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Title: Structural and Solubility Parameter Correlations of Gelation Abilities for Dihydroxylated Derivatives of Long‐Chain, Naturally Occurring Fatty Acids

Abstract

Abstract Creating structure–property correlations at different distance scales is one of the important challenges to the rational design of molecular gelators. Here, a series of dihydroxylated derivatives of long‐chain fatty acids, derived from three naturally occurring molecules—oleic, erucic and ricinoleic acids—are investigated as gelators of a wide variety of liquids. Conclusions about what constitutes a more (or less!) efficient gelator are based upon analyses of a variety of thermal, structural, molecular modeling, and rheological results. Correlations between the manner of molecular packing in the neat solid or gel states of the gelators and Hansen solubility data from the liquids leads to the conclusion that diol stereochemistry, the number of carbon atoms separating the two hydroxyl groups, and the length of the alkanoic chains are the most important structural parameters controlling efficiency of gel formation for these gelators. Some of the diol gelators are as efficient or even more efficient than the well‐known, excellent gelator, ( R )‐12‐hydroxystearic acid; others are much worse. The ability to form extensive intermolecular H‐bonding networks along the alkyl chains appears to play a key role in promoting fiber growth and, thus, gelation. In toto, the results demonstrate how the efficiency of gelation can be modulatedmore » by very small structural changes and also suggest how other structural modifications may be exploited to create efficient gelators.« less

Authors:
; ; ; ;
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1400712
Grant/Contract Number:  
DE‐FG36‐08GO088160
Resource Type:
Publisher's Accepted Manuscript
Journal Name:
Chemistry - A European Journal
Additional Journal Information:
Journal Name: Chemistry - A European Journal Journal Volume: 21 Journal Issue: 23; Journal ID: ISSN 0947-6539
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Zhang, Mohan, Selvakumar, Sermadurai, Zhang, Xinran, Sibi, Mukund P., and Weiss, Richard G. Structural and Solubility Parameter Correlations of Gelation Abilities for Dihydroxylated Derivatives of Long‐Chain, Naturally Occurring Fatty Acids. Germany: N. p., 2015. Web. doi:10.1002/chem.201500096.
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Zhang, Mohan, Selvakumar, Sermadurai, Zhang, Xinran, Sibi, Mukund P., & Weiss, Richard G. Structural and Solubility Parameter Correlations of Gelation Abilities for Dihydroxylated Derivatives of Long‐Chain, Naturally Occurring Fatty Acids. Germany. https://doi.org/10.1002/chem.201500096
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Zhang, Mohan, Selvakumar, Sermadurai, Zhang, Xinran, Sibi, Mukund P., and Weiss, Richard G. Wed . "Structural and Solubility Parameter Correlations of Gelation Abilities for Dihydroxylated Derivatives of Long‐Chain, Naturally Occurring Fatty Acids". Germany. https://doi.org/10.1002/chem.201500096.
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@article{osti_1400712,
title = {Structural and Solubility Parameter Correlations of Gelation Abilities for Dihydroxylated Derivatives of Long‐Chain, Naturally Occurring Fatty Acids},
author = {Zhang, Mohan and Selvakumar, Sermadurai and Zhang, Xinran and Sibi, Mukund P. and Weiss, Richard G.},
abstractNote = {Abstract Creating structure–property correlations at different distance scales is one of the important challenges to the rational design of molecular gelators. Here, a series of dihydroxylated derivatives of long‐chain fatty acids, derived from three naturally occurring molecules—oleic, erucic and ricinoleic acids—are investigated as gelators of a wide variety of liquids. Conclusions about what constitutes a more (or less!) efficient gelator are based upon analyses of a variety of thermal, structural, molecular modeling, and rheological results. Correlations between the manner of molecular packing in the neat solid or gel states of the gelators and Hansen solubility data from the liquids leads to the conclusion that diol stereochemistry, the number of carbon atoms separating the two hydroxyl groups, and the length of the alkanoic chains are the most important structural parameters controlling efficiency of gel formation for these gelators. Some of the diol gelators are as efficient or even more efficient than the well‐known, excellent gelator, ( R )‐12‐hydroxystearic acid; others are much worse. The ability to form extensive intermolecular H‐bonding networks along the alkyl chains appears to play a key role in promoting fiber growth and, thus, gelation. In toto, the results demonstrate how the efficiency of gelation can be modulated by very small structural changes and also suggest how other structural modifications may be exploited to create efficient gelators.},
doi = {10.1002/chem.201500096},
journal = {Chemistry - A European Journal},
number = 23,
volume = 21,
place = {Germany},
year = {Wed Apr 29 00:00:00 EDT 2015},
month = {Wed Apr 29 00:00:00 EDT 2015}
}
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https://doi.org/10.1002/chem.201500096
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