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Title: Biocompatible Nanocoatings of Fluorinated Polyphosphazenes through Aqueous Assembly

Abstract

Nonionic fluorinated polyphosphazenes, such as poly[bis(trifluoroethoxy)phosphazene] (PTFEP), display superb biocompatibility, yet their deposition to surfaces has been limited to solution casting from organic solvents or thermal molding. Here in this paper, hydrophobic coatings of fluorinated polyphosphazenes are demonstrated through controlled deposition of ionic fluorinated polyphosphazenes (iFPs) from aqueous solutions using the layer-by-layer (LbL) technique. Specifically, the assemblies included poly[(carboxylatophenoxy)(trifluoroethoxy)phosphazenes] with varied content of fluorine atoms as iFPs (or poly[bis(carboxyphenoxy)phosphazene] (PCPP) as a control nonfluorinated polyphosphazene) and a variety of polycations. Hydrophobic interactions largely contributed to the formation of LbL films of iFPs with polycations, leading to linear growth and extremely low water uptake. Hydrophobicity-enhanced ionic pairing within iFP/BPEI assemblies gave rise to large-amplitude oscillations in surface wettability as a function of capping layer, which were the largest for the most fluorinated iFP, while control PCPP/polycation systems remained hydrophilic regardless of the film top layer. Neutron reflectometry (NR) studies indicated superior layering and persistence of such layering in salt solution for iFP/BPEI films as compared to control PCPP/polycation systems. Hydrophobicity of iFP-capped LbL coatings could be further enhanced by using a highly porous polyester surgical felt rather than planar substrates for film deposition. Importantly, iFP/polycation coatings displayed biocompatibility which was similarmore » to or superior to that of solution-cast coatings of a clinically validated material (PTFEP), as demonstrated by the hemolysis of the whole blood and protein adsorption studies.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2];  [3];  [3]; ORCiD logo [1]
  1. Texas A & M Univ., College Station, TX (United States). Dept. of Materials Science & Engineering
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)
  3. Univ. of Maryland, Rockville, MD (United States). Inst. for Bioscience and Biotechnology Research
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1430612
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 10; Journal Issue: 11; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Selin, Victor, Albright, Victoria, Ankner, John Francis, Marin, Alexander, Andrianov, Alexander K., and Sukhishvili, Svetlana A. Biocompatible Nanocoatings of Fluorinated Polyphosphazenes through Aqueous Assembly. United States: N. p., 2018. Web. doi:10.1021/acsami.8b02072.
Selin, Victor, Albright, Victoria, Ankner, John Francis, Marin, Alexander, Andrianov, Alexander K., & Sukhishvili, Svetlana A. Biocompatible Nanocoatings of Fluorinated Polyphosphazenes through Aqueous Assembly. United States. https://doi.org/10.1021/acsami.8b02072
Selin, Victor, Albright, Victoria, Ankner, John Francis, Marin, Alexander, Andrianov, Alexander K., and Sukhishvili, Svetlana A. Fri . "Biocompatible Nanocoatings of Fluorinated Polyphosphazenes through Aqueous Assembly". United States. https://doi.org/10.1021/acsami.8b02072. https://www.osti.gov/servlets/purl/1430612.
@article{osti_1430612,
title = {Biocompatible Nanocoatings of Fluorinated Polyphosphazenes through Aqueous Assembly},
author = {Selin, Victor and Albright, Victoria and Ankner, John Francis and Marin, Alexander and Andrianov, Alexander K. and Sukhishvili, Svetlana A.},
abstractNote = {Nonionic fluorinated polyphosphazenes, such as poly[bis(trifluoroethoxy)phosphazene] (PTFEP), display superb biocompatibility, yet their deposition to surfaces has been limited to solution casting from organic solvents or thermal molding. Here in this paper, hydrophobic coatings of fluorinated polyphosphazenes are demonstrated through controlled deposition of ionic fluorinated polyphosphazenes (iFPs) from aqueous solutions using the layer-by-layer (LbL) technique. Specifically, the assemblies included poly[(carboxylatophenoxy)(trifluoroethoxy)phosphazenes] with varied content of fluorine atoms as iFPs (or poly[bis(carboxyphenoxy)phosphazene] (PCPP) as a control nonfluorinated polyphosphazene) and a variety of polycations. Hydrophobic interactions largely contributed to the formation of LbL films of iFPs with polycations, leading to linear growth and extremely low water uptake. Hydrophobicity-enhanced ionic pairing within iFP/BPEI assemblies gave rise to large-amplitude oscillations in surface wettability as a function of capping layer, which were the largest for the most fluorinated iFP, while control PCPP/polycation systems remained hydrophilic regardless of the film top layer. Neutron reflectometry (NR) studies indicated superior layering and persistence of such layering in salt solution for iFP/BPEI films as compared to control PCPP/polycation systems. Hydrophobicity of iFP-capped LbL coatings could be further enhanced by using a highly porous polyester surgical felt rather than planar substrates for film deposition. Importantly, iFP/polycation coatings displayed biocompatibility which was similar to or superior to that of solution-cast coatings of a clinically validated material (PTFEP), as demonstrated by the hemolysis of the whole blood and protein adsorption studies.},
doi = {10.1021/acsami.8b02072},
journal = {ACS Applied Materials and Interfaces},
number = 11,
volume = 10,
place = {United States},
year = {Fri Feb 23 00:00:00 EST 2018},
month = {Fri Feb 23 00:00:00 EST 2018}
}

Journal Article:
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Cited by: 14 works
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Figures / Tables:

Scheme 1 Scheme 1: Chemical Structures of the Components and Schematic Representation of the LbL Assembly

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Works referenced in this record:

Coronary Stents
journal, August 2010

  • Garg, Scot; Serruys, Patrick W.
  • Journal of the American College of Cardiology, Vol. 56, Issue 10
  • DOI: 10.1016/j.jacc.2010.06.007

Coronary stents: A materials perspective
journal, March 2007


Drug-Eluting Bioresorbable Stents for Various Applications
journal, August 2006


Stent Thrombosis
journal, October 2010

  • Holmes, David R.; Kereiakes, Dean J.; Garg, Scot
  • Journal of the American College of Cardiology, Vol. 56, Issue 17
  • DOI: 10.1016/j.jacc.2010.07.016

Biomaterials for Drug Delivery and Tissue Engineering
journal, June 2006


Plasma Protein Adsorption and Platelet Adhesion on Poly[bis(trifluoroethoxy)phosphazene] and Reference Material Surfaces
journal, January 1998

  • Welle, Alexander; Grunze, Michael; Tur, Dsidra
  • Journal of Colloid and Interface Science, Vol. 197, Issue 2
  • DOI: 10.1006/jcis.1997.5238

Drug-Eluting Coronary Stent Very Late Thrombosis Revisited
journal, July 2008

  • Lanzer, Peter; Sternberg, Katrin; Schmitz, Klaus-Peter
  • Herz Kardiovaskuläre Erkrankungen, Vol. 33, Issue 5
  • DOI: 10.1007/s00059-008-3080-x

Stents as a platform for drug delivery
journal, March 2011


Predicting microstructure development during casting of drug-eluting coatings
journal, February 2011


Polymer assemblies for controlled delivery of bioactive molecules from surfaces
journal, August 2011


Layer-by-layer self-assembled multilayers on PEEK implants improve osseointegration in an osteoporosis rabbit model
journal, May 2017

  • Liu, Xilin; Han, Fei; Zhao, Peng
  • Nanomedicine: Nanotechnology, Biology and Medicine, Vol. 13, Issue 4
  • DOI: 10.1016/j.nano.2017.01.011

Polyphosphazene elastomers, gels, and other soft materials
journal, January 2012


Hydrophobic and superhydrophobic surfaces from polyphosphazenes
journal, January 2006

  • Allcock, Harry R.; Steely, Lee B.; Singh, Anurima
  • Polymer International, Vol. 55, Issue 6
  • DOI: 10.1002/pi.2030

9-Month Clinical and Angiographic Outcomes of the COBRA Polyzene-F NanoCoated Coronary Stent System
journal, January 2017

  • Cutlip, Donald E.; Garratt, Kirk N.; Novack, Victor
  • JACC: Cardiovascular Interventions, Vol. 10, Issue 2
  • DOI: 10.1016/j.jcin.2016.10.037

A case report of the new Polyzene™-F COBRA PzF™ Nanocoated Coronary Stent System (NCS): Addressing an unmet clinical need
journal, April 2016


Conductivity Spectra of Polyphosphazene-Based Polyelectrolyte Multilayers
journal, July 2007

  • Akgöl, Yahya; Hofmann, Christian; Karatas, Yunus
  • The Journal of Physical Chemistry B, Vol. 111, Issue 29
  • DOI: 10.1021/jp068872w

Ion Conduction and Water Transport in Polyphosphazene-Based Multilayers
journal, December 2009

  • Argun, Avni A.; Ashcraft, J. Nathan; Herring, Marie K.
  • Chemistry of Materials, Vol. 22, Issue 1
  • DOI: 10.1021/cm902769m

Fluorinated polyphosphazene polyelectrolytes
journal, January 2006

  • Andrianov, Alexander K.; Marin, Alexander; Peterson, Paul
  • Journal of Applied Polymer Science, Vol. 103, Issue 1
  • DOI: 10.1002/app.23963

Investigation of the Influence of Polyelectrolyte Charge Density on the Growth of Multilayer Thin Films Prepared by the Layer-by-Layer Technique
journal, January 2002

  • Schoeler, Bjoern; Kumaraswamy, Guruswamy; Caruso, Frank
  • Macromolecules, Vol. 35, Issue 3
  • DOI: 10.1021/ma011349p

Determination of optical constants of molecular films assembled via alternate polyion adsorption
journal, January 1995


Influence of Polymer Molecular Weight on the Parabolic and Linear Growth Regime of PDADMAC/PSS Multilayers
journal, July 2013

  • Nestler, Peter; Paßvogel, Malte; Helm, Christiane A.
  • Macromolecules, Vol. 46, Issue 14
  • DOI: 10.1021/ma400333f

Molecular Weight Dependence of Polymer Chain Mobility within Multilayer Films
journal, September 2013

  • Xu, Li; Selin, Victor; Zhuk, Aliaksandr
  • ACS Macro Letters, Vol. 2, Issue 10
  • DOI: 10.1021/mz400413v

Nonlinear Layer-by-Layer Films: Effects of Chain Diffusivity on Film Structure and Swelling
journal, August 2017


Diffusional Response of Layer-by-Layer Assembled Polyelectrolyte Chains to Salt Annealing
journal, June 2015


Chain Conformation and Dynamics in Spin-Assisted Weak Polyelectrolyte Multilayers
journal, March 2015


Self-Defensive Layer-by-Layer Films with Bacteria-Triggered Antibiotic Release
journal, July 2014

  • Zhuk, Iryna; Jariwala, Freneil; Attygalle, Athula B.
  • ACS Nano, Vol. 8, Issue 8
  • DOI: 10.1021/nn500674g

Midterm Results of Uterine Artery Embolization Using Narrow-Size Calibrated Embozene Microspheres
journal, October 2010

  • Stampfl, Ulrike; Radeleff, Boris; Sommer, Christof
  • CardioVascular and Interventional Radiology, Vol. 34, Issue 2
  • DOI: 10.1007/s00270-010-9986-8

Synthesis and Biologically Relevant Properties of Polyphosphazene Polyacids
journal, September 2004

  • Andrianov, Alexander K.; Svirkin, Yuri Y.; LeGolvan, Mark P.
  • Biomacromolecules, Vol. 5, Issue 5
  • DOI: 10.1021/bm049745d

Poly(dichlorophosphazene) As a Precursor for Biologically Active Polyphosphazenes:  Synthesis, Characterization, and Stabilization
journal, December 2003

  • Andrianov, Alexander K.; Chen, Jianping; LeGolvan, Mark P.
  • Macromolecules, Vol. 37, Issue 2
  • DOI: 10.1021/ma0355655

Factors Controlling the Growth of Polyelectrolyte Multilayers
journal, November 1999

  • Dubas, Stephan T.; Schlenoff, Joseph B.
  • Macromolecules, Vol. 32, Issue 24
  • DOI: 10.1021/ma981927a

Standardization of incubation conditions for hemolysis testing of biomaterials
journal, June 2009

  • Henkelman, Sandra; Rakhorst, Gerhard; Blanton, John
  • Materials Science and Engineering: C, Vol. 29, Issue 5
  • DOI: 10.1016/j.msec.2009.01.002

Steric Effects in Ionic Pairing and Polyelectrolyte Interdiffusion within Multilayered Films: A Neutron Reflectometry Study
journal, August 2011

  • Xu, Li; Ankner, John F.; Sukhishvili, Svetlana A.
  • Macromolecules, Vol. 44, Issue 16
  • DOI: 10.1021/ma200986d

Diffusion of Sites versus Polymers in Polyelectrolyte Complexes and Multilayers
journal, October 2017

  • Fares, Hadi M.; Schlenoff, Joseph B.
  • Journal of the American Chemical Society, Vol. 139, Issue 41
  • DOI: 10.1021/jacs.7b07905

Layer-by-layer self-assembly: The contribution of hydrophobic interactions
journal, January 1999


Hydrophobic and Ultrahydrophobic Multilayer Thin Films from Perfluorinated Polyelectrolytes
journal, January 2005

  • Jisr, Rana M.; Rmaile, Hassan H.; Schlenoff, Joseph B.
  • Angewandte Chemie International Edition, Vol. 44, Issue 5
  • DOI: 10.1002/anie.200461645

Influence of Free Volume Change on the Relative Permittivity and Refractive Index in Fluoropolyimides
journal, January 1996

  • Hougham, Gareth; Tesoro, Guiliana; Viehbeck, Alfred
  • Macromolecules, Vol. 29, Issue 10
  • DOI: 10.1021/ma9503423

Effect of orientation and mobility of polymer molecules at surfaces on contact angle and its hysteresis
journal, September 1981

  • Yasuda, H.; Sharma, Ashok K.; Yasuda, Takeshi
  • Journal of Polymer Science: Polymer Physics Edition, Vol. 19, Issue 9
  • DOI: 10.1002/pol.1981.180190901

High-Resolution Adhesion Mapping of the Odd–Even Effect on a Layer-by-Layer Coated Biomaterial by Atomic-Force-Microscopy
journal, April 2017

  • Casdorff, Kirstin; Keplinger, Tobias; Bellanger, Hervé
  • ACS Applied Materials & Interfaces, Vol. 9, Issue 15
  • DOI: 10.1021/acsami.7b02564

Odd-even effect during layer-by-layer assembly of polyelectrolytes inspired by marine mussel
journal, November 2016

  • Wang, Weina; Xu, Yisheng; Han, Haoya
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 55, Issue 3
  • DOI: 10.1002/polb.24266

Thermal Behavior of Polyelectrolyte Multilayer Microcapsules. 1. The Effect of Odd and Even Layer Number
journal, October 2005

  • Köhler, Karen; Shchukin, Dmitry G.; Möhwald, Helmuth
  • The Journal of Physical Chemistry B, Vol. 109, Issue 39
  • DOI: 10.1021/jp052208i

The effect of support material and conditioning on wettability of PAH/PSS multilayer films
journal, April 2005


The effect of nature of polyions and treatment after deposition on wetting characteristics of polyelectrolyte multilayers
journal, October 2005


Linear versus Exponential Growth of Weak Polyelectrolyte Multilayers: Correlation with Polyelectrolyte Complexes
journal, April 2012

  • Xu, Li; Pristinski, Denis; Zhuk, Aliaksandr
  • Macromolecules, Vol. 45, Issue 9
  • DOI: 10.1021/ma300157p

Detailed Structure of Molecularly Thin Polyelectrolyte Multilayer Films on Solid Substrates as Revealed by Neutron Reflectometry
journal, December 1998

  • Lösche, Mathias; Schmitt, Johannes; Decher, Gero
  • Macromolecules, Vol. 31, Issue 25
  • DOI: 10.1021/ma980910p

Hydrogen-Bonded Polymer Multilayers Probed by Neutron Reflectivity
journal, October 2008

  • Kharlampieva, Eugenia; Kozlovskaya, Veronika; Ankner, John F.
  • Langmuir, Vol. 24, Issue 20
  • DOI: 10.1021/la802502c

Surface functionalization of nanostructured silver-coated polyester fabric by magnetron sputtering
journal, August 2010


Resistance Of Solid Surfaces To Wetting By Water
journal, August 1936

  • Wenzel, Robert N.
  • Industrial & Engineering Chemistry, Vol. 28, Issue 8, p. 988-994
  • DOI: 10.1021/ie50320a024

Proteins, platelets, and blood coagulation at biomaterial interfaces
journal, December 2014


Biomaterials and Implants in Cardiac and Vascular Surgery - Review
journal, October 2014


Works referencing / citing this record:

The Background and Scope of Polyphosphazenes as Biomedical Materials
journal, September 2019


The effect of ionic strength and phosphate ions on the construction of redox polyelectrolyte–enzyme self-assemblies
journal, January 2019

  • Zappi, Daniele; Coria-Oriundo, Lucy L.; Piccinini, Esteban
  • Physical Chemistry Chemical Physics, Vol. 21, Issue 41
  • DOI: 10.1039/c9cp04037d

Hierarchy of Hybrid Materials—The Place of Inorganics-in-Organics in it, Their Composition and Applications
journal, April 2019

  • Saveleva, Mariia S.; Eftekhari, Karaneh; Abalymov, Anatolii
  • Frontiers in Chemistry, Vol. 7
  • DOI: 10.3389/fchem.2019.00179

Hierarchy of Hybrid Materials—The Place of Inorganics-in-Organics in it, Their Composition and Applications
journal, April 2019

  • Saveleva, Mariia S.; Eftekhari, Karaneh; Abalymov, Anatolii
  • Frontiers in Chemistry, Vol. 7
  • DOI: 10.3389/fchem.2019.00179

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