Assessing Chemical Transformation of Reactive, Interfacial Thin Films Made of End-Tethered Poly(2-vinyl-4,4-dimethyl azlactone) (PVDMA) Chains

Aden, Bethany; Kite, Camille M.; Hopkins, Benjamin W.; Zetterberg, Anna; Lokitz, Bradley S.; Ankner, John Francis; Kilbey, S. Michael

doi:10.1021/acs.macromol.6b01999

Title: Assessing Chemical Transformation of Reactive, Interfacial Thin Films Made of End-Tethered Poly(2-vinyl-4,4-dimethyl azlactone) (PVDMA) Chains

Journal Article · Tue Jan 24 00:00:00 UTC 2017 · Macromolecules

DOI: https://doi.org/10.1021/acs.macromol.6b01999 · OSTI ID:1426561

Aden, Bethany ^[1]; Kite, Camille M. ^[1]; Hopkins, Benjamin W. ^[2]; Zetterberg, Anna ^[2];

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Univ. of Tennessee, Knoxville, TN (United States). Department of Chemistry
Univ. of Tennessee, Knoxville, TN (United States). Department of Chemical and Biomolecular Engineering
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS) ; Univ. of Tennessee, Knoxville, TN (United States). Department of Chemistry and Department of Chemical and Biomolecular Engineering

Designing thin films or surface scaffolds with an appropriate display of chemical functionality is useful for biomedical applications, sensing platforms, adhesives, and barrier coatings. Relationships between the structural characteristics of model thin films based on reactive poly(2-vinyl-4,4-dimethyl azlactone) (PVDMA) brushes and the amount and distribution of primary amines used to chemically functionalize these layers in situ are quantitatively detailed via neutron reflectometry and compared with results from ellipsometry. After functionalization, the PVDMA brush thickness increases as a result of the primary amines reacting with the azlactone rings. Both techniques show that the extent of functionalization by small-molecule amines depends on the size of the amine, the grafting density of brush chains, and their molecular weight. However, constrained analysis of neutron reflectivity data predicated on that technique’s sensitivity to isotopic substitution and its ability to resolve structure at the nanoscale shows that the extent of functionalization is not accurately represented by the average extent of functionalization determined from ellipsometric thickness: reactive modification is not uniform, even in modestly dense brushes, except when the penetrant is small. In addition, there appears to be a loss of PVDMA chains during functionalization, attributed to chain scission resulting from additional stretching brought about by functionalization. In conclusion, these findings provide unprecedented insight into the alteration of surface properties by reactive modification and broadly support efforts to produce tailored surfaces in which properties such as friction, colloidal stability, adhesion, wettability, and biocompatibility can be modulated in situ by chemical modification.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1426561

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 2 Vol. 50; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (52)

Controlling Cell Adhesion to Titanium: Functionalization of Poly[oligo(ethylene glycol)methacrylate] Brushes with Cell-Adhesive Peptides Raynor, J. E.; Petrie, T. A.; García, A. J. Advanced Materials, Vol. 19, Issue 13 https://doi.org/10.1002/adma.200602129	journal	July 2007
Reversibly Switchable Double-Responsive Block Copolymer Brushes Wang, Xi; Xiao, Xing; Wang, Xiaohong Macromolecular Rapid Communications, Vol. 28, Issue 7 https://doi.org/10.1002/marc.200600796	journal	April 2007
Synthesis of High Density Polymer Brushes on Nanoparticles by Combined RAFT Polymerization and Click Chemistry Ranjan, Rajesh; Brittain, William J. Macromolecular Rapid Communications, Vol. 29, Issue 12–13 https://doi.org/10.1002/marc.200800085	journal	July 2008
Chemistry and technology of 2-alkenyl azlactones Heilmann, Steven M.; Rasmussen, Jerald K.; Krepski, Larry R. Journal of Polymer Science Part A: Polymer Chemistry, Vol. 39, Issue 21 https://doi.org/10.1002/pola.10007	journal	January 2001
Synthesis and monomer reactivity ratios of methyl methacrylate and 2-vinyl-4,4?-dimethylazlactone copolymers Stanek, Lee G.; Heilmann, Steven M.; Gleason, William B. Journal of Polymer Science Part A: Polymer Chemistry, Vol. 41, Issue 19 https://doi.org/10.1002/pola.10897	journal	August 2003
A structural definition of polymer brushes Brittain, William J.; Minko, Sergiy Journal of Polymer Science Part A: Polymer Chemistry, Vol. 45, Issue 16 https://doi.org/10.1002/pola.22180	journal	January 2007
Polymer brushes: surface-immobilized macromolecules Zhao, B.; Brittain, W. J. Progress in Polymer Science, Vol. 25, Issue 5 https://doi.org/10.1016/S0079-6700(00)00012-5	journal	June 2000
RGD—Functionalized polymer brushes as substrates for the integrin specific adhesion of human umbilical vein endothelial cells Tugulu, Stefano; Silacci, Paolo; Stergiopulos, Nikolaos Biomaterials, Vol. 28, Issue 16 https://doi.org/10.1016/j.biomaterials.2007.02.006	journal	June 2007
The effect of integrin-specific bioactive coatings on tissue healing and implant osseointegration Petrie, Timothy A.; Raynor, Jenny E.; Reyes, Catherine D. Biomaterials, Vol. 29, Issue 19 https://doi.org/10.1016/j.biomaterials.2008.03.036	journal	July 2008
Surface functionalization by smart coatings: Stimuli-responsive binary polymer brushes Uhlmann, Petra; Ionov, Leonid; Houbenov, Nikolay Progress in Organic Coatings, Vol. 55, Issue 2 https://doi.org/10.1016/j.porgcoat.2005.09.014	journal	February 2006
Applications of surface-grafted macromolecules derived from post-polymerization modification reactions Galvin, Casey J.; Genzer, Jan Progress in Polymer Science, Vol. 37, Issue 7 https://doi.org/10.1016/j.progpolymsci.2011.12.001	journal	July 2012
Amidine-Functionalized Poly(2-vinyl-4,4-dimethylazlactone) for Selective and Efficient CO ₂ Fixing Barkakaty, Balaka; Browning, Katie L.; Sumpter, Bobby Macromolecules, Vol. 49, Issue 5 https://doi.org/10.1021/acs.macromol.5b02483	journal	February 2016
Degrafting of Poly(poly(ethylene glycol) methacrylate) Brushes from Planar and Spherical Silicon Substrates Ataman, Nariye Cavusoglu; Klok, Harm-Anton Macromolecules, Vol. 49, Issue 23 https://doi.org/10.1021/acs.macromol.6b01445	journal	November 2016
Expanding the Polymer Mechanochemistry Toolbox through Surface-Initiated Polymerization Klok, Harm-Anton; Genzer, Jan ACS Macro Letters, Vol. 4, Issue 6 https://doi.org/10.1021/acsmacrolett.5b00295	journal	May 2015
Protein-Resistant NTA-Functionalized Polymer Brushes for Selective and Stable Immobilization of Histidine-Tagged Proteins Gautrot, Julien E.; Huck, Wilhelm T. S.; Welch, Martin ACS Applied Materials & Interfaces, Vol. 2, Issue 1 https://doi.org/10.1021/am9006484	journal	December 2009
Protein-Functionalized Polymer Brushes Tugulu, Stefano; Arnold, Anke; Sielaff, India Biomacromolecules, Vol. 6, Issue 3 https://doi.org/10.1021/bm050016n	journal	May 2005
Lectin-Functionalized Poly(glycidyl methacrylate)- block -poly(vinyldimethyl azlactone) Surface Scaffolds for High Avidity Microbial Capture Hansen, Ryan R.; Hinestrosa, Juan Pablo; Shubert, Katherine R. Biomacromolecules, Vol. 14, Issue 10 https://doi.org/10.1021/bm4011358	journal	September 2013
High-Capacity Purification of His-tagged Proteins by Affinity Membranes Containing Functionalized Polymer Brushes Jain, Parul; Sun, Lei; Dai, Jinhua Biomacromolecules, Vol. 8, Issue 10 https://doi.org/10.1021/bm700515m	journal	September 2007
Stability and Nonfouling Properties of Poly(poly(ethylene glycol) methacrylate) Brushes under Cell Culture Conditions Tugulu, Stefano; Klok, Harm-Anton Biomacromolecules, Vol. 9, Issue 3 https://doi.org/10.1021/bm701293g	journal	February 2008
Polymer Brushes via Surface-Initiated Controlled Radical Polymerization: Synthesis, Characterization, Properties, and Applications Barbey, Raphael; Lavanant, Laurent; Paripovic, Dusko Chemical Reviews, Vol. 109, Issue 11 https://doi.org/10.1021/cr900045a	journal	November 2009
Synthesis and Surface Morphology of High-Density Poly(ethylene glycol) Grafted Layers Zdyrko, Bogdan; Klep, Viktor; Luzinov, Igor Langmuir, Vol. 19, Issue 24 https://doi.org/10.1021/la034974r	journal	November 2003
Effect of Molecular Weight on Synthesis and Surface Morphology of High-Density Poly(ethylene glycol) Grafted Layers Zdyrko, Bogdan; Varshney, Sunil K.; Luzinov, Igor Langmuir, Vol. 20, Issue 16 https://doi.org/10.1021/la049359h	journal	August 2004
High-Capacity Binding of Proteins by Poly(Acrylic Acid) Brushes and Their Derivatives Dai, Jinhua; Bao, Zhiyi; Sun, Lei Langmuir, Vol. 22, Issue 9 https://doi.org/10.1021/la0600550	journal	April 2006
Submicron Streptavidin Patterns for Protein Assembly Christman, Karen L.; Requa, Michael V.; Enriquez-Rios, Vanessa D. Langmuir, Vol. 22, Issue 17 https://doi.org/10.1021/la0608213	journal	August 2006
Room Temperature, Aqueous Post-Polymerization Modification of Glycidyl Methacrylate-Containing Polymer Brushes Prepared via Surface-Initiated Atom Transfer Radical Polymerization Barbey, Raphael; Klok, Harm-Anton Langmuir, Vol. 26, Issue 23 https://doi.org/10.1021/la102400z	journal	December 2010
Versatility of Alkyne-Modified Poly(Glycidyl Methacrylate) Layers for Click Reactions Soto-Cantu, Erick; Lokitz, Bradley S.; Hinestrosa, Juan Pablo Langmuir, Vol. 27, Issue 10 https://doi.org/10.1021/la2000798	journal	May 2011
Enhanced Stability of Low Fouling Zwitterionic Polymer Brushes in Seawater with Diblock Architecture Quintana, Robert; Gosa, Maria; Jańczewski, Dominik Langmuir, Vol. 29, Issue 34 https://doi.org/10.1021/la402287a	journal	August 2013
Polymeric Brushes as Functional Templates for Immobilizing Ribonuclease A: Study of Binding Kinetics and Activity Cullen, Sean P.; Liu, Xiaosong; Mandel, Ian C. Langmuir, Vol. 24, Issue 3 https://doi.org/10.1021/la702510z	journal	December 2007
Adsorption of poly(2-vinylpyridine)-poly (styrene) block copolymers from toluene solutions Parsonage, Edward; Tirrell, Matthew; Watanabe, Hiroshi Macromolecules, Vol. 24, Issue 8 https://doi.org/10.1021/ma00008a041	journal	April 1991
Structure and Scaling of Polymer Brushes near the ϑ Condition Kilbey, S. Michael; Watanabe, Hiroshi; Tirrell, Matthew Macromolecules, Vol. 34, Issue 15 https://doi.org/10.1021/ma001343k	journal	July 2001
Theory of the grafted polymer brush Milner, S. T.; Witten, T. A.; Cates, M. E. Macromolecules, Vol. 21, Issue 8 https://doi.org/10.1021/ma00186a051	journal	August 1988
Effects of polydispersity in the end-grafted polymer brush Milner, S. T.; Witten, T. A.; Cates, M. E. Macromolecules, Vol. 22, Issue 2 https://doi.org/10.1021/ma00192a057	journal	March 1989
Polystyrene Layers Grafted to Macromolecular Anchoring Layer Iyer, K. Swaminatha; Zdyrko, Bogdan; Malz, Hauke Macromolecules, Vol. 36, Issue 17 https://doi.org/10.1021/ma034460z	journal	August 2003
Versatile Pathway to Functional Telechelics via RAFT Polymerization and Click Chemistry Gondi, Sudershan R.; Vogt, Andrew P.; Sumerlin, Brent S. Macromolecules, Vol. 40, Issue 3 https://doi.org/10.1021/ma061959v	journal	January 2007
Synthesis of Functionalized Polymer Monolayers from Active Ester Brushes Murata, Hironobu; Prucker, Oswald; Rühe, Jürgen Macromolecules, Vol. 40, Issue 15 https://doi.org/10.1021/ma0624550	journal	June 2007
Neutron Reflectivity Study on the Postpolymerization Modification of Poly(2-hydroxyethyl methacrylate) Brushes Schüwer, Nicolas; Geue, Thomas; Hinestrosa, Juan Pablo Macromolecules, Vol. 44, Issue 17 https://doi.org/10.1021/ma201069d	journal	September 2011
Surface-Initiated Polymerization by Means of Novel, Stable, Non-Ester-Based Radical Initiator Bain, Erich D.; Dawes, Keith; Özçam, A. Evren Macromolecules, Vol. 45, Issue 9 https://doi.org/10.1021/ma300491e	journal	April 2012
Manipulating Interfaces through Surface Confinement of Poly(glycidyl methacrylate)- block -poly(vinyldimethylazlactone), a Dually Reactive Block Copolymer Lokitz, Bradley S.; Wei, Jifeng; Hinestrosa, Juan Pablo Macromolecules, Vol. 45, Issue 16 https://doi.org/10.1021/ma300991p	journal	July 2012
Postpolymerization Modification of Poly(glycidyl methacrylate) Brushes: An XPS Depth-Profiling Study Barbey, Raphael; Laporte, Vincent; Alnabulsi, Saad Macromolecules, Vol. 46, Issue 15 https://doi.org/10.1021/ma400819a	journal	July 2013
Conformations of Polymers Attached to an Interface de Gennes, P. G. Macromolecules, Vol. 13, Issue 5 https://doi.org/10.1021/ma60077a009	journal	September 1980
Highly Tailorable Materials based on 2-Vinyl-4,4-dimethyl Azlactone: (Co)Polymerization, Synthetic Manipulation and Characterization Messman, Jamie M.; Lokitz, Bradley S.; Pickel, Joseph M. Macromolecules, Vol. 42, Issue 12 https://doi.org/10.1021/ma900316t	journal	May 2009
Role of Surface Reorganization on Preferential Adsorption of Macromolecular Ensembles at the Solid/Fluid Interface Hinestrosa, Juan Pablo; Alonzo, Jose; Mays, Jimmy W. Macromolecules, Vol. 42, Issue 20 https://doi.org/10.1021/ma901347r	journal	September 2009
Dilute Solution Properties and Surface Attachment of RAFT Polymerized 2-Vinyl-4,4-dimethyl Azlactone (VDMA) Lokitz, Bradley S.; Messman, Jamie M.; Hinestrosa, Juan Pablo Macromolecules, Vol. 42, Issue 22 https://doi.org/10.1021/ma9015399	journal	November 2009
Hydration in Weak Polyelectrolyte Brushes Deodhar, Chaitra; Soto-Cantu, Erick; Uhrig, David ACS Macro Letters, Vol. 2, Issue 5 https://doi.org/10.1021/mz300615v	journal	April 2013
Synthesis of multifunctional polymer brush surfaces via sequential and orthogonal thiol-click reactions Rahane, Santosh B.; Hensarling, Ryan M.; Sparks, Bradley J. J. Mater. Chem., Vol. 22, Issue 3 https://doi.org/10.1039/C1JM14762E	journal	January 2012
Azlactone-functionalized polymers as reactive platforms for the design of advanced materials: Progress in the last ten years Buck, Maren E.; Lynn, David M. Polym. Chem., Vol. 3, Issue 1 https://doi.org/10.1039/C1PY00314C	journal	January 2012
Microphase separation in thin films of lamellar forming polydisperse di-block copolymers Kumar, Rajeev; Lokitz, Bradley S.; Sides, Scott W. RSC Advances, Vol. 5, Issue 27 https://doi.org/10.1039/C5RA00974J	journal	January 2015
Azlactone-functionalized polymers as reactive templates for parallel polymer synthesis: synthesis and screening of a small library of cationic polymers in the context of DNA delivery Sun, Bin; Liu, Xianghui; Buck, Maren E. Chemical Communications, Vol. 46, Issue 12 https://doi.org/10.1039/b921664b	journal	January 2010
Adsorption of chain molecules with a polar head a scaling description Alexander, S. Journal de Physique, Vol. 38, Issue 8 https://doi.org/10.1051/jphys:01977003808098300	journal	January 1977
Polymer Brushes Milner, S. T. Science, Vol. 251, Issue 4996 https://doi.org/10.1126/science.251.4996.905	journal	February 1991
Applications of Polymer Brushes in Protein Analysis and Purification Jain, Parul; Baker, Gregory L.; Bruening, Merlin L. Annual Review of Analytical Chemistry, Vol. 2, Issue 1 https://doi.org/10.1146/annurev-anchem-060908-155153	journal	July 2009
Biofunctional and Biomimetic Polymer Brushes Prepared via Surface-Initiated Atom Transfer Radical Polymerization Lavanant, Laurent; Klok, Harm-Anton CHIMIA International Journal for Chemistry, Vol. 62, Issue 10 https://doi.org/10.2533/chimia.2008.793	journal	October 2008

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Quasi-3D-Structured Interfaces by Polymer Brushes Benetti, Edmondo M. Macromolecular Rapid Communications, Vol. 39, Issue 14 https://doi.org/10.1002/marc.201800189	journal	May 2018

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