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

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 morphologies that are sensitive to surfactant molecular structure and the nature of the headgroups an...

Ausführliche Beschreibung

Gespeichert in:
Bibliographische Detailangaben
Veröffentlicht in:The journal of physical chemistry. B 2017-01, Vol.121 (3), p.565-576
Hauptverfasser: Mantha, Sriteja, McDaniel, Jesse G., Perroni, Dominic V., Mahanthappa, Mahesh K., Yethiraj, Arun
Format: Artikel
Sprache:eng
Online-Zugang:Volltext
Tags: Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
container_end_page 576
container_issue 3
container_start_page 565
container_title The journal of physical chemistry. B
container_volume 121
creator Mantha, Sriteja
McDaniel, Jesse G.
Perroni, Dominic V.
Mahanthappa, Mahesh K.
Yethiraj, Arun
description 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 morphologies that are sensitive to surfactant molecular structure and the nature 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 surfactants. In this work, we investigate this “odd/even effect” using computer simulations, focusing on experimentally studied gemini dicarboxylates with Na+ counterions, seven nonterminal carbon atoms in the tails, and either three, four, five, or six carbon atoms in the linker (denoted Na-73, Na-74, Na-75, and Na-76, respectively). We find that the relative electrostatic repulsion between headgroups in the different morphologies is correlated with the 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 orientations of Na-74 and Na-76 compared to those of 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 the hexagonal and gyroid phases. 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_str_mv 10.1021/acs.jpcb.6b06882
format Article
fullrecord <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_miscellaneous_1853741327</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>1853741327</sourcerecordid><originalsourceid>FETCH-LOGICAL-a444t-87a30526f67b0617f38ec525e187fcdf888be4b49ad350f16dc4c1a332bca25e3</originalsourceid><addsrcrecordid>eNp1kLFOwzAQhi0EoqWwMyGPDKS1ncRxx6oKpVKlDgUxRo5zllIlTrGTSt36IPByfRJcWtgYTnfD9__SfQjdUzKkhNGRVG643qh8yHPChWAXqE9jRgI_yeX55pTwHrpxbk0Ii5ng16jHBGF8HLE-KtMKVGsb18q2VHhuWrBStWVjHJ41W7AGH_afy6IYpVswh_0XTrX2CYdLg9-lp4O5KToFBZ5BXZoSrzqrfYM0LV5BpYOJc1Dn1e4WXWlZObg77wF6e05fpy_BYjmbTyeLQEZR1AYikSGJGdc88T_RRIcCVMxioCLRqtBCiByiPBrLIoyJprxQkaIyDFmupMfCAXo89W5s89GBa7O6dAqqShpoOpdREYdJREOWeJScUOUFOAs629iylnaXUZIdBWdecHYUnJ0F-8jDub3Layj-Ar9GPfB0An6iTWeNf_b_vm-nZYm7</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>1853741327</pqid></control><display><type>article</type><title>Electrostatic Interactions Govern “Odd/Even” Effects in Water-Induced Gemini Surfactant Self-Assembly</title><source>American Chemical Society Journals</source><creator>Mantha, Sriteja ; McDaniel, Jesse G. ; Perroni, Dominic V. ; Mahanthappa, Mahesh K. ; Yethiraj, Arun</creator><creatorcontrib>Mantha, Sriteja ; McDaniel, Jesse G. ; Perroni, Dominic V. ; Mahanthappa, Mahesh K. ; Yethiraj, Arun</creatorcontrib><description>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 morphologies that are sensitive to surfactant molecular structure and the nature 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 surfactants. In this work, we investigate this “odd/even effect” using computer simulations, focusing on experimentally studied gemini dicarboxylates with Na+ counterions, seven nonterminal carbon atoms in the tails, and either three, four, five, or six carbon atoms in the linker (denoted Na-73, Na-74, Na-75, and Na-76, respectively). We find that the relative electrostatic repulsion between headgroups in the different morphologies is correlated with the 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 orientations of Na-74 and Na-76 compared to those of 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 the hexagonal and gyroid phases. 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.</description><identifier>ISSN: 1520-6106</identifier><identifier>EISSN: 1520-5207</identifier><identifier>DOI: 10.1021/acs.jpcb.6b06882</identifier><identifier>PMID: 28026942</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><ispartof>The journal of physical chemistry. B, 2017-01, Vol.121 (3), p.565-576</ispartof><rights>Copyright © 2016 American Chemical Society</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a444t-87a30526f67b0617f38ec525e187fcdf888be4b49ad350f16dc4c1a332bca25e3</citedby><cites>FETCH-LOGICAL-a444t-87a30526f67b0617f38ec525e187fcdf888be4b49ad350f16dc4c1a332bca25e3</cites><orcidid>0000-0002-8579-449X</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/acs.jpcb.6b06882$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/acs.jpcb.6b06882$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,780,784,2765,27076,27924,27925,56738,56788</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/28026942$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Mantha, Sriteja</creatorcontrib><creatorcontrib>McDaniel, Jesse G.</creatorcontrib><creatorcontrib>Perroni, Dominic V.</creatorcontrib><creatorcontrib>Mahanthappa, Mahesh K.</creatorcontrib><creatorcontrib>Yethiraj, Arun</creatorcontrib><title>Electrostatic Interactions Govern “Odd/Even” Effects in Water-Induced Gemini Surfactant Self-Assembly</title><title>The journal of physical chemistry. B</title><addtitle>J. Phys. Chem. B</addtitle><description>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 morphologies that are sensitive to surfactant molecular structure and the nature 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 surfactants. In this work, we investigate this “odd/even effect” using computer simulations, focusing on experimentally studied gemini dicarboxylates with Na+ counterions, seven nonterminal carbon atoms in the tails, and either three, four, five, or six carbon atoms in the linker (denoted Na-73, Na-74, Na-75, and Na-76, respectively). We find that the relative electrostatic repulsion between headgroups in the different morphologies is correlated with the 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 orientations of Na-74 and Na-76 compared to those of 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 the hexagonal and gyroid phases. 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.</description><issn>1520-6106</issn><issn>1520-5207</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2017</creationdate><recordtype>article</recordtype><recordid>eNp1kLFOwzAQhi0EoqWwMyGPDKS1ncRxx6oKpVKlDgUxRo5zllIlTrGTSt36IPByfRJcWtgYTnfD9__SfQjdUzKkhNGRVG643qh8yHPChWAXqE9jRgI_yeX55pTwHrpxbk0Ii5ng16jHBGF8HLE-KtMKVGsb18q2VHhuWrBStWVjHJ41W7AGH_afy6IYpVswh_0XTrX2CYdLg9-lp4O5KToFBZ5BXZoSrzqrfYM0LV5BpYOJc1Dn1e4WXWlZObg77wF6e05fpy_BYjmbTyeLQEZR1AYikSGJGdc88T_RRIcCVMxioCLRqtBCiByiPBrLIoyJprxQkaIyDFmupMfCAXo89W5s89GBa7O6dAqqShpoOpdREYdJREOWeJScUOUFOAs629iylnaXUZIdBWdecHYUnJ0F-8jDub3Layj-Ar9GPfB0An6iTWeNf_b_vm-nZYm7</recordid><startdate>20170126</startdate><enddate>20170126</enddate><creator>Mantha, Sriteja</creator><creator>McDaniel, Jesse G.</creator><creator>Perroni, Dominic V.</creator><creator>Mahanthappa, Mahesh K.</creator><creator>Yethiraj, Arun</creator><general>American Chemical Society</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0002-8579-449X</orcidid></search><sort><creationdate>20170126</creationdate><title>Electrostatic Interactions Govern “Odd/Even” Effects in Water-Induced Gemini Surfactant Self-Assembly</title><author>Mantha, Sriteja ; McDaniel, Jesse G. ; Perroni, Dominic V. ; Mahanthappa, Mahesh K. ; Yethiraj, Arun</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a444t-87a30526f67b0617f38ec525e187fcdf888be4b49ad350f16dc4c1a332bca25e3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2017</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Mantha, Sriteja</creatorcontrib><creatorcontrib>McDaniel, Jesse G.</creatorcontrib><creatorcontrib>Perroni, Dominic V.</creatorcontrib><creatorcontrib>Mahanthappa, Mahesh K.</creatorcontrib><creatorcontrib>Yethiraj, Arun</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>The journal of physical chemistry. B</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Mantha, Sriteja</au><au>McDaniel, Jesse G.</au><au>Perroni, Dominic V.</au><au>Mahanthappa, Mahesh K.</au><au>Yethiraj, Arun</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Electrostatic Interactions Govern “Odd/Even” Effects in Water-Induced Gemini Surfactant Self-Assembly</atitle><jtitle>The journal of physical chemistry. B</jtitle><addtitle>J. Phys. Chem. B</addtitle><date>2017-01-26</date><risdate>2017</risdate><volume>121</volume><issue>3</issue><spage>565</spage><epage>576</epage><pages>565-576</pages><issn>1520-6106</issn><eissn>1520-5207</eissn><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 morphologies that are sensitive to surfactant molecular structure and the nature 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 surfactants. In this work, we investigate this “odd/even effect” using computer simulations, focusing on experimentally studied gemini dicarboxylates with Na+ counterions, seven nonterminal carbon atoms in the tails, and either three, four, five, or six carbon atoms in the linker (denoted Na-73, Na-74, Na-75, and Na-76, respectively). We find that the relative electrostatic repulsion between headgroups in the different morphologies is correlated with the 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 orientations of Na-74 and Na-76 compared to those of 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 the hexagonal and gyroid phases. 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.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>28026942</pmid><doi>10.1021/acs.jpcb.6b06882</doi><tpages>12</tpages><orcidid>https://orcid.org/0000-0002-8579-449X</orcidid><oa>free_for_read</oa></addata></record>
fulltext fulltext
identifier ISSN: 1520-6106
ispartof The journal of physical chemistry. B, 2017-01, Vol.121 (3), p.565-576
issn 1520-6106
1520-5207
language eng
recordid cdi_proquest_miscellaneous_1853741327
source American Chemical Society Journals
title Electrostatic Interactions Govern “Odd/Even” Effects in Water-Induced Gemini Surfactant Self-Assembly
url https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2024-12-25T02%3A48%3A33IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-proquest_cross&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Electrostatic%20Interactions%20Govern%20%E2%80%9COdd/Even%E2%80%9D%20Effects%20in%20Water-Induced%20Gemini%20Surfactant%20Self-Assembly&rft.jtitle=The%20journal%20of%20physical%20chemistry.%20B&rft.au=Mantha,%20Sriteja&rft.date=2017-01-26&rft.volume=121&rft.issue=3&rft.spage=565&rft.epage=576&rft.pages=565-576&rft.issn=1520-6106&rft.eissn=1520-5207&rft_id=info:doi/10.1021/acs.jpcb.6b06882&rft_dat=%3Cproquest_cross%3E1853741327%3C/proquest_cross%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_pqid=1853741327&rft_id=info:pmid/28026942&rfr_iscdi=true