kurita,et al.  Efficient direct electron transfer with enzyme on a nanostructured carbon film fabricated with a maskless top-down UV/ozone process. , 2011, Journal of the American Chemical Society.

[55]  R. McCreery,et al.  Microstructural and morphological changes induced in glassy carbon electrodes by laser irradiation , 1992 .

[56]  A. Bard,et al.  Ellipsometric, electrochemical, and elemental characterization of the surface phase produced on glassy carbon electrodes by electrochemical activation , 1988 .

[57]  T. Ohsaka,et al.  A Miniature glucose/O2 biofuel cell with single-walled carbon nanotubes-modified carbon fiber microelectrodes as the substrate , 2008 .

[58]  M. Smyth,et al.  Electrochemical pretreatment of carbon fibre microelectrodes for the determination of folic acid , 1991 .

[59]  L. Dai,et al.  Electrochemistry at carbon nanotube electrodes: is the nanotube tip more active than the sidewall? , 2008, Angewandte Chemie.

[60]  J. M. May,et al.  Vitamin C function in the brain: vital role of the ascorbate transporter SVCT2. , 2009, Free radical biology & medicine.

[61]  G. Rebec,et al.  Behavioral Activation in Rats Requires Endogenous Ascorbate Release in Striatum , 2001, The Journal of Neuroscience.

[62]  L. Mao,et al.  Electrochemical Microsensor for In Vivo Measurements of Oxygen Based on Nafion and Methylviologen Modified Carbon Fiber Microelectrode , 1999 .

[63]  T. Ohsaka,et al.  Online electrochemical monitoring of dynamic change of hippocampal ascorbate: toward a platform for in vivo evaluation of antioxidant neuroprotective efficiency against cerebral ischemia injury. , 2013, Analytical chemistry.

[64]  Christian Amatore,et al.  Electrochemical monitoring of single cell secretion: vesicular exocytosis and oxidative stress. , 2008, Chemical reviews.

[65]  B. J. Venton,et al.  Rapid, sensitive detection of neurotransmitters at microelectrodes modified with self-assembled SWCNT forests. , 2012, Analytical chemistry.

[66]  Lei Su,et al.  Continuous on-line monitoring of extracellular ascorbate depletion in the rat striatum induced by global ischemia with carbon nanotube-modified glassy carbon electrode integrated into a thin-layer radial flow cell. , 2005, Analytical chemistry.

[67]  R. Wightman,et al.  Heterogeneous mechanisms of the oxidation of catechols and ascorbic acid at carbon electrodes. , 1986, Analytical chemistry.

[68]  Filip Braet,et al.  Carbon nanomaterials in biosensors: should you use nanotubes or graphene? , 2010, Angewandte Chemie.

[69]  R. Adams,et al.  Probing brain chemistry with electroanalytical techniques. , 1976, Analytical chemistry.

[70]  R. McCreery,et al.  Advanced carbon electrode materials for molecular electrochemistry. , 2008, Chemical reviews.

[71]  Joseph Wang Carbon‐Nanotube Based Electrochemical Biosensors: A Review , 2005 .

[72]  Liming Dai,et al.  Patterned Growth and Contact Transfer of Well-Aligned Carbon Nanotube Films , 1999 .

[73]  A. Andrews,et al.  The real catecholamine content of secretory vesicles in the CNS revealed by electrochemical cytometry , 2013, Scientific Reports.

[74]  Ping Yu,et al.  In vivo electrochemical monitoring of the change of cochlear perilymph ascorbate during salicylate-induced tinnitus. , 2012, Analytical chemistry.

[75]  Xulin Lu,et al.  A New Microfluidic Chip‐Based Online Electrochemical Platform for Extracellular Neurochemicals Monitoring in Rat Brain , 2013 .

[76]  D. Anjo,et al.  Characterization of a conductive carbon film electrode for voltammetry , 1986 .

[77]  R. Wightman,et al.  Monitoring rapid chemical communication in the brain. , 2008, Chemical reviews.

[78]  Xiaolan Chai,et al.  A two-channel ratiometric electrochemical biosensor for in vivo monitoring of copper ions in a rat brain using gold truncated octahedral microcages. , 2013, Angewandte Chemie.