Fast and Simple Preparation of Patterned Surfaces with Hydrophilic Polymer Brushes by Micromolding in Capillaries

Vonhören, B., Langer, M., Abt, D., Barner-Kowollik, C., & Ravoo, B. J. (2015) Fast and Simple Preparation of Patterned Surfaces with Hydrophilic Polymer Brushes by Micromolding in Capillaries. Langmuir, 31(50).

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Micropatterns of hydrophilic polymer brushes were prepared by micromolding in capillaries (MIMIC). The polymers are covalently bound to the surfaces by a rapid hetero Diels-Alder reaction, constituting the first example of polymers grafted to surfaces in a defined pattern by MIMIC. The polymers [poly(acrylic acid), poly(hydroxyethyl acrylate), and poly(tetraethylene glycol acrylate) ranging in molecular weight from 1500 to 6000 g mol-1] were prepared with narrow dispersities via the reversible addition-fragmentation chain transfer (RAFT) process using a highly electron deficient RAFT agent that can react with surface-anchored dienes such as cyclopentadiene. We demonstrate that the anchoring method is facile to perform and highly suitable for preparing patterned surfaces that are passivated against biological impact in well-defined areas. © 2015 American Chemical Society.

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ID Code: 99447
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :3
Export Date: 5 September 2016
Correspondence Address: Barner-Kowollik, C.; Soft Matter Synthesis Laboratory, Institut für Biologische Grenzflächen, Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, Germany; email:
References: Nie, Z., Kumacheva, E., Patterning Surfaces with Functional Polymers (2008) Nat. Mater., 7 (4), pp. 277-290; Chen, T., Amin, I., Jordan, R., Patterned Polymer Brushes (2012) Chem. Soc. Rev., 41 (8), pp. 3280-3296; Li, B., Yu, B., Ye, Q., Zhou, F., Tapping the Potential of Polymer Brushes through Synthesis (2015) Acc. Chem. Res., 48 (2), pp. 229-237; Rodriguez-Emmenegger, C., Preuss, C.M., Yameen, B., Pop-Georgievski, O., Bachmann, M., Mueller, J.O., Bruns, M., Barner-Kowollik, C., Controlled Cell Adhesion on Poly(dopamine) Interfaces Photopatterned with Non-Fouling Brushes (2013) Adv. Mater., 25, pp. 6123-6127; Senaratne, W., Andruzzi, L., Ober, C.K., Self-Assembled Monolayers and Polymer Brushes in Biotechnology: Current Applications and Future Perspectives (2005) Biomacromolecules, 6 (5), pp. 2427-2448; Murugan, P., Krishnamurthy, M., Jaisankar, S.N., Samanta, D., Mandal, A.B., Controlled Decoration of the Surface with Macromolecules: Polymerization on a Self-Assembled Monolayer (SAM) (2015) Chem. Soc. Rev., 44 (10), pp. 3212-3243; Wei, Q., Becherer, T., Angioletti-Uberti, S., Dzubiella, J., Wischke, C., Neffe, A.T., Lendlein, A., Haag, R., Protein Interactions with Polymer Coatings and Biomaterials (2014) Angew. Chem., Int. Ed., 53 (31), pp. 8004-8031; Rodriguez-Emmenegger, C., Houska, M., Alles, A.B., Brynda, E., Surfaces Resistant to Fouling from Biological Fluids: Towards Bioactive Surfaces for Real Applications (2012) Macromol. Biosci., 12 (10), pp. 1413-1422; Rodriguez-Emmenegger, C., Brynda, E., Riedel, T., Houska, M., Šubr, V., Alles, A.B., Hasan, E., Huck, W.T.S., Polymer Brushes Showing Non-Fouling in Blood Plasma Challenge the Currently Accepted Design of Protein Resistant Surfaces (2011) Macromol. Rapid Commun., 32 (13), pp. 952-957; Pop-Georgievski, O., Rodriguez-Emmenegger, C., Pereira, D.L.A.S., Proks, V., Brynda, E., Rypáček, F., Biomimetic Non-Fouling Surfaces: Extending the Concepts (2013) J. Mater. Chem. B, 1 (22), pp. 2859-2867; Kostina, N.Y., Rodriguez-Emmenegger, C., Houska, M., Brynda, E., Michálek, J., Non-Fouling Hydrogels of 2-Hydroxyethyl Methacrylate and Zwitterionic Carboxybetaine (Meth)acrylamides (2012) Biomacromolecules, 13 (12), pp. 4164-4170; Banerjee, I., Pangule, R.C., Kane, R.S., Antifouling Coatings: Recent Developments in the Design of Surfaces That Prevent Fouling by Proteins, Bacteria, and Marine Organisms (2011) Adv. Mater., 23 (6), pp. 690-718; Blaszykowski, C., Sheikh, S., Thompson, M., Surface Chemistry to Minimize Fouling from Blood-Based Fluids (2012) Chem. Soc. Rev., 41 (17), pp. 5599-5612; Vogler, E.A., Structure and Reactivity of Water at Biomaterial Surfaces (1998) Adv. Colloid Interface Sci., 74 (13), pp. 69-117; Azzaroni, O., Polymer Brushes Here, There, and Everywhere: Recent Advances in Their Practical Applications and Emerging Opportunities in Multiple Research Fields (2012) J. Polym. Sci., Part A: Polym. Chem., 50 (16), pp. 3225-3258; Zdyrko, B., Luzinov, I., Polymer Brushes by the "grafting To" Method (2011) Macromol. Rapid Commun., 32 (12), pp. 859-869; Quick, A.S., Rothfuss, H., Welle, A., Richter, B., Fischer, J., Wegener, M., Barner-Kowollik, C., Fabrication and Spatially Resolved Functionalization of 3D Microstructures via Multiphoton-Induced Diels-Alder Chemistry (2014) Adv. Funct. Mater., 24 (23), pp. 3571-3580; Husemann, M., Morrison, M., Benoit, D., Frommer, J., Mate, C.M., Hinsberg, W.D., Hedrick, J.L., Hawker, C.J., Manipulation of Surface Properties by Patterning of Covalently Bound Polymer Brushes (2000) J. Am. Chem. Soc., 122 (8), pp. 1844-1845; Jia, X., Jiang, X., Liu, R., Yin, J., Facile Approach to Patterned Binary Polymer Brush through Photolithography and Surface-Initiated Photopolymerization (2010) ACS Appl. Mater. Interfaces, 2 (4), pp. 1200-1205; Poelma, J.E., Fors, B.P., Meyers, G.F., Kramer, J.W., Hawker, C.J., Fabrication of Complex Three-Dimensional Polymer Brush Nanostructures through Light-Mediated Living Radical Polymerization (2013) Angew. Chem., Int. Ed., 52 (27), pp. 6844-6848; Hirtz, M., Brinks, M.K., Miele, S., Studer, A., Fuchs, H., Chi, L., Structured Polymer Brushes by AFM Lithography (2009) Small, 5 (8), pp. 919-923; Wagner, H., Li, Y., Hirtz, M., Chi, L., Fuchs, H., Studer, A., Site Specific Protein Immobilization into Structured Polymer Brushes Prepared by AFM Lithography (2011) Soft Matter, 7 (21), pp. 9854-9858; Gates, B.D., Xu, Q., Stewart, M., Ryan, D., Willson, C.G., Whitesides, G.M., New Approaches to Nanofabrication: Molding, Printing, and Other Techniques (2005) Chem. Rev., 105 (4), pp. 1171-1196; Alom Ruiz, S., Chen, C.S., Microcontact Printing: A Tool to Pattern (2007) Soft Matter, 3 (2), pp. 168-177; Perl, A., Reinhoudt, D.N., Huskens, J., Microcontact Printing: Limitations and Achievements (2009) Adv. Mater., 21 (22), pp. 2257-2268; Kettling, F., Vonhören, B., Krings, J.A., Saito, S., Ravoo, B.J., One-Step Synthesis of Patterned Polymer Brushes by Photocatalytic Microcontact Printing (2015) Chem. Commun., 51 (6), pp. 1027-1030; Roling, O., Mardyukov, A., Krings, J.A., Studer, A., Ravoo, B.J., Polymer Brushes Exhibiting Versatile Supramolecular Interactions Grown by Nitroxide-Mediated Polymerization and Structured via Microcontact Chemistry (2014) Macromolecules, 47 (7), pp. 2411-2419; Roling, O., Mardyukov, A., Lamping, S., Vonhören, B., Rinnen, S., Arlinghaus, H.F., Studer, A., Ravoo, B.J., Surface Patterning with Natural and Synthetic Polymers via an Inverse Electron Demand Diels-Alder Reaction Employing Microcontact Chemistry (2014) Org. Biomol. Chem., 12 (39), pp. 7828-7835; Roling, O., De Bruycker, K., Vonhören, B., Stricker, L., Körsgen, M., Arlinghaus, H.F., Ravoo, B.J., Du Prez, F.E., Rewritable Polymer Brush Micropatterns Grafted by Triazolinedione Click Chemistry (2015) Angew. Chem., Int. Ed., 54 (44), pp. 13126-13129; Zhou, F., Zheng, Z., Yu, B., Liu, W., Huck, W.T.S., Multicomponent Polymer Brushes (2006) J. Am. Chem. Soc., 128 (50), pp. 16253-16258; Chen, T., Jordan, R., Zauscher, S., Dynamic Microcontact Printing for Patterning Polymer-Brush Microstructures (2011) Small, 7 (15), pp. 2148-2152; Kelby, T.S., Wang, M., Huck, W.T.S., Controlled Folding of 2D Au-Polymer Brush Composites into 3D Microstructures (2011) Adv. Funct. Mater., 21 (4), pp. 652-657; Kim, E., Xia, Y., Whitesides, G.M., Polymer Microstructures Formed by Moulding in Capillaries (1995) Nature, 376 (6541), pp. 581-584; Xia, Y., Whitesides, G.M., Soft Lithography (1998) Angew. Chem., Int. Ed., 37 (5), pp. 550-575; Cavallini, M., Albonetti, C., Biscarini, F., Nanopatterning Soluble Multifunctional Materials by Unconventional Wet Lithography (2009) Adv. Mater., 21 (1011), pp. 1043-1053; Kim, E., Xia, Y., Whitesides, G.M., Micromolding in Capillaries: Applications in Materials Science (1996) J. Am. Chem. Soc., 118 (24), pp. 5722-5731; Kim, E., Xia, Y., Whitesides, G.M., Two- and Three-Dimensional Crystallization of Polymeric Microspheres by Micromolding in Capillaries (1996) Adv. Mater., 8 (3), pp. 245-247; Cavallini, M., Bystrenova, E., Timko, M., Koneracka, M., Zavisova, V., Kopcansky, P., Multiple-Length-Scale Patterning of Magnetic Nanoparticles by Stamp Assisted Deposition (2008) J. Phys.: Condens. Matter, 20 (20), pp. 204144-204149; Zhang, F., Nyberg, T., Inganäs, O., Conducting Polymer Nanowires and Nanodots Made with Soft Lithography (2002) Nano Lett., 2 (12), pp. 1373-1377; Bystrenova, E., Facchini, M., Cavallini, M., Cacace, M.G., Biscarini, F., Multiple Length-Scale Patterning of DNA by Stamp-Assisted Deposition (2006) Angew. Chem., Int. Ed., 45 (29), pp. 4779-4782; Delamarche, E., Bernard, A., Schmid, H., Michel, B., Biebuyck, H., Patterned Delivery of Immunoglobulins to Surfaces Using Microfluidic Networks (1997) Science, 276 (5313), pp. 779-781; Quémener, D., Davis, T.P., Barner-Kowollik, C., Stenzel, M.H., RAFT and Click Chemistry: A Versatile Approach to Well-Defined Block Copolymers (2006) Chem. Commun., 48, pp. 5051-5053; Inglis, A.J., Sinnwell, S., Stenzel, M.H., Barner-Kowollik, C., Ultrafast Click Conjugation of Macromolecular Building Blocks at Ambient Temperature (2009) Angew. Chem., Int. Ed., 48 (13), pp. 2411-2414; Delaittre, G., Guimard, N.K., Barner-Kowollik, C., Cycloadditions in Modern Polymer Chemistry (2015) Acc. Chem. Res., 48 (5), pp. 1296-1307; Glassner, M., Delaittre, G., Kaupp, M., Blinco, J.P., Barner-Kowollik, C., (Ultra)Fast Catalyst-Free Macromolecular Conjugation in Aqueous Environment at Ambient Temperature (2012) J. Am. Chem. Soc., 134 (17), pp. 7274-7277; Zydziak, N., Preuss, C.M., Winkler, V., Bruns, M., Hübner, C., Barner-Kowollik, C., Hetero Diels-Alder Chemistry for the Functionalization of Single-Walled Carbon Nanotubes with Cyclopentadienyl End-Capped Polymer Strands (2013) Macromol. Rapid Commun., 34 (8), pp. 672-680; Blinco, J.P., Trouillet, V., Bruns, M., Gerstel, P., Gliemann, H., Barner-Kowollik, C., Dynamic Covalent Chemistry on Surfaces Employing Highly Reactive Cyclopentadienyl Moieties (2011) Adv. Mater., 23 (38), pp. 4435-4439; Brittain, W.J., Minko, S., A structural definition of polymer brushes (2007) J. Polym. Sci., Part A: Polym. Chem., 45 (16), pp. 3505-3512; Beamson, G., Briggs, D., (1992) High Resolution XPS of Organic Polymers: The Scienta ESCA300 Database, , Wiley: Chichester, U.K
Keywords: Acrylics, Capillarity, Dendrimers, Free radical polymerization, Hydrophilicity, Micromachining, Molding, Olefins, Electron-deficient, Hetero Diels-Alder reaction, Hydrophilic polymers, Hydroxyethyl acrylate, Micromolding in capillaries, Poly(acrylic acid ), Reversible addition fragmentation chain transfer, Tetraethylene glycols, Polymers
DOI: 10.1021/acs.langmuir.5b03924
ISSN: 07437463
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: 26 Sep 2016 03:51

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