, Volume 81, Issue 2, pp 239–245 | Cite as

HPLC Characterization of the Association Mechanism of Organic Compounds with β Cyclodextrin Using a Novel Boron Nitride Nanotube Particulate Stationary Phase

  • Yves Claude Guillaume
  • Lydie Lethier
  • Claire Andre


In this paper, a simple homogeneous coating of silica spherical particles with pristine boron nitride nanotubes (BNNTs) was described. BNNTs dissolved in dimethylacetamide (DMAc) were mixed with amino-functionalized silica particles having a 5 μm diameter. Favorable interaction between the amino group and the BNNT surfaces induces the absorption of the BNNTs on the silica. The BNNT-coated silica particles were used as stationary phase for HPLC. For the first time, it was demonstrated that this new particulate BNNT stationary phase can be used for the study of the complexation of solute molecules (terpene molecules used as test drugs in this work) with β cyclodextrin (βCD). The apparent formation constants Kf of terpene derivative/βCD were in the same magnitude as those reported in the literature. The plot of Kf versus the water fraction in the methanol/water mobile phase showed that the BNNT surface played an active role in the complex formation due to terpene/BNNT-specific polar interactions. This work demonstrated that our novel particulate BNNT HPLC stationary phase was an efficient tool to study molecular recognition mechanism and more specifically the association between a drug substance and a target molecule with the aim of reaching biopharmaceutic and clinical applications.


HPLC Boron nitride nanotubes Silica particle βCD Methanol Association constant 


Compliance with ethical standards

Conflict of interest

The three authors declare that there is no conflict of interest.

Ethical approval

This article does not contain any studies with human participants or animals performed by any of the authors.


  1. 1.
    Li QL, Yuan DX (2003) Evaluation of multiwalled carbon nanotubes as gas chromatographic column packing. J Chromatogr A 1003:203–209CrossRefGoogle Scholar
  2. 2.
    Saridara C, Mitra S (2005) Chromatography on self assembled carbon nanotubes. Anal Chem 77:7094–7097CrossRefGoogle Scholar
  3. 3.
    Karwa M, Mitra S (2006) Gas chromatography on self assembled, single walled carbon nanotubes. Anal Chem 78:2064–2070CrossRefGoogle Scholar
  4. 4.
    Stadermann M, McBrady AD, Dick B, Reid VR, Noy A, Synovec RE, Bakajin O (2006) Ultra fast gas chromatography on single wall carbon nanotube stationary phases in microfabricated channels. Anal Chem 78:5639–5644CrossRefGoogle Scholar
  5. 5.
    Zhao L, Ai P, Duan AH, Yuan LM (2011) Single wall carbon nanotubes for improved enantioseparations on a chiral liquid stationary phase in GC. Anal Bioanal Chem 399:143–147CrossRefGoogle Scholar
  6. 6.
    Speltini A, Merli D, Quartarone E, Profumo A (2010) Separation of alkanes and aromatic compounds by packed column gas chromatography using functionalized multi walled carbon nanotubes as stationary phases. J Chromatogr A 1217:2918–2924CrossRefGoogle Scholar
  7. 7.
    Li Y, Chen Y, Xiang R, Ciuparu D, Pfefferle LD, Horvath LC, Wilkins JA (2005) Incorporation of single walled carbon nanotubes into organic polymer monolithic stationary phase for u-HPLC and capillary electrochromatography. Anal Chem 77:1398–1406CrossRefGoogle Scholar
  8. 8.
    Andre C, Gharbi T, Guillaume YC (2009) A novel stationary phase based on amino derivatized nanotubes for HPLC separations: theoretical and practical aspects. J Sep Sci 32:1757–1764CrossRefGoogle Scholar
  9. 9.
    Andre C, Aljhni R, Gharbi T, Guillaume YC (2011) Incorporation of carbon nanotubes in a silica HPLC column to enhance the chromatographic performance of peptides: theoretical and practical aspects. J Sep Sci 34:1221–1227CrossRefGoogle Scholar
  10. 10.
    Menna E, Della Negra F, Prato M, Tagmatarchis N, Ciogli A, Gasparrrini F, Misita D, Villani C (2006) Carbon nanotubes on HPLC silica microspheres. Carbon 44:1609–1613CrossRefGoogle Scholar
  11. 11.
    Chang YX, Zhou LL, Li GX, Li L, Yuan LM (2007) Single wall carbon nanotubes used as stationary phase in HPLC. J Liq Chromatogr and Relat Technol 30:2953–2958CrossRefGoogle Scholar
  12. 12.
    André C, Aljhni R, Lethier L, Guillaume YC (2014) Development and evaluation of a double wall carbon nanotubes HPLC stationary phase. Chromatographia 77:1257–1265CrossRefGoogle Scholar
  13. 13.
    Andre C, Aljhni R, Lethier L, Guillaume YC (2014) Carbon nanotube poroshell silica as novel stationary phase for fast HPLC analysis of monoclonal antibodies. Anal Bioanal Chem 406:905–909CrossRefGoogle Scholar
  14. 14.
    Guillaume YC, Andre C (2013) Fast enantioseparation by HPLC on a modified carbon nanotube monolithic phase with a pyrenyl aminoglycoside derivative. Talanta 115:418–421CrossRefGoogle Scholar
  15. 15.
    Aljhni R, Andre C, Lethier L, Guillaume YC (2015) An HPLC chromatographic framework to analyse the & #x03B2; cyclodextrin/solute complexation mechanism using a carbon nanotube stationary phase. Talanta 144:226–232CrossRefGoogle Scholar
  16. 16.
    Andre C, Guillaume YC (2012) Boron nitride nanotubes and their functionalization via quinuclidine 3-thiol with gold nanoparticles for the development and enhancement of the HPLC performance of HPLC monolithic columns. Talanta 93:274–278CrossRefGoogle Scholar
  17. 17.
    Andre C, Lethier L, Guillaume YC (2015) A novel fluorinated boron nitride nanotube organic monolithic column for capillary liquid chromatography. Chromatographia 78:39–43CrossRefGoogle Scholar
  18. 18.
    Lee CH, Zhang D, Yap YK (2012) Functionalisation, dispersion and cutting of boron nitride nanotubes in water. J Phys Chem 116:1798–1804Google Scholar
  19. 19.
    Guillaume YC, Andre C (2017) Development of a simple technique for the coating of monolithic silica with pristine boron nitride nanotubes (BNNTs): HPLC chromatographic applications. Talanta 164:39–44CrossRefGoogle Scholar
  20. 20.
    Bland JM, Altman DG (1996) Statistical method for assessing agreement between two methods of clinical measurements. Lancet 327:307–310CrossRefGoogle Scholar
  21. 21.
    Matarin O, Rimola A (2016) Influence of defects in BNNTs in the adsorption of molecules. Insights from B3LYP-D2 periodic simulations. Crystals 6:63CrossRefGoogle Scholar
  22. 22.
    Zhao YU, Xiaojun W, Jinlong Y, Xiao CZ (2011) Ab initio theoretical study of non-covalent adsorption of aromatic molecules on boron nitride nanotubes. Phys Chem Chem Phys 13:11766–11772CrossRefGoogle Scholar
  23. 23.
    Chatjigakis AK, Clarot I, Cardot PJP, Nowakowski R, Coleman A (1999) Reversed phase chromatographic study of the inclusion selectivity of terpene derivatives with β cyclodextrin in water/cosolvent mixtures. J Liq Chromatogr Relat Technol 22:1267–1284CrossRefGoogle Scholar
  24. 24.
    Lawtrakul L, Inthajak K, Toochinda P (2014) Molecular calculations on β cyclodextrin inclusion complexes with five essential oil compounds from Ocimum basilicum (sweet basil). Science Asia 40:145–151CrossRefGoogle Scholar
  25. 25.
    Glod BK, Haddad PR, Alexander P (1992) Ion-exclusion chromatography using mobile phases containing cyclodextrin. J Chromatogr 595:149–154CrossRefGoogle Scholar
  26. 26.
    Fujimura K, Ueda T, Kitagawa M, Tagayanagi H, Ando T (1986) Evidence for temperature dependent mechanism of host-guest complexation. Anal Chem 58:2668–2674CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany 2017

Authors and Affiliations

  • Yves Claude Guillaume
    • 1
    • 2
    • 3
  • Lydie Lethier
    • 1
    • 2
    • 3
  • Claire Andre
    • 1
    • 2
    • 3
  1. 1.Univ Franche-ComtéBesanconFrance
  2. 2.CHRU BesançonBesanconFrance
  3. 3.Pôle Chimie Analytique Bioanalytique et Physique (PCABP) EA481 Neurosciences Intégratives et CliniquesBesanconFrance

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