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Electrochemical behaviour of cationic polyelectrolytes at a polarized liquid/liquid interface

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Abstract

The behaviours of several cationic polyelectrolytes (chitosan; polyquaternium-4; diethylaminoethyl dextran; polyquaternium-10, and aminoacrylmethacrylate copolymer, Eudragit® E100) at a polarised liquid/liquid interface are analysed and compared in the present paper. Based on the analysis of the voltammetric results, it was possible to determine some of the relationships between polymer structure and the tendency to adsorb at the interface. It was also possible to determine the substitution degree of a polymer comprising a chitosan main chain modified with glycidyltrimethylammonium chloride, and the values obtained are in agreement with those calculated using other methodologies. Finally, we report a comparative study concerning the effect of cationic (chitosan) and anionic (dextran sulphate) polyelectrolytes on the compactness of a phospholipid film.

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References

  1. Angelova N, Hunkeler D (1999) Rationalizing the design of polymeric biomaterials. Trends Biotechnol 17(10):409–421

    Article  CAS  Google Scholar 

  2. Roller S, Covill N (1999) The antifungal properties of chitosan in laboratory media and apple juice. Int J Food Microbiol 47(1–2):67–77

    Article  CAS  Google Scholar 

  3. Alasino RV, Ausar SF, Bianco ID, Castagna LF, Contigiani M, Beltramo DM (2005) Amphipathic and membrane-destabilizing properties of the cationic acrylate polymer Eudragit® E100. Macromol Biosci 5(3):207–213

    Article  CAS  Google Scholar 

  4. Bianco ID, Balsinde J, Beltramo DM, Castagna LF, Landa CA, Dennis EA (2000) Chitosan-induced phospholipase A2 activation and arachidonic acid mobilization in P388D1 macrophages. FEBS Lett 466(2–3):292–294

    Article  CAS  Google Scholar 

  5. Girault HH (ed) (1993) Charge transfer across liquid–liquid interfases en modern aspect of electrochemistry, vol 25. Plenum Press, New York

    Google Scholar 

  6. Reymond F, Girault HH, Steyaert G, Carrupt P-A, Testa B (1996) Mechanism of transfer of a basic drug across the water/1,2-dichloroethane interface: the case of quinidine. Helv Chim Acta 79(1):101–117. doi:10.1002/hlca.19960790111

    Article  CAS  Google Scholar 

  7. Reymond F, Fermίn D, Lee HJ, Girault HH (2000) Electrochemistry at liquid/liquid interfaces: methodology and potential applications. Electrochim Acta 45(15–16):2647–2662. doi:10.1016/S0013-4686(00)00343-1

    Article  CAS  Google Scholar 

  8. Hakkarainen S, Gilbert SL, Kontturi AK, Kontturi K (2004) Amperometric method for determining the degree of complexation of polyelectrolytes with cationic surfactants. J Colloid Interface Sci 272(2):404–410

    Article  CAS  Google Scholar 

  9. Osborne MD, Girault HH (1994) Nafion® adsorption. J Electroanal Chem 370(1–2):287–293

    Article  CAS  Google Scholar 

  10. Zhang L, Kitazumi Y, Kakiuchi T (2011) Potential-dependent adsorption and transfer of poly(diallyldialkylammonium) ions at the nitrobenzene|water interface. Langmuir 27(21):13037–13042. doi:10.1021/la2028077

    Article  CAS  Google Scholar 

  11. Ulmeanu S, Hye Jin L, Girault HH (2001) Voltammetric characterisation of polyelectrolyte adsorption/transfer at the water. Electrochem Commun 3(10):539–543

    Article  CAS  Google Scholar 

  12. Katano H, Kameoka I, Murayama Y, Tatsumi H, Tsukatani T, Makino M (2004) Voltammetric study of the transfer of polyammonium ions at nitrobenzene/water interface. Anal Sci 20(11):1581–1586. doi:10.2116/analsci.20.1581

  13. Riva JS, Juarez AV, Beltramo DM, Yudi LM (2012) Interaction of Chitosan with mono and di-valent anions in aqueous solution studied by cyclic voltammetry at a water/1,2-dichloroethane interface. Electrochim Acta 59:39–44

    Article  CAS  Google Scholar 

  14. Riva JS, Bierbrauer K, Beltramo DM, Yudi LM (2012) Electrochemical study of the interfacial behavior of cationic polyelectrolytes and their complexation with monovalent anionic surfactants. Electrochim Acta 85:659–664

    Article  CAS  Google Scholar 

  15. Calderon M, Monzón LMA, Martinelli M, Juarez AV, Strumia MC, Yudi LM (2008) Electrochemical study of a dendritic family at the water/1,2-dichloroethane interface. Langmuir 24(12):6343–6350

    Article  CAS  Google Scholar 

  16. Herzog G, Flynn S, Johnson C, Arrigan DWM (2012) Electroanalytical behavior of poly-l-lysine dendrigrafts at the interface between two immiscible electrolyte solutions. Anal Chem 84(13):5693–5699. doi:10.1021/ac300856w

    Article  CAS  Google Scholar 

  17. Scanlon MD, Jennings E, Arrigan DWM (2009) Electrochemical behaviour of hen-egg-white lysozyme at the polarised water/1,2-dichloroethane interface. Phys Chem Chem Phys 11(13):2272–2280

    Article  CAS  Google Scholar 

  18. Samec Z, Trojánek A, Langmaier J, Samcová E (2003) Cyclic voltammetry of biopolymer heparin at PVC plasticized liquid membrane. Electrochem Commun 5(10):867–870. doi:10.1016/j.elecom.2003.08.009

    Article  CAS  Google Scholar 

  19. Guo J, Yuan Y, Amemiya S (2005) Voltammetric detection of heparin at polarized blood plasma/1,2-dichloroethane interfaces. Anal Chem 77(17):5711–5719. doi:10.1021/ac050833d

    Article  CAS  Google Scholar 

  20. Guo J, Amemiya S (2006) Voltammetric heparin-selective electrode based on thin liquid membrane with conducting polymer-modified solid support. Anal Chem 78(19):6893–6902. doi:10.1021/ac061003i

    Article  CAS  Google Scholar 

  21. Rodgers PJ, Jing P, Kim Y, Amemiya S (2008) Electrochemical recognition of synthetic heparin mimetic at liquid/liquid microinterfaces. J Am Chem Soc 130(23):7436–7442. doi:10.1021/ja800568q

    Article  CAS  Google Scholar 

  22. Jing P, Kim Y, Amemiya S (2009) Voltammetric extraction of heparin and low-molecular-weight heparin across 1,2-dichloroethane/water interfaces. Langmuir 25(23):13653–13660. doi:10.1021/la902336w

    Article  CAS  Google Scholar 

  23. Herzog G, Eichelmann-Daly P, Arrigan DWM (2010) Electrochemical behaviour of denatured haemoglobin at the liquid|liquid interface. Electrochem Commun 12(3):335–337. doi:10.1016/j.elecom.2009.12.020

    Article  CAS  Google Scholar 

  24. Herzog G, Nolan M-T, Arrigan DWM (2011) Haemoglobin unfolding studies at the liquid–liquid interface. Electrochem Commun 13(7):723–725. doi:10.1016/j.elecom.2011.04.020

    Article  CAS  Google Scholar 

  25. O’Sullivan S, Arrigan DWM (2012) Electrochemical behaviour of myoglobin at an array of microscopic liquid–liquid interfaces. Electrochim Acta 77:71–76. doi:10.1016/j.electacta.2012.05.070

    Article  Google Scholar 

  26. Kivlehan F, Lanyon YH, Arrigan DWM (2008) Electrochemical study of insulin at the polarized liquid–liquid interface. Langmuir 24(17):9876–9882. doi:10.1021/la800842f

    Article  CAS  Google Scholar 

  27. Amemiya S, Yang X, Wazenegger TL (2003) Voltammetry of the phase transfer of polypeptide protamines across polarized liquid/liquid interfaces. J Am Chem Soc 125(39):11832–11833. doi:10.1021/ja036572b

    Article  CAS  Google Scholar 

  28. Yuan Y, Amemiya S (2004) Facilitated protamine transfer at polarized water/1,2-dichloroethane interfaces studied by cyclic voltammetry and chronoamperometry at micropipet electrodes. Anal Chem 76(23):6877–6886. doi:10.1021/ac048879e

    Article  CAS  Google Scholar 

  29. Trojánek A, Langmaier J, Samcová E, Samec Z (2007) Counterion binding to protamine polyion at a polarised liquid–liquid interface. J Electroanal Chem 603(2):235–242. doi:10.1016/j.jelechem.2007.02.006

    Article  Google Scholar 

  30. Shinshi M, Sugihara T, Osakai T, Goto M (2006) Electrochemical extraction of proteins by reverse micelle formation. Langmuir 22(13):5937–5944. doi:10.1021/la060858n

    Article  CAS  Google Scholar 

  31. Méndez MA, Nazemi Z, Uyanik I, Lu Y, Girault HH (2011) Melittin adsorption and lipid monolayer disruption at liquid–liquid interfaces. Langmuir 27(22):13918–13924. doi:10.1021/la202970g

    Article  Google Scholar 

  32. Osakai T, Yuguchi Y, Gohara E, Katano H (2010) Direct label-free electrochemical detection of proteins using the polarized oil/water interface. Langmuir 26(13):11530–11537. doi:10.1021/la100769q

    Article  CAS  Google Scholar 

  33. Slevin CJ, Malkia A, Liljeroth P, Toiminen M, Kontturi K (2003) Electrochemical characterization of polyelectrolyte multilayers deposited at liquid–liquid interfaces. Langmuir 19(4):1287–1294. doi:10.1021/la0266841

    Article  CAS  Google Scholar 

  34. Hartvig RA, Méndez MA, Mvd Weert, Jorgensen L, Østergaard J, Girault HH, Jensen H (2010) Interfacial complexes between a protein and lipophilic ions at an oil–water interface. Anal Chem 82(18):7699–7705. doi:10.1021/ac101528r

    Article  CAS  Google Scholar 

  35. Riva JS, Iglesias R, Yudi LM (2013) Electrochemical adsorption of a cationic cellulosic polymer by ion pair formation at the interface between two immiscible electrolyte solutions. Electrochim Acta 107:584–591

    Article  CAS  Google Scholar 

  36. Riva JS, Beltramo DM, Yudi LM (2014) Adsorption–desorption mechanism of a cationic polyelectrolyte based on dimethylaminoethyl polymethacrylates at the water/1,2-dichloroethane interface. Electrochim Acta 115:370–377

    Article  CAS  Google Scholar 

  37. Cámara CI, Quiroga MVC, Wilke N, Jimenez-Kairuz A, Yudi LM (2013) Effect of chitosan on distearoylphosphatidylglycerol films at air/water and liquid/liquid interfaces. Electrochim Acta 94:124–133. doi:10.1016/j.electacta.2013.01.137

    Article  Google Scholar 

  38. Cámara CI, Yudi LM (2013) Potential-mediated interaction between dextran sulfate and negatively charged phospholipids films at air/water and liquid/liquid interfaces. Electrochim Acta 113:644–652. doi:10.1016/j.electacta.2013.09.137

    Article  Google Scholar 

  39. Santos HA, Manzanares JA, Murtomäki L, Kontturi K (2007) Thermodynamic analysis of binding between drugs and glycosaminoglycans by isothermal titration calorimetry and fluorescence spectroscopy. Eur J Pharm Sci 32(2):105–114. doi:10.1016/j.ejps.2007.06.003

    Article  CAS  Google Scholar 

  40. Bruce Alberts DB, Lewis J, Raff M, Roberts K, Watson JD (ed) (1996) Biología molecular de la célula. 3 edn, Barcelona

  41. Mercado FV, Maggio B, Wilke N (2011) Phase diagram of mixed monolayers of stearic acid and dimyristoylphosphatidylcholine. Effect of the acid ionization. Chem Phys Lipids 164(5):386–392. doi:10.1016/j.chemphyslip.2011.05.004

    Article  CAS  Google Scholar 

  42. Petrov JG, Pfohl T, Möhwald H (1999) Ellipsometric chain length dependence of fatty acid langmuir monolayers. A heads-and-tails model. J Phys Chem B 103(17):3417–3424. doi:10.1021/jp984393o

    Article  CAS  Google Scholar 

  43. Ducharme D, Max JJ, Salesse C, Leblanc RM (1990) Ellipsometric study of the physical states of phosphatidylcholines at the air-water interface. J Phys Chem 94(5):1925–1932

    Article  CAS  Google Scholar 

  44. Monzón LMA, Yudi LM (2006) Flunitrazepam effect on distearoylphosphatidylglycerol, cholesterol and distearoylphosphatidylglycerol + cholesterol mixed monolayers structure at a DCE/water interface. Electrochim Acta 51(22):4573–4581. doi:10.1016/j.electacta.2005.12.036

    Article  Google Scholar 

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Acknowledgments

Financial support from Consejo Nacional de Investigaciones Científicas y Tecnológicas (CONICET), Agencia Nacional de Promoción Científica y Tecnológica (FONCyT) and Secretaría de Ciencia y Técnica de la Universidad Nacional de Córdoba (SECyT) is gratefully acknowledged. J.S. Riva and C.I. Cámara thank CONICET for the fellowships awarded. L.M. Yudi and A.V. Juárez are members of the Research Career of CONICET.

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Authors and Affiliations

  1. INFIQC - Instituto de Investigaciones en Físico Química de Córdoba CONICET-UNC, Departamento de Físico Química, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, Ala 1, Pabellón Argentina, Ciudad Universitaria, X5000HUA, Córdoba, Argentina

    Julieta S. Riva, Candelaria I. Cámara, Ana V. Juarez & Lidia M. Yudi

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  1. Julieta S. Riva
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  2. Candelaria I. Cámara
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  3. Ana V. Juarez
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  4. Lidia M. Yudi
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Corresponding authors

Correspondence to Ana V. Juarez or Lidia M. Yudi.

Additional information

Julieta S. Riva and Candelaria I. Cámara have contributed equally to this work.

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Riva, J.S., Cámara, C.I., Juarez, A.V. et al. Electrochemical behaviour of cationic polyelectrolytes at a polarized liquid/liquid interface. J Appl Electrochem 44, 1381–1392 (2014). https://doi.org/10.1007/s10800-014-0747-2

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  • DOI: https://doi.org/10.1007/s10800-014-0747-2

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