DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Chemical copatterning strategies using azlactone-based block copolymers

Abstract

Interfaces can be modified with azlactone-functional polymers in order to manipulate the chemical surface reactivity. Azlactone groups are highly reactive toward amine, thiol, and alcohol nucleophiles, providing a versatile coupling chemistry for secondary surface modification. Azlactone-based surface polymers have been explored in numerous applications, including chemical and biological capture, sensing, and cell culture. These applications often require that the polymer is copatterned within a chemically or biologically inert background; however, common fabrication methods degrade azlactone groups during processing steps or result in polymer films with poorly controlled thicknesses. Here, the authors develop fabrication strategies using parylene lift-off and interface-directed assembly methods to generate microscale patterns of azlactone-based block copolymer in chemically or biologically inert backgrounds. The functionality of azlactone groups was preserved during fabrication, and patterned films appeared as uniform, 80–120nm brushlike films. The authors also develop a patterning approach that uses a novel microcontact stamping method to generate cross-linked, three-dimensional structures of azlactone-based polymers with controllable, microscale thicknesses. The authors identify the benefits of each approach and expect these polymers and patterning strategies to provide a versatile toolbox for developing synthetic interfaces with tuned chemical and physical features for sensing, cell culture, or material capture applications.

Authors:
 [1];  [1]; ORCiD logo [2]; ORCiD logo [2];  [1]
  1. Kansas State Univ., Manhattan, KS (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1427670
Alternate Identifier(s):
OSTI ID: 1378117
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Vacuum Science and Technology B
Additional Journal Information:
Journal Volume: 35; Journal Issue: 6; Journal ID: ISSN 2166-2746
Publisher:
American Vacuum Society/AIP
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Masigol, Mohammadali, Barua, Niloy, Retterer, Scott T., Lokitz, Bradley S., and Hansen, Ryan. Chemical copatterning strategies using azlactone-based block copolymers. United States: N. p., 2017. Web. doi:10.1116/1.4991881.
Masigol, Mohammadali, Barua, Niloy, Retterer, Scott T., Lokitz, Bradley S., & Hansen, Ryan. Chemical copatterning strategies using azlactone-based block copolymers. United States. https://doi.org/10.1116/1.4991881
Masigol, Mohammadali, Barua, Niloy, Retterer, Scott T., Lokitz, Bradley S., and Hansen, Ryan. Fri . "Chemical copatterning strategies using azlactone-based block copolymers". United States. https://doi.org/10.1116/1.4991881. https://www.osti.gov/servlets/purl/1427670.
@article{osti_1427670,
title = {Chemical copatterning strategies using azlactone-based block copolymers},
author = {Masigol, Mohammadali and Barua, Niloy and Retterer, Scott T. and Lokitz, Bradley S. and Hansen, Ryan},
abstractNote = {Interfaces can be modified with azlactone-functional polymers in order to manipulate the chemical surface reactivity. Azlactone groups are highly reactive toward amine, thiol, and alcohol nucleophiles, providing a versatile coupling chemistry for secondary surface modification. Azlactone-based surface polymers have been explored in numerous applications, including chemical and biological capture, sensing, and cell culture. These applications often require that the polymer is copatterned within a chemically or biologically inert background; however, common fabrication methods degrade azlactone groups during processing steps or result in polymer films with poorly controlled thicknesses. Here, the authors develop fabrication strategies using parylene lift-off and interface-directed assembly methods to generate microscale patterns of azlactone-based block copolymer in chemically or biologically inert backgrounds. The functionality of azlactone groups was preserved during fabrication, and patterned films appeared as uniform, 80–120nm brushlike films. The authors also develop a patterning approach that uses a novel microcontact stamping method to generate cross-linked, three-dimensional structures of azlactone-based polymers with controllable, microscale thicknesses. The authors identify the benefits of each approach and expect these polymers and patterning strategies to provide a versatile toolbox for developing synthetic interfaces with tuned chemical and physical features for sensing, cell culture, or material capture applications.},
doi = {10.1116/1.4991881},
journal = {Journal of Vacuum Science and Technology B},
number = 6,
volume = 35,
place = {United States},
year = {Fri Sep 01 00:00:00 EDT 2017},
month = {Fri Sep 01 00:00:00 EDT 2017}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 5 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Assessing Chemical Transformation of Reactive, Interfacial Thin Films Made of End-Tethered Poly(2-vinyl-4,4-dimethyl azlactone) (PVDMA) Chains
journal, January 2017


Nanopatterned Smart Polymer Surfaces for Controlled Attachment, Killing, and Release of Bacteria
journal, September 2013

  • Yu, Qian; Cho, Janghwan; Shivapooja, Phanindhar
  • ACS Applied Materials & Interfaces, Vol. 5, Issue 19, p. 9295-9304
  • DOI: 10.1021/am4022279

Fabrication and Selective Functionalization of Amine-Reactive Polymer Multilayers on Topographically Patterned Microwell Cell Culture Arrays
journal, April 2011

  • Broderick, Adam H.; Azarin, Samira M.; Buck, Maren E.
  • Biomacromolecules, Vol. 12, Issue 6
  • DOI: 10.1021/bm200296a

Preparation and characterization of azlactone functionalized polymer supports and their application as scavengers
journal, October 2004


Peptide Conjugation to a Polymer Coating via Native Chemical Ligation of Azlactones for Cell Culture
journal, February 2016


Poly(azlactone)s: versatile scaffolds for tandem post-polymerisation modification and glycopolymer synthesis
journal, January 2013

  • Jones, Mathew W.; Richards, Sarah-Jane; Haddleton, David M.
  • Polym. Chem., Vol. 4, Issue 3
  • DOI: 10.1039/C2PY20757E

Amidine-Functionalized Poly(2-vinyl-4,4-dimethylazlactone) for Selective and Efficient CO 2 Fixing
journal, February 2016


Polyethylene Glycol Coatings on Plastic Substrates for Chemically Defined Stem Cell Culture
journal, May 2015

  • Schmitt, Samantha K.; Xie, Angela W.; Ghassemi, Raha M.
  • Advanced Healthcare Materials, Vol. 4, Issue 10
  • DOI: 10.1002/adhm.201500191

Surface-Anchored Poly(2-vinyl-4,4-dimethyl azlactone) Brushes as Templates for Enzyme Immobilization
journal, October 2008

  • Cullen, Sean P.; Mandel, Ian C.; Gopalan, Padma
  • Langmuir, Vol. 24, Issue 23
  • DOI: 10.1021/la8024952

Nonleaching Bacteria-Responsive Antibacterial Surface Based on a Unique Hierarchical Architecture
journal, September 2016

  • Yan, Shunjie; Shi, Hengchong; Song, Lingjie
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 37
  • DOI: 10.1021/acsami.6b08436

Microstructured Block Copolymer Surfaces for Control of Microbe Adhesion and Aggregation
journal, March 2014

  • Hansen, Ryan; Shubert, Katherine; Morrell-Falvey, Jennifer
  • Biosensors, Vol. 4, Issue 1
  • DOI: 10.3390/bios4010063

Lectin-Functionalized Poly(glycidyl methacrylate)- block -poly(vinyldimethyl azlactone) Surface Scaffolds for High Avidity Microbial Capture
journal, September 2013

  • Hansen, Ryan R.; Hinestrosa, Juan Pablo; Shubert, Katherine R.
  • Biomacromolecules, Vol. 14, Issue 10
  • DOI: 10.1021/bm4011358

Self-Assembly and Post-Fabrication Functionalization of Microphase Separated Thin Films of a Reactive Azlactone-Containing Block Copolymer
journal, October 2016


Manipulating Interfaces through Surface Confinement of Poly(glycidyl methacrylate)- block -poly(vinyldimethylazlactone), a Dually Reactive Block Copolymer
journal, July 2012

  • Lokitz, Bradley S.; Wei, Jifeng; Hinestrosa, Juan Pablo
  • Macromolecules, Vol. 45, Issue 16
  • DOI: 10.1021/ma300991p

Dilute Solution Properties and Surface Attachment of RAFT Polymerized 2-Vinyl-4,4-dimethyl Azlactone (VDMA)
journal, November 2009

  • Lokitz, Bradley S.; Messman, Jamie M.; Hinestrosa, Juan Pablo
  • Macromolecules, Vol. 42, Issue 22
  • DOI: 10.1021/ma9015399

Highly Selective Protein Patterning on Gold−Silicon Substrates for Biosensor Applications
journal, July 2002

  • Veiseh, Mandana; Zareie, M. Hadi; Zhang, Miqin
  • Langmuir, Vol. 18, Issue 17
  • DOI: 10.1021/la025529j

Elaboration of micro-domains of supported bilayer membranes using micro-contact printing
journal, May 2007


Controlling condensation and frost growth with chemical micropatterns
journal, January 2016

  • Boreyko, Jonathan B.; Hansen, Ryan R.; Murphy, Kevin R.
  • Scientific Reports, Vol. 6, Issue 1
  • DOI: 10.1038/srep19131

Surface Engineering and Patterning Using Parylene for Biological Applications
journal, March 2010

  • Tan, Christine P.; Craighead, Harold G.
  • Materials, Vol. 3, Issue 3
  • DOI: 10.3390/ma3031803

Nanoscale Resolution, Multicomponent Biomolecular Arrays Generated By Aligned Printing With Parylene Peel-Off
journal, February 2010

  • Tan, Christine P.; Cipriany, Benjamin R.; Lin, David M.
  • Nano Letters, Vol. 10, Issue 2
  • DOI: 10.1021/nl903968s

Cell and Protein Compatibility of Parylene-C Surfaces
journal, October 2007

  • Chang, Tracy Y.; Yadav, Vikramaditya G.; De Leo, Sarah
  • Langmuir, Vol. 23, Issue 23
  • DOI: 10.1021/la7017049

Stochastic Assembly of Bacteria in Microwell Arrays Reveals the Importance of Confinement in Community Development
journal, May 2016


The effect of retinal pigment epithelial cell patch size on growth factor expression
journal, April 2014


Soft lithography for micro- and nanoscale patterning
journal, February 2010


Stamps, inks and substrates: polymers in microcontact printing
journal, January 2010

  • Kaufmann, Tobias; Ravoo, Bart Jan
  • Polymer Chemistry, Vol. 1, Issue 4
  • DOI: 10.1039/b9py00281b

Lectin functionalized ZnO nanoarrays as a 3D nano-biointerface for bacterial detection
journal, May 2017


Heparin micropatterning onto fouling-release perfluoropolyether-based polymers via photobiotin activation
journal, October 2016


Evaporation Stains: Suppressing the Coffee-Ring Effect by Contact Angle Hysteresis
journal, June 2013

  • Li, Yueh-Feng; Sheng, Yu-Jane; Tsao, Heng-Kwong
  • Langmuir, Vol. 29, Issue 25
  • DOI: 10.1021/la400948e

Advanced printing and deposition methodologies for the fabrication of biosensors and biodevices
journal, January 2010

  • Gonzalez-Macia, Laura; Morrin, Aoife; Smyth, Malcolm R.
  • The Analyst, Vol. 135, Issue 5
  • DOI: 10.1039/b916888e

Works referencing / citing this record:

Electrospun Nanofibers for Label-Free Sensor Applications
journal, August 2019

  • Aliheidari, Nahal; Aliahmad, Nojan; Agarwal, Mangilal
  • Sensors, Vol. 19, Issue 16
  • DOI: 10.3390/s19163587

Electrospun Nanofibers for Label-Free Sensor Applications
journal, August 2019

  • Aliheidari, Nahal; Aliahmad, Nojan; Agarwal, Mangilal
  • Sensors, Vol. 19, Issue 16
  • DOI: 10.3390/s19163587