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Title: Enhanced liquid-liquid anion exchange using macrocyclic anion receptors: effect of receptor structure on sulphate-nitrate exchange selectivity

Abstract

When certain macrocyclic anion receptors are added to a chloroform solution of the nitrate form of a lipophilic quaternary ammonium salt (methyltri-C8,10-ammonium nitrate, Aliquat 336N), the extraction of sulphate from an aqueous sodium nitrate solution via exchange with the organic-phase nitrate is significantly enhanced. Eight macrocycles were surveyed, including two derivatives of a tetraamide macrocycle, five derivatives of calix[4]pyrrole and -decafluorocalix[5]pyrrole. Under the hypothesis that the enhancement originates from sulphate binding by the anion receptors in the chloroform phase, it was possible to obtain reasonable fits to the sulphate distribution survey data based on the formation of 1:1 and 2:1 receptor:sulphate complexes in the chloroform phase. Apparent 1:1 sulphate-binding constants obtained from the model in this system fell in the range . Comparison of the results for the various anion receptors included in this study reveals that sulphate binding is sensitive to the nature of the substituents on the parent macrocycle scaffolds in a way that does not follow straightforwardly from simple chemical expectations, such as electron-withdrawing effects on hydrogen-bond donor strength.

Authors:
 [1];  [2];  [1];  [1];  [1];  [1];  [1];  [3];  [3];  [4];  [5];  [5];  [4];  [5];  [4]
  1. ORNL
  2. {Fred} V [ORNL
  3. University of Kansas
  4. University of Texas
  5. University of Texas, Austin
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1081759
DOE Contract Number:  
DE-AC05-00OR22725
Resource Type:
Journal Article
Journal Name:
Supramolecular Chemistry
Additional Journal Information:
Journal Volume: 22; Journal Issue: 11-12; Journal ID: ISSN 1061--0278
Country of Publication:
United States
Language:
English

Citation Formats

Moyer, Bruce A, Sloop Jr, Frederick, Fowler, Christopher J, Haverlock, Tamara, Kang, Hyun Ah, Delmau, Laetitia Helene, Bau, Diadra, Hossain, Alamgir, Bowman-James, Kristin, Shriver, James A., Gross, Mr. Dustin E., Bill, Nathan, Marquez, Manuel, Lynch, Vincent M., and Sessler, Jonathan L. Enhanced liquid-liquid anion exchange using macrocyclic anion receptors: effect of receptor structure on sulphate-nitrate exchange selectivity. United States: N. p., 2010. Web. doi:10.1080/10610271003763263.
Moyer, Bruce A, Sloop Jr, Frederick, Fowler, Christopher J, Haverlock, Tamara, Kang, Hyun Ah, Delmau, Laetitia Helene, Bau, Diadra, Hossain, Alamgir, Bowman-James, Kristin, Shriver, James A., Gross, Mr. Dustin E., Bill, Nathan, Marquez, Manuel, Lynch, Vincent M., & Sessler, Jonathan L. Enhanced liquid-liquid anion exchange using macrocyclic anion receptors: effect of receptor structure on sulphate-nitrate exchange selectivity. United States. doi:10.1080/10610271003763263.
Moyer, Bruce A, Sloop Jr, Frederick, Fowler, Christopher J, Haverlock, Tamara, Kang, Hyun Ah, Delmau, Laetitia Helene, Bau, Diadra, Hossain, Alamgir, Bowman-James, Kristin, Shriver, James A., Gross, Mr. Dustin E., Bill, Nathan, Marquez, Manuel, Lynch, Vincent M., and Sessler, Jonathan L. Fri . "Enhanced liquid-liquid anion exchange using macrocyclic anion receptors: effect of receptor structure on sulphate-nitrate exchange selectivity". United States. doi:10.1080/10610271003763263.
@article{osti_1081759,
title = {Enhanced liquid-liquid anion exchange using macrocyclic anion receptors: effect of receptor structure on sulphate-nitrate exchange selectivity},
author = {Moyer, Bruce A and Sloop Jr, Frederick and Fowler, Christopher J and Haverlock, Tamara and Kang, Hyun Ah and Delmau, Laetitia Helene and Bau, Diadra and Hossain, Alamgir and Bowman-James, Kristin and Shriver, James A. and Gross, Mr. Dustin E. and Bill, Nathan and Marquez, Manuel and Lynch, Vincent M. and Sessler, Jonathan L.},
abstractNote = {When certain macrocyclic anion receptors are added to a chloroform solution of the nitrate form of a lipophilic quaternary ammonium salt (methyltri-C8,10-ammonium nitrate, Aliquat 336N), the extraction of sulphate from an aqueous sodium nitrate solution via exchange with the organic-phase nitrate is significantly enhanced. Eight macrocycles were surveyed, including two derivatives of a tetraamide macrocycle, five derivatives of calix[4]pyrrole and -decafluorocalix[5]pyrrole. Under the hypothesis that the enhancement originates from sulphate binding by the anion receptors in the chloroform phase, it was possible to obtain reasonable fits to the sulphate distribution survey data based on the formation of 1:1 and 2:1 receptor:sulphate complexes in the chloroform phase. Apparent 1:1 sulphate-binding constants obtained from the model in this system fell in the range . Comparison of the results for the various anion receptors included in this study reveals that sulphate binding is sensitive to the nature of the substituents on the parent macrocycle scaffolds in a way that does not follow straightforwardly from simple chemical expectations, such as electron-withdrawing effects on hydrogen-bond donor strength.},
doi = {10.1080/10610271003763263},
journal = {Supramolecular Chemistry},
issn = {1061--0278},
number = 11-12,
volume = 22,
place = {United States},
year = {2010},
month = {1}
}