Electrochemical nanoprobes for single-cell analysis.

The measurement of key molecules in individual cells with minimal disruption to the biological milieu is the next frontier in single-cell analyses. Nanoscale devices are ideal analytical tools because of their small size and their potential for high spatial and temporal resolution recordings. Here, we report the fabrication of disk-shaped carbon nanoelectrodes whose radius can be precisely tuned within the range 5-200 nm. The functionalization of the nanoelectrode with platinum allowed the monitoring of oxygen consumption outside and inside a brain slice. Furthermore, we show that nanoelectrodes of this type can be used to impale individual cells to perform electrochemical measurements within the cell with minimal disruption to cell function. These nanoelectrodes can be fabricated combined with scanning ion conductance microscopy probes, which should allow high resolution electrochemical mapping of species on or in living cells.

[1]  D. Pletcher,et al.  Studies of the electrodeposition of platinum metal from a hexachloroplatinic acid bath , 2009 .

[2]  T. Matsue,et al.  Fabrication, Characterization, and Functionalization of Dual Carbon Electrodes as Probes for Scanning Electrochemical Microscopy (SECM) , 2013, Analytical chemistry.

[3]  Nader Pourmand,et al.  Compartmental genomics in living cells revealed by single-cell nanobiopsy. , 2014, ACS nano.

[4]  Martin Egelhaaf,et al.  Prototypical Components of Honeybee Homing Flight Behavior Depend on the Visual Appearance of Objects Surrounding the Goal , 2012, Front. Behav. Neurosci..

[5]  W. Schuhmann,et al.  Microelectrochemical visualization of oxygen consumption of single living cells. , 2013, Faraday discussions.

[6]  Nader Pourmand,et al.  Voltage controlled nano-injection system for single-cell surgery. , 2012, Nanoscale.

[7]  J. Fruehauf,et al.  Reactive oxygen species: an Achilles’ heel of melanoma? , 2008, Expert review of anticancer therapy.

[8]  François O. Laforge,et al.  Nanoelectrochemistry of mammalian cells , 2008, Proceedings of the National Academy of Sciences.

[9]  J. Drapier,et al.  Monitoring in Real Time with a Microelectrode the Release of Reactive Oxygen and Nitrogen Species by a Single Macrophage Stimulated by its Membrane Mechanical Depolarization , 2006, Chembiochem : a European journal of chemical biology.

[10]  Julia Gorelik,et al.  Nanoscale-Targeted Patch-Clamp Recordings of Functional Presynaptic Ion Channels , 2013, Neuron.

[11]  L. A. Baker,et al.  Scanning ion conductance microscopy. , 2012, Annual review of analytical chemistry.

[12]  W. Schultz,et al.  Monitoring extracellular pH, oxygen, and dopamine during reward delivery in the striatum of primates , 2012, Front. Behav. Neurosci..

[13]  A. Ewing,et al.  Pulse Voltammetry in Single Cells Using Platinum Microelectrodes , 1992 .

[14]  A. Ewing,et al.  Carbon-ring electrodes with 1-.mu.m tip diameter , 1986 .

[15]  Guy Denuault,et al.  Detection of hydrogen peroxide at mesoporous platinum microelectrodes. , 2002, Analytical chemistry.

[16]  H. Shiku,et al.  Multifunctional nanoprobes for nanoscale chemical imaging and localized chemical delivery at surfaces and interfaces. , 2011, Angewandte Chemie.

[17]  A. Bard,et al.  Scanning electrochemical microscopy part 13. Evaluation of the tip shapes of nanometer size microelectrodes , 1992 .

[18]  P. Pelicci,et al.  Electrochemical study of hydrogen peroxide formation in isolated mitochondria. , 2012, Bioelectrochemistry.

[19]  Charlotte Schubert,et al.  Single-cell analysis: The deepest differences , 2011, Nature.

[20]  D. Klenerman,et al.  Nanoscale live-cell imaging using hopping probe ion conductance microscopy , 2009, Nature Methods.

[21]  Y. Korchev,et al.  Nanosensors for the detection of hydrogen peroxide , 2014 .

[22]  Haim H. Bau,et al.  Cell electrophysiology with carbon nanopipettes. , 2009, ACS nano.

[23]  Pradyumna S. Singh,et al.  Single-molecule electrochemistry: present status and outlook. , 2013, Accounts of chemical research.

[24]  N. Nioradze,et al.  Origins of nanoscale damage to glass-sealed platinum electrodes with submicrometer and nanometer size. , 2013, Analytical chemistry.

[25]  B. Halliwell,et al.  Free radicals in biology and medicine , 1985 .

[26]  M. Dresselhaus,et al.  Studying disorder in graphite-based systems by Raman spectroscopy. , 2007, Physical chemistry chemical physics : PCCP.

[27]  R. Putnam,et al.  Oxygen measurements in brain stem slices exposed to normobaric hyperoxia and hyperbaric oxygen. , 2001, Journal of applied physiology.

[28]  N. Pourmand,et al.  Functionalized nanopipettes: toward label-free, single cell biosensors , 2010, Bioanalytical reviews.

[29]  C. P. Winlove,et al.  Scanning electrochemical microscopy as a local probe of oxygen permeability in cartilage. , 2000, Biophysical journal.

[30]  Y. Gogotsi,et al.  Platinized carbon nanoelectrodes as potentiometric and amperometric SECM probes , 2013, Journal of Solid State Electrochemistry.

[31]  M J Lab,et al.  Scanning ion conductance microscopy of living cells. , 1997, Biophysical journal.

[32]  Michelle D. Wang,et al.  Small Molecule Injection into Single-Cell C. elegans Embryos via Carbon-Reinforced Nanopipettes , 2013, PloS one.

[33]  Sergiy Sylantyev,et al.  Electric Fields Due to Synaptic Currents Sharpen Excitatory Transmission , 2008, Science.

[34]  D. Klenerman,et al.  Local delivery of molecules from a nanopipette for quantitative receptor mapping on live cells. , 2013, Analytical chemistry.

[35]  Kosuke Hamaguchi,et al.  Intracellular Neural Recording with Pure Carbon Nanotube Probes , 2013, PloS one.

[36]  W. Schuhmann,et al.  Visualization of oxygen consumption of single living cells by scanning electrochemical microscopy: the influence of the faradaic tip reaction. , 2013, Angewandte Chemie.

[37]  Charles M. Lieber,et al.  Three-Dimensional, Flexible Nanoscale Field-Effect Transistors as Localized Bioprobes , 2010, Science.

[38]  Ning Wang,et al.  Nanoneedle: a multifunctional tool for biological studies in living cells. , 2010, Nanoscale.

[39]  Jun Wang,et al.  Chemical analysis of single cells. , 2013, Analytical chemistry.

[40]  M. Mirkin,et al.  Atomic force microscopy of electrochemical nanoelectrodes. , 2012, Analytical chemistry.

[41]  Seung-Man Yang,et al.  Nanowire-based single-cell endoscopy. , 2012, Nature nanotechnology.

[42]  Yuandong Zhao,et al.  Recent advances in electrochemical sensing for hydrogen peroxide: a review. , 2012, The Analyst.

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

[44]  Yury Gogotsi,et al.  Multifunctional carbon-nanotube cellular endoscopes. , 2011, Nature nanotechnology.

[45]  S. Bodovitz,et al.  Single cell analysis: the new frontier in 'omics'. , 2010, Trends in biotechnology.

[46]  C. Lefrou,et al.  A unified new analytical approximation for negative feedback currents with a microdisk SECM tip , 2007 .

[47]  Derek Pletcher,et al.  A study of cathodic oxygen reduction at platinum using microelectrodes , 1993 .

[48]  R. Wightman,et al.  Microelectrodes for the measurement of catecholamines in biological systems. , 1996, Analytical chemistry.

[49]  B. Zhang,et al.  Nanoscale electrochemistry. , 2013, Analytical chemistry.

[50]  Yung-Ting Chen,et al.  AlxGa1−xN/GaN band offsets determined by deep-level emission , 2001 .

[51]  A. Bhasin,et al.  Accurate and simplified consideration of the probe geometrical defaults in scanning electrochemical microscopy: theoretical and experimental investigations. , 2011, Analytical chemistry.

[52]  T. Teyler.  Brain slice preparation: Hippocampus , 1980, Brain Research Bulletin.

[53]  H. Shiku,et al.  Topographical and electrochemical nanoscale imaging of living cells using voltage-switching mode scanning electrochemical microscopy , 2012, Proceedings of the National Academy of Sciences.

[54]  L. A. Baker,et al.  Applications of nanopipettes in the analytical sciences. , 2010, The Analyst.

[55]  Anthony Kucernak,et al.  Electrocatalysis under Conditions of High Mass Transport Rate: Oxygen Reduction on Single Submicrometer-Sized Pt Particles Supported on Carbon , 2004 .

[56]  J. Devynck,et al.  Chemically modified microelectrodes designed for the electrochemical determination of nitric oxide in biological systems , 1996 .

[57]  Matthew R Angle,et al.  Neuronal Recordings with Solid-Conductor Intracellular Nanoelectrodes (SCINEs) , 2012, PloS one.

[58]  Jean-Marc Noël,et al.  Nanoelectrodes for determination of reactive oxygen and nitrogen species inside murine macrophages , 2012, Proceedings of the National Academy of Sciences.

[59]  X. Zheng,et al.  Single cell analysis at the nanoscale. , 2012, Chemical Society reviews.