Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science
RESEARCH FRONT

RAFT Polymer End-Group Modification and Chain Coupling/Conjugation Via Disulfide Bonds

Cyrille Boyer A , Jingquan Liu A , Volga Bulmus B C and Thomas P. Davis A C
+ Author Affiliations
- Author Affiliations

A Centre for Advanced Macromolecular Design (CAMD), School of Chemical Sciences and Engineering, The University of New South Wales, Sydney, NSW 2052, Australia.

B School of Biotechnology and Biomolecular Sciences (BABS), The University of New South Wales, Sydney, NSW 2052, Australia.

C Corresponding authors. Email: t.davis@unsw.edu.au; vbulmus@unsw.edu.au

Australian Journal of Chemistry 62(8) 830-847 https://doi.org/10.1071/CH09062
Submitted: 30 January 2009  Accepted: 25 March 2009   Published: 13 August 2009

Abstract

End-group modification of polymers prepared by reversible addition–fragmentation chain transfer (RAFT) polymerization was accomplished by the conversion of trithiocarbonate or dithioester end-groups into a pyridyl disulfide (PDS) functionality. Several different polymers, such as poly(methyl methacrylate), polystyrene, poly(oligoethylene glycol-acrylate), poly(hydroxypropylacrylamide), and poly(N-isopropylacrylamide) were prepared by RAFT polymerization, and subjected to aminolysis in the presence of 2,2′-dithiodipyridine to yield thiol-terminated polymers with yields in the range 65–90% dependent on the polymer structure. Furthermore, this PDS end-group was utilized to generate higher-order architectures, such as diblock copolymers with high yields and selectively. In addition, the PDS end-groups were used for the bioconjugation of different biomolecules, such as oligonucleotides, carbohydrates, and peptides. The successful modification of well-defined polymers was confirmed by a combination of UV-vis, NMR spectroscopy, and gel permeation chromatography.


Acknowledgements

We acknowledge the Australian Research Council for the award of Discovery Grants (to V.B. and T.P.D.). In addition, we acknowledge the receipt of a Federation Fellowship (T.P.D.).


References


[1]   G. Moad, E. Rizzardo, S. H. Thang, Polymer 2008, 49,  1079.
        | CrossRef |   

[2]   L. Barner, C. Barner-Kowollik, T. P. Davis, M. H. Stenzel, Aust. J. Chem. 2004, 57,  19.
        | CrossRef |   

[3]   L. Barner, T. P. Davis, M. H. Stenzel, C. Barner-Kowollik, Macromol. Rapid Commun. 2007, 28,  539.
        | CrossRef |   

[4]   S. Perrier, P. Takolpuckdee, J. Polym. Sci., Part A: Polym. Chem. 2005, 43,  5347.
        | CrossRef |   

[5]   S. Perrier, P. Takolpuckdee, C. A. Mars, Macromolecules 2005, 38,  2033.
        | CrossRef |   

[6]   B. Boutevin, C. Boyer, G. David, P. Lutz, Macromol. Eng. 2007, 2,  775.
         

[7]   B. Boutevin, G. David, C. Boyer, Adv. Polym. Sci. 2007, 206,  31.
        | CrossRef |   

[8]   A. B. Lowe, C. L. McCormick, Prog. Polym. Sci. 2007, 32,  283.
        | CrossRef |   

[9]   A. W. York, S. E. Kirkland, C. L. McCormick, Adv. Drug Delivery Rev. 2008, 60,  1018.
        | CrossRef |   

[10]   A. J. Convertine, B. S. Lokitz, Y. Vasileva, L. J. Myrick, C. W. Scales, A. B. Lowe, C. L. McCormick, Macromolecules 2006, 39,  1724.
        | CrossRef |   

[11]   M. H. Stenzel, T. P. Davis, Aust. J. Chem. 2003, 56,  1035.
        | CrossRef |   

[12]   M. H. Stenzel, T. P. Davis, C. Barner-Kowollik, Chem. Commun. 2004,  1546.
        | CrossRef |   

[13]   M. H. Stenzel, T. P. Davis, A. G. Fane, J. Mater. Chem. 2003, 13,  2090.
        | CrossRef |   

[14]   T. S. C. Pai, C. Barner-Kowollik, T. P. Davis, M. H. Stenzel, Polymer 2004, 45,  4383.
        | CrossRef |   

[15]   X. Hao, M. H. Stenzel, C. Barner-Kowollik, T. P. Davis, E. Evans, Polymer 2004, 45,  7401.
        | CrossRef |   

[16]   M. Hales, C. Barner-Kowollik, T. P. Davis, M. H. Stenzel, Langmuir 2004, 20,  10809.
        | CrossRef |   

[17]   L. Albertin, M. H. Stenzel, C. Barner-Kowollik, L. J. R. Foster, T. P. Davis, Macromolecules 2005, 38,  9075.
        | CrossRef |   

[18]   E. Min, K. H. Wong, M. H. Stenzel, Adv. Mater. 2008, 20,  3550.
        | CrossRef |   

[19]   B. S. Sumerlin, A. B. Lowe, P. A. Stroud, P. Zhang, M. W. Urban, C. L. McCormick, Langmuir 2003, 19,  5559.
        | CrossRef |   

[20]   B. S. Lokitz, J. E. Stempka, A. W. York, Y. Li, H. K. Goel, G. R. Bishop, C. L. McCormick, Aust. J. Chem. 2006, 59,  749.
        | CrossRef |   

[21]   Barner L., Perrier S., Polymers with Well-defined End Groups via RAFT—Synthesis, Applications and Postmodifications, in Handbook of RAFT Polymerization (Ed. C. Barner-Kowollik) 2008, Ch 12, p. 455 (Wiley: Weinheim).

[22]   K. Matyjaszewski, J. Xia, Chem. Rev. 2001, 101,  2921.
        | CrossRef |   

[23]   G. David, C. Boyer, J. Tonnar, B. Ameduri, P. Lacroix-Desmazes, B. Boutevin, Chem. Rev. 2006, 106,  3936.
        | CrossRef |   

[24]   C. J. Hawker, A. W. Bosman, E. Harth, Chem. Rev. 2001, 101,  3661.
        | CrossRef |   

[25]   C. Boyer, V. Bulmus, J. Liu, T. P. Davis, M. H. Stenzel, C. Barner-Kowollik, J. Am. Chem. Soc. 2007, 129,  7145.
        | CrossRef |   

[26]   J. Liu, V. Bulmus, D. L. Herlambang, C. Barner-Kowollik, M. H. Stenzel, T. P. Davis, Angew. Chem. Int. Ed. 2007, 46,  3099.
        | CrossRef |   

[27]   Y. Zhao, S. Perrier, Chem. Commun. 2007,  4294.
        | CrossRef |   

[28]   P. De, M. Li, S. R. Gondi, B. S. Sumerlin, J. Am. Chem. Soc. 2008, 130,  11288.
        | CrossRef |   

[29]   M. Bathfield, F. D’Agosto, R. Spitz, M.-T. Charreyre, T. Delair, J. Am. Chem. Soc. 2006, 128,  2546.
        | CrossRef |   

[30]   A. B. Lowe, R. Wang, V. Tiriveedhi, P. Butko, C. L. McCormick, Macromol. Chem. Phys. 2007, 208,  2339.
        | CrossRef |   

[31]   A. W. York, C. W. Scales, F. Huang, C. L. McCormick, Biomacromolecules 2007, 8,  2337.
        | CrossRef |   

[32]   Lowe A. B., McCormick C. L., RAFT Polymerization in Homogeneous Aqueous Media: Initiation Systems, RAFT Agent Stability, Monomers and Polymer Structures, in Handbook of RAFT Polymerization (Ed. C. Barner-Kowollik) 2008, Ch 7, pp. 235–275 (Wiley: Weinheim).

[33]   C. L. McCormick, S. E. Kirkland, A. W. York, Polym. Rev. 2006, 46,  421.
        | CrossRef |   

[34]   P. Vana, L. Albertin, L. Barner, T. P. Davis, C. Barner-Kowollik, J. Polym. Sci., Part A: Polym. Chem. 2002, 40,  4032.
        | CrossRef |   

[35]   A. Postma, T. P. Davis, G. Moad, M. S. O’Shea, Macromolecules 2005, 38,  5371.
        | CrossRef |   

[36]   M. R. Whittaker, Y.-K. Goh, H. Gemici, T. M. Legge, S. Perrier, M. J. Monteiro, Macromolecules 2006, 39,  9028.
        | CrossRef |   

[37]   L. Wong, C. Boyer, Z. Jia, H. M. Zareie, T. P. Davis, V. Bulmus, Biomacromolecules 2008, 9,  1934.
        | CrossRef |   

[38]   C. W. Scales, Y. A. Vasilieva, A. J. Convertine, A. B. Lowe, C. L. McCormick, Biomacromolecules 2005, 6,  1846.
        | CrossRef |   

[39]   M. Li, P. De, S. R. Gondi, B. S. Sumerlin, J. Polym. Sci., Part A: Polym. Chem. 2008, 46,  5093.
        | CrossRef |   

[40]   H. Gemici, T. M. Legge, M. Whittaker, M. J. Monteiro, S. Perrier, J. Polym. Sci., Part A: Polym. Chem. 2007, 45,  2334.
        | CrossRef |   

[41]   X.-P. Qiu, F. M. Winnik, Macromolecules 2007, 40,  872.
        | CrossRef |   

[42]   J. Xu, J. He, D. Fan, X. Wang, Y. Yang, Macromolecules 2006, 39,  8616.
        | CrossRef |   

[43]   X.-P. Qiu, F. M. Winnik, Macromol. Rapid Commun. 2006, 27,  1648.
        | CrossRef |   

[44]   L. Zhang, Y. Chen, Polymer 2006, 47,  5259.
        | CrossRef |   

[45]   D. L. Patton, M. Mullings, T. Fulghum, R. C. Advincula, Macromolecules 2005, 38,  8597.
        | CrossRef |   

[46]   G. Moad, Y. K. Chong, A. Postma, E. Rizzardo, S. H. Thang, Polymer 2005, 46,  8458.
        | CrossRef |   

[47]   V. Lima, X. Jiang, J. Brokken-Zijp, P. J. Schoenmakers, B. Klumperman, R. Van Der Linde, J. Polym. Sci., Part A: Polym. Chem. 2005, 43,  959.
        | CrossRef |   

[48]   D. B. Thomas, A. J. Convertine, R. D. Hester, A. B. Lowe, C. L. McCormick, Macromolecules 2004, 37,  1735.
        | CrossRef |   

[49]   S. R. Gondi, A. P. Vogt, B. S. Sumerlin, Macromolecules 2007, 40,  474.
        | CrossRef |   

[50]   C. Boyer, V. Bulmus, P. Priyanto, W. Y. Teoh, R. Amal, T. P. Davis, J. Mater. Chem. 2009, 19,  111.
        | CrossRef |   

[51]   C. Boyer, A. Granuille, T. P. Davis, V. Bulmus, J. Polym. Sci., Part A: Polym. Chem. 2009, 47,  3773.
        | CrossRef |   

[52]   K. L. Killops, L. M. Campos, C. J. Hawker, J. Am. Chem. Soc. 2008, 130,  5062.
        | CrossRef |   

[53]   N. ten Brummelhuis, C. Diehl, H. Schlaad, Macromolecules 2008, 41,  9946.
        | CrossRef |   

[54]   C. Rissing, D. Y. Son, Organometallics 2008, 27,  5394.
        | CrossRef |   

[55]   G. Niu, H. Zhang, L. Song, X. Cui, H. Cao, Y. Zheng, S. Zhu, Z. Yang, H. Yang, Biomacromolecules 2008, 9,  2621.
        | CrossRef |   

[56]   S. Fan, F. Y. C. Boey, M. J. M. Abadie, Eur. Polym. J. 2008, 44,  2123.
        | CrossRef |   

[57]   P. Jonkheijm, D. Weinrich, M. Koehn, H. Engelkamp, P. C. M. Christianen, J. Kuhlmann, J. C. Maan, D. Nuesse, H. Schroeder, R. Wacker, R. Breinbauer, C. M. Niemeyer, H. Waldmann, Angew. Chem. Int. Ed. 2008, 47,  4421.
        | CrossRef |   

[58]   A. Pogantsch, S. Rentenberger, G. Langer, J. Keplinger, W. Kern, E. Zojer, Adv. Funct. Mater. 2005, 15,  403.
        | CrossRef |   

[59]   Z. Yang, D. A. Wicks, C. E. Hoyle, H. Pu, J. Yuan, D. Wan, Y. Liu, Polymer 2009, 50,  1717.
        | CrossRef |   

[60]   G. Chen, S. Amajjahe, M. H. Stenzel, Chem. Commun. 2009,  1198.
        | CrossRef |   

[61]   L. A. Connal, C. R. Kinnane, A. N. Zelikin, F. Caruso, Chem. Mater. 2009, 21,  576.
        | CrossRef |   

[62]   C. Nilsson, E. Malmstroem, M. Johansson, S. M. Trey, J. Polym. Sci., Part A: Polym. Chem. 2009, 47,  589.
        | CrossRef |   

[63]   T. Clark, L. Kwisnek, C. E. Hoyle, S. Nazarenko, J. Polym. Sci., Part A: Polym. Chem. 2009, 47,  14.
        | CrossRef |   

[64]   C. W. Scales, A. J. Convertine, C. L. McCormick, Biomacromolecules 2006, 7,  1389.
        | CrossRef |   

[65]   J. W. Chan, B. Yu, C. E. Hoyle, A. B. Lowe, Chem. Commun. 2008,  4959.
        | CrossRef |   

[66]   C. Boyer, T. P. Davis, V. Bulmus, Macromol. Rapid Commun. 2009, 30,  493.
        | CrossRef |   

[67]   N. Murthy, J. Campbell, N. Fausto, A. S. Hoffman, P. S. Stayton, Bioconjug. Chem. 2003, 14,  412.
        | CrossRef |   

[68]   V. Bulmus, M. Woodward, L. Lin, N. Murthy, P. Stayton, A. S. Hoffman, J. Controlled Release 2003, 93,  105.
        | CrossRef |   

[69]   K. L. Heredia, T. H. Nguyen, C.-W. Chang, V. Bulmus, T. P. Davis, H. D. Maynard, Chem. Commun. 2008, 28,  3245.
        | CrossRef |   

[70]   A. Dondoni, Angew. Chem. Int. Ed. 2008, 47,  8995.
        | CrossRef |   

[71]   D. Bontempo, K. L. Heredia, B. A. Fish, H. D. Maynard, J. Am. Chem. Soc. 2004, 126,  15372.
        | CrossRef |   

[72]   C. Boyer, J. Liu, V. Bulmus, T. P. Davis, C. Barner-Kowollik, M. H. Stenzel, Macromolecules 2008, 41,  5641.
        | CrossRef |   

[73]   C. Boyer, J. Liu, L. Wong, M. Tippett, V. Bulmus, T. P. Davis, J. Polym. Sci., Part A: Polym. Chem. 2008, 46,  7207.
        | CrossRef |   

[74]   Xu J., Boyer C., Bulmus V., Davis T. P., J. Polym. Sci., Part A: Polym. Chem. 2009, in press.

[75]   T. R. Darling, T. P. Davis, M. Fryd, A. A. Gridnev, D. M. Haddleton, S. D. Ittel, R. R. Matheson, G. Moad, E. Rizzardo, J. Polym. Sci., Part A: Polym. Chem. 2000, 38,  1706.
        | CrossRef |   

[76]   G. T. Zugates, D. G. Anderson, S. R. Little, I. E. B. Lawhorn, R. Langer, J. Am. Chem. Soc. 2006, 128,  12726.
        | CrossRef |   

[77]   S. Harrisson, Macromolecules 2009, 42,  897.
        | CrossRef |   

[78]   P. J. Roth, D. Kessler, R. Zentel, P. Theato, Macromolecules 2008, 41,  8316.
        | CrossRef |   

[79]   K. L. Heredia, D. Bontempo, T. Ly, J. T. Byers, S. Halstenberg, H. D. Maynard, J. Am. Chem. Soc. 2005, 127,  16955.
        | CrossRef |   

[80]   G. J. L. Bernardes, D. P. Gamblin, B. G. Davis, Angew. Chem. Int. Ed. 2006, 45,  4007.
        | CrossRef |   

[81]   J. T. Lai, D. Filla, R. Shea, Macromolecules 2002, 35,  6754.
        | CrossRef |   

[82]   Y. Mitsukami, M. S. Donovan, A. B. Lowe, C. L. McCormick, Macromolecules 2001, 34,  2248.
        | CrossRef |   

[83]   Hermanson G. T., Bioconjugate Techniques 1996 (Academic Press: New York, NY).



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