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

Title: Hybrid-Supported Bilayers Formed with Mixed-Charge Surfactants on C18-Functionalized Silica Surfaces

Abstract

Mixtures of cationic-anionic surfactants have been demonstrated to spontaneously form ordered monolayers at hydrophobic-hydrophilic boundaries including air-water and oil-water interfaces. Here, confocal Raman microscopy is used to investigate the structure of hybrid-supported surfactant bilayers (HSSBs) formed by deposition of a distal leaflet of mixed cationic-anionic surfactants onto a proximal leaflet of n-alkane (C18) chains on the interior surfaces of chromatographic silica particles. The surface coverage of the two surfactants in a hybrid bilayer was determined from carbon analysis and the relative Raman scattering of their respective head-groups. Within the measurement uncertainty, the stoichiometric ratio of the two surfactants is one-to-one, equivalent to mixed-charge-surfactant monolayers at air-water and oil-water interfaces and consistent with the role of the head-group electrostatic interactions in their formation. When self-assembled on the hydrophobic surface, pairs of oppositely-charged n-alkyl-chain surfactants resemble a phospholipid (phosphati¬dylcholine) molecule, with its zwitterionic head group and two hydrophobic acyl-chain tails. Indeed, the structure of these hybrid-supported surfactant bilayers on C18-modified silica surfaces is similar to that of hybrid-supported lipid bilayers (HSLBs) on the same supports, but with denser and more-ordered n-alkyl chains. Hybrid-supported surfactant bilayers exhibit a melting phase transition (gel to liquid-crystalline phase) with structural and energetic characteristics similar to hybrid-supportedmore » bilayers prepared from a zwitterionic phospholipid of the same alkyl chain length. These mixed-charge surfactants on n-alkane modified silica are stable in water over time (months), results that suggest the potential use of these hybrid bilayers for generating supported lipid bilayer-like surfaces or for separation applications.« less

Authors:
 [1];  [1];  [1]
  1. Univ. of Utah, Salt Lake City, UT (United States)
Publication Date:
Research Org.:
Univ. of Utah, Salt Lake City, UT (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1632291
Grant/Contract Number:  
FG03-93ER14333
Resource Type:
Accepted Manuscript
Journal Name:
Langmuir
Additional Journal Information:
Journal Volume: 36; Journal Issue: 26; Journal ID: ISSN 0743-7463
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; Lipid bilayers; nanoporous materials; chemical separations

Citation Formats

Zare, Maryam, Kitt, Jay P., and Harris, Joel M. Hybrid-Supported Bilayers Formed with Mixed-Charge Surfactants on C18-Functionalized Silica Surfaces. United States: N. p., 2020. Web. doi:10.1021/acs.langmuir.0c01210.
Zare, Maryam, Kitt, Jay P., & Harris, Joel M. Hybrid-Supported Bilayers Formed with Mixed-Charge Surfactants on C18-Functionalized Silica Surfaces. United States. https://doi.org/10.1021/acs.langmuir.0c01210
Zare, Maryam, Kitt, Jay P., and Harris, Joel M. Fri . "Hybrid-Supported Bilayers Formed with Mixed-Charge Surfactants on C18-Functionalized Silica Surfaces". United States. https://doi.org/10.1021/acs.langmuir.0c01210. https://www.osti.gov/servlets/purl/1632291.
@article{osti_1632291,
title = {Hybrid-Supported Bilayers Formed with Mixed-Charge Surfactants on C18-Functionalized Silica Surfaces},
author = {Zare, Maryam and Kitt, Jay P. and Harris, Joel M.},
abstractNote = {Mixtures of cationic-anionic surfactants have been demonstrated to spontaneously form ordered monolayers at hydrophobic-hydrophilic boundaries including air-water and oil-water interfaces. Here, confocal Raman microscopy is used to investigate the structure of hybrid-supported surfactant bilayers (HSSBs) formed by deposition of a distal leaflet of mixed cationic-anionic surfactants onto a proximal leaflet of n-alkane (C18) chains on the interior surfaces of chromatographic silica particles. The surface coverage of the two surfactants in a hybrid bilayer was determined from carbon analysis and the relative Raman scattering of their respective head-groups. Within the measurement uncertainty, the stoichiometric ratio of the two surfactants is one-to-one, equivalent to mixed-charge-surfactant monolayers at air-water and oil-water interfaces and consistent with the role of the head-group electrostatic interactions in their formation. When self-assembled on the hydrophobic surface, pairs of oppositely-charged n-alkyl-chain surfactants resemble a phospholipid (phosphati¬dylcholine) molecule, with its zwitterionic head group and two hydrophobic acyl-chain tails. Indeed, the structure of these hybrid-supported surfactant bilayers on C18-modified silica surfaces is similar to that of hybrid-supported lipid bilayers (HSLBs) on the same supports, but with denser and more-ordered n-alkyl chains. Hybrid-supported surfactant bilayers exhibit a melting phase transition (gel to liquid-crystalline phase) with structural and energetic characteristics similar to hybrid-supported bilayers prepared from a zwitterionic phospholipid of the same alkyl chain length. These mixed-charge surfactants on n-alkane modified silica are stable in water over time (months), results that suggest the potential use of these hybrid bilayers for generating supported lipid bilayer-like surfaces or for separation applications.},
doi = {10.1021/acs.langmuir.0c01210},
journal = {Langmuir},
number = 26,
volume = 36,
place = {United States},
year = {Fri Jun 05 00:00:00 EDT 2020},
month = {Fri Jun 05 00:00:00 EDT 2020}
}

Works referenced in this record:

Monolayer characteristics of saturated 1,2-diacyl phosphatidylcholines (lecithins) and phosphatidylethanolamines at the air-water interface
journal, November 1968


Phospholipid and Phospholipid-Protein Monolayers at the Air/Water Interface
journal, October 1990


Phospholipids at the Interface: Current Trends and Challenges
journal, June 2013

  • Pichot, Roman; Watson, Richard; Norton, Ian
  • International Journal of Molecular Sciences, Vol. 14, Issue 6
  • DOI: 10.3390/ijms140611767

Phospholipid monolayers at non-polar oil/water interfaces. Part 1.—Phase transitions in distearoly-lecithin films at the n-heptane aqueous sodium chloride interface
journal, January 1976

  • Yue, Beatrice Y.; Jackson, Craig M.; Taylor, John A. G.
  • Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 72, Issue 0
  • DOI: 10.1039/f19767202685

Phase changes and mosaic formation in single and mixed phospholipid monolayers at the oil-water interface
journal, September 1973

  • Taylor, J. A. G.; Mingins, J.; Pethica, B. A.
  • Biochimica et Biophysica Acta (BBA) - Biomembranes, Vol. 323, Issue 1
  • DOI: 10.1016/0005-2736(73)90439-2

Self-assembled phospholipid/alkanethiol biomimetic bilayers on gold
journal, November 1993


Supported Hybrid Bilayer Membranes as Rugged Cell Membrane Mimics
journal, July 1999


Hybrid Bilayer Membranes in Air and Water: Infrared Spectroscopy and Neutron Reflectivity Studies
journal, March 1998


Real-time monitoring of lipid transfer between vesicles and hybrid bilayers on Au nanoshells using surface enhanced Raman scattering (SERS)
journal, January 2009

  • Kundu, Janardan; Levin, Carly S.; Halas, Naomi J.
  • Nanoscale, Vol. 1, Issue 1
  • DOI: 10.1039/b9nr00063a

Phospholipid/Alkanethiol Bilayers for Cell-Surface Receptor Studies by Surface Plasmon Resonance
journal, April 1995

  • Plant, A. L.; Brighamburke, M.; Petrella, E. C.
  • Analytical Biochemistry, Vol. 226, Issue 2
  • DOI: 10.1006/abio.1995.1234

Analysis of antimicrobial peptide interactions with hybrid bilayer membrane systems using surface plasmon resonance
journal, May 2001

  • Mozsolits, Henriette; Wirth, Hans-Jürgen; Werkmeister, Jerome
  • Biochimica et Biophysica Acta (BBA) - Biomembranes, Vol. 1512, Issue 1
  • DOI: 10.1016/S0005-2736(01)00303-0

Characterization of hybrid bilayer membranes on silver electrodes as biocompatible SERS substrates to study membrane–protein interactions
journal, November 2010


Noncovalent immobilized artificial membrane chromatography, an improved method for describing peptide–lipid bilayer interactions
journal, July 1999


Biomembrane lipids as components of chromatographic phases: Comparative chromatography on coated and bonded phases
journal, December 2000

  • Hanna, M.; de Biasi, V.; Bond, B.
  • Chromatographia, Vol. 52, Issue 11-12
  • DOI: 10.1007/BF02490994

Characterization of dynamically prepared phospholipid-modified reversed-phase columns
journal, June 2001


Characterization of Flavonoid–Biomembrane Interactions
journal, March 2002

  • Ollila, Fredrik; Halling, Katrin; Vuorela, Pia
  • Archives of Biochemistry and Biophysics, Vol. 399, Issue 1
  • DOI: 10.1006/abbi.2001.2759

Monolayers formed by mixtures of anionic and cationic surface-active agents
journal, January 1967

  • Corkill, J. M.; Goodman, J. F.; Harrold, S. P.
  • Transactions of the Faraday Society, Vol. 63
  • DOI: 10.1039/tf9676300247

Surface and bulk properties of mixed anionic/cationic surfactant systems i. equilibrium surface tensions
journal, May 1981

  • Lucassen-Reynders, E. H.; Lucassen, J.; Giles, D.
  • Journal of Colloid and Interface Science, Vol. 81, Issue 1
  • DOI: 10.1016/0021-9797(81)90312-X

Catanionic surfactant films at the air–water interface
journal, December 2006


Phase behavior and morphology of equimolar mixed cationic–anionic surfactant monolayers at the air/water interface: Isotherm and Brewster angle microscopy analysis
journal, May 2008

  • Chou, Tzung-Han; Lin, Yu-Shun; Li, Wei-Ta
  • Journal of Colloid and Interface Science, Vol. 321, Issue 2
  • DOI: 10.1016/j.jcis.2008.02.008

Dependence of Alkyl Chain Conformation of Simple Ionic Surfactants on Head Group Functionality As Studied by Vibrational Sum-Frequency Spectroscopy
journal, August 1997

  • Conboy, John C.; Messmer, Marie C.; Richmond, Geraldine L.
  • The Journal of Physical Chemistry B, Vol. 101, Issue 34
  • DOI: 10.1021/jp971867v

Observation of a Liquid−Gas Phase Transition in Monolayers of Alkyltrimethylammonium Alkyl Sulfates Adsorbed at the Air/Water Interface
journal, January 2005

  • Varga, Imre; Keszthelyi, Tamás; Mészáros, Róbert
  • The Journal of Physical Chemistry B, Vol. 109, Issue 2
  • DOI: 10.1021/jp048006o

Phase equilibria of catanionic surfactant-water systems
journal, June 1987

  • Jokela, Paeivi.; Joensson, Bengt.; Khan, Ali.
  • The Journal of Physical Chemistry, Vol. 91, Issue 12
  • DOI: 10.1021/j100296a037

Confocal Raman Microscopy for in Situ Detection of Solid-Phase Extraction of Pyrene into Single C 18 –Silica Particles
journal, January 2014

  • Kitt, Jay P.; Harris, Joel M.
  • Analytical Chemistry, Vol. 86, Issue 3
  • DOI: 10.1021/ac403514r

Temperature-Controlled Confocal Raman Microscopy to Detect Phase Transitions in Phospholipid Vesicles
journal, May 2007


Confocal Raman Microscopy Investigation of the Wetting of Reversed-Phase Liquid Chromatographic Stationary Phase Particles
journal, August 2009

  • Gasser-Ramirez, Jennifer L.; Harris, Joel M.
  • Analytical Chemistry, Vol. 81, Issue 18
  • DOI: 10.1021/ac901037d

Quantitative Confocal Raman Microscopy Study of Ion-Interaction Retention at Reversed-Phase Chromatographic Interfaces
journal, June 2010

  • Gasser-Ramirez, Jennifer L.; Harris, Joel M.
  • Analytical Chemistry, Vol. 82, Issue 13
  • DOI: 10.1021/ac100781p

Critical micelle concentration of tridecane, tetradecane and hexadecane phosphonic acids and their mono- and disodium salts
journal, September 2009

  • Di Anibal, Carolina V.; Moroni, Marcela A.; Verdinelli, Valeria
  • Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 348, Issue 1-3
  • DOI: 10.1016/j.colsurfa.2009.07.042

Interaction of solid organic acids with carbon nanotube field effect transistors
journal, October 2006


Confocal Raman Microscopy for Monitoring Chemical Reactions on Single Optically Trapped, Solid-Phase Support Particles
journal, July 2002

  • Houlne, Michael P.; Sjostrom, Christopher M.; Uibel, Rory H.
  • Analytical Chemistry, Vol. 74, Issue 17
  • DOI: 10.1021/ac020325t

Spatial Filtering of a Diode Laser Beam for Confocal Raman Microscopy
journal, April 2015

  • Kitt, Jay P.; Bryce, David A.; Harris, Joel M.
  • Applied Spectroscopy, Vol. 69, Issue 4
  • DOI: 10.1366/14-07671

Use of a rapid scanning stigmatic Raman imaging spectrograph in the industrial environment
journal, January 1994

  • Williams, K. P. J.; Pitt, G. D.; Smith, B. J. E.
  • Journal of Raman Spectroscopy, Vol. 25, Issue 1
  • DOI: 10.1002/jrs.1250250119

Detecting Phase Transitions in Phosphatidylcholine Vesicles by Raman Microscopy and Self-Modeling Curve Resolution
journal, October 2007

  • Fox, Christopher B.; Uibel, Rory H.; Harris, Joel M.
  • The Journal of Physical Chemistry B, Vol. 111, Issue 39
  • DOI: 10.1021/jp0735886

Raman- and infrared-spectroscopic investigations of dilute aqueous phosphoric acid solutions
journal, January 2010


Evidence for acyl chain trans/gauche isomerization during the thermal pretransition of dipalmitoyl phosphatidylcholine bilayer dispersions
journal, February 1981


Raman active vibrations in long-chain fatty acids and phospholipid sonicates
journal, September 1972


Quantitative Correlation of Raman Spectral Indicators in Determining Conformational Order in Alkyl Chains
journal, July 2002

  • Orendorff, Christopher J.; Ducey, Michael W.; Pemberton, Jeanne E.
  • The Journal of Physical Chemistry A, Vol. 106, Issue 30
  • DOI: 10.1021/jp014311n

Vibrational Spectroscopy of Biomembranes
journal, July 2011


Application of laser Raman and infrared spectroscopy to the analysis of membrane structure
journal, August 1979

  • Wallach, Donald F. H.; Verma, Surendra P.; Fookson, Jeffrey
  • Biochimica et Biophysica Acta (BBA) - Reviews on Biomembranes, Vol. 559, Issue 2-3
  • DOI: 10.1016/0304-4157(79)90001-7

Raman Spectroscopy of Thermotropic and High-Pressure Phases of Aqueous Phospholipid Dispersions
journal, June 1984


Interpretation of biomembrane structure by Raman difference spectroscopy. Nature of the endothermic transitions in phosphatidylcholines
journal, February 1978


The Sorption Behavior of Alkyl Bonded Phases in Reverse-Phase, High Performance Liquid Chromatography
journal, October 1979


Effect of Conditioning Solvent on the Orientation of Bonded Hydrocarbon Moieties in Totally Aqueous Mobile Phases
journal, August 1982

  • Gilpin, R. K.; Gangoda, M. E.; Krishen, A. E.
  • Journal of Chromatographic Science, Vol. 20, Issue 8
  • DOI: 10.1093/chromsci/20.8.345

The phase transition behavior of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) model membrane influenced by 2,4-dichlorophenol—an FT-Raman Spectroscopy Study
journal, February 2006


Carbon-hydrogen stretching modes and the structure of n-alkyl chains. 1. Long, disordered chains
journal, December 1982

  • Snyder, R. G.; Strauss, H. L.; Elliger, C. A.
  • The Journal of Physical Chemistry, Vol. 86, Issue 26
  • DOI: 10.1021/j100223a018

Studies on lysosomes—X
journal, December 1968


Packing and molecular orientation of alkanethiol monolayers on gold surfaces
journal, September 1989

  • Ulman, Abraham; Eilers, James E.; Tillman, Nolan
  • Langmuir, Vol. 5, Issue 5
  • DOI: 10.1021/la00089a003

Phases and phase transitions of the phosphatidylcholines
journal, June 1998

  • Koynova, Rumiana; Caffrey, Martin
  • Biochimica et Biophysica Acta (BBA) - Reviews on Biomembranes, Vol. 1376, Issue 1
  • DOI: 10.1016/S0304-4157(98)00006-9

Phase Behavior of Model Lipid Bilayers
journal, April 2005

  • Kranenburg, Marieke; Smit, Berend
  • The Journal of Physical Chemistry B, Vol. 109, Issue 14
  • DOI: 10.1021/jp0457646

Temperature Dependence of Polypeptide Partitioning between Water and Phospholipid Bilayers
journal, January 1996

  • Russell, Charles J.; Thorgeirsson, Thorgeir Elís; Shin, Yeon-Kyun
  • Biochemistry, Vol. 35, Issue 29
  • DOI: 10.1021/bi960614+

Self Modeling Curve Resolution
journal, August 1971


Factor analysis for isolation of the Raman spectra of aqueous sulfuric acid components
journal, April 1984

  • Malinowski, Edmund R.; Cox, Robin A.; Haldna, Ulo L.
  • Analytical Chemistry, Vol. 56, Issue 4
  • DOI: 10.1021/ac00268a043

Principles and methodologies in self-modeling curve resolution
journal, April 2004

  • Jiang, Jian-Hui; Liang, Yizeng; Ozaki, Yukihiro
  • Chemometrics and Intelligent Laboratory Systems, Vol. 71, Issue 1
  • DOI: 10.1016/j.chemolab.2003.07.002

Interaction of phospholipid dispersions with water-soluble porphyrins as monitored by their Raman temperature profiles
journal, December 2004


Neutrally Charged Gas/Liquid Interface by a Catanionic Langmuir Monolayer
journal, June 2010

  • Vaknin, David; Bu, Wei
  • The Journal of Physical Chemistry Letters, Vol. 1, Issue 13
  • DOI: 10.1021/jz1005434

Differential scanning calorimetry: An invaluable tool for a detailed thermodynamic characterization of macromolecules and their interactions
journal, January 2011

  • Prenner, ElmarJ; Chiu, MichaelH
  • Journal of Pharmacy and Bioallied Sciences, Vol. 3, Issue 1
  • DOI: 10.4103/0975-7406.76463

Understanding protein adsorption phenomena at solid surfaces
journal, February 2011

  • Rabe, Michael; Verdes, Dorinel; Seeger, Stefan
  • Advances in Colloid and Interface Science, Vol. 162, Issue 1-2
  • DOI: 10.1016/j.cis.2010.12.007

Fabrication of Phospholipid Bilayer-Coated Microchannels for On-Chip Immunoassays
journal, January 2001

  • Yang, Tinglu; Jung, Seung-yong; Mao, Hanbin
  • Analytical Chemistry, Vol. 73, Issue 2
  • DOI: 10.1021/ac000997o

Solid supported lipid bilayers: From biophysical studies to sensor design
journal, November 2006


Applications of Surface Second Harmonic Generation in Biological Sensing
journal, June 2017


Confocal-Raman Microscopy Characterization of Supported Phospholipid Bilayers Deposited on the Interior Surfaces of Chromatographic Silica
journal, February 2018

  • Bryce, David A.; Kitt, Jay P.; Harris, Joel M.
  • Journal of the American Chemical Society, Vol. 140, Issue 11
  • DOI: 10.1021/jacs.7b13777

Partitioning behavior of solutes eluted with micellar mobile phases in liquid chromatography
journal, September 1981

  • Armstrong, Daniel W.; Nome, Faruk.
  • Analytical Chemistry, Vol. 53, Issue 11
  • DOI: 10.1021/ac00234a026