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Pyrene-Labeled Water-Soluble Macromolecules as Fluorescent Mimics of Associative Thickeners

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Fluorescence Studies of Polymer Containing Systems

Part of the book series: Springer Series on Fluorescence ((SS FLUOR,volume 16))

Abstract

The strong hydrophobicity of the chromophore pyrene combined with its ability to form an excimer has led to its use as a fluorescent replacement of the hydrophobes typically used in associative thickeners to prepare water-soluble polymers (WSPs) labeled with a small number of pyrene pendants to yield pyrene-labeled WSPs (Py-WSPs). Since the kinetics of excimer formation by diffusion are coupled, the fluorescence decays of the pyrene monomer and excimer can be analyzed globally to assess the fraction of pyrene labels that are isolated in solution and form excimer by diffusion and the fraction (f agg) of pyrenes that are pre-associated and form excimer instantaneously upon direct absorption of a photon. This review describes how new developments in the global analysis of the fluorescence decays of the pyrene monomer and excimer of Py-WSP aqueous solutions yield quantitative information about the associative strength f agg of Py-WSP. Most importantly for fluorescent mimics of associative thickeners, the review describes the viscoelastic behavior of a series of pyrene-labeled hydrophobically modified alkali swellable emulsion copolymers. Based on the viscoelasticity results, Py-WSPs appear to be excellent fluorescent mimics of non-fluorescent commercial associative thickeners, displaying similar behavior in terms of massive shear thinning and increase in zero-shear viscosity with polymer concentration. Consequently, the experiments described in this review provide a solid foundation for the characterization of the behavior of Py-WSP in aqueous solution by both fluorescence and rheology measurements.

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References

  1. Glass JE (ed) (1989) Polymers in aqueous media: performance through Association Advances in chemistry series 226. American Chemical Society, Washington, DC

    Google Scholar 

  2. Schulze DN, Glass JE (eds) (1991) Polymers as rheology modifiers; ACS symposium series 462. American Chemical Society, Washington, DC

    Google Scholar 

  3. Kwak JCT (ed) (1998) Polymer-surfactant systems; Surfactant science series 77. Dekker, New York

    Google Scholar 

  4. Goddard EO, Ananthapadamanabham KP (eds) (1993) Interactions of surfactants with polymers and proteins. CRC Press, Boca Raton, FL

    Google Scholar 

  5. Winnik MA, Yekta A (1997) Associative polymers in aqueous solution. Curr Opin Colloid Interface Sci 2:424–436

    Article  CAS  Google Scholar 

  6. Glass JE (2001) A perspective on the history of and current research in surfactant-modified, water-soluble polymers. J Coat Technol 73:79–98

    Article  CAS  Google Scholar 

  7. Da GM,M, Burrows HD, Lindman B (2002) Polymer-surfactant association as seen by fluorescence. Progr Colloid Polym Sci 120:13–22

    Article  Google Scholar 

  8. Tam KC, Wyn-Jones E (2006) Insights on polymer surfactant complex structures during the binding of surfactants to polymers as measured by equilibrium and structural techniques. Chem Soc Rev 35:693–709

    Article  CAS  Google Scholar 

  9. Annabale T, Buscall R, Ettelaie R, Whittlestone D (1993) The rheology of solutions of associating polymers: comparison of experimental behavior with transient network theory. J Rheol 37:695–726

    Article  Google Scholar 

  10. Lundberg DJ, Glass JE, Eley RR (1991) Viscoelastic behaviour among HEUR thickeners. J Rheol 35:1255–1274

    Article  CAS  Google Scholar 

  11. Zhao G, Khin CC, Chen SB (2005) Nonionic surfactant and temperature effects on the viscosity of hydrophobically modified hydroxyethyl cellulose solutions. J Phys Chem B 109:14198–14204

    Article  CAS  Google Scholar 

  12. Glass JE (1999) Adsorption of hydrophobically modified, ethoxylated urethane thickeners on latex and titanium dioxide disperse phases. Adv Colloid Interface Sci 79:123–148

    Article  CAS  Google Scholar 

  13. Magny B, Iliopoulos I, Zana R, Audebert R (1994) Mixed micelles formed by cationic surfactants and anionic hydrophobically modified polyelectrolytes. Langmuir 10:3180–3187

    Article  CAS  Google Scholar 

  14. Ringsdorf H, Venzmer J, Winnik FM (1991) Fluorescence studies of hydrophobically modified poly(N-isopropylacrylamide) or how to play accordion on a liposome. Makromol Chem Macromol Symp 46:427–431

    Article  CAS  Google Scholar 

  15. Annabale T, Buscall R, Ettelaie R, Shepherd P, Whittlestone D (1994) Influence of surfactants on the rheology of associating polymers in solution. Langmuir 10:1060–1070

    Article  Google Scholar 

  16. Jiménez-Regalado E, Selb J, Candau F (2000) Effect of surfactant on the viscoelastic behavior of semidilute solutions of multisticker associating polyacrylamides. Langmuir 16:8611–8621

    Article  Google Scholar 

  17. Tripathi A, Tam KC, McKinley GH (2006) Rheology and dynamics of associative polymers in shear and extension: theory and experiments. Macromolecules 39:1981–1999

    Article  CAS  Google Scholar 

  18. Dai S, Tam KC, Wyn-Jones E, Jenkins RD (2004) Isothermal titration calorimetry and electromotive forces studies on binding interactions of hydrophobic ethoxylated urethane and sodium dodecyl sulfate of different molecular masses. J Phys Chem B 108:4979–4988

    Article  CAS  Google Scholar 

  19. Chassenieux C, Nicolai T, Durand D (1997) Association of hydrophobically end-capped poly(ethylene oxide). Macromolecules 30:4952–4958

    Article  CAS  Google Scholar 

  20. Yekta A, Xu B, Duhamel J, Adiwidjaja H, Winnik MA (1995) Fluorescence studies of associating polymers in water. Determination of the chain-end aggregation number and a model for the association process. Macromolecules 28:956–966

    Article  CAS  Google Scholar 

  21. Beaudoin E, Borisov O, Lapp A, Billon L, Hiorns RC, François J (2002) Neutron scattering of hydrophobically modified poly(ethylene oxide) in aqueous solutions. Macromolecules 35:7436–7447

    Article  CAS  Google Scholar 

  22. Volpert E, Selb J, Candau F (1996) Influence of the hydrophobe structure on composition, microstructure, and rheology in associating polyacrylamides prepared by micellar copolymerization. Macromolecules 29:1452–1463

    Article  CAS  Google Scholar 

  23. Candau F, Regalado EJ, Selb J (1998) Scaling behaviour of the zero-shear viscosity of hydrophobically modified polyacrylamides. Macromolecules 31:5550–5552

    Article  CAS  Google Scholar 

  24. Regalado EJ, Selb J, Candau F (1999) Viscoelastic behavior of semidilute solutions of multisticker polymer chains. Macromolecules 32:8580–8588

    Article  CAS  Google Scholar 

  25. Morishima Y, Nomura S, Ikeda T, Seki M, Kamachi M (1995) Characterization of unimolecular micelles of random copolymers of sodium 2-(Acrylamido)-2-methylpropanesulfonate and methacrylamides bearing bulky hydrophobic substituents. Macromolecules 28:2874–2881

    Article  CAS  Google Scholar 

  26. Sheng WP, Tam KC, Jenkins RD, Bassett DR (2000) Calorimetric studies of model hydrophobically modified alkali-soluble emulsion polymers with varying spacer chain length in ionic surfactant solutions. Macromolecules 33:1727–1733

    Article  Google Scholar 

  27. Winnik FM (1993) Photophysics of preassociated pyrenes in aqueous polymer solutions and in other organized media. Chem Rev 93:587–614

    Article  CAS  Google Scholar 

  28. Siddique B, Duhamel J (2011) Effect of polypeptide sequence on polypeptide self-assembly. Langmuir 27:6639–6650

    Article  CAS  Google Scholar 

  29. Winnik FM, Regismond STA (1996) Fluorescence methods in the study of the interactions of surfactants with polymers. Colloids Surf A: Physicochem Eng Aspects 118:1–39

    Article  CAS  Google Scholar 

  30. Duhamel J (2012) Internal dynamics of dendritic molecules probed by pyrene excimer formation. Polymers 4:211–239

    Article  CAS  Google Scholar 

  31. Birks JB, Dyson DJ, Munro IH (1963) ‘Excimer’ fluorescence. II. Lifetime studies of pyrene solutions. Proc R Soc A 275:575–588

    Article  CAS  Google Scholar 

  32. Duhamel J (2006) Polymer chain dynamics in solution probed with a fluorescence Blob model. Acc Chem Res 39:953–960

    Article  CAS  Google Scholar 

  33. Duhamel J (2012) New insights in the study of pyrene excimer fluorescence to characterize macromolecules and their supramolecular assemblies in solution. Langmuir 28:6527–6538

    Article  CAS  Google Scholar 

  34. Duhamel J (2014) Global analysis of fluorescence decays to probe the internal dynamics of fluorescently labeled macromolecules. Langmuir 30:2307–2324

    Article  CAS  Google Scholar 

  35. James DR, Ware WR (1985) A Fallacy in the interpretation of fluorescence decay parameters. Chem Phys Lett 120:455–459

    Article  CAS  Google Scholar 

  36. Mathew A, Siu H, Duhamel J (1999) A Blob model to study chain folding by fluorescence. Macromolecules 32:7100–7108

    Article  CAS  Google Scholar 

  37. Siu H, Duhamel J (2005) Comparison of the association level of a hydrophobically modified associative polymer obtained from an analysis based on two different models. J Phys Chem B 109:1770–1780

    Article  CAS  Google Scholar 

  38. Seixas de Melo J, Costa T, Francisco A, Maçanita AL, Gago S, Gonçalves IS (2007) Phys Chem Chem Phys 9:1370–1385

    Article  CAS  Google Scholar 

  39. Seixas de Melo J, Costa T, Miguel MG, Lindman B, Schillén KJ (2003) Phys Chem 107:12605–12621

    Article  CAS  Google Scholar 

  40. Zachariasse KA, Busse R, Duveneck G, Kühnle W (1985) Intramolecular monomer and excimer fluorescence with dipyrenylpropanes: double-exponential versus triple-exponential decays. J Photochem 28:237–253

    Article  CAS  Google Scholar 

  41. Fowler MA, Duhamel J, Bahun GJ, Adronov A, Zaragoza-Galán G, Rivera E (2012) Studying pyrene-labeled macromolecules with the model free analysis. J Phys Chem B 116:14689–14699

    Article  CAS  Google Scholar 

  42. Char K, Frank CW, Gast AP (1989) Consideration of hydrophobic attractions in end-to-end cyclization. Macromolecules 22:3177–3180

    Article  CAS  Google Scholar 

  43. Lee S, Duhamel J (1998) Monitoring the hydrophobic interactions of internally pyrene-labeled poly(ethylene oxide)s in water by fluorescence spectroscopy. Macromolecules 31:9193–9200

    Article  CAS  Google Scholar 

  44. Chen S, Duhamel J (2013) Probing the hydrophobic interactions of a series of pyrene end-labeled poly(ethylene oxide)s in aqueous solution using time-resolved fluorescence. Langmuir 29:2821–2834

    Article  CAS  Google Scholar 

  45. Kanagalingam S, Ngan CF, Duhamel J (2002) Effect of solvent quality on the level of association and encounter kinetics of hydrophobic pendants covalently attached onto a water-soluble polymer. Macromolecules 35:8560–8570

    Article  CAS  Google Scholar 

  46. Prazeres TJV, Beingessner R, Duhamel J, Olesen K, Shay G, Bassett DR (2001) Characterisation of the association level of pyrene-labelled HASEs by fluorescence. Macromolecules 34:7876–7884

    Article  CAS  Google Scholar 

  47. Prazeres TJV, Duhamel J, Olesen K, Shay G (2005) Correlations between the viscoelastic behavior of pyrene-labeled associative polymers and the associations of their fluorescent hydrophobes. J Phys Chem B 109:17406–17416

    Article  CAS  Google Scholar 

  48. Siu H, Duhamel J (2004) Global analysis of the fluorescence decays of a pyrene-labelled polymer using a blob model. Macromolecules 37:9287–9289

    Article  CAS  Google Scholar 

  49. Siu H, Duhamel J (2005) The importance of considering non-fluorescent pyrene aggregates for the study of pyrene-labeled associative thickeners by fluorescence. Macromolecules 38:7184–7186

    Article  CAS  Google Scholar 

  50. Siu H, Duhamel J (2006) Associations between a pyrene-labeled hydrophobically modified alkali swellable emulsion copolymer and sodium dodecyl sulfate probed by fluorescence, surface tension, and rheology. Macromolecules 39:1144–1155

    Article  CAS  Google Scholar 

  51. Chen S, Siu H, Duhamel J (2014) Interactions between hydrophobically modified alkali-swellable emulsion polymers and sodium dodecyl sulfate probed by fluorescence and rheology. J Phys Chem B 118:351–361

    Article  CAS  Google Scholar 

  52. Siu H, Duhamel J, Sasaki D, Pincus JL (2010) Nanodomain formation in lipid membranes probed by time-resolved fluorescence. Langmuir 26:10985–10994

    Article  CAS  Google Scholar 

  53. Siu H, Prazeres TJV, Duhamel J, Olesen K, Shay G (2005) Characterization of the aggregates made by short poly(ethylene oxide) chains labelled at one end with the dye pyrene. Macromolecules 38:2865–2875

    Article  CAS  Google Scholar 

  54. Costa T, Seixas de Melo J, Burrows HD (2009) Fluorescence behavior of a pyrene-end-capped poly(ethylene oxide) in organic solvents and in dioxane-water mixtures. J Phys Chem B 113:618–626

    Article  CAS  Google Scholar 

  55. Costa T, Seixas de Melo J, Migeul MD, Lindman B, Schillén K (2009) Complex formation between a fluorescently-labeled polyelectrolyte and a triblock copolymer. J Phys Chem B 113:6205–6214

    Article  CAS  Google Scholar 

  56. Costa T, Seixas de Melo JS, Castro CS, Gago S, Pillinger M, Gonçalves IS (2010) Picosecond dynamics of dimer formation in a pyrene labeled polymer. J Phys Chem B 114:12439–12447

    Article  CAS  Google Scholar 

  57. Keyes-Baig C, Duhamel J, Wettig S (2011) Characterization of the behavior of a pyrene substituted Gemini surfactant in water by fluorescence. Langmuir 27:3361–3371

    Article  CAS  Google Scholar 

  58. Yip J, Duhamel J, Bahun G, Adronov A (2010) A study of the branch ends of a series of pyrene-labeled dendrimers based on pyrene excimer formation. J Phys Chem B 114:10254–10265

    Article  CAS  Google Scholar 

  59. Chen S, Duhamel J, Bahun G, Adronov A (2011) Effect of fluorescent impurities in the study of pyrene-labeled macromolecules by fluorescence. J Phys Chem B 115:9921–9929

    Article  CAS  Google Scholar 

  60. Malinovskii VL, Wenger D, Häner R (2010) Nucleic acid-guided assembly of aromatic chromophores. Chem Soc Rev 39:410–422

    Article  CAS  Google Scholar 

  61. Østergaard ME, Hrdlicka PJ (2011) Pyrene-functionalized oligonucleotides and locked nucleic acids (LNAs): tools for fundamental research, diagnostics, and nanotechnology. Chem Soc Rev 40:5771–5788

    Article  Google Scholar 

  62. Bains G, Patel AB, Narayanaswami V (2011) Pyrene: a probe to study protein conformation and conformational changes. Molecules 16:7909–7935

    Article  CAS  Google Scholar 

  63. Richey B, Kirk AB, Eisenhart EK, Fitzwater S, Hook J (1991) Interactions of associative thickeners with paint components as studied by the use of a fluorescently labeled model thickener. J Coat Technol 63:31–40

    CAS  Google Scholar 

  64. Cheung S-T, Winnik MA, Redpath AEC (1982) The effects of solvent on end-to-end cyclization of poly(ethylene oxide) probed by intramolecular pyrene excimer formation. Makromol Chem 183:1815–1824

    Article  CAS  Google Scholar 

  65. Char K, Gast AP, Frank CW (1988) Fluorescence studies of polymer adsorption. I. Rearrangement and displacement of pyrene-terminated poly(ethylene glycol) on colloidal silica particles. Langmuir 4:989–998

    Article  CAS  Google Scholar 

  66. Char K, Frank CW, Gast AP (1989) Fluorescence studies of polymer adsorption. 3. Adsorption of pyrene-end-labeled poly(ethylene glycol) on colloidal polystyrene particles. Langmuir 5:1335–1340

    Article  CAS  Google Scholar 

  67. Quina F, Abuin E, Lissi E (1990) Effect of pyrene chain end labeling on the interaction of poly(ethylene oxide) with sodium dodecyl sulfate in aqueous solution. Macromolecules 23:5173–5175

    Article  CAS  Google Scholar 

  68. Hu Y-Z, Zhao C-L, Winnik MA, Sundararajan PR (1990) Fluorescence studies of the interaction of sodium dodecyl sulfate with hydrophobically modified poly(ethylene oxide). Langmuir 6:880–883

    Article  CAS  Google Scholar 

  69. Duhamel J, Yekta A, Hu Y, Winnik MA (1992) Evidence for intramolecular hydrophobic association in aqueous solutions of pyrene end-capped poly(ethylene oxide). Macromolecules 25:7024–7030

    Article  CAS  Google Scholar 

  70. Chen S, Duhamel J, Winnik MA (2011) Probing end-to-end cyclization beyond Willemski and Fixmann. J Phys Chem B 115:3289–3302

    Article  CAS  Google Scholar 

  71. Siu H, Duhamel J (2008) Molar extinction coefficient of pyrene aggregates in water. J Phys Chem B 112:15301–15312

    Article  CAS  Google Scholar 

  72. Siu H, Duhamel J (2012) Molar absorption coefficient of pyrene aggregates in water generated by a poly(ethylene oxide) capped at a single end with pyrene. J Phys Chem B 116:1226–1233

    Article  CAS  Google Scholar 

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Acknowledgements

Although all former and present graduate students from the Duhamel laboratory contributed to some extent in the work described in this review, I would like to extend a special thanks to Drs. Sabesh Kanagalingam, Telmo Prazeres, Howard Siu, Christine Keyes, and Shaohua Chen on whose contributions this review was mostly based. Also, none of this work could have been carried out without the generous funding of the Natural Science and Engineering Research Council of Canada.

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  1. Department of Chemistry, Institute for Polymer Research, Waterloo Institute for Nanotechnology, University of Waterloo, Waterloo, ON, Canada, N2L 3G1

    Jean Duhamel

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  1. Jean Duhamel
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Correspondence to Jean Duhamel .

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  1. Faculty of Science, Charles University in Prague, Prague 2, Czech Republic

    Karel Procházka

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Duhamel, J. (2016). Pyrene-Labeled Water-Soluble Macromolecules as Fluorescent Mimics of Associative Thickeners. In: Procházka, K. (eds) Fluorescence Studies of Polymer Containing Systems. Springer Series on Fluorescence, vol 16. Springer, Cham. https://doi.org/10.1007/978-3-319-26788-3_7

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