Skip to main content
SpringerLink
Log in

The electrokinetic properties of cationic surfactants adsorbed on a hydrophobic substrate: effect of chain length and concentration

  • Research Paper
  • Published:
Microfluidics and Nanofluidics Aims and scope Submit manuscript

Abstract

Electrokinetic (EK) properties, such as the electro-osmotic flow (EOF), are influenced by surfactant adsorption at the solid–liquid interface. With the growing popularity of poly(methyl methacrylate) (PMMA) as the substrate for polymeric-based microfluidics, it is important to understand the effect of surfactants on EOF in these devices. Here, we investigate the effect of surfactant chain length and concentration on the electro-osmotic (EO) mobility induced by three cationic surfactants cetyl trimethylammonium bromide (CTAB), trimethylammonium bromide (TTAB), dodecyl trimethylammonium bromide (DTAB) in PMMA microcapillaries. The EO mobility curve as a function of concentration shows three regimes. First, at very low concentrations below 0.002 mM, the mobility is constant and approximately equal to the value obtained with the surfactant-free electrolyte (1 mM KCl). Next, the EOF reverses and mobility increases linearly with surfactant concentration. Finally, the mobility reaches a plateau at a concentration well below surfactant CMC (0.2-mM CTAB, 0.5-mM TTAB and 2-mM DTAB) and decreases at the vicinity of CMC. Our results show that the rate of change in mobility with respect to concentration is a linear function of chain length and increases with longer-chain surfactants. In addition, we deduce the magnitude of Van der Waals or cohesive energy between the adsorbed alkyl chains from the EO mobility values. For the alkyl trimethylammonium surfactants adsorbed on the hydrophobic surface of PMMA, this energy was found to be 0.114 kT smaller than the reported value for ionic surfactants adsorbed on a hydrophilic surface.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

References

  • Alila S, Boufi S, Belgacem MN, Beneventi D (2005) Adsorption of a cationic surfactant onto cellulosic fibers I. Surface charge effects. Langmuir 21:8106–8113

    Google Scholar 

  • Atkin R, Craig VSJ, Biggs S (2000) Adsorption kinetics and structural arrangements of cationic surfactants on silica surfaces. Langmuir 16:9374–9380

    Google Scholar 

  • Atkin R, Craig VSJ, Wanless EJ, Biggs S (2003a) The influence of chain length and electrolyte on the adsorption kinetics of cationic surfactants at the silica–aqueous solution interface. Adv Colloid Interface Sci 103:219–304

    Google Scholar 

  • Atkin R, Craig VSJ, Wanless EJ, Biggs S (2003b) The influence of chain length and electrolyte on the adsorption kinetics of cationic surfactants at the silica–aqueous solution interface. J Colloid Interface Sci 266:236–244

    Google Scholar 

  • Azadi G, Tripathi A (2012) Surfactant-induced electroosmotic flow in microfluidic capillaries. Electrophoresis 33:2094–2101

    Google Scholar 

  • Badal MY, Wong M, Chiem N, Salimi-Moosavi H, Harrison DJ (2002) Protein separation and surfactant control of electroosmotic flow in poly(dimethylsiloxane)-coated capillaries and microchips. J Chromatogr A 947:277–286

    Google Scholar 

  • Bandyopadhyay S, Shelley JC, Tarek M, Moore PB, Klein ML (1998) Surfactant aggregation at a hydrophobic surface. J Phys Chem B 102:6318–6322

    Google Scholar 

  • Beattie JK (2006) The intrinsic charge on hydrophobic microfluidic substrates. Lab Chip 6:1409–1411

    Google Scholar 

  • Belder D, Ludwig M (2003) Surface modification in microchip electrophoresis. Electrophoresis 24:3595–3606

    Google Scholar 

  • Brinck J, Jonsson B, Tiberg F (1999) Influence of long-chain alcohols on the adsorption of nonionic surfactants to silica. Langmuir 15:7719–7724

    Google Scholar 

  • Caruso F, Serizawa T, Furlong DN, Okahata Y (1995) Quartz-crystal microbalance and surface-plasmon resonance study of surfactant adsorption onto gold and chromium-oxide surfaces. Langmuir 11:1546–1552

    Google Scholar 

  • Dang F, Zhang L, Hagiwara H, Mishina Y, Baba Y (2003) Ultrafast analysis of oligosaccharides on microchip with light-emitting diode confocal fluorescence detection. Electrophoresis 24:714–721

    Google Scholar 

  • Dang FQ, Hasegawa T, Biju V, Ishikawa M, Kaji N, Yasui T, Baba Y (2009) Spontaneous adsorption on a hydrophobic surface governed by hydrogen bonding. Langmuir 25:9296–9301

    Google Scholar 

  • Fa KQ, Paruchuri VK, Brown SC, Moudgil BM, Miller JD (2005) The significance of electrokinetic characterization for interpreting interfacial phenomena at planar, macroscopic interfaces. Phys Chem Chem Phys 7:678–684

    Google Scholar 

  • Fuerstenau DW, Jang HM (1991) On the nature of alkylsulfonate adsorption at the rutile water interface. Langmuir 7:3138–3143

    Google Scholar 

  • Garcia AL, Ista LK, Petsev DN, O’Brien MJ, Bisong P, Mammoli AA, Brueck SRJ, Lopez GP (2005) Electrokinetic molecular separation in nanoscale fluidic channels. Lab Chip 5:1271–1276

    Google Scholar 

  • Goloub TP, Koopal LK (1997) Adsorption of cationic surfactants on silica. Comparison of experiment and theory. Langmuir 13:673–681

    Google Scholar 

  • Goloub TP, Koopal LK, Bijsterbosch BH, Sidorova MP (1996) Adsorption of cationic surfactants on silica. Surface charge effects. Langmuir 12:3188–3194

    Google Scholar 

  • Graca M, Bongaerts JHH, Stokes JR, Granick S (2007) Friction and adsorption of aqueous polyoxyethylene (Tween) surfactants at hydrophobic surfaces. J Colloid Interface Sci 315:662–670

    Google Scholar 

  • Gutig C, Grady BP, Striolo A (2008) Experimental studies on the adsorption of two surfactants on solid–aqueous interfaces: adsorption isotherms and kinetics. Langmuir 24:4806–4816

    Google Scholar 

  • Huang B, Kim S, Wu H, Zare RN (2007) Use of a mixture of n-dodecyl-beta-d-maltoside and sodium dodecyl sulfate in poly(dimethylsiloxane) microchips to suppress adhesion and promote separation of proteins. Anal Chem 79:9145–9149

    Google Scholar 

  • Kirby BJ, Hasselbrink EF (2004) Zeta potential of microfluidic substrates: theory, experimental techniques, and effects on separations. Electrophoresis 25:187–202

    Google Scholar 

  • Manne S, Cleveland JP, Gaub HE, Stucky GD, Hansma PK (1994) Direct visualization of surfactant hemimicelles by force microscopy of the electrical double-layer. Langmuir 10:4409–4413

    Google Scholar 

  • Mersal GAM, Bilitewski U (2005) Manipulation of the electroosmotic flow in glass und PMMA microchips with respect to specific enzymatic glucose determinations. Microchim Acta 151:29–38

    Google Scholar 

  • Miller R, Fainerman VB, Makievski AV, Kragel J, Grigoriev DO, Kazakov VN, Sinyachenko OV (2000) Dynamics of protein and mixed protein/surfactant adsorption layers at the water/fluid interface. Adv Colloid Interface Sci 86:39–82

    Google Scholar 

  • Mosquera V, Ruso JM, Prieto G, Sarmiento F (1996) Characterization of the interactions between lysozyme and n-alkyltrimethylammonium bromides by zeta potential measurements. J Phys Chem 100:16749–16753

    Google Scholar 

  • Moulik SP, Haque ME, Jana PK, Das AR (1996) Micellar properties of cationic surfactants in pure and mixed states. J Phys Chem 100:701–708

    Google Scholar 

  • Nagata H, Tabuchi M, Hirano K, Baba Y (2005) Microchip electrophoretic protein separation using electroosmotic flow induced by dynamic sodium dodecyl sulfate-coating of uncoated plastic chips. Electrophoresis 26:2247–2253

    Google Scholar 

  • Naruishi N, Tanaka Y, Higashi T, Wakida S (2006) Highly efficient dynamic modification of plastic microfluidic devices using proteins in microchip capillary electrophoresis. J Chromatogr A 1130:169–174

    Google Scholar 

  • Nielsen SO, Srinivas G, Lopez CF, Klein ML (2005) Modeling surfactant adsorption on hydrophobic surfaces. Phys Rev Lett 94:228301

    Google Scholar 

  • Paria S, Khilar KC (2004) A review on experimental studies of surfactant adsorption at the hydrophilic solid–water interface. Adv Colloid Interface Sci 110:75–95

    Google Scholar 

  • Penfold J, Staples E, Thompson L, Tucker I, Hines J, Thomas RK, Lu JR (1995) Solution and adsorption behavior of the mixed surfactant system sodium dodecyl sulfate/n-hexaethylene glycol monododecyl ether. Langmuir 11:2496–2503

    Google Scholar 

  • Rani SA, Pitts B, Stewart PS (2005) Rapid diffusion of fluorescent tracers into Staphylococcus epidermidis biofilms visualized by time lapse microscopy. Antimicrob Agents Chemother 49:728–732

    Google Scholar 

  • Reuss FF (1809) Sur un nouvel effet de l’electricite galvanique. Mem Soc Imp Nat Moscou 2:327–337

    Google Scholar 

  • Rodriguez A, Graciani MD, Moreno-Vargas AJ, Moya ML (2008) Mixtures of monomeric and dimeric surfactants: hydrophobic chain length and spacer group length effects on non ideality. J Phys Chem B 112:11942–11949

    Google Scholar 

  • Schoch RB, Han JY, Renaud P (2008) Transport phenomena in nanofluidics. Rev Mod Phys 80:839–883

    Google Scholar 

  • Somasundaran P, Fuerstenau DW, Healy TW (1964) Surfactant adsorption at solid–liquid interface—dependence of mechanism on chain length. J Phys Chem 68:3562

    Google Scholar 

  • Squires TM, Quake SR (2005) Microfluidics: fluid physics at the nanoliter scale. Rev Mod Phys 77:977–1026

    Google Scholar 

  • Subramanian V, Ducker WA (2000) Counterion effects on adsorbed micellar shape: experimental study of the role of polarizability and charge. Langmuir 16:4447–4454

    Google Scholar 

  • Tavares MFM, Colombara R, Massaro S (1997) Modified electroosmotic flow by cationic surfactant additives in capillary electrophoresis: evaluation of electrolyte systems for anion analysis. J Chromatogr A 772:171–178

    Google Scholar 

  • Towns JK, Regnier FE (1991) Capillary electrophoretic separations of proteins using nonionic surfactant coatings. Anal Chem 63:1126–1132

    Google Scholar 

  • Wakamatsu T, Fuerstenau DW (1968) The effect of hydrocarbon chain length on the adsorption of sulfonates at solid/water interface. In: Weber WJ, Matijević E (eds) Adsorption from aqueous solution. Advances in Chemistry Vol. 79. American Chemical Society, pp. 161–172

  • Walker SL, Bhattacharjee S, Hoek EMV, Elimelech M (2002) A novel asymmetric clamping cell for measuring streaming potential of flat surfaces. Langmuir 18:2193–2198

    Google Scholar 

  • Yeung KKC, Lucy CA (1997) Suppression of electroosmotic flow and prevention of wall adsorption in capillary zone electrophoresis using zwitterionic surfactants. Anal Chem 69:3435–3441

    Google Scholar 

  • Zhang Y, Ping GC, Zhu BM, Kaji N, Tokeshi M, Baba Y (2007) Enhanced electrophoretic resolution of monosulfate glycosaminoglycan disaccharide isomers on poly(methyl methacrylate) chips. Electrophoresis 28:414–421

    Google Scholar 

Download references

Acknowledgements

We acknowledge support from the National Science Foundation (Grant CBET-0621216) and the Brown University Graduate student fellowship (A. T. and G. A.).

Author information

Authors and Affiliations

  1. Center for Biomedical Engineering, Brown University, Providence, RI, 02912, USA

    Adam Snider, Francis R. Cui, Glareh Azadi & Anubhav Tripathi

  2. School of Engineering, Brown University, Providence, RI, 02912, USA

    Adam Snider, Francis R. Cui, Glareh Azadi & Anubhav Tripathi

Authors
  1. Adam Snider
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Francis R. Cui
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Glareh Azadi
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Anubhav Tripathi
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Anubhav Tripathi.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Snider, A., Cui, F.R., Azadi, G. et al. The electrokinetic properties of cationic surfactants adsorbed on a hydrophobic substrate: effect of chain length and concentration. Microfluid Nanofluid 23, 133 (2019). https://doi.org/10.1007/s10404-019-2288-9

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s10404-019-2288-9

Search

Navigation