Acrylamide-based copolymers bearing photoreleasable thiols for subsequent thiol-ene functionalization

Delaittre, G., Pauloehrl, T., Bastmeyer, M., & Barner-Kowollik, C. (2012) Acrylamide-based copolymers bearing photoreleasable thiols for subsequent thiol-ene functionalization. Macromolecules, 45(4).

View at publisher


A new set of monomers is presented in order to incorporate thiols into radical polymers using a protecting chemistry/photocleavage route. The (co)polymerization kinetics of an o-nitrobenzyl thioether-containing acrylamide derivative are reported. The presence of the o-nitrobenzyl moiety is found to strongly affect the polymerization. Nevertheless, water-soluble copolymers with N,N-dimethylacrylamide (DMAAm) as a comonomer are obtained either by free radical polymerization (10 000 ≤ M n ≤ 17 500 g mol -1; 1.5 ≤ PDI ≤ 1.8) or by reversible addition-fragmentation transfer (RAFT)-mediated controlled/living radical polymerization (2000 ≤ M n ≤ 5700 g mol -1; 1.1 ≤ PDI ≤ 1.2). Deprotection under UV light (λ = 366 nm) at ambient temperature is followed by UV/vis monitoring of the protecting group release, which proceeds to completion between 40 min and 2 h within the studied range of concentration as demonstrated by 1H NMR spectroscopy. Thiol-maleimide addition is subsequently carried out and found to proceed with a nearly quantitative yield (ca. 90%) as measured by 1H NMR. Different block copolymers (9400 ≤ M n ≤ 16 500 g mol -1; 1.3 ≤ PDI ≤ 1.4) with a PDMAAm water-soluble block, a polystyrene hydrophobic block, or a poly(N-isopropylacrylamide) thermosensitive block as the first segment and possessing the photoreleasable thiol moieties in the second block are subsequently synthesized by RAFT-mediated polymerization. We finally demonstrate the orthogonal sequential deprotection and reaction with benzyl maleimide of two different thiol species originating from the thiocarbonylthio functionality and the o-nitrobenzyl protected lateral groups, respectively. © 2012 American Chemical Society.

Impact and interest:

38 citations in Scopus
Search Google Scholar™
42 citations in Web of Science®

Citation counts are sourced monthly from Scopus and Web of Science® citation databases.

These databases contain citations from different subsets of available publications and different time periods and thus the citation count from each is usually different. Some works are not in either database and no count is displayed. Scopus includes citations from articles published in 1996 onwards, and Web of Science® generally from 1980 onwards.

Citations counts from the Google Scholar™ indexing service can be viewed at the linked Google Scholar™ search.

ID Code: 99304
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :35
Export Date: 5 September 2016
Correspondence Address: Barner-Kowollik, C.; Preparative Macromolecular Chemistry, Institut für Technische Chemie und Polymerchemie, Karlsruhe Institute of Technology (KIT), Engesserstr. 18, 76128 Karlsruhe, Germany; email:
References: Hawker, C.J., Wooley, K.L., (2005) Science, 309, p. 1200; Binder, W.H., Sachsenhofer, R., (2007) Macromol. Rapid Commun., 28, p. 15; Barner-Kowollik, C., Inglis, A.J., (2009) Macromol. Chem. Phys., 210, p. 987; Iha, R.K., Wooley, K.L., Nystrom, A.N., Burke, D.J., Kade, M.J., Hawker, C.J., (2009) Chem. Rev., 109, p. 5620; Golas, P.L., Matyjaszewski, K., (2010) Chem. Soc. Rev., 39, p. 1338; Sumerlin, B.S., Vogt, A.P., (2010) Macromolecules, 43, p. 1; Barner-Kowollik, C., Du Prez, F.E., Espeel, P., Hawker, C.J., Junkers, T., Schlaad, H., Van Camp, W., (2011) Angew. Chem., Int. Ed., 50, p. 60; Kolb, H.C., Finn, M.G., Sharpless, K.B., (2001) Angew. Chem., Int. Ed., 40, p. 2004; Meldal, M., Tornøe, C.W., (2008) Chem. Rev., 108, p. 2952; Lutz, J.-F., (2007) Angew. Chem., Int. Ed., 46, p. 1018; Dirks, A.J., Cornelissen, J.J.L.M., Van Delft, F.L., Van Hest, J.C.M., Nolte, R.J.M., Rowan, A.E., Rutjes, F.P.J.T., (2007) QSAR Comb. Sci., 26, p. 1200; Meldal, M., (2008) Macromol. Rapid Commun., 29, p. 1016; Lundberg, P., Hawker, C.J., Hult, A., Malkoch, M., (2008) Macromol. Rapid Commun., 29, p. 998; Aragão-Leoneti, V., Campo, V.L., Gomes, A.S., Field, R.A., Carvalho, I., (2010) Tetrahedron, 66, p. 9475; Hoyle, C.E., Bowman, C.N., (2010) Angew. Chem., Int. Ed., 49, p. 1540; Hoogenboom, R., (2010) Angew. Chem., Int. Ed., 49, p. 3415; Hoyle, C.E., Lowe, A.B., Bowman, C.N., (2010) Chem. Soc. Rev., 39, p. 1355; Sinnwell, S., Inglis, A.J., Davis, T.P., Stenzel, M.H., Barner-Kowollik, C., (2008) Chem. Commun., p. 2052; Inglis, A.J., Sinnwell, S., Stenzel, M.H., Barner-Kowollik, C., (2009) Angew. Chem., Int. Ed., 48, p. 2411; Nebhani, L., Gerstel, P., Atanasova, P., Bruns, M., Barner-Kowollik, C., (2009) J. Polym. Sci., Polym. Chem., 47, p. 7090; Paulöhrl, T., Inglis, A.J., Barner-Kowollik, C., (2010) Adv. Mater., 22, p. 2788; Inglis, A.J., Nebhani, L., Altintas, O., Schmidt, F.-G., Barner-Kowollik, C., (2010) Macromolecules, 43, p. 5515; Goldmann, A.S., Tischer, T., Barner, L., Bruns, M., Barner-Kowollik, C., (2011) Biomacromolecules, 12, p. 1137; Ott, C., Hoogenboom, R., Schubert, U.S., (2008) Chem. Commun., p. 3516; Becer, C.R., Babiuch, K., Pilz, D., Hornig, S., Heinze, T., Gottschaldt, M., Schubert, U.S., (2009) Macromolecules, 42, p. 2387; Babiuch, K., Becer, C.R., Gottschaldt, M., Delaney, J.T., Weisser, J., Beer, B., Wyrwa, R., Schubert, U.S., (2011) Macromol. Biosci., 11, p. 535; Li, R.C., Broyer, R.M., Maynard, H.D., (2006) J. Polym. Sci., Part A: Polym. Chem., 44, p. 5004; Heredia, K.L., Maynard, H.D., (2007) Org. Biomol. Chem., 5, p. 45; Heredia, K.L., Tolstyka, Z.P., Maynard, H.D., (2007) Macromolecules, 40, p. 4772; Kopping, J.T., Tolstyka, Z.P., Maynard, H.D., (2007) Macromolecules, 40, p. 8593; Christman, K.L., Broyer, R.M., Schopf, E., Kolodziej, C.M., Chen, Y., Maynard, H.D., (2011) Langmuir, 27, p. 4715; Singh, I., Zarafshani, Z., Lutz, J.-F., Heaney, F., (2009) Macromolecules, 42, p. 5411; Singh, I., Zarafshani, Z., Heaney, F., Lutz, J.-F., (2011) Polym. Chem., 2, p. 372; Tsarevsky, N.V., Bencherif, S.A., Matyjaszewski, K., (2007) Macromolecules, 40, p. 4439; Kade, M.J., Burke, D.J., Hawker, C.J., (2010) J. Polym. Sci., Part A: Polym. Chem., 48, p. 743; Love, J.C., Estroff, L.A., Kriebel, J.K., Nuzzo, R.G., Whitesides, G.M., (2005) Chem. Rev., 105, p. 1103; Ueda, A., Nagai, S., (1999) Polymer Handbook, p. 97. , In, 4 th ed. Brandrup, J. Immergut, E. H. Grulke, E. A. Wiley: New York; Chiefari, J., Rizzardo, E., (2002) Handbook of Radical Polymerization, p. 629. , In, 2 nd ed. Matyjaszewski, K. Davis, T. P. John Wiley and Sons: New York; Nagel, B., Gajovic-Eichelmann, N., Scheller, F.W., Katterle, M., (2010) Langmuir, 26, p. 9088; Crownover, E.F., Convertine, A.J., Stayton, P.S., (2011) Polym. Chem., 2, p. 1499; Bontempo, D., Heredia, K.L., Fish, B.A., Maynard, H.D., (2004) J. Am. Chem. Soc., 126, p. 15372; Heredia, K.L., Bontempo, D., Ly, T., Byers, J.T., Halstenberg, S., Maynard, H.D., (2005) J. Am. Chem. Soc., 127, p. 16955; Iwasaki, Y., Omichi, Y., Iwata, R., (2008) Langmuir, 24, p. 8427; Vázquez-Dorbatt, V., Tolstyka, Z.P., Chang, C.-W., Maynard, H.D., (2009) Biomacromolecules, 10, p. 2207; Liu, J., Bulmus, V., Barner-Kowollik, C., Stenzel, M.H., Davis, T.P., (2007) Macromol. Rapid Commun., 28, p. 303; Boyer, C., Liu, J., Wong, L., Tippett, M., Bulmus, V., Davis, T.P., (2008) J. Polym. Sci., Part A: Polym. Chem., 46, p. 7207; Chang, C.-W., Nguyen, T.H., Maynard, H.D., (2010) Macromol. Rapid Commun., 31, p. 1691; Van Dijk-Wolthuis, W.N.E., Van De Wetering, P., Hinrichs, W.L.J., Hofmeyer, L.J.F., Liskamp, R.M.J., Crommelin, D.J.A., Hennink, W.E., (1999) Bioconjug. Chem., 10, p. 687; Tsarevsky, N.V., Matyjaszewski, K., (2002) Macromolecules, 35, p. 9009; Li, L., Jiang, X., Zhuo, R., (2009) J. Polym. Sci., Part A: Polym. Chem., 47, p. 5989; Carrot, G., Hilborn, J., Hedrick, J.L., Trollsås, M., (1999) Macromolecules, 32, p. 5171; Ye, M., Zhang, D., Han, L., Tejada, J., Ortiz, C., (2006) Soft Matter, 2, p. 243; Javakhishvili, I., Hvilsted, S., (2009) Biomacromolecules, 10, p. 74; Hill, N.L., Jarvis, J.L., Pettersson, F., Braslau, R., (2008) React. Funct. Polym., 68, p. 361; Barner, L., Perrier, S., (2008) Handbook of RAFT Polymerization, p. 455. , In; Barner-Kowollik, C. Wiley-VCH: Weinheim; Willcock, H., O'Reilly, R.K., (2010) Polym. Chem., 1, p. 149; Moad, G., Rizzardo, E., Thang, S.H., (2011) Polym. Int., 60, p. 9; Garamszegi, L., Donzel, C., Carrot, G., Nguyen, T.Q., Hilborn, J., (2003) React. Funct. Polym., 55, p. 179; Uygun, M., Tasdelen, M.A., Yagci, Y., (2010) Macromol. Chem. Phys., 211, p. 103; Boyer, C., Soeriyadi, A.H., Roth, P.J., Whittaker, M.R., Davis, T.P., (2011) Chem. Commun., 47, p. 1318; Liras, M., García, O., Quijada-Garrido, I., París, R., (2011) Macromolecules, 44, p. 1335; Wuts, P.G.M., Greene, T.W., (2007) Greene's Protective Groups in Organic Synthesis, , Eds. John Wiley and Sons: New York; Pauloehrl, T., Delaittre, G., Bastmeyer, M., Barner-Kowollik, C., (2012) Polym. Chem., , 10.1039/C1PY00372K; Kostiainen, M.A., Smith, D.K., Ikkala, O., (2007) Angew. Chem., Int. Ed., 46, pp. 7600-7604; Kostiainen, M.A., Kasyutich, O., Cornelissen, J.J.L.M., Nolte, R.J.M., (2010) Nature Chem., 2, pp. 394-399; Braun, F., Eng, L., Trogisch, S., Voit, B., (2003) Macromol. Chem. Phys., 204, p. 1486; Ryan, D., Parviz, B.A., Linder, V., Semetey, V., Sia, S.K., Su, J., Mrksich, M., Whitesides, G.M., (2004) Langmuir, 20, p. 9080; Brown, A.A., Azzaroni, O., Huck, W.T.S., (2009) Langmuir, 25, p. 1744; Aoyagi, B., Endo, T., (2009) J. Polym. Sci., Part A: Polym. Chem., 47, p. 3702; Bivigou-Koumba, A.M., Kristen, J., Laschewsky, A., Mueller-Buschbaum, P., Papadakis, C.M., (2009) Macromol. Chem. Phys., 210, p. 565; Clevenger, R.C., Turnbull, K.D., (2000) Synth. Commun., 30, p. 1379; Gosh, S., Tochtrop, G.P., (2009) Tetrahedron Lett., 50, p. 1723; Strazielle, C., Benoit, H., Vogl, O., (1978) Eur. Polym. J., 14, p. 331; Bajpai, U.D.N., Bajpai, A.K., Bajpai, J., (1991) J. Appl. Polym. Sci., 42, p. 2005; Schumers, J.-M., Fustin, C.-A., Can, A., Hoogenboom, R., Schubert, U.S., Gohy, J.-F., (2009) J. Polym. Sci., Part A: Polym. Chem., 47, pp. 6504-6513; Greene, A.C., Grubbs, R.B., (2010) Macromolecules, 43, p. 10320; Nakayama, Y., Matsuda, T., (1999) Langmuir, 15, p. 5560; Il'ichev, Y.V., Schwörer, M.A., Wirz, J., (2004) J. Am. Chem. Soc., 126, p. 4581; Marriott, G., Miyata, H., Kinosita, K., (1992) Biochem. Int., 26, p. 943; Nagasaki, Y., Okada, T., Scholz, C., Iijima, M., Kato, M., Kataoka, K., (1998) Macromolecules, 31, p. 1473; Lu, J., Shi, M., Shoichet, M.S., (2008) Bioconjugate Chem., 20, p. 87; Nicolas, N., Bensaid, F., Desmaële, D., Grogna, M., Detrembleur, C., Andrieux, K., Couvreur, P., (2008) Macromolecules, 41, p. 8418; Bae, J.W., Lee, E., Park, K.M., Park, K.D., (2009) Macromolecules, 42, p. 3437; Delaittre, G., Justribó-Hernández, G., Nolte, R.J.M., Cornelissen, J.J.L.M., (2011) Macromol. Rapid Commun., 32, p. 19; Opsteen, J.A., Brinkhuis, R.P., Teeuwen, R.L.M., Löwik, D.W.P.M., Van Hest, J.C.M., (2007) Chem. Commun., p. 3136; Meng, Z., Hendrickson, G.R., Lyon, L.A., (2009) Macromolecules, 42, p. 7664; Delaittre, G., Rieger, J., Charleux, B., (2011) Macromolecules, 44, p. 462. , references therein; Teodorescu, M., Matyjaszewski, K., (1999) Macromolecules, 32, p. 4826; Rademacher, J.T., Baum, M., Pallack, M.E., Brittain, W.J., Simonsick, W.J., (1999) Macromolecules, 33, p. 284; Xia, Y., Yin, X., Burke, N.A.D., Stöver, H.D.H., (2005) Macromolecules, 38, p. 5937; Moad, G., Rizzardo, E., Thang, S.H., (2005) Aust. J. Chem., 58, p. 379; Favier, A., Charreyre, M.-T., (2006) Macromol. Rapid Commun., 27, p. 653
Keywords: Acrylamides, Co-monomer, Controlled/living radical polymerization, Deprotection, Functionalizations, H NMR spectroscopy, Hydrophobic blocks, Maleimides, N ,n-dimethylacrylamide, N-isopropylacrylamides, Polymerization kinetics, Protecting group, Quantitative yields, Radical polymers, RAFT-mediated polymerization, Reversible addition-fragmentation transfers, Thermo sensitive, Thiol species, Thiol-enes, Water soluble copolymers, Water-soluble block, Amides, Block copolymers, Free radical polymerization, Polystyrenes, Acrylic monomers
DOI: 10.1021/ma202670d
ISSN: 00249297
Divisions: Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > Institutes > Institute for Future Environments
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Deposited On: 22 Sep 2016 04:50
Last Modified: 04 Oct 2016 03:55

Export: EndNote | Dublin Core | BibTeX

Repository Staff Only: item control page