Alternative mannosylation method for nanomaterials: application to oxidized debris-free multiwalled carbon nanotubes

  • Marcelo de Sousa
  • Diego Stéfani Teodoro Martinez
  • Oswaldo Luiz Alves
Research Paper


Mannosylation is a method commonly used to deliver nanomaterials to specific organs and tissues via cellular macrophage uptake. In this work, for the first time, we proposed a method that involves the binding of d-mannose to ethylenediamine to form mannosylated ethylenediamine, which is then coupled to oxidized and purified multiwalled carbon nanotubes. The advantage of this approach is that mannosylated ethylenediamine precipitates in methanol, which greatly facilitates the separation of this product in the synthesis process. Carbon nanotubes were oxidized using concentrated H2SO4 and HNO3 by conventional reflux method. However, during this oxidation process, carbon nanotubes generated carboxylated carbonaceous fragments (oxidation debris). These by-products were removed from the oxidized carbon nanotubes to ensure that the functionalization would occur only on the carbon nanotube surface. The coupling of mannosylated ethylenediamine to debris-free carbon nanotubes was accomplished using n-(3-dimethylaminopropyl)-n-ethylcarbodiimide and n-hydroxysuccinimide. Deconvoluted N1s spectra obtained from X-ray photoelectron spectroscopy gave binding energies of 399.8 and 401.7 eV, which we attributed to the amide and amine groups, respectively, of carbon nanotubes functionalized with mannosylated ethylenediamine. Deconvoluted O1s spectra showed a binding energy of 532.4 eV, which we suggest is caused by an overlap in the binding energies of the aliphatic CO groups of d-mannose and the O=C group of the amide bond. The functionalization degree was approximately 3.4 %, according to the thermogravimetric analysis. Scanning electron microscopy demonstrated that an extended carbon nanotube morphology was preserved following the oxidation, purification, and functionalization steps.


Nanotubes Mannose Mannosylated ethylenediamine Functionalization Debris Binding energy Nanostructured catalysts 



The authors gratefully acknowledge financial support from CNPq, FAPESP, INCT-Inomat, the Brazilian Nanotoxicology Network (Cigenanotox) and NanoBioss-SisNANO/MCTI. We also extend gratitude to the Nanostructured Materials Laboratory (XPS Facility) at LNNano/CNPEM.

Supplementary material

11051_2016_3399_MOESM1_ESM.docx (1.2 mb)
Supplementary material 1 (DOCX 1251 kb)


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Copyright information

© Springer Science+Business Media Dordrecht 2016

Authors and Affiliations

  • Marcelo de Sousa
    • 1
  • Diego Stéfani Teodoro Martinez
    • 2
  • Oswaldo Luiz Alves
    • 1
  1. 1.Solid State Chemistry Laboratory (LQES) and NanoBioss Laboratory, Institute of ChemistryUniversity of Campinas (Unicamp)CampinasBrazil
  2. 2.Brazilian Nanotechnology National Laboratory (LNNano)Brazilian Center for Research in Energy and Materials (CNPEM)CampinasBrazil

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