Advertisement

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

  • Adam Snider
  • Francis R. Cui
  • Glareh Azadi
  • Anubhav TripathiEmail author
Research Paper
  • 48 Downloads

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.

Notes

Acknowledgements

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

References

  1. Alila S, Boufi S, Belgacem MN, Beneventi D (2005) Adsorption of a cationic surfactant onto cellulosic fibers I. Surface charge effects. Langmuir 21:8106–8113Google Scholar
  2. Atkin R, Craig VSJ, Biggs S (2000) Adsorption kinetics and structural arrangements of cationic surfactants on silica surfaces. Langmuir 16:9374–9380Google Scholar
  3. 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 103:219–304Google Scholar
  4. 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 266:236–244Google Scholar
  5. Azadi G, Tripathi A (2012) Surfactant-induced electroosmotic flow in microfluidic capillaries. Electrophoresis 33:2094–2101Google Scholar
  6. 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 947:277–286Google Scholar
  7. Bandyopadhyay S, Shelley JC, Tarek M, Moore PB, Klein ML (1998) Surfactant aggregation at a hydrophobic surface. J Phys Chem B 102:6318–6322Google Scholar
  8. Beattie JK (2006) The intrinsic charge on hydrophobic microfluidic substrates. Lab Chip 6:1409–1411Google Scholar
  9. Belder D, Ludwig M (2003) Surface modification in microchip electrophoresis. Electrophoresis 24:3595–3606Google Scholar
  10. Brinck J, Jonsson B, Tiberg F (1999) Influence of long-chain alcohols on the adsorption of nonionic surfactants to silica. Langmuir 15:7719–7724Google Scholar
  11. 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 11:1546–1552Google Scholar
  12. 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 24:714–721Google Scholar
  13. 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 25:9296–9301Google Scholar
  14. 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 7:678–684Google Scholar
  15. Fuerstenau DW, Jang HM (1991) On the nature of alkylsulfonate adsorption at the rutile water interface. Langmuir 7:3138–3143Google Scholar
  16. 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 5:1271–1276Google Scholar
  17. Goloub TP, Koopal LK (1997) Adsorption of cationic surfactants on silica. Comparison of experiment and theory. Langmuir 13:673–681Google Scholar
  18. Goloub TP, Koopal LK, Bijsterbosch BH, Sidorova MP (1996) Adsorption of cationic surfactants on silica. Surface charge effects. Langmuir 12:3188–3194Google Scholar
  19. Graca M, Bongaerts JHH, Stokes JR, Granick S (2007) Friction and adsorption of aqueous polyoxyethylene (Tween) surfactants at hydrophobic surfaces. J Colloid Interface Sci 315:662–670Google Scholar
  20. Gutig C, Grady BP, Striolo A (2008) Experimental studies on the adsorption of two surfactants on solid–aqueous interfaces: adsorption isotherms and kinetics. Langmuir 24:4806–4816Google Scholar
  21. 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 79:9145–9149Google Scholar
  22. Kirby BJ, Hasselbrink EF (2004) Zeta potential of microfluidic substrates: theory, experimental techniques, and effects on separations. Electrophoresis 25:187–202Google Scholar
  23. 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 10:4409–4413Google Scholar
  24. Mersal GAM, Bilitewski U (2005) Manipulation of the electroosmotic flow in glass und PMMA microchips with respect to specific enzymatic glucose determinations. Microchim Acta 151:29–38Google Scholar
  25. 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 86:39–82Google Scholar
  26. 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 100:16749–16753Google Scholar
  27. Moulik SP, Haque ME, Jana PK, Das AR (1996) Micellar properties of cationic surfactants in pure and mixed states. J Phys Chem 100:701–708Google Scholar
  28. 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 26:2247–2253Google Scholar
  29. 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 1130:169–174Google Scholar
  30. Nielsen SO, Srinivas G, Lopez CF, Klein ML (2005) Modeling surfactant adsorption on hydrophobic surfaces. Phys Rev Lett 94:228301Google Scholar
  31. Paria S, Khilar KC (2004) A review on experimental studies of surfactant adsorption at the hydrophilic solid–water interface. Adv Colloid Interface Sci 110:75–95Google Scholar
  32. 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 11:2496–2503Google Scholar
  33. Rani SA, Pitts B, Stewart PS (2005) Rapid diffusion of fluorescent tracers into Staphylococcus epidermidis biofilms visualized by time lapse microscopy. Antimicrob Agents Chemother 49:728–732Google Scholar
  34. Reuss FF (1809) Sur un nouvel effet de l’electricite galvanique. Mem Soc Imp Nat Moscou 2:327–337Google Scholar
  35. 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 112:11942–11949Google Scholar
  36. Schoch RB, Han JY, Renaud P (2008) Transport phenomena in nanofluidics. Rev Mod Phys 80:839–883Google Scholar
  37. Somasundaran P, Fuerstenau DW, Healy TW (1964) Surfactant adsorption at solid–liquid interface—dependence of mechanism on chain length. J Phys Chem 68:3562Google Scholar
  38. Squires TM, Quake SR (2005) Microfluidics: fluid physics at the nanoliter scale. Rev Mod Phys 77:977–1026Google Scholar
  39. Subramanian V, Ducker WA (2000) Counterion effects on adsorbed micellar shape: experimental study of the role of polarizability and charge. Langmuir 16:4447–4454Google Scholar
  40. 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 772:171–178Google Scholar
  41. Towns JK, Regnier FE (1991) Capillary electrophoretic separations of proteins using nonionic surfactant coatings. Anal Chem 63:1126–1132Google Scholar
  42. 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. 161–172Google Scholar
  43. Walker SL, Bhattacharjee S, Hoek EMV, Elimelech M (2002) A novel asymmetric clamping cell for measuring streaming potential of flat surfaces. Langmuir 18:2193–2198Google Scholar
  44. Yeung KKC, Lucy CA (1997) Suppression of electroosmotic flow and prevention of wall adsorption in capillary zone electrophoresis using zwitterionic surfactants. Anal Chem 69:3435–3441Google Scholar
  45. 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 28:414–421Google Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  • Adam Snider
    • 1
    • 2
  • Francis R. Cui
    • 1
    • 2
  • Glareh Azadi
    • 1
    • 2
  • Anubhav Tripathi
    • 1
    • 2
    Email author
  1. 1.Center for Biomedical EngineeringBrown UniversityProvidenceUSA
  2. 2.School of EngineeringBrown UniversityProvidenceUSA

Personalised recommendations