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

Title: In Situ Infrared Ellipsometry for Protein Adsorption Studies on Ultrathin Smart Polymer Brushes in Aqueous Environment

Abstract

The protein-adsorbing and -repelling properties of various smart nanometer-thin polymer brushes with high potential for biosensing and biomedical applications are studied by in-situ infrared-spectroscopic ellipsometry (IRSE). IRSE as a highly sensitive non-destructive technique allows us to investigate protein adsorption on polymer brushes in aqueous environment in dependence of external stimuli like temperature and pH. These stimuli are, for instance, relevant in switchable mixed brushes containing poly(N-isopropyl acrylamide) and poly(acrylic acid), respectively. We use such brushes as model surfaces for controlling protein adsorption of human serum albumin and human fibrinogen. IRSE can distinguish between polymer-specific vibrational bands, which yield insights into the hydration state of the brushes, and changes in the protein-specific amide bands, which are related to changes of the protein secondary structure.

Authors:
 [1];  [1];  [1];  [2];  [2];  [2];  [2];  [3];  [3];  [4];  [5];  [6];  [1]
  1. Leibniz Inst. for Analytical sciences (ISAS), Berlin (Germany)
  2. Leibniz Inst. of Polymer Research (IPF), Dresden (Germany)
  3. Clemson Univ., SC (United States). School of Materials Science and Engineering
  4. Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry and of Chemical Engineering
  5. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)
  6. Univ. of Georgia, Athens, GA (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Sponsoring Org.:
USDOE Office of Science (SC); German Research Foundation (DFG); National Science Foundation (NSF)
OSTI Identifier:
1286795
Grant/Contract Number:  
AC05-00OR22725; DMR-1107786; DFG HI 793/4-1
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 7; Journal Issue: 23; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
59 BASIC BIOLOGICAL SCIENCES; 36 MATERIALS SCIENCE; in situ infrared ellipsometry; infrared spectroscopy; polymer brushes; protein adsorption; solid−liquid interface; stimuli-responsive

Citation Formats

Kroning, Annika, Furchner, Andreas, Aulich, Dennis, Bittrich, Eva, Rauch, Sebastian, Uhlmann, Petra, Eichhorn, Klaus-Jochen, Seeber, Michael, Luzinov, Igor, Kilbey, S. Michael, Lokitz, Bradley S., Minko, Sergiy, and Hinrichs, Karsten. In Situ Infrared Ellipsometry for Protein Adsorption Studies on Ultrathin Smart Polymer Brushes in Aqueous Environment. United States: N. p., 2015. Web. doi:10.1021/am5075997.
Kroning, Annika, Furchner, Andreas, Aulich, Dennis, Bittrich, Eva, Rauch, Sebastian, Uhlmann, Petra, Eichhorn, Klaus-Jochen, Seeber, Michael, Luzinov, Igor, Kilbey, S. Michael, Lokitz, Bradley S., Minko, Sergiy, & Hinrichs, Karsten. In Situ Infrared Ellipsometry for Protein Adsorption Studies on Ultrathin Smart Polymer Brushes in Aqueous Environment. United States. https://doi.org/10.1021/am5075997
Kroning, Annika, Furchner, Andreas, Aulich, Dennis, Bittrich, Eva, Rauch, Sebastian, Uhlmann, Petra, Eichhorn, Klaus-Jochen, Seeber, Michael, Luzinov, Igor, Kilbey, S. Michael, Lokitz, Bradley S., Minko, Sergiy, and Hinrichs, Karsten. Tue . "In Situ Infrared Ellipsometry for Protein Adsorption Studies on Ultrathin Smart Polymer Brushes in Aqueous Environment". United States. https://doi.org/10.1021/am5075997. https://www.osti.gov/servlets/purl/1286795.
@article{osti_1286795,
title = {In Situ Infrared Ellipsometry for Protein Adsorption Studies on Ultrathin Smart Polymer Brushes in Aqueous Environment},
author = {Kroning, Annika and Furchner, Andreas and Aulich, Dennis and Bittrich, Eva and Rauch, Sebastian and Uhlmann, Petra and Eichhorn, Klaus-Jochen and Seeber, Michael and Luzinov, Igor and Kilbey, S. Michael and Lokitz, Bradley S. and Minko, Sergiy and Hinrichs, Karsten},
abstractNote = {The protein-adsorbing and -repelling properties of various smart nanometer-thin polymer brushes with high potential for biosensing and biomedical applications are studied by in-situ infrared-spectroscopic ellipsometry (IRSE). IRSE as a highly sensitive non-destructive technique allows us to investigate protein adsorption on polymer brushes in aqueous environment in dependence of external stimuli like temperature and pH. These stimuli are, for instance, relevant in switchable mixed brushes containing poly(N-isopropyl acrylamide) and poly(acrylic acid), respectively. We use such brushes as model surfaces for controlling protein adsorption of human serum albumin and human fibrinogen. IRSE can distinguish between polymer-specific vibrational bands, which yield insights into the hydration state of the brushes, and changes in the protein-specific amide bands, which are related to changes of the protein secondary structure.},
doi = {10.1021/am5075997},
journal = {ACS Applied Materials and Interfaces},
number = 23,
volume = 7,
place = {United States},
year = {Tue Feb 10 00:00:00 EST 2015},
month = {Tue Feb 10 00:00:00 EST 2015}
}

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

Citation Metrics:
Cited by: 31 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Poly (N-isopropylacrylamide) Microgel-Based Optical Devices for Sensing and Biosensing
journal, May 2014

  • Islam, Molla; Ahiabu, Andrews; Li, Xue
  • Sensors, Vol. 14, Issue 5
  • DOI: 10.3390/s140508984

In Situ Studies on the Switching Behavior of Ultrathin Poly(acrylic acid) Polyelectrolyte Brushes in Different Aqueous Environments
journal, August 2010

  • Aulich, Dennis; Hoy, Olha; Luzinov, Igor
  • Langmuir, Vol. 26, Issue 15
  • DOI: 10.1021/la101762f

Advantage of Fluorescence Correlation Spectroscopy for the Study of Polyelectrolytes
journal, September 2012

  • Jia, Pengxiang; Gong, Yongkuan; Wang, Shengqin
  • Chinese Journal of Chemistry, Vol. 30, Issue 9
  • DOI: 10.1002/cjoc.201200596

Temperature, ionic strength and pH induced electrochemical switching of smart polymer interfaces
journal, January 2006

  • Zhou, Jianhua; Wang, Geng; Hu, Jianqiang
  • Chemical Communications, Issue 46
  • DOI: 10.1039/b611405a

Synthetic Hydrophilic Materials with Tunable Strength and a Range of Hydrophobic Interactions
journal, June 2010

  • Hoy, Olha; Zdyrko, Bogdan; Lupitskyy, Robert
  • Advanced Functional Materials, Vol. 20, Issue 14
  • DOI: 10.1002/adfm.201000170

A Cytocompatible Poly( N -isopropylacrylamide- co -glycidylmethacrylate) Coated Surface as New Substrate for Corneal Tissue Engineering
journal, January 2010

  • Joseph, Nithya; Prasad, Tilak; Raj, Vidya
  • Journal of Bioactive and Compatible Polymers, Vol. 25, Issue 1
  • DOI: 10.1177/0883911509353481

Dynamic Contact Angle Measurement of Temperature-Responsive Surface Properties for Poly(N-isopropylacrylamide) Grafted Surfaces
journal, October 1994

  • Takei, Yoshiyuki G.; Aoki, Takashi; Sanui, Kohei
  • Macromolecules, Vol. 27, Issue 21
  • DOI: 10.1021/ma00099a035

Temperature-Sensitive Swelling of Poly( N -isopropylacrylamide) Brushes with Low Molecular Weight and Grafting Density
journal, February 2012

  • Bittrich, Eva; Burkert, Sina; Müller, Martin
  • Langmuir, Vol. 28, Issue 7
  • DOI: 10.1021/la204230a

Protein Adsorption on Poly( N -isopropylacrylamide) Brushes: Dependence on Grafting Density and Chain Collapse
journal, July 2011

  • Xue, Changying; Yonet-Tanyeri, Nihan; Brouette, Nicolas
  • Langmuir, Vol. 27, Issue 14
  • DOI: 10.1021/la2001909

Protein Resistance of PNIPAAm Brushes: Application to Switchable Protein Adsorption
journal, September 2009

  • Burkert, Sina; Bittrich, Eva; Kuntzsch, Marco
  • Langmuir, Vol. 26, Issue 3
  • DOI: 10.1021/la902505q

Protein adsorption on poly(N-isopropylacrylamide)-modified silicon surfaces: Effects of grafted layer thickness and protein size
journal, April 2010


Programmed Adsorption and Release of Proteins in a Microfluidic Device
journal, July 2003

  • Huber, Dale; Manginell, Ronald; Samara, Michael
  • Science, Vol. 301, Issue 5631, p. 352-354
  • DOI: 10.1126/science.1080759

Temperature dependent activity and structure of adsorbed proteins on plasma polymerized N -isopropyl acrylamide
journal, March 2006

  • Cheng, Xuanhong; Canavan, Heather E.; Graham, Daniel J.
  • Biointerphases, Vol. 1, Issue 1
  • DOI: 10.1116/1.2187980

Protein Adsorption Modes Determine Reversible Cell Attachment on Poly(N-isopropyl acrylamide) Brushes
journal, March 2012

  • Xue, Changying; Choi, Byun-Chan; Choi, Sangwook
  • Advanced Functional Materials, Vol. 22, Issue 11
  • DOI: 10.1002/adfm.201103056

Methods of Investigating Protein Interactions on Artificial and Natural Surfaces
journal, December 1987


Biomaterials: Where We Have Been and Where We Are Going
journal, August 2004


Thermoresponsive Copolymer Decorated Surface Enables Controlling the Adsorption of a Target Protein in Plasma
journal, June 2014

  • Yang, Weikang; Tang, Zengchao; Luan, Yafei
  • ACS Applied Materials & Interfaces, Vol. 6, Issue 13
  • DOI: 10.1021/am501193b

In-Situ Investigation of the Adsorption of Globular Model Proteins on Stimuli-Responsive Binary Polyelectrolyte Brushes
journal, December 2006

  • Uhlmann, Petra; Houbenov, Nikolay; Brenner, Nina
  • Langmuir, Vol. 23, Issue 1
  • DOI: 10.1021/la061557g

Complex pH- and temperature-sensitive swelling behavior of mixed polymer brushes: Swelling Behavior of Mixed Polymer Brushes
journal, June 2010

  • Bittrich, Eva; Kuntzsch, Marco; Eichhorn, Klaus-Jochen
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 48, Issue 14
  • DOI: 10.1002/polb.22021

Dissociation Behavior of Weak Polyelectrolyte Brushes on a Planar Surface
journal, April 2009

  • Dong, Rong; Lindau, Manfred; Ober, Christopher K.
  • Langmuir, Vol. 25, Issue 8
  • DOI: 10.1021/la8039384

Behavior of Surface-Anchored Poly(acrylic acid) Brushes with Grafting Density Gradients on Solid Substrates: 1. Experiment
journal, November 2007

  • Wu, Tao; Gong, Peng; Szleifer, Igal
  • Macromolecules, Vol. 40, Issue 24, p. 8756-8764
  • DOI: 10.1021/ma0710176

Functional Polymer Brushes in Aqueous Media from Self-Assembled and Surface-Initiated Polymers
journal, May 2008


Adsorption of the Protein Bovine Serum Albumin in a Planar Poly(acrylic acid) Brush Layer As Measured by Optical Reflectometry
journal, May 2008

  • de Vos, Wiebe M.; Biesheuvel, P. Maarten; de Keizer, Arie
  • Langmuir, Vol. 24, Issue 13
  • DOI: 10.1021/la8006469

Protein adsorption on and swelling of polyelectrolyte brushes: A simultaneous ellipsometry-quartz crystal microbalance study
journal, December 2010

  • Bittrich, Eva; Rodenhausen, Keith Brian; Eichhorn, Klaus-Jochen
  • Biointerphases, Vol. 5, Issue 4
  • DOI: 10.1116/1.3530841

Interaction of proteins with spherical polyelectrolyte brushes in solution as studied by small-angle x-ray scattering
journal, December 2004


Responsive Polymer Brushes
journal, December 2006


Surface and Thin Film Analysis
book, April 2011


Dynamic atomic force microscopy methods
journal, September 2002


Real-time analysis of protein adsorption to a variety of thin films
journal, April 2004


Fine-Tuning the Structure of Stimuli-Responsive Polymer Films by Hydrostatic Pressure and Temperature
journal, August 2013

  • Reinhardt, Matthias; Dzubiella, Joachim; Trapp, Marcus
  • Macromolecules, Vol. 46, Issue 16
  • DOI: 10.1021/ma400962p

In situ conformational analysis of fibrinogen adsorbed on Si surfaces
journal, May 2005


The Density and Refractive Index of Adsorbing Protein Layers
journal, July 2004


Handbook of Ellipsometry
book, January 2005


Spectroscopic infrared ellipsometry to determine the structure of layered samples
journal, October 2002

  • Korte, Ernst-Heiner; Hinrichs, Karsten; Röseler, Arnulf
  • Spectrochimica Acta Part B: Atomic Spectroscopy, Vol. 57, Issue 10
  • DOI: 10.1016/S0584-8547(02)00100-3

In Situ Infrared Ellipsometric Study of Stimuli-Responsive Mixed Polyelectrolyte Brushes
journal, September 2007

  • Mikhaylova, Yulia; Ionov, Leonid; Rappich, Jörg
  • Analytical Chemistry, Vol. 79, Issue 20
  • DOI: 10.1021/ac070853a

Alternate Molecular Layers of Metal Oxides and Hydroxyl Polymers Prepared by the Surface Sol-Gel Process
journal, May 1998


Thermal conformational changes of bovine fibrinogen by differential scanning calorimetry and circular dichroism
journal, November 1999

  • Chen, Yongli; Mao, Haibin; Zhang, Xiufang
  • International Journal of Biological Macromolecules, Vol. 26, Issue 2-3
  • DOI: 10.1016/S0141-8130(99)00073-2

Application of ellipsometry techniques to biological materials
journal, February 2011


Tethered polymer chains: surface chemistry and their impact on colloidal and surface properties
journal, February 2003


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

A structural definition of polymer brushes
journal, January 2007

  • Brittain, William J.; Minko, Sergiy
  • Journal of Polymer Science Part A: Polymer Chemistry, Vol. 45, Issue 16
  • DOI: 10.1002/pola.22180

Loading and Distribution of a Model Small Molecule Drug in Poly( N -isopropylacrylamide) Brushes: a Neutron Reflectometry and AFM Study
journal, February 2013

  • Elliott, Lindsay C. C.; Jing, Benxin; Akgun, Bulent
  • Langmuir, Vol. 29, Issue 10
  • DOI: 10.1021/la305088k

Conformation of human plasma proteins at polymer surfaces: the effectiveness of surface heparinization
journal, October 1994


Behavior of Surface-Anchored Poly(acrylic acid) Brushes with Grafting Density Gradients on Solid Substrates  2. Theory
journal, November 2007

  • Gong, Peng; Wu, Tao; Genzer, Jan
  • Macromolecules, Vol. 40, Issue 24, p. 8765-8773
  • DOI: 10.1021/ma071018y

Ellipsometry as a tool to study the adsorption behavior of synthetic and biopolymers at the air-water interface
journal, July 1978


Works referencing / citing this record:

Controlling Protein Adsorption through Nanostructured Polymeric Surfaces
journal, November 2017

  • Firkowska-Boden, Izabela; Zhang, Xiaoyuan; Jandt, Klaus D.
  • Advanced Healthcare Materials, Vol. 7, Issue 1
  • DOI: 10.1002/adhm.201700995

Broadband infrared Mueller-matrix ellipsometry for studies of structured surfaces and thin films
journal, January 2018

  • Furchner, Andreas; Walder, Cordula; Zellmeier, Matthias
  • Applied Optics, Vol. 57, Issue 27
  • DOI: 10.1364/ao.57.007895

Preprogrammed Dynamic Microstructured Polymer Interfaces
journal, August 2019


A Novel Soft Contact Piezo-Controlled Liquid Cell for Probing Polymer Films under Confinement using Synchrotron FTIR Microspectroscopy
journal, December 2018


Topological Indices Study of Molecular Structure in Anticancer Drugs
journal, January 2016

  • Gao, Wei; Wang, Weifan; Farahani, Mohammad Reza
  • Journal of Chemistry, Vol. 2016
  • DOI: 10.1155/2016/3216327

Targeted grafting of thermoresponsive polymers from a penetrative honeycomb structure for cell sheet engineering
journal, January 2015

  • Chen, Shuangshuang; Lu, Xuemin; Zhu, Dandan
  • Soft Matter, Vol. 11, Issue 37
  • DOI: 10.1039/c5sm01769f

A Novel Soft Contact Piezo-Controlled Liquid Cell for Probing Polymer Films under Confinement using Synchrotron FTIR Microspectroscopy
journal, December 2018


Topological Indices Study of Molecular Structure in Anticancer Drugs
journal, January 2016

  • Gao, Wei; Wang, Weifan; Farahani, Mohammad Reza
  • Journal of Chemistry, Vol. 2016
  • DOI: 10.1155/2016/3216327

Swelling of thin polymer films: understanding the mechanisms and dynamics
dissertation, January 2019