Advertisement

Analytical and Bioanalytical Chemistry

, Volume 403, Issue 2, pp 601–611 | Cite as

Two-dimensional liquid chromatography of PDMS–PS block copolymers

  • Muhammad Imran MalikEmail author
  • Gareth W. Harding
  • Harald Pasch
Original Paper

Abstract

In this study, liquid chromatography at critical conditions of polystyrene (PS) and polydimethylsiloxane (PDMS) is used as the first dimension for the two-dimensional analysis of polydimethylsiloxane-block-polystyrene copolymers. Comprehensive two-dimensional liquid chromatography with size exclusion chromatography as the second dimension reveals information about the molar mass distributions of all separated fractions from the first dimension. Furthermore, fractions eluting at the critical conditions were collected and subjected to analysis in the second dimension at the critical adsorption point of the other block. These fractions were analyzed by Fourier transform infrared spectroscopy to determine their chemical compositions. The combination of the above approaches and the calibration of the evaporative light scattering detector for the first-dimension analysis yield deep insights into the molecular heterogeneity of the block copolymer samples. The composition of the samples and the chemical composition of the real block copolymer are also calculated by combining the results obtained at both critical conditions.

Keywords

Hybrid materials Block copolymers Critical adsorption point (CAP) Liquid chromatography at critical conditions (LCCC) Polydimethylsiloxane (PDMS) Polystyrene (PS) Two-dimensional liquid chromatography (2D-LC) FTIR 

Notes

Acknowledgments

MIM thanks the Claude Leon Foundation for a postdoctoral fellowship. The authors also extend their gratitude to Prof. Peter E. Mallon and Dr. Gareth M. Bayley for providing samples.

References

  1. 1.
    Jäkle F (2010) Chem Rev 110:3985CrossRefGoogle Scholar
  2. 2.
    Waterman R, Hayes PG, Tilley TD (2007) Acc Chem Res 40:712CrossRefGoogle Scholar
  3. 3.
    Segawa Y, Yamashita M, Nozaki K (2006) Science 314:113CrossRefGoogle Scholar
  4. 4.
    Welch GC, Juan RRS, Masuda JD et al (2006) Science 314:1124CrossRefGoogle Scholar
  5. 5.
    Peng Y, Ellis BD, Wang X et al (2009) Science 325:1668CrossRefGoogle Scholar
  6. 6.
    Braunschweig H, Herbst T, Rais D et al (2009) J Am Chem Soc 131:8989CrossRefGoogle Scholar
  7. 7.
    Hudnall TW, Chiu C-W, Gabbai FP (2009) Acc Chem Res 42:388CrossRefGoogle Scholar
  8. 8.
    Ro HW, Kim KJ, Theato P et al (2005) Macromolecules 38:1031CrossRefGoogle Scholar
  9. 9.
    Ndoni S, Vigild ME, Berg RH (2003) J Am Chem Soc 125:13366CrossRefGoogle Scholar
  10. 10.
    Takashi M, Seiji O, Tadashi U (2000) J Polym Sci Part B: Polym Phys 38:584CrossRefGoogle Scholar
  11. 11.
    Barton TJ, Bull LM, Klemperer WG et al (1999) Chem Mater 11:2633CrossRefGoogle Scholar
  12. 12.
    Somasundaran P, Mehta SC, Purohit P (2006) Adv Colloid Interface Sci 128–130:103CrossRefGoogle Scholar
  13. 13.
    Krulevitch P, Benett W, Hamilton J et al (2002) Biomed Microdevices 4:301CrossRefGoogle Scholar
  14. 14.
    Lebaron PC, Wang Z, Pinnavaia TJ (1999) Appl Clay Sci 15:11CrossRefGoogle Scholar
  15. 15.
    Mark JE (1996) J Macromol Sci Pure Appl Chem A 33:2005CrossRefGoogle Scholar
  16. 16.
    Chen X, Gardella JA, Kumler PL (1992) Macromolecules 25:6631CrossRefGoogle Scholar
  17. 17.
    Chen X, Gardella JA, Kumler PL (1993) Macromolecules 26:3778CrossRefGoogle Scholar
  18. 18.
    Chen J, Gardella JA Jr (1998) Macromolecules 31:9328CrossRefGoogle Scholar
  19. 19.
    Han JT, Xu X, Cho K (2005) Langmuir 21:6662CrossRefGoogle Scholar
  20. 20.
    Bayley GM, Mallon PE (2008) Polym Eng Sci 48:1923CrossRefGoogle Scholar
  21. 21.
    Swart M, Mallon PE (2009) Pure Appl Chem 81:495CrossRefGoogle Scholar
  22. 22.
    Miller PJ, Matyjaszewski K (1999) Macromolecules 32:8760CrossRefGoogle Scholar
  23. 23.
    Shinoda H, Miller, P J, Matyjaszewski K (2001) Macromolecules 34:3186Google Scholar
  24. 24.
    Shinoda H, Matyjaszewski K, Okrasa L et al (2003) Macromolecules 36:4772CrossRefGoogle Scholar
  25. 25.
    Matyjaszewski K, Xia JH (2001) Chem Rev 101:2921CrossRefGoogle Scholar
  26. 26.
    Matyjaszewski K, Wei M, Xia J et al (1998) Macromol Chem Phys 199:2289CrossRefGoogle Scholar
  27. 27.
    Brown DA, Price GJ (2001) Polymer 42:4767CrossRefGoogle Scholar
  28. 28.
    Harrod JF, Chalk AJ (1964) J Am Chem Soc 86:1776CrossRefGoogle Scholar
  29. 29.
    Sakaki S, Mizoe N, Sugimoto M (1998) Organometallics 17:2510CrossRefGoogle Scholar
  30. 30.
    Tezuka Y, Nobe S, Shiomi T (1995) Macromolecules 28:8251CrossRefGoogle Scholar
  31. 31.
    Bellas V, Iatrou H, Hadjichristidis N (2000) Macromolecules 33:6993CrossRefGoogle Scholar
  32. 32.
    Hamurcu EE, Baki H, Zülal M et al (1996) J Appl Polym Sci 62:1415CrossRefGoogle Scholar
  33. 33.
    Pavlović D, Linhardt JG, Künzler JF et al (2010) Macromol Chem Phys 211:1482CrossRefGoogle Scholar
  34. 34.
    Cvetkovska M, Coseva S, Buzarovska A et al (1996) Glas Hem Tehnol Maked 15:15Google Scholar
  35. 35.
    Falkenhagen J, Krüger R-P, Schulz G (2003) In: Jutzi P, Schubert US (eds) Silicon chemistry, pp 406. Wiley-VCH, Weinhem, GermanyGoogle Scholar
  36. 36.
    Macko T, Hunkeler D (2003) Adv Polym Sci 163:61Google Scholar
  37. 37.
    Pasch H, Trathnigg B (1999) Hplc of Polymers. Springer, BerlinGoogle Scholar
  38. 38.
    Adrian J, Esser E, Hellmann G et al (2000) Polymer 41:2439CrossRefGoogle Scholar
  39. 39.
    Trathnigg B, Gorbunov AA (2006) Macromol Symp 237:18CrossRefGoogle Scholar
  40. 40.
    Malik MI, Trathnigg B, Kappe CO (2007) Macromol Chem Phys 208:2510CrossRefGoogle Scholar
  41. 41.
    Malik MI, Ahmed H, Trathnigg B (2009) Anal Bioanal Chem 393:1797CrossRefGoogle Scholar
  42. 42.
    Malik MI, Trathnigg B, Kappe CO (2009) J Chromatogr A 1216:1167CrossRefGoogle Scholar
  43. 43.
    Malik MI, Trathnigg B, Kappe CO (2009) Eur Polym J 45:899CrossRefGoogle Scholar
  44. 44.
    Malik MI, Trathnigg B, Saf R (2009) J Chromatogr A 1216:6627CrossRefGoogle Scholar
  45. 45.
    Malik MI, Trathnigg B, Bartl K et al (2010) Anal Chim Acta 658:217CrossRefGoogle Scholar
  46. 46.
    Pasch H (2001) Macromol Symp 174:403CrossRefGoogle Scholar
  47. 47.
    Adler M, Rittig F, Becker S et al (2005) Macromol Chem Phys 206:2269CrossRefGoogle Scholar
  48. 48.
    Pasch H, Adler M, Rittig F et al (2005) Macromol Rapid Commun 26:438CrossRefGoogle Scholar
  49. 49.
    Knecht D, Rittig F, Lange RFM et al (2006) J Chromatogr A 1130:43CrossRefGoogle Scholar
  50. 50.
    Trathnigg B, Abrar S (2010) Procedia Chemistry 2:130CrossRefGoogle Scholar
  51. 51.
    Gorbunov AA, Vakhrushev AV (2010) J Chromatogr A 1217:4825CrossRefGoogle Scholar
  52. 52.
    Baran K, Laugier S, Cramail H (2001) J Chromatogr B 753:139CrossRefGoogle Scholar
  53. 53.
    Van Hulst M, Van Der Horst A, Kok WT et al (2010) J Sep Sci 33:1414CrossRefGoogle Scholar
  54. 54.
    Girod M, Phan TNT, Charles L (2008) Rapid Commun Mass Spectrom 22:3767CrossRefGoogle Scholar
  55. 55.
    Raust J-A, Brüll A, Moire C et al (2008) J Chromatogr A 1203:207CrossRefGoogle Scholar
  56. 56.
    Raust J-A, Houillot L, Save M et al (2010) Macromolecules 43:8755CrossRefGoogle Scholar
  57. 57.
    Mass V, Bellas V, Pasch H (2008) Macromol Chem Phys 209:2026CrossRefGoogle Scholar
  58. 58.
    Malik MI, Sinha P, Bayley GM et al (2011) Macromol Chem Phys 212:1221CrossRefGoogle Scholar
  59. 59.
    Chen J, Gardella JA (1998) Appl Spectrosc 52:361CrossRefGoogle Scholar
  60. 60.
    Trathnigg B, Ahmed H (2011) Anal Bioanal Chem 399:1523CrossRefGoogle Scholar
  61. 61.
    Berek D, Russ A (2006) Chem Pap 60:249CrossRefGoogle Scholar
  62. 62.
    Berek D (2010) Anal Bioanal Chem 396:421CrossRefGoogle Scholar

Copyright information

© Springer-Verlag 2012

Authors and Affiliations

  • Muhammad Imran Malik
    • 1
    • 2
    Email author
  • Gareth W. Harding
    • 1
  • Harald Pasch
    • 1
  1. 1.Department of Chemistry and Polymer ScienceUniversity of StellenboschMatielandSouth Africa
  2. 2.H.E.J. Research Institute of Chemistry, International Centre for Chemical and Biological Sciences (ICCBS)University of KarachiKarachiPakistan

Personalised recommendations