Skip to main content

Measurement Bias on Nanoparticle Size Characterization by Asymmetric Flow Field-Flow Fractionation Using Dynamic Light-Scattering Detection

Abstract

In this work, we highlight the influence of the particle–particle interaction on the retention behavior in asymmetric flow field-flow fractionation (A4F) and the misunderstanding considering the size determination by a light-scattering detector (static and dynamic light scattering) by comparing fullerene nanoparticles to similar sized polystyrene nanoparticle standards. The phenomena described here suggest that there are biases in the hydrodynamic size and diffusion determination induced by particle–particle interactions, as characterized by their virial coefficient. The dual objectives of this paper are to (1) demonstrate the uncertainties resulting from the current practice of size determination by detectors coupled to an A4F system and (2) initiate a discussion of the effects of particle–particle interactions using fullerene nanoparticles on their characterization as well as their origins. The results presented here clearly illustrate that the simple diffusion coefficient equation that is generally used to calculate the hydrodynamic size of nanoparticles (NPs) cannot be considered for whole fractograms according to their size distribution. We tried to identify particle interactions that appear during fractionation and demonstrated using the fully developed diffusion coefficient equation. We postulate that the observed interaction-dependent retention behavior may be attributed to differences in the virial coefficient between NPs and between NPs and the accumulation wall (membrane surface) without quantifying it. We hope that our results will stimulate discussion and a reassessment of the size determination procedure by A4F-LS to more fully account for all the influential material parameters that are relevant to the fractionation of nanoscale particles by A4F.

This is a preview of subscription content, access via your institution.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

References

  1. 1.

    Ashby J, Schachermeyer S, Pan S, Zhong W (2013) Dissociation-based screening of nanoparticle-protein interaction via flow field-flow fractionation. Anal Chem 85:7494–7501

    CAS  Article  Google Scholar 

  2. 2.

    Bolea E, Jiménez-Lamana J, Laborda F, Castillo JR (2011) Size characterization and quantification of silver nanoparticles by asymmetric flow field-flow fractionation coupled with inductively coupled plasma mass spectrometry. Anal Bioanal Chem 401:2723–2732

    CAS  Article  Google Scholar 

  3. 3.

    Gigault J, Pettibone JM, Schmitt C, Hackley VA (2014) Rational strategy for characterization of nanoscale particles by asymmetric-flow field flow fractionation: a tutorial. Anal Chim Acta 809:9–24

    CAS  Article  Google Scholar 

  4. 4.

    Gigault J, Zhang W, Lespes G et al (2014) Asymmetrical flow field–flow fractionation analysis of water suspensions of polymer nanofibers synthesized via RAFT-mediated emulsion polymerization. Anal Chim Acta 819:116–121

    CAS  Article  Google Scholar 

  5. 5.

    Gigault J, Nguyen T, Pettibone J, Hackley V (2014) Accurate determination of the size distribution for polydisperse, cationic metallic nanomaterials by asymmetric-flow field flow fractionation. J Nanopart Res 16:1–10

    CAS  Article  Google Scholar 

  6. 6.

    Herrero P, Bäuerlein PS, Emke E et al (2015) Size and concentration determination of (functionalised) fullerenes in surface and sewage water matrices using field flow fractionation coupled to an online accurate mass spectrometer: method development and validation. Anal Chim Acta 871:77–84

    CAS  Article  Google Scholar 

  7. 7.

    Kato H, Nakamura A, Noda N (2014) Determination of size distribution of silica nanoparticles: a comparison of scanning electron microscopy, dynamic light scattering, and flow field-flow fractionation with multiangle light scattering methods. Mater Express 4:144–152

    CAS  Article  Google Scholar 

  8. 8.

    Nguyen TM, Gigault J, Hackley VA (2013) PEGylated gold nanorod separation based on aspect ratio: characterization by asymmetric-flow field flow fractionation with UV-Vis detection. Anal Bioanal Chem 406:1651–1659

    Article  Google Scholar 

  9. 9.

    Wahlund KG (2013) Flow field-flow fractionation: critical overview. J Chromatogr A 1287:97–112

    CAS  Article  Google Scholar 

  10. 10.

    Williams SKR, Runyon JR, Ashames AA (2011) Field-flow fractionation: addressing the nano challenge. Anal Chem 83:634–642

    CAS  Article  Google Scholar 

  11. 11.

    Lespes G, Gigault J (2011) Hyphenated analytical techniques for multidimensional characterisation of submicron particles: a review. Anal Chim Acta 692:26–41

    CAS  Article  Google Scholar 

  12. 12.

    Baalousha M, Lead JR (2012) Rationalizing nanomaterial sizes measured by atomic force microscopy, flow field-flow fractionation, and dynamic light scattering: sample preparation, polydispersity, and particle structure. Environ Sci Technol 46:6134–6142

    CAS  Article  Google Scholar 

  13. 13.

    Bednar AJ, Poda AR, Mitrano DM et al (2013) Comparison of on-line detectors for field flow fractionation analysis of nanomaterials. Talanta 104:140–148

    CAS  Article  Google Scholar 

  14. 14.

    Gigault J, Grassl B, Lespes G (2012) A new analytical approach based on asymmetrical flow field-flow fractionation coupled to ultraviolet spectrometry and light scattering detection for SWCNT aqueous dispersion studies. Analyst 137:917–923

    CAS  Article  Google Scholar 

  15. 15.

    von der Kammer F, Legros S, Hofmann T et al (2011) Separation and characterization of nanoparticles in complex food and environmental samples by field-flow fractionation. TrAC Trends Anal Chem 30:425–436

    Article  Google Scholar 

  16. 16.

    Gigault J, Le Hécho I, Dubascoux S et al (2010) Single walled carbon nanotube length determination by asymmetrical-flow field-flow fractionation hyphenated to multi-angle laser-light scattering. J Chromatogr A 1217:7891–7897

    CAS  Article  Google Scholar 

  17. 17.

    Gigault J, Hackley VA (2013) Observation of size-independent effects in nanoparticle retention behavior during asymmetric-flow field-flow fractionation. Anal Bioanal Chem 405:6251–6258

    CAS  Article  Google Scholar 

  18. 18.

    Korgel BA, van Zanten JH, Monbouquette HG (1998) Vesicle size distributions measured by flow field-flow fractionation coupled with multiangle light scattering. Biophys J 74:3264–3272

    CAS  Article  Google Scholar 

  19. 19.

    Ehrhart J, Mingotaud A-F, Violleau F (2011) Asymmetrical flow field-flow fractionation with multi-angle light scattering and quasi elastic light scattering for characterization of poly(ethyleneglycol-b-ɛ-caprolactone) block copolymer self-assemblies used as drug carriers for photodynamic therapy. J Chromatogr A 1218:4249–4256

    CAS  Article  Google Scholar 

  20. 20.

    John C, Langer K (2014) Asymmetrical flow field-flow fractionation for human serum albumin based nanoparticle characterisation and a deeper insight into particle formation processes. J Chromatogr A 1346:97–106

    CAS  Article  Google Scholar 

  21. 21.

    Moquin A, Winnik FM, Maysinger D (2013) Separation science: principles and applications for the analysis of bionanoparticles by asymmetrical flow field-flow fractionation (AF4). Methods Mol Biol 991:325–341

    CAS  Article  Google Scholar 

  22. 22.

    Tuoriniemi J, Johnsson ACJH, Holmberg JP et al (2014) Intermethod comparison of the particle size distributions of colloidal silica nanoparticles. Sci Technol Adv Mater 15:035009

    Article  Google Scholar 

  23. 23.

    Jargalan N, Tropin TV, Avdeev MV, Aksenov VL (2015) Investigation of the dissolution kinetics of fullerene C60 in solvents with different polarities by UV–vis spectroscopy. J Surf Investig 9:12–16

    CAS  Article  Google Scholar 

  24. 24.

    Alargova RG, Deguchi S, Tsujii K (2001) Stable colloidal dispersions of fullerenes in polar organic solvents. J Am Chem Soc 123:10460–10467

    CAS  Article  Google Scholar 

  25. 25.

    Deguchi S, Alargova RG, Tsujii K (2001) Stable dispersions of fullerenes, C60 and C70, in water. Preparation and characterization. Langmuir 17:6013–6017

    CAS  Article  Google Scholar 

  26. 26.

    Ramakanth I, Patnaik A (2008) Characteristics of solubilization and encapsulation of fullerene C60 in non-ionic Triton X-100 micelles. Carbon 46:692–698

    CAS  Article  Google Scholar 

  27. 27.

    Prylutskyy YI, Buchelnikov AS, Voronin DP et al (2013) C60 fullerene aggregation in aqueous solution. Phys Chem Chem Phys 15:9351–9360

    CAS  Article  Google Scholar 

  28. 28.

    Burchard W (1983) Static and dynamic light scattering from branched polymers and biopolymers. Light scatter polymer. Springer, Berlin, pp 1–124

    Chapter  Google Scholar 

  29. 29.

    Andersson M, Wittgren B, Wahlund K-G (2003) Accuracy in multiangle light scattering measurements for molar mass and radius estimations. Model calculations and experiments. Anal Chem 75:4279–4291

    CAS  Article  Google Scholar 

  30. 30.

    Gigault J, Cho TJ, MacCuspie RI, Hackley VA (2012) Gold nanorod separation and characterization by asymmetric-flow field flow fractionation with UV–vis detection. Anal Bioanal Chem 405:1191–1202

    Article  Google Scholar 

  31. 31.

    Beckett R, Giddings JC (1997) Entropic contribution to the retention of nonspherical particles in field-flow fractionation. J Colloid Interface Sci 186:53–59

    CAS  Article  Google Scholar 

  32. 32.

    Felderhof BU (1978) Diffusion of interacting Brownian particles. J Phys Math Gen 11:929

    Article  Google Scholar 

  33. 33.

    Cichocki B, Felderhof BU (1990) Diffusion coefficients and effective viscosity of suspensions of sticky hard spheres with hydrodynamic interactions. J Chem Phys 93(6):4427–4432

    CAS  Article  Google Scholar 

  34. 34.

    Yadav S, Scherer TM, Shire SJ, Kalonia DS (2011) Use of dynamic light scattering to determine second virial coefficient in a semidilute concentration regime. Anal Biochem 411:292–296

    CAS  Article  Google Scholar 

  35. 35.

    Van den Broeck C, Bena I, Reimann P, Lehmann J (2000) Coupled Brownian motors on a tilted washboard. Ann Phys 9:713–720

    Article  Google Scholar 

  36. 36.

    Becker T, Nelissen K, Cleuren B et al (2013) Diffusion of interacting particles in discrete geometries. Phys Rev Lett 111:110601

    CAS  Article  Google Scholar 

  37. 37.

    27687:2008(E). I (2008) Nanotechnologies—Terminology and definitions for nano-objects—Nanoparticle, nanofibre and nanoplate

  38. 38.

    SCENIHR (2010) Scientific Committee on Emerging and Newly Identified Health Risks : scientific basis for the definition of the term “nanomaterial.” European Commission

Download references

Acknowledgements

The authors wish to thank the PEPS funding program supported by the Initiative of Excellence (IDEX Initiative) of the University of Bordeaux and the French National Center for Scientific Research (CNRS). The authors also gratefully acknowledge Gerald Clisson for the technical support and SOLVAY.

Author information

Affiliations

Authors

Corresponding author

Correspondence to Julien Gigault.

Ethics declarations

Conflict of interest

All the authors declare no conflict of interest.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 1149 kb)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Gigault, J., Mignard, E., Hadri, H.E. et al. Measurement Bias on Nanoparticle Size Characterization by Asymmetric Flow Field-Flow Fractionation Using Dynamic Light-Scattering Detection. Chromatographia 80, 287–294 (2017). https://doi.org/10.1007/s10337-017-3250-1

Download citation

Keywords

  • Asymmetric flow field-flow fractionation
  • Light scattering
  • Nanoparticles
  • Fullerenes
  • Size characterization