An analytical system for single nanomaterials: combination of capillary electrophoresis with Raman spectroscopy or with scanning probe microscopy for individual single-walled carbon nanotube analysis.

Nanomaterials continue to attract widespread attention in many scientific and technological fields. The sizes and shapes of nanomaterials determine their physical and chemical properties. We have developed an analytical system for single nanomaterials that combines capillary electrophoresis (CE) with a highly sensitive detection method. In this manuscript, we combined CE with Raman spectroscopy or with scanning probe microscopy (SPM) for the analysis of individual single-walled carbon nanotubes (SWNTs). To combine CE with these detection techniques, we fabricated a fraction collection system that can collect droplets of small volume (<300 nL) in a small hydrophilic spot on a fractionation glass plate. The CE-separated fractions were concentrated by the evaporation of effluent, thus increasing the sensitivity by more than a factor of 10 in the case of Raman spectroscopic analysis. We characterized the fractionated SWNTs by means of Raman spectroscopy and SPM, both of which detected single SWNTs. Raman analysis enabled us to recognize a diameter difference of only 0.02 nm between SWNTs, and it was supposed that the separation by CE occurred based on the diameters of the SWNTs. We also observed a fibrous SWNT structure 1 nm high via SPM, and this structure was thought to be a single SWNT. These combined analytical systems enable the precise separation and characterization of individual SWNTs. We expect that methods developed herein can be applied to the analysis of many nanomaterials, because these methods offer separation and analysis with nanometer-scale precision. The characterization of nanomaterials at the single-compound level will be a necessity as the field of nanomaterials continues to evolve, and these combined methods may become indispensable techniques for the analysis of widely available nanomaterials.

[1]  S. Solares,et al.  Influence of Elastic Deformation on Single-Wall Carbon Nanotube Atomic Force Microscopy Probe Resolution , 2004 .

[2]  T. Toyo’oka,et al.  On-line trypsin-encapsulated enzyme reactor by the sol-gel method integrated into capillary electrophoresis. , 2002, Analytical chemistry.

[3]  R. Smalley,et al.  Structure-Assigned Optical Spectra of Single-Walled Carbon Nanotubes , 2002, Science.

[4]  S. Bachilo,et al.  Near-infrared fluorescence microscopy of single-walled carbon nanotubes in phagocytic cells. , 2004, Journal of the American Chemical Society.

[5]  M. Strano,et al.  Near-infrared optical sensors based on single-walled carbon nanotubes , 2004, Nature materials.

[6]  Longzhou Ma,et al.  Micro-structural characterization of precipitation-synthesized fluorapatite nano-material by transmission electron microscopy using different sample preparation techniques. , 2008, Micron.

[7]  大房 健 基礎講座 電気泳動(Electrophoresis) , 2005 .

[8]  Satoshi Takahashi,et al.  Multiple-sheathflow capillary array DNA analyser , 1993, Nature.

[9]  Ado Jorio,et al.  Carbon Nanotubes: Advanced Topics in the Synthesis, Structure, Properties and Applications , 2007 .

[10]  R. Zare,et al.  Integration of on-line protein digestion, peptide separation, and protein identification using pepsin-coated photopolymerized sol-gel columns and capillary electrophoresis/mass spectrometry. , 2004, Analytical chemistry.

[11]  A. Kerlavage,et al.  Complementary DNA sequencing: expressed sequence tags and human genome project , 1991, Science.

[12]  Michael S. Strano,et al.  Capillary Electrophoresis Separations of Bundled and Individual Carbon Nanotubes , 2003 .

[13]  L. Kavan,et al.  Spectroelectrochemistry of carbon nanostructures. , 2007, Chemphyschem : a European journal of chemical physics and physical chemistry.

[14]  B. Karger,et al.  Design of a high-precision fraction collector for capillary electrophoresis. , 1995, Analytical chemistry.

[15]  A. Amini,et al.  Analysis of calcitonin and its analogues by capillary zone electrophoresis and matrix-assisted laser-desorption ionization time-of-flight mass spectrometry. , 2004, Journal of separation science.

[16]  K. Markides,et al.  Capillary electrophoresis off-line matrix-assisted laser desorption/ionisation mass spectrometry of intact and digested proteins using cationic-coated capillaries. , 2004, Rapid communications in mass spectrometry : RCM.

[17]  Charles L. Wilkins,et al.  Matrix-assisted laser desorption/ionization of capillary electrophoresis effluents by Fourier transform mass spectrometry , 1992 .

[18]  Photoluminescence sidebands of carbon nanotubes below the bright singlet excitonic levels , 2008, 0810.4987.

[19]  B. Monsarrat,et al.  Structural characterization of Mycobacterium tuberculosis lipoarabinomannans by the combination of capillary electrophoresis and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. , 2001, Analytical chemistry.

[20]  M. Dresselhaus,et al.  Optical transition energies for carbon nanotubes from resonant Raman spectroscopy: environment and temperature effects. , 2004, Physical review letters.

[21]  H. Kataura,et al.  Optical Properties of Single-Wall Carbon Nanotubes , 1999 .

[22]  E. Nordhoff,et al.  A CE-MALDI interface based on the use of prestructured sample supports. , 2001, Analytical chemistry.

[23]  M. Dresselhaus,et al.  Linewidth of the Raman features of individual single-wall carbon nanotubes , 2002 .

[24]  Vahid Majidi,et al.  High resolution capillary electrophoresis of carbon nanotubes. , 2002, Journal of the American Chemical Society.

[25]  T. Toyo’oka,et al.  A protein-encapsulation technique by the sol-gel method for the preparation of monolithic columns for capillary electrochromatography. , 2002, Analytical chemistry.

[26]  T. Webster,et al.  Nanotechnology and nanomaterials: Promises for improved tissue regeneration , 2009 .

[27]  M. Valcárcel,et al.  Separation of single-walled carbon nanotubes by use of ionic liquid-aided capillary electrophoresis. , 2008, Analytical chemistry.

[28]  J. C. Tsang,et al.  Electrically Induced Optical Emission from a Carbon Nanotube FET , 2003, Science.

[29]  S. Amon,et al.  Capillary zone electrophoresis of glycopeptides under controlled electroosmotic flow conditions coupled to electrospray and matrix‐assisted laser desorption/ionization mass spectrometry , 2006, Electrophoresis.

[30]  Michael Przybylski,et al.  Capillary electrophoresis—matrix-assisted laser-desorption ionization mass spectrometry of proteins , 1994 .

[31]  Satoshi Takahashi,et al.  Direct Observation of Aβ Amyloid Fibril Growth and Inhibition , 2004 .

[32]  D. Balding,et al.  HLA Sequence Polymorphism and the Origin of Humans , 2006 .

[33]  M. Arnold,et al.  Enrichment of single-walled carbon nanotubes by diameter in density gradients. , 2005, Nano letters.

[34]  Mark C. Hersam,et al.  Sorting carbon nanotubes by electronic structure using density differentiation , 2006, Nature nanotechnology.

[35]  D. Bornhop,et al.  Detection in capillary electrophoresis , 2000, Electrophoresis.

[36]  H. Perreault,et al.  Isolation and identification of sialylated glycopeptides from bovine α1-acid glycoprotein by off-line capillary electrophoresis MALDI-TOF mass spectrometry , 2006 .

[37]  M. Valcárcel,et al.  Separation of carbon nanotubes in aqueous medium by capillary electrophoresis. , 2006, Journal of chromatography. A.

[38]  T. Iwatsubo,et al.  Analytical Method for β-Amyloid Fibrils Using CE-Laser Induced Fluorescence and Its Application to Screening for Inhibitors of β-Amyloid Protein Aggregation , 2007 .

[39]  D. Warheit,et al.  Health effects related to nanoparticle exposures: environmental, health and safety considerations for assessing hazards and risks. , 2008, Pharmacology & therapeutics.

[40]  David Andreu,et al.  A receptor for the enantioselective recognition of phenylalanine and tryptophan under neutral conditions , 1992 .

[41]  Masaru Kato,et al.  Surfactant-Stabilized Single-Walled Carbon Nanotubes Using Triphenylene Derivatives Remain Individually Dispersion in Both Liquid and Dried Solid States , 2009 .

[42]  S. Nie,et al.  Quantum dot bioconjugates for ultrasensitive nonisotopic detection. , 1998, Science.

[43]  Tatsuhiro Yamamoto,et al.  Improved Bath Sonication Method for Dispersion of Individual Single-Walled Carbon Nanotubes Using New Triphenylene-Based Surfactant , 2008 .

[44]  X. Zhang,et al.  Comprehensive two‐dimensional chromatography and capillary electrophoresis coupled with tandem time‐of‐flight mass spectrometry for high‐speed proteome analysis , 2004, Electrophoresis.

[45]  R. Nicholas,et al.  Highly selective dispersion of single-walled carbon nanotubes using aromatic polymers. , 2007, Nature nanotechnology.