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Title: Simple guanidinium motif for the selective binding and extraction of sulfate

Abstract

A simple bidentate anion receptor, shown previously to adopt a rigid pseudobicyclic conformation while binding anions in the solid state, selectively binds sulfate in aqueous solutions with log K1 and log K2 values of 3.78 ± 0.12 M-1 and 2.10 ± 0.23 M-1, respectively. This anion receptor has little to no affinity for nitrate and chloride in the same solutions. A lipophilic derivative was synthesized in four steps to yield an extractant that is capable of partitioning sulfate into 1,2 dichloroethane from water in the presence of large excesses of chloride. This extractant demonstrated D values as high as 2.5 with only 30 mM of anion receptor.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [3]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Texas at Austin, Austin, TX (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1408027
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Separation Science and Technology
Additional Journal Information:
Journal Volume: 53; Journal Issue: 12; Journal ID: ISSN 0149-6395
Publisher:
Taylor & Francis
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; guanidinium; anion binding; sulfate; extraction; density functional theory

Citation Formats

Seipp, Charles A., Williams, Neil J., Bryantsev, Vyacheslav S., and Moyer, Bruce A. Simple guanidinium motif for the selective binding and extraction of sulfate. United States: N. p., 2017. Web. doi:10.1080/01496395.2017.1318922.
Seipp, Charles A., Williams, Neil J., Bryantsev, Vyacheslav S., & Moyer, Bruce A. Simple guanidinium motif for the selective binding and extraction of sulfate. United States. doi:10.1080/01496395.2017.1318922.
Seipp, Charles A., Williams, Neil J., Bryantsev, Vyacheslav S., and Moyer, Bruce A. Fri . "Simple guanidinium motif for the selective binding and extraction of sulfate". United States. doi:10.1080/01496395.2017.1318922. https://www.osti.gov/servlets/purl/1408027.
@article{osti_1408027,
title = {Simple guanidinium motif for the selective binding and extraction of sulfate},
author = {Seipp, Charles A. and Williams, Neil J. and Bryantsev, Vyacheslav S. and Moyer, Bruce A.},
abstractNote = {A simple bidentate anion receptor, shown previously to adopt a rigid pseudobicyclic conformation while binding anions in the solid state, selectively binds sulfate in aqueous solutions with log K1 and log K2 values of 3.78 ± 0.12 M-1 and 2.10 ± 0.23 M-1, respectively. This anion receptor has little to no affinity for nitrate and chloride in the same solutions. A lipophilic derivative was synthesized in four steps to yield an extractant that is capable of partitioning sulfate into 1,2 dichloroethane from water in the presence of large excesses of chloride. This extractant demonstrated D values as high as 2.5 with only 30 mM of anion receptor.},
doi = {10.1080/01496395.2017.1318922},
journal = {Separation Science and Technology},
number = 12,
volume = 53,
place = {United States},
year = {2017},
month = {6}
}

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Cited by: 2 works
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Works referenced in this record:

Anion binding with urea and thiourea derivatives
journal, July 2015

  • Blažek Bregović, Vesna; Basarić, Nikola; Mlinarić-Majerski, Kata
  • Coordination Chemistry Reviews, Vol. 295
  • DOI: 10.1016/j.ccr.2015.03.011

Enhanced Anion Exchange for Selective Sulfate Extraction: Overcoming the Hofmeister Bias
journal, November 2008

  • Fowler, Christopher J.; Haverlock, Tamara J.; Moyer, Bruce A.
  • Journal of the American Chemical Society, Vol. 130, Issue 44
  • DOI: 10.1021/ja806511b

A conformationally persistent pseudo-bicyclic guanidinium for anion coordination as stabilized by dual intramolecular hydrogen bonds
journal, January 2015

  • Seipp, Charles A.; Williams, Neil J.; Bryantsev, Vyacheslav S.
  • RSC Advances, Vol. 5, Issue 130
  • DOI: 10.1039/C5RA21864K

Molecular recognition of oxoanions based on guanidinium receptors
journal, January 2007

  • Blondeau, Pascal; Segura, Margarita; Pérez-Fernández, Ruth
  • Chem. Soc. Rev., Vol. 36, Issue 2
  • DOI: 10.1039/b603089k

Anion Partitioning and Ion-Pairing Behavior of Anions in the Extraction of Cesium Salts by 4,5‘ ‘-Bis( tert -octylbenzo)dibenzo-24-crown-8 in 1,2-Dichloroethane
journal, January 2007

  • Levitskaia, Tatiana G.; Maya, Leon; Van Berkel, Gary J.
  • Inorganic Chemistry, Vol. 46, Issue 1
  • DOI: 10.1021/ic061605k

A Case for Molecular Recognition in Nuclear Separations: Sulfate Separation from Nuclear Wastes
journal, June 2012

  • Moyer, Bruce A.; Custelcean, Radu; Hay, Benjamin P.
  • Inorganic Chemistry, Vol. 52, Issue 7
  • DOI: 10.1021/ic3016832

α,α′,α″,α′″- meso -tetrahexyltetramethyl-calix[4]pyrrole: an easy-to-prepare, isomerically pure anion extractant with enhanced solubility in organic solvents
journal, October 2015


Urea-functionalized crystalline capsules for recognition and separation of tetrahedral oxoanions
journal, January 2013


Ion Pairing
journal, November 2006

  • Marcus, Yizhak; Hefter, Glenn
  • Chemical Reviews, Vol. 106, Issue 11
  • DOI: 10.1021/cr040087x

Artificial Organic Host Molecules for Anions
journal, August 1997

  • Schmidtchen, Franz P.; Berger, Michael
  • Chemical Reviews, Vol. 97, Issue 5
  • DOI: 10.1021/cr9603845

Nuclear Magnetic Resonance as a Tool for Determining Protonation Constants of Natural Polyprotic Bases in Solution
journal, November 1995

  • Frassineti, Chiara; Ghelli, Stefano; Gans, Peter
  • Analytical Biochemistry, Vol. 231, Issue 2
  • DOI: 10.1006/abio.1995.9984

Determining association constants from titration experiments in supramolecular chemistry
journal, January 2011


Selective Nitrate Binding in Competitive Hydrogen Bonding Solvents: Do Anion-π Interactions Facilitate Nitrate Selectivity?
journal, August 2013

  • Watt, Michelle M.; Zakharov, Lev N.; Haley, Michael M.
  • Angewandte Chemie International Edition, Vol. 52, Issue 39
  • DOI: 10.1002/anie.201303881

Zwitterionic Guanidinium Compounds Serve as Electroneutral Anion Hosts
journal, November 1999

  • Berger, Michael; Schmidtchen, Franz P.
  • Journal of the American Chemical Society, Vol. 121, Issue 43
  • DOI: 10.1021/ja992028k

A C 3 Symmetric Nitrate Complex with a Thiophene-Based Tripodal Receptor
journal, April 2011

  • Işıklan, Muhammet; Saeed, Musabbir A.; Pramanik, Avijit
  • Crystal Growth & Design, Vol. 11, Issue 4
  • DOI: 10.1021/cg2001859

The Binding of Sulfate Anions by Guanidinium Receptors is Entropy-Driven
journal, October 1998


Dipyridyl-Guanidin und seine Derivate
journal, January 1934


Quantum Mechanical Continuum Solvation Models
journal, August 2005

  • Tomasi, Jacopo; Mennucci, Benedetta; Cammi, Roberto
  • Chemical Reviews, Vol. 105, Issue 8
  • DOI: 10.1021/cr9904009

Selectivity Control in Synergistic Liquid–Liquid Anion Exchange of Univalent Anions via Structure-Specific Cooperativity between Quaternary Ammonium Cations and Anion Receptors
journal, September 2012

  • Borman, Christopher J.; Bonnesen, Peter V.; Moyer, Bruce A.
  • Analytical Chemistry, Vol. 84, Issue 19
  • DOI: 10.1021/ac301315c

Cubic, Hydrogen-Bonded (10,3)-a Networks in the Family [C(NH2)3][N(CH3)4][XO4] (X=S, Cr, and Mo)
journal, November 2004

  • Abrahams, Brendan F.; Haywood, Marissa G.; Hudson, Timothy A.
  • Angewandte Chemie International Edition, Vol. 43, Issue 45
  • DOI: 10.1002/anie.200461678

Structural Investigations of the Phase Transitions of Tetramethylammonium Sulfate
journal, August 1998

  • Malchus, M.; Jansen, M.
  • Acta Crystallographica Section B Structural Science, Vol. 54, Issue 4
  • DOI: 10.1107/S0108768197018351

Long-range corrected hybrid density functionals with damped atom–atom dispersion corrections
journal, January 2008

  • Chai, Jeng-Da; Head-Gordon, Martin
  • Physical Chemistry Chemical Physics, Vol. 10, Issue 44
  • DOI: 10.1039/b810189b

    Works referencing / citing this record:

    Simple guanidinium motif for the selective binding and extraction of sulfate
    dataset, October 2017


    Ion-pair induced supramolecular assembly formation for selective extraction and sensing of potassium sulfate
    journal, January 2019

    • Jagleniec, Damian; Dobrzycki, Łukasz; Karbarz, Marcin
    • Chemical Science, Vol. 10, Issue 41
    • DOI: 10.1039/c9sc02923k

    Cubic, Hydrogen-Bonded (10,3)-a Networks in the Family [C(NH2)3][N(CH3)4][XO4] (X=S, Cr, and Mo)
    journal, November 2004

    • Abrahams, Brendan F.; Haywood, Marissa G.; Hudson, Timothy A.
    • Angewandte Chemie International Edition, Vol. 43, Issue 45
    • DOI: 10.1002/anie.200461678

    Selective Nitrate Binding in Competitive Hydrogen Bonding Solvents: Do Anion-π Interactions Facilitate Nitrate Selectivity?
    journal, August 2013

    • Watt, Michelle M.; Zakharov, Lev N.; Haley, Michael M.
    • Angewandte Chemie International Edition, Vol. 52, Issue 39
    • DOI: 10.1002/anie.201303881

    Dipyridyl-Guanidin und seine Derivate
    journal, January 1934


    Nuclear Magnetic Resonance as a Tool for Determining Protonation Constants of Natural Polyprotic Bases in Solution
    journal, November 1995

    • Frassineti, Chiara; Ghelli, Stefano; Gans, Peter
    • Analytical Biochemistry, Vol. 231, Issue 2
    • DOI: 10.1006/abio.1995.9984

    Anion binding with urea and thiourea derivatives
    journal, July 2015

    • Blažek Bregović, Vesna; Basarić, Nikola; Mlinarić-Majerski, Kata
    • Coordination Chemistry Reviews, Vol. 295
    • DOI: 10.1016/j.ccr.2015.03.011

    Selectivity Control in Synergistic Liquid–Liquid Anion Exchange of Univalent Anions via Structure-Specific Cooperativity between Quaternary Ammonium Cations and Anion Receptors
    journal, September 2012

    • Borman, Christopher J.; Bonnesen, Peter V.; Moyer, Bruce A.
    • Analytical Chemistry, Vol. 84, Issue 19
    • DOI: 10.1021/ac301315c

    A C 3 Symmetric Nitrate Complex with a Thiophene-Based Tripodal Receptor
    journal, April 2011

    • Işıklan, Muhammet; Saeed, Musabbir A.; Pramanik, Avijit
    • Crystal Growth & Design, Vol. 11, Issue 4
    • DOI: 10.1021/cg2001859

    Ion Pairing
    journal, November 2006

    • Marcus, Yizhak; Hefter, Glenn
    • Chemical Reviews, Vol. 106, Issue 11
    • DOI: 10.1021/cr040087x

    Artificial Organic Host Molecules for Anions
    journal, August 1997

    • Schmidtchen, Franz P.; Berger, Michael
    • Chemical Reviews, Vol. 97, Issue 5
    • DOI: 10.1021/cr9603845

    Quantum Mechanical Continuum Solvation Models
    journal, August 2005

    • Tomasi, Jacopo; Mennucci, Benedetta; Cammi, Roberto
    • Chemical Reviews, Vol. 105, Issue 8
    • DOI: 10.1021/cr9904009

    Anion Partitioning and Ion-Pairing Behavior of Anions in the Extraction of Cesium Salts by 4,5‘ ‘-Bis( tert -octylbenzo)dibenzo-24-crown-8 in 1,2-Dichloroethane
    journal, January 2007

    • Levitskaia, Tatiana G.; Maya, Leon; Van Berkel, Gary J.
    • Inorganic Chemistry, Vol. 46, Issue 1
    • DOI: 10.1021/ic061605k

    A Case for Molecular Recognition in Nuclear Separations: Sulfate Separation from Nuclear Wastes
    journal, June 2012

    • Moyer, Bruce A.; Custelcean, Radu; Hay, Benjamin P.
    • Inorganic Chemistry, Vol. 52, Issue 7
    • DOI: 10.1021/ic3016832

    Enhanced Anion Exchange for Selective Sulfate Extraction: Overcoming the Hofmeister Bias
    journal, November 2008

    • Fowler, Christopher J.; Haverlock, Tamara J.; Moyer, Bruce A.
    • Journal of the American Chemical Society, Vol. 130, Issue 44
    • DOI: 10.1021/ja806511b

    Zwitterionic Guanidinium Compounds Serve as Electroneutral Anion Hosts
    journal, November 1999

    • Berger, Michael; Schmidtchen, Franz P.
    • Journal of the American Chemical Society, Vol. 121, Issue 43
    • DOI: 10.1021/ja992028k

    Molecular recognition of oxoanions based on guanidinium receptors
    journal, January 2007

    • Blondeau, Pascal; Segura, Margarita; Pérez-Fernández, Ruth
    • Chem. Soc. Rev., Vol. 36, Issue 2
    • DOI: 10.1039/b603089k

    Long-range corrected hybrid density functionals with damped atom–atom dispersion corrections
    journal, January 2008

    • Chai, Jeng-Da; Head-Gordon, Martin
    • Physical Chemistry Chemical Physics, Vol. 10, Issue 44
    • DOI: 10.1039/b810189b

    Determining association constants from titration experiments in supramolecular chemistry
    journal, January 2011


    Urea-functionalized crystalline capsules for recognition and separation of tetrahedral oxoanions
    journal, January 2013


    α,α′,α″,α′″- meso -tetrahexyltetramethyl-calix[4]pyrrole: an easy-to-prepare, isomerically pure anion extractant with enhanced solubility in organic solvents
    journal, October 2015


    Ion-pair induced supramolecular assembly formation for selective extraction and sensing of potassium sulfate
    journal, January 2019

    • Jagleniec, Damian; Dobrzycki, Łukasz; Karbarz, Marcin
    • Chemical Science, Vol. 10, Issue 41
    • DOI: 10.1039/c9sc02923k