To tailor cell-surface interactions, precise and controlled attachment of cell-adhesive motifs is required, while any background non-specific cell and protein adhesion has to be blocked effectively. Herein, a versatile and highly reproducible antifouling surface modification based on "clickable" groups and hierarchically structured diblock copolymer brushes for the controlled attachment of cells is reported. The polymer brush architecture combines an antifouling bottom block of poly(2-hydroxyethyl methacrylate) poly(HEMA) and an ultrathin azide-bearing top block, which can participate in well-established "click" reactions including the highly selective copper-catalyzed alkyne-azide cycloaddition (CuAAC) reaction under mild conditions. This straightforward approach allows the rapid conjugation of a cell-adhesive, alkyne-bearing cyclic RGD peptide motif, enabling subsequent specific attachment of NIH 3T3 fibroblasts, their extensive proliferation and confluent cell sheet formation after 48 h of incubation. The generally applicable strategy presented in this report can be employed for surface functionalization with diverse alkyne-bearing biological moieties via CuAAC or copper-free alkyne-azide cycloaddition protocols, making it a versatile functionalization approach and a promising tool for tissue engineering, biomaterial implant design, and other applications that require surfaces supporting highly specific cell attachment.

Institute of Macromolecular Chemistry Czech Academy of Sciences Heyrovsky sq 2 Prague 162 06 Czech Republic

Physical Chemistry 1 and Research Center of Micro and Nanochemistry and Engineering Department of Chemistry and Biology University of Siegen Adolf Reichwein Str 2 57076 Siegen Germany

Zobrazit více v PubMed

D. E. Discher, D. J. Mooney, P. W. Zandstra, Science 2009, 324, 1673.

M. G. F. Hartmuth C. Kolb, K. Barry Sharpless, Angew. Chem., Int. Ed. 2001, 40, 2004.

C. Rodriguez-Emmenegger, C. M. Preuss, B. Yameen, O. Pop-Georgievski, M. Bachmann, J. O. Mueller, M. Bruns, A. S. Goldmann, M. Bastmeyer, C. Barner-Kowollik, Adv. Mater. 2013, 25, 6123.

B. Wehrle-Haller, Curr. Opin. Cell Biol. 2012, 24, 569.

J. E. Gautrot, C. Wang, X. Liu, S. J. Goldie, B. Trappmann, W. T. Huck, F. M. Watt, Biomaterials 2012, 33, 5221.

A. A. Khalili, M. R. Ahmad, Int. J. Mol. Sci. 2015, 16, 18149.

M. D. Pierschbacher, E. Ruoslahti, Nature 1984, 309, 30.

A. J. Garcia, C. D. Reyes, J. Dent. Res. 2005, 84, 407.

D. J. Siegwart, J. K. Oh, K. Matyjaszewski, Prog. Polym. Sci. 2012, 37, 18.

F. Surman, T. Riedel, M. Bruns, N. Y. Kostina, Z. Sedlakova, C. Rodriguez-Emmenegger, Macromol. Biosci. 2015, 15, 636.

M. Badoux, M. Billing, H.-A. Klok, Polym. Chem. 2019, 10, 2925.

R. Barbey, L. Lavanant, D. Paripovic, N. Schuwer, C. Sugnaux, S. Tugulu, H. A. Klok, Chem. Rev. 2009, 109, 5437.

J. O. Zoppe, N. C. Ataman, P. Mocny, J. Wang, J. Moraes, H. A. Klok, Chem. Rev. 2017, 117, 1105.

H. G. Börner, K. Beers, K. Matyjaszewski, S. S. Sheiko, M. Möller, Macromolecules 2001, 34, 4375.

I. Lilge, H. Schönherr, Polymer 2016, 98, 409.

A. de los Santos Pereira, N. Y. Kostina, M. Bruns, C. Rodriguez-Emmenegger, C. Barner-Kowollik, Langmuir 2015, 31, 5899.

I. Lilge, H. Schonherr, Angew. Chem., Int. Ed. 2016, 55, 13114.

S. Tugulu, A. Arnold, I. Sielaff, K. Johnsson, H. A. Klok, Biomacromolecules 2005, 6, 1602.

H. Vaisocherova, V. Sevcu, P. Adam, B. Spackova, K. Hegnerova, A. de los Santos Pereira, C. Rodriguez-Emmenegger, T. Riedel, M. Houska, E. Brynda, J. Homola, Biosens. Bioelectron. 2014, 51, 150.

N. Akeroyd, B. Klumperman, Eur. Polym. J. 2011, 47, 1207.

V. Parrillo, A. de Los Santos Pereira, T. Riedel, C. Rodriguez-Emmenegger, Anal. Chim. Acta 2017, 971, 78.

U. Bog, A. de Los Santos Pereira, S. L. Mueller, S. Havenridge, V. Parrillo, M. Bruns, A. E. Holmes, C. Rodriguez-Emmenegger, H. Fuchs, M. Hirtz, ACS Appl. Mater. Interfaces 2017, 9, 12109.

Z. Ma, Z. Mao, C. Gao, Colloids Surf., B 2007, 60, 137.

J.-F. Lutz, H. G. Börner, Prog. Polym. Sci. 2008, 33, 1.

J. F. Lutz, Angew. Chem., Int. Ed. 2007, 46, 1018.

N. V. Tsarevsky, S. A. Bencherif, K. Matyjaszewski, Macromolecules 2007, 40, 4439.

X. Ren, Y. Wu, Y. Cheng, H. Ma, S. Wei, Langmuir 2011, 27, 12069.

D. Peelen, V. Kodoyianni, J. Lee, T. Zheng, M. R. Shortreed, L. M. Smith, J. Proteome Res. 2006, 5, 1580.

C. Zhao, L. Li, Q. Wang, Q. Yu, J. Zheng, Langmuir 2011, 27, 4906.

C. Rodriguez-Emmenegger, O. A. Avramenko, E. Brynda, J. Skvor, A. B. Alles, Biosens. Bioelectron. 2011, 26, 4545.

C. Rodriguez-Emmenegger, S. Janel, A. de los Santos Pereira, M. Bruns, F. Lafont, Polym. Chem. 2015, 6, 5740.

K. Matyjaszewski, P. J. Miller, N. Shukla, B. Immaraporn, A. Gelman, B. B. Luokala, T. M. Siclovan, G. Kickelbick, T. Vallant, H. Hoffmann, T. Pakula, Macromolecules 1999, 32, 8716.

J. Liu, N. Feng, S. Chang, H. Kang, Appl. Surf. Sci. 2012, 258, 6127.

A. de los Santos Pereira, S. Sheikh, C. Blaszykowski, O. Pop-Georgievski, K. Fedorov, M. Thompson, C. Rodriguez-Emmenegger, Biomacromolecules 2016, 17, 1179.

Y. Iwakura, F. Toda, T. Ito, K. Aoshima, Makromol. Chem. 1967, 104, 26.

C. Rodriguez-Emmenegger, M. Houska, A. B. Alles, E. Brynda, Macromol. Biosci. 2012, 12, 1413.

P. J. O. d. T. M.H. Espinosa, D.Z. Silva, Polymer 2001, 42, 3393.

M. Navarro, E. M. Benetti, S. Zapotoczny, J. A. Planell, G. J. Vancso, Langmuir 2008, 24, 10996.

J. G. Steele, B. A. Dalton, G. Johnson, P. A. Underwood, J. Biomed. Mater. Res. 1993, 27, 927.

A. S. Curtis, J. V. Forrester, C. McInnes, F. Lawrie, J. Cell Biol. 1983, 97, 1500.

B. Li, J. Chen, J. H. Wang, J. Biomed. Mater. Res., Part A 2006, 79A, 989.

S. Tugulu, P. Silacci, N. Stergiopulos, H. A. Klok, Biomaterials 2007, 28, 2536.

L. Li, J. Wu, C. Gao, Colloids Surf., B 2011, 85, 12.

D. Zhang, K. A. Kilian, J. Mater. Chem. B 2014, 2, 4280.

V. Proks, J. Jaros, O. Pop-Georgievski, J. Kucka, S. Popelka, P. Dvorak, A. Hampl, F. Rypacek, Macromol. Biosci. 2012, 12, 1232.

O. Pop-Georgievski, N. Neykova, V. Proks, J. Houdkova, E. Ukraintsev, J. Zemek, A. Kromka, F. Rypaček, Thin Solid Films 2013, 543, 180.

Surface Design of Antifouling Vascular Constructs Bearing Biofunctional Peptides for Tissue Regeneration Applications

Functionalizable Antifouling Coatings as Tunable Platforms for the Stress-Driven Manipulation of Living Cell Machinery