Abstract
The diffusional behavior of amphiphilic poly(2-oxazoline) diblock copolymers in aqueous solution is studied using photon correlation spectroscopy (PCS) and fluorescence correlation spectroscopy (FCS). The polymers were synthesized by living cationic polymerization and were fluorescence-labeled with tetramethyl rhodamine isothiocyanate either at the end of the hydrophilic or the hydrophobic block. Temperature-resolved PCS showed that, at room temperature, large metastable aggregates are present along with unimers and micelles. An annealing above ~40 °C resulted in stable equilibrium micellar solutions. By means of FCS, the hydrodynamic radii of the unimers and the micelles were measured simultaneously in a broad concentration range, and the critical micelle concentration could be determined. Comparison of the results from conventional PCS measurements with this first FCS study showed excellent agreement and the high potential of the FCS technique.
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References
Price C (1982) Colloidal properties of block copolymers. In: Goodmann I (ed) Developments in block copolymers, vol 1. Applied Science Publishers, London, pp 39–79
Riess G, Hurtrez G, Bahadur P (1985) Block copolymers. In: Mark HF, Bikales NM, Overberger CG, Menges G (eds.) Encylopedia of polymer sciences and engineering, vol. 2, 2nd edn. Wiley, New York, pp 324–434
Piirma I (1992) Polymeric surfactants. Surfactant sciences series 42. Marcel Dekker, New York
Tuzar Z, Kratochvíl P (1993) Micelles of block and graft copolymers in solution. In: E. Matijević (ed.) Surface and colloid science, vol 15. Plenum Press, New York, pp 1–83
Alexandridis P, Hatton TA (1996) Block copolymers. Polymeric materials encyclopedia 1. CRC Press, Boca Raton, pp 743–754
Webber SE, Munk P, Tuzar Z (1996) Solvents and self-organization of polymer. NATO ASI series, series E: applied sciences 327.Kluwer Academic Publisher
Hamley IW (1998) The physics of block copolymers. Oxford Science Publications, Oxford, chap 3, p 131
Alexandridis P, Lindman B (eds.) (2000), Amphiphilic block copolymers: self-assembly and applications. Elsevier, Amsterdam
Riess G (2003) Prog Polym Sci 28:1107
Hillmyer MA, Bates FS (1996) Macromolecules 29:6994
Allgaier J, Poppe A, Willner L, Richter D (1997) Macromolecules 30:1582
Hajduk DA, Kossuth MB, Hillmyer MA, Bates FS (1998) J Phys Chem B 102:4269
Förster S, Krämer E (1999) Macromolecules 32:2783
Discher BM, Won YY, Ege DS, Lee JCM, Bates FS, Discher DS Hammer DA (1999) Science 284:1143
Förster S, Berton B, Hentze H-P, Krämer E, Antonietti M, Lindner P (2001) Macromolecules 34:4610
Dimova R, Seifert U, Pouligny B, Förster S, Döbereiner H-G (2002) Eur Phys J E 7:241
Haluska CK, Góźdź WT, Döbereiner H-G, Förster S, Gompper G (2002) Phys Rev Lett 89:238302
Castelletto V, Hamley IW, Holmqvist P, Rekatas C, Booth C, Grossmann JG (2001) Colloid Polym Sci 279:621
Litt M, Rahl F, Roldan LG (1969) J Polym Sci A-2 7:463
Aoi K, Okada M (1996) Prog Polym Sci 21:151
Kobayashi S (1990) Prog Polym Sci 15:752
Jordan R, Martin K, Räder HJ, Unger KK (2001) Macromolecules 38:8858
Kobayashi S, Uyama H (2002) J Polym Sci A Polym Chem 40:192
Velander WH, Madurawe RD, Subramanian A, Kumar G, Sinai-Zingde G, Riffle JS, Orthner CL (1992) Biotech Bioeng 39:1024
Woodle MC, Engbers CM, Zalipsky S (1994) Bioconjugate Chem 5:493
Lasic DD, Needham D (1995) Chem Rev 95:2601
Zalipsky S, Hansen CB, Oaks JM, Allen TM (1996) J Pharm Sci 85:133
Purrucker O, Förtig A, Jordan R, Tanaka M (2004) Chem Phys Chem 5:327
Persigehl P, Jordan R, Nuyken O (2000) Macromolecules 33:6977
Kotré T, Nuyken O, Weberskirch R (2002) Macromol Rapid Commun 23:871
Krause JO, Zarka MT, Anders U, Weberskirch R, Nuyken O, Buchmeiser MR (2003) Angew Chemie Int Ed 42:5965
Zarka MT, Nuyken O, Weberskirch R (2003) Chem Eur J 9:3228
Nuyken O, Weberskirch R, Kotré T, Schönfelder D, Wörndle A (2003) Polymers for micellar catalysis. In: Buchmeiser M (Ed) Polymeric materials in organic synthesis and catalysis. Wiley-VCH, Weinheim, p 277
Heischkel Y, Stoeckel N, Nuyken O, Jordan R (2003) PCT Int Appl. BASF Aktiengesellschaft, Germany. Wo 2003, p 32
Evans DF, Wennerström H (1999) The colloidal domain. Wiley-VCH, p 173–217
Khougaz K, Gao Z, Eisenberg A (1994) Macromolecules 27:6241
Nivaggioli T, Alexandridis P, Hatton TA, Yekta A, Winnik MA (1994) Langmuir 11:730
Procházka K, Limpouchová Z, Webber SE (1996) Block copolymer micelles. 2. Fluorimetric studies and computer modeling. In: Salamone JA (ed) Polymeric materials encyclopedia, vol 1 A-B. CRC Press, Boca Raton, pp 764–772
Schuch H, Klingler J, Rossmanith P, Frechen T, Gerst M, Feldthusen J, Müller AHE (2000) Macromolecules 33:1734
Jada A, Hurtrez G, Siffert B, Riess G (1996) Macromol Chem Phys 197:3697 and references therein
Wanka G, Hoffmann H, Ulbricht W (1994) Macromolecules 27:4145
Glatter O, Scherf G, Schillén K, Brown W (1994) Macromolecules 27:6046
Hecht E, Mortensen K, Hoffmann H (1995) Macromolecules 28:5465
Zhang K, Khan A (1995) Macromolecules 28:3807
Mortensen K, Brown W, Nordén B (1992) Phys Rev Lett 68:2340
Mortensen K (1993) J Phys IV 3:157
Mortensen K (1996) J Phys Condens Matter 8:A103
Förster S, Hermsdorf N, Böttcher C, Lindner P (2002) Macromolecules 35:4096
Brown W, Schillén K, Hvidt S (1992) J Phys Chem 96:6038
Brown W, Schillén K, Almgren M, Hvidt S, Bahadur P (1992) J Phys Chem 95:6038
Fleischer G (1993) J Phys Chem 97:517
Schillén K, Brown W, Johnsen RM (1994) Macromolecules 27:4825
Mortensen K, Brown W, Jørgensen E (1994) Macromolecules 27:5654
Scheller H, Fleischer G, Kärger J (1997) Colloid Polym Sci 275:730
Hvidt S, Jørgensen EB, Brown W, Schillén K (1994) J Phys Chem 98:12320
Nyström B, Walderhaug H (1996) J Phys Chem 100:5433
Hvidt S (1995) Colloids Surf 112:201
Elson EL, Magde D (1974) Biopolymers 13:1
Magde D, Elson EL, Webb WW (1974) Biopolymers 13:29
Webb WW (1976) Q Rev Biophys 9:49
Rigler R, Elson E (ed) (2000) Fluorescence correlation spectroscopy. Theory and applications. Springer, Berlin Heidelberg New York
Hess ST, Huang S, Heikal AA, Webb WW (2002) Biochemistry 41:697
Riesner D (2000) Protein aggregation associated with Alzheimer and Prion diseases. In: Rigler R, Elson E (eds) Fluorescence correlation spectroscopy. Theory and applications. Springer, Berlin Heidelberg New York, pp 225–250
Sevenich FW, Langowski J, Weiss V, Rippe K (1998) Nucleic Acids Res 26:1373
Sukhishvili SA, Chen Y, Müller JD, Gratton E, Schweizer KS, Granick S (2000) Nature 406:146
Erhardt R, Böker A, Zettl H, Kaya H, Pyckhout-Hintzen W, Krausch G, Abetz V, Müller AHE (2001) Macromolecules 34:1069
Komenda T, Jordan R (2003) Polym Prepr (Am Chem Soc Div Polym Chem) 44:986
Jakeš J (1995) Coll Czech Chem Commun 60:1781
http://www.fki.uu.se/robert.johnsen/gendist.htm
Widengren J, Mets Ü, Rigler R (1995) J Phys Chem 99:13368
Nuyken O, Maier G, Gross A, Fischer H (1996) Macromol Chem Phys 197:83
Aicher TD, Anderson RC, Gao J, Shetty SS, Coppola GM, Stanton JL, Knorr DC, Sperbeck DM, Brand LJ, Vinluan CC, Kaplan EL, Dragland CJ, Tomaselli HC, Islam A, Lozito RJ, Liu X, Maniara WM, Fillers WS, DelGrande D, Walter RE, Mann WR (2000) J Med Chem 43:236
Stejskal J, Koňák Č, Helmstedt M, Kratochvíl P (1993) Collect Czech Chem Commun 58:2282
Munk P (1996) Equilibrium and nonequilibrium micelles. In: Webber SE, Munk P, Tuzar Z (eds) Solvents and self-organization of polymer. NATO, ASI series, series E: Applied sciences, vol 327. Kluwer Academic Publisher (Dordrecht), pp 19–32
Bassiri TG, Levy A, Litt M (1969) J Polym Sci B 43:871
Litt M, Rahl F, Roldan LG (1969) J Polym Sci A-2 7:463
Estimated using CS Chem 3D ultra 7.0.0
Kärger J, Fleischer G, Roland U (1998) PFG NMR studies of anomalous diffusion. In: Kärger J, Heitjans P, Haberlandt R (eds) Diffusion in condensed matter. Friedr Vieweg & Sohn, pp 144–168
Siqueira DF, Nunes SP, Wolf BA (1994) Macromolecules 27:4561
Langowski J, Wachsmuth M, Rippe K, Tewes M (2000) Biomolecular shape and interactions determined by fluorescence correlation spectroscopy. In: Frénoy J-P (ed) Energies et Forces de l’Interaction entre Macromolécules Biologiques: l’Aspect Quantitatif, vol. 2, Publications CNRS, Paris, pp 65–77
Acknowledgements
We wish to thank F. Kremer, Fakultät für Physik und Geowissenschaften, Universität Leipzig, for financial support and fruitful discussions and U. Hahn, A. Beck-Sickinger, and T. Greiner-Stöffele, Fakultät für Biowissenschaften, Pharmazie und Psychologie, Universität Leipzig, for providing the FCS instrument and for help with the measurements. We also gratefully acknowledge financial support by the Deutsche Forschungsgemeinschaft, by the European Union under a Marie Curie Training Site program (contract No. HPMT-CT-2001-00396) and by the Grant Agency of the Academy of Sciences of the Czech Republic (grant No. 4050403).
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Dedicated to Prof. Dr. Erhard W. Fischer on the occasion of his 75th birthday
An erratum to this article can be found at http://dx.doi.org/10.1007/s00396-004-1196-y
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Bonné, T.B., Lüdtke, K., Jordan, R. et al. Aggregation behavior of amphiphilic poly(2-alkyl-2-oxazoline) diblock copolymers in aqueous solution studied by fluorescence correlation spectroscopy. Colloid Polym Sci 282, 833–843 (2004). https://doi.org/10.1007/s00396-004-1131-2
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DOI: https://doi.org/10.1007/s00396-004-1131-2