Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Electrostatic Interactions Govern “Odd/Even” Effects in Water-Induced Gemini Surfactant Self-Assembly

Abstract

Gemini surfactants comprise two single-tailed surfactants connected by a linker at or near the hydrophilic headgroup. They display a variety of water concentration-dependent lyotropic liquid crystal (LLC) morphologies that are sensitive to surfactant molecular structure, and na- ture of the headgroups and counterions. Recently, an interesting dependence of the aqueous phase behavior on the length of the linker has been discovered; odd-numbered linker length surfactants exhibit characteristically different phase diagrams than even-numbered linker sur- factants. In this work, we investigate this “odd/even effect” using computer simulations, focusing on experimentally studied gemini dicarboxylates with Na+ counterions, 7 non-terminal carbon atoms in the tails, and either 3, 4, 5, or 6 carbon atoms in the linker (denoted Na-73, Na-74, Na-75, and Na-76 respectively). We find that the relative electrostatic repulsion be- tween headgroups in the different morphologies is correlated with qualitative features of the experimental phase diagrams, predicting destabilization of hexagonal phases as the cylinders pack close together at low water content. Significant differences in the relative headgroup ori- entations of Na-74 and Na-76 compared to Na-73 and Na-75 surfactants lead to differences in linker-linker packing, and long-range headgroup/headgroup electrostatic repulsion, which affects the delicate electrostatic balance between hexagonal and gyroid phases.more » Finally, much of the fundamental insight presented in this work is enabled by the ability to computationally construct and analyze metastable phases that are not observable in experiments.« less

Authors:
 [1];  [1];  [1];  [2]; ORCiD logo [1]
+ Show Author Affiliations
  1. Univ. of Wisconsin, Madison, WI (United States). Dept. of Chemistry and Theoretical Chemistry Inst.
  2. Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemical Engineering and Materials Science
Publication Date:
Research Org.:
Univ. of Wisconsin, Madison, WI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1341624
Report Number(s):
DOE-UWMadison-46938-6th product
Journal ID: ISSN 1520-6106; DE-FG02-13ER46938
Grant/Contract Number:  
SC0010328; TG-CHE090065; CHE-0840494
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
Additional Journal Information:
Journal Volume: 121; Journal Issue: 3; Journal ID: ISSN 1520-6106
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Self-assembly; lyotropic; liquid crystal; gemini surfactant

Citation Formats

Mantha, Sriteja, McDaniel, Jesse G., Perroni, Dominic V., Mahanthappa, Mahesh K., and Yethiraj, Arun. Electrostatic Interactions Govern “Odd/Even” Effects in Water-Induced Gemini Surfactant Self-Assembly. United States: N. p., 2016. Web. doi:10.1021/acs.jpcb.6b06882.
Copy to clipboard
Mantha, Sriteja, McDaniel, Jesse G., Perroni, Dominic V., Mahanthappa, Mahesh K., & Yethiraj, Arun. Electrostatic Interactions Govern “Odd/Even” Effects in Water-Induced Gemini Surfactant Self-Assembly. United States. https://doi.org/10.1021/acs.jpcb.6b06882
Copy to clipboard
Mantha, Sriteja, McDaniel, Jesse G., Perroni, Dominic V., Mahanthappa, Mahesh K., and Yethiraj, Arun. Tue . "Electrostatic Interactions Govern “Odd/Even” Effects in Water-Induced Gemini Surfactant Self-Assembly". United States. https://doi.org/10.1021/acs.jpcb.6b06882. https://www.osti.gov/servlets/purl/1341624.
Copy to clipboard
@article{osti_1341624,
title = {Electrostatic Interactions Govern “Odd/Even” Effects in Water-Induced Gemini Surfactant Self-Assembly},
author = {Mantha, Sriteja and McDaniel, Jesse G. and Perroni, Dominic V. and Mahanthappa, Mahesh K. and Yethiraj, Arun},
abstractNote = {Gemini surfactants comprise two single-tailed surfactants connected by a linker at or near the hydrophilic headgroup. They display a variety of water concentration-dependent lyotropic liquid crystal (LLC) morphologies that are sensitive to surfactant molecular structure, and na- ture of the headgroups and counterions. Recently, an interesting dependence of the aqueous phase behavior on the length of the linker has been discovered; odd-numbered linker length surfactants exhibit characteristically different phase diagrams than even-numbered linker sur- factants. In this work, we investigate this “odd/even effect” using computer simulations, focusing on experimentally studied gemini dicarboxylates with Na+ counterions, 7 non-terminal carbon atoms in the tails, and either 3, 4, 5, or 6 carbon atoms in the linker (denoted Na-73, Na-74, Na-75, and Na-76 respectively). We find that the relative electrostatic repulsion be- tween headgroups in the different morphologies is correlated with qualitative features of the experimental phase diagrams, predicting destabilization of hexagonal phases as the cylinders pack close together at low water content. Significant differences in the relative headgroup ori- entations of Na-74 and Na-76 compared to Na-73 and Na-75 surfactants lead to differences in linker-linker packing, and long-range headgroup/headgroup electrostatic repulsion, which affects the delicate electrostatic balance between hexagonal and gyroid phases. Finally, much of the fundamental insight presented in this work is enabled by the ability to computationally construct and analyze metastable phases that are not observable in experiments.},
doi = {10.1021/acs.jpcb.6b06882},
journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
number = 3,
volume = 121,
place = {United States},
year = {Tue Dec 27 00:00:00 EST 2016},
month = {Tue Dec 27 00:00:00 EST 2016}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acs.jpcb.6b06882
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 14 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Fluctuation effects in the theory of microphase separation in block copolymers
journal, July 1987

  • Fredrickson, Glenn H.; Helfand, Eugene
  • The Journal of Chemical Physics, Vol. 87, Issue 1
  • DOI: 10.1063/1.453566

Phase Behavior of Aqueous Solutions of a Dimeric Surfactant
journal, June 1997

  • Buhler, E.; Mendes, E.; Boltenhagen, P.
  • Langmuir, Vol. 13, Issue 12
  • DOI: 10.1021/la961099j

Dimeric (Gemini) Surfactants: Effect of the Spacer Group on the Association Behavior in Aqueous Solution
journal, April 2002

Phase Behavior of Gemini Surfactants
journal, February 2007

Fluctuations and phase transformations in a lyotropic liquid crystal
journal, November 1988

  • Rancon, Y.; Charvolin, J.
  • The Journal of Physical Chemistry, Vol. 92, Issue 22
  • DOI: 10.1021/j100333a032

The ability of single-chain surfactants to emulsify an aqueous-based liquid crystal oscillates with odd–even parity of alkyl-chain length
journal, December 2013

  • Varghese, Nisha; Shetye, Gauri S.; Yang, Sijie
  • Journal of Colloid and Interface Science, Vol. 412
  • DOI: 10.1016/j.jcis.2013.08.044

Odd/Even Effect in the Chain Length on the Enthalpy of Micellization of Gemini Surfactants in Aqueous Solution
journal, July 2005

  • Li, Yajuan; Li, Peixun; Wang, Jinben
  • Langmuir, Vol. 21, Issue 15
  • DOI: 10.1021/la050343g

Lipid bilayers: thermodynamics, structure, fluctuations, and interactions
journal, January 2004

Polymerized Lyotropic Liquid Crystal Assemblies for Membrane Applications
journal, March 2008

  • Gin, Douglas L.; Bara, Jason E.; Noble, Richard D.
  • Macromolecular Rapid Communications, Vol. 29, Issue 5
  • DOI: 10.1002/marc.200700707

Cylinder ↔ Gyroid Epitaxial Transitions in Complex Polymeric Liquids
journal, May 1998

Hexagonal closest-packed spheres liquid crystalline phases stabilised by strongly hydrated counterions
journal, January 2014

A family of alkyl sulfate gemini surfactants. 1. Characterization of surface properties
journal, August 2013

Linker Length-Dependent Control of Gemini Surfactant Aqueous Lyotropic Gyroid Phase Stability
journal, March 2015

  • Perroni, Dominic V.; Baez-Cotto, Carlos M.; Sorenson, Gregory P.
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 6
  • DOI: 10.1021/acs.jpclett.5b00092

Synthesis and properties of a novel class of anionic gemini surfactants with polyoxyethylene spacers
journal, June 2010

  • Liu, Xue-Peng; Feng, Jie; Zhang, Lu
  • Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 362, Issue 1-3
  • DOI: 10.1016/j.colsurfa.2010.03.037

GROMACS 4.5: a high-throughput and highly parallel open source molecular simulation toolkit
journal, February 2013

Heterogeneous Catalysis Using a Nanostructured Solid Acid Resin Based on Lyotropic Liquid Crystals
journal, February 2004

  • Xu, Yanjie; Gu, Weiqiang; Gin, Douglas L.
  • Journal of the American Chemical Society, Vol. 126, Issue 6
  • DOI: 10.1021/ja038501i

Progress in liquid crystalline dispersions: Cubosomes
journal, December 2005

Synthesis and surface properties of anionic gemini surfactants with amide groups
journal, August 2004

Self-Assembly of Didodecyldimethylammonium Surfactants Modulated by Multivalent, Hydrolyzable Counterions
journal, September 2014

  • Liu, Connie K.; Warr, Gregory G.
  • Langmuir, Vol. 31, Issue 10
  • DOI: 10.1021/la502930p

Effects of alkyl chain length on surface and micellar properties of octaethyleneglycol-n alkyl ethers
journal, July 1981

  • Ueno, M.; Takasawa, Y.; Miyashige, H.
  • Colloid and Polymer Science, Vol. 259, Issue 7
  • DOI: 10.1007/BF01419322

Role of Spacer Chain Length in Dimeric Micellar Organization. Small Angle Neutron Scattering and Fluorescence Studies
journal, January 1996

  • De, Soma; Aswal, Vinod K.; Goyal, Prem S.
  • The Journal of Physical Chemistry, Vol. 100, Issue 28
  • DOI: 10.1021/jp9535598

The self-assembly properties of a series of polymerizable cationic gemini surfactants: Effect of the acryloxyl group
journal, March 2014

  • Li, Rongqiang; Yan, Fengmei; Zhang, Junli
  • Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 444
  • DOI: 10.1016/j.colsurfa.2013.12.079

Recent Advances in the Design of Polymerizable Lyotropic Liquid-Crystal Assemblies for Heterogeneous Catalysis and Selective Separations
journal, May 2006

  • Gin, D. L.; Lu, X.; Nemade, P. R.
  • Advanced Functional Materials, Vol. 16, Issue 7
  • DOI: 10.1002/adfm.200500280

Cationic Gemini Surfactants with Oligo(oxyethylene) Spacer Groups and Their Use in the Polymerization of Styrene in Ternary Microemulsion
journal, January 1999

  • Dreja, Michael; Pyckhout-Hintzen, Wim; Mays, Holger
  • Langmuir, Vol. 15, Issue 2
  • DOI: 10.1021/la981354v

Double-Chain Surfactants with Two Carboxylate Groups and Their Relation to Similar Double-Chain Compounds
journal, June 1993

  • Zhu, Yun-Peng; Masuyama, Araki; Kobata, Yusaku
  • Journal of Colloid and Interface Science, Vol. 158, Issue 1
  • DOI: 10.1006/jcis.1993.1226

Gemini Surfactants
journal, June 2000

Highly Efficient Gene Silencing Activity of siRNA Embedded in a Nanostructured Gyroid Cubic Lipid Matrix
journal, December 2010

  • Leal, Cecília; Bouxsein, Nathan F.; Ewert, Kai K.
  • Journal of the American Chemical Society, Vol. 132, Issue 47
  • DOI: 10.1021/ja1059763

The Electronic Constitution of Normal Carbon Chain Compounds, Saturated and Unsaturated.
journal, March 1920

  • Cuy, Eustace J.
  • Journal of the American Chemical Society, Vol. 42, Issue 3
  • DOI: 10.1021/ja01448a016

Dynamics of Water in Gemini Surfactant-Based Lyotropic Liquid Crystals
journal, October 2016

  • McDaniel, Jesse G.; Mantha, Sriteja; Yethiraj, Arun
  • The Journal of Physical Chemistry B, Vol. 120, Issue 41
  • DOI: 10.1021/acs.jpcb.6b08087

Nanoporous, Bicontinuous Cubic Lyotropic Liquid Crystal Networks via Polymerizable Gemini Ammonium Surfactants
journal, August 2010

  • Hatakeyama, Evan S.; Wiesenauer, Brian R.; Gabriel, Christopher J.
  • Chemistry of Materials, Vol. 22, Issue 16
  • DOI: 10.1021/cm1013027

Self-Assembly of Gemini Surfactants: A Computer Simulation Study
journal, September 2012

  • Mondal, Jagannath; Mahanthappa, Mahesh; Yethiraj, Arun
  • The Journal of Physical Chemistry B, Vol. 117, Issue 16
  • DOI: 10.1021/jp304933k

Unusually Stable Aqueous Lyotropic Gyroid Phases from Gemini Dicarboxylate Surfactants
journal, September 2011

  • Sorenson, Gregory P.; Coppage, Keiva L.; Mahanthappa, Mahesh K.
  • Journal of the American Chemical Society, Vol. 133, Issue 38
  • DOI: 10.1021/ja2063555

Molecular dynamics with coupling to an external bath
journal, October 1984

  • Berendsen, H. J. C.; Postma, J. P. M.; van Gunsteren, W. F.
  • The Journal of Chemical Physics, Vol. 81, Issue 8
  • DOI: 10.1063/1.448118

New Type of Li Ion Conductor with 3D Interconnected Nanopores via Polymerization of a Liquid Organic Electrolyte-Filled Lyotropic Liquid-Crystal Assembly
journal, November 2009

  • Kerr, Robert L.; Miller, Seth A.; Shoemaker, Richard K.
  • Journal of the American Chemical Society, Vol. 131, Issue 44
  • DOI: 10.1021/ja905208f

Fluctuation effects in a symmetric diblock copolymer near the order–disorder transition
journal, May 1990

  • Bates, Frank S.; Rosedale, Jeffrey H.; Fredrickson, Glenn H.
  • The Journal of Chemical Physics, Vol. 92, Issue 10
  • DOI: 10.1063/1.458350

Gemini (dimeric) surfactants
journal, October 1996

New Type of Membrane Material for Water Desalination Based on a Cross-Linked Bicontinuous Cubic Lyotropic Liquid Crystal Assembly
journal, August 2007

  • Zhou, Meijuan; Nemade, Parag R.; Lu, Xiaoyun
  • Journal of the American Chemical Society, Vol. 129, Issue 31
  • DOI: 10.1021/ja073067w

An improved GROMOS96 force field for aliphatic hydrocarbons in the condensed phase
journal, January 2001

  • Schuler, Lukas D.; Daura, Xavier; van Gunsteren, Wilfred F.
  • Journal of Computational Chemistry, Vol. 22, Issue 11
  • DOI: 10.1002/jcc.1078

Cross-Linked Normal Hexagonal and Bicontinuous Cubic Assemblies via Polymerizable Gemini Amphiphiles
journal, March 2003

  • Pindzola, Brad A.; Jin, Jizhu; Gin, Douglas L.
  • Journal of the American Chemical Society, Vol. 125, Issue 10
  • DOI: 10.1021/ja0208106

Functional Liquid-Crystalline Assemblies: Self-Organized Soft Materials
journal, January 2006

  • Kato, Takashi; Mizoshita, Norihiro; Kishimoto, Kenji
  • Angewandte Chemie International Edition, Vol. 45, Issue 1
  • DOI: 10.1002/anie.200501384

A Combinatorially-Derived Structural Phase Diagram for 42 Zwitterionic Geminis
journal, June 2001

  • Menger, Fredric M.; Peresypkin, Andrey V.
  • Journal of the American Chemical Society, Vol. 123, Issue 23
  • DOI: 10.1021/ja003779l

Gemini surfactants: a new class of self-assembling molecules
journal, November 1993

  • Menger, F. M.; Littau, C. A.
  • Journal of the American Chemical Society, Vol. 115, Issue 22
  • DOI: 10.1021/ja00075a025

Novel Results on the Adsorption Properties of n -Alkyldimethylphosphine Oxides at the Air/Water Interface
journal, February 1999

  • Lunkenheimer, K.; Haage, K.; Hirte, R.
  • Langmuir, Vol. 15, Issue 4
  • DOI: 10.1021/la980611t

Settle: An analytical version of the SHAKE and RATTLE algorithm for rigid water models
journal, October 1992

  • Miyamoto, Shuichi; Kollman, Peter A.
  • Journal of Computational Chemistry, Vol. 13, Issue 8
  • DOI: 10.1002/jcc.540130805

Role of the spacer in the non ideal behavior of alkanedyil-α,ω-bis(dodecyldimethylammonium) bromide-MEGA10 binary mixtures
journal, February 2013

  • Martín, Victoria Isabel; Rodríguez, Amalia; López-Cornejo, Pilar
  • Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 418
  • DOI: 10.1016/j.colsurfa.2012.11.038

Heterogeneous Catalysis with Cross-Linked Lyotropic Liquid Crystal Assemblies: Organic Analogues to Zeolites and Mesoporous Sieves
journal, October 1999

The role of counterions on the elasticity of highly charged lamellar phases: A small-angle x-ray and neutron-scattering determination
journal, July 2005

  • Brotons, Guillaume; Dubois, Monique; Belloni, Luc
  • The Journal of Chemical Physics, Vol. 123, Issue 2
  • DOI: 10.1063/1.1950667

A smooth particle mesh Ewald method
journal, November 1995

  • Essmann, Ulrich; Perera, Lalith; Berkowitz, Max L.
  • The Journal of Chemical Physics, Vol. 103, Issue 19
  • DOI: 10.1063/1.470117

Aggregation behavior of anionic sulfonate gemini surfactants with dodecylphenyl tails
journal, November 2015

  • Hordyjewicz-Baran, Zofia; Woch, Julia; Kuliszewska, Edyta
  • Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 484
  • DOI: 10.1016/j.colsurfa.2015.08.012

Interaction Models for Water in Relation to Protein Hydration
book, January 1981

  • Berendsen, H. J. C.; Postma, J. P. M.; van Gunsteren, W. F.
  • The Jerusalem Symposia on Quantum Chemistry and Biochemistry
  • DOI: 10.1007/978-94-015-7658-1_21
    Sort by:
    [ × clear filter / sort ]

    Works referencing / citing this record:

    Designed construction of tween 60@2β-CD self-assembly vesicles as drug delivery carrier for cancer chemotherapy
    journal, January 2018

      Sort by:
      [ × clear filter / sort ]

      Similar Records in DOE PAGES and OSTI.GOV collections: