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Title: Amphiphile Organization in Organic Solutions: An Alternative Explanation for Small-Angle X-ray Scattering Features in Malonamide/Alkane Mixtures

Abstract

In this work, the role of different intermolecular interactions in the aggregation of amphiphiles in an organic solvent is studied for systems of relevance to liquid-liquid extraction (LLE), a chemical process used to selectively recover metals from complex mixtures. Of specific interest is the role, or lack thereof, of hydrogen bonding, which is often assumed to be a main driver of the organic phase structural organization that has been linked to separation efficacy. Toward that end, a series of malonamide extractants in n-dodecane have been studied in the absence of any extracted aqueous solutes, including water. The series of extractants includes N,N'-dimethyl-N,N'-dibutyltetradecylmalonamide (DMDBTDMA), two of its homologs, and N,N'-dimethyl-N,N'-dioctylhexylethoxymalonamide (DMDOHEMA). This simplified model LLE system enables systematic investigation of the role of dipole-dipole and alkyl tail steric interactions in amphiphile aggregation. Small-angle X-ray scattering (SAXS) profiles computed from molecular dynamics trajectories are in good agreement with experimental SAXS data. Molecular dynamics simulations show that malonamide aggregation results from dipole-driven self-association and lacks characteristic aggregate sizes. Mid-q correlation peaks in the SAXS profiles emerge at high concentration for each malonamide. In those densely packed solutions, the correlation peaks are observed to result from alkyl tail-induced spacing between electron-rich polar head groups,more » with peak positions determined by the different alkyl tail lengths present in the malonamide molecule. This explanation of the SAXS correlation peaks contrasts with the prevailing literature, which attributes mesoscale features observed in small-angle scattering to the formation of microemulsions. Instead, this work finds that these features are present in the absence of water or any reverse micellar organization of the malonamides. As such, molecular-scale malonamide self-association and packing, rather than microemulsion-based colloidal-scale descriptions, is a more appropriate framework for these LLE systems.« less

Authors:
ORCiD logo [1];  [2]; ORCiD logo [2]; ORCiD logo [2];  [3]
+ Show Author Affiliations
  1. Argonne National Lab. (ANL), Argonne, IL (United States); Washington State Univ., Pullman, WA (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
  3. Washington State Univ., Pullman, WA (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1797771
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
Additional Journal Information:
Journal Volume: 124; Journal Issue: 47; Journal ID: ISSN 1520-6106
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Scattering; Alkyls; Cluster chemistry; X-ray scattering; Molecules

Citation Formats

Servis, Michael J., Piechowicz, Marek, Shkrob, Ilya A., Soderholm, L., and Clark, Aurora E. Amphiphile Organization in Organic Solutions: An Alternative Explanation for Small-Angle X-ray Scattering Features in Malonamide/Alkane Mixtures. United States: N. p., 2020. Web. doi:10.1021/acs.jpcb.0c07080.
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Servis, Michael J., Piechowicz, Marek, Shkrob, Ilya A., Soderholm, L., & Clark, Aurora E. Amphiphile Organization in Organic Solutions: An Alternative Explanation for Small-Angle X-ray Scattering Features in Malonamide/Alkane Mixtures. United States. https://doi.org/10.1021/acs.jpcb.0c07080
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Servis, Michael J., Piechowicz, Marek, Shkrob, Ilya A., Soderholm, L., and Clark, Aurora E. Tue . "Amphiphile Organization in Organic Solutions: An Alternative Explanation for Small-Angle X-ray Scattering Features in Malonamide/Alkane Mixtures". United States. https://doi.org/10.1021/acs.jpcb.0c07080. https://www.osti.gov/servlets/purl/1797771.
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@article{osti_1797771,
title = {Amphiphile Organization in Organic Solutions: An Alternative Explanation for Small-Angle X-ray Scattering Features in Malonamide/Alkane Mixtures},
author = {Servis, Michael J. and Piechowicz, Marek and Shkrob, Ilya A. and Soderholm, L. and Clark, Aurora E.},
abstractNote = {In this work, the role of different intermolecular interactions in the aggregation of amphiphiles in an organic solvent is studied for systems of relevance to liquid-liquid extraction (LLE), a chemical process used to selectively recover metals from complex mixtures. Of specific interest is the role, or lack thereof, of hydrogen bonding, which is often assumed to be a main driver of the organic phase structural organization that has been linked to separation efficacy. Toward that end, a series of malonamide extractants in n-dodecane have been studied in the absence of any extracted aqueous solutes, including water. The series of extractants includes N,N'-dimethyl-N,N'-dibutyltetradecylmalonamide (DMDBTDMA), two of its homologs, and N,N'-dimethyl-N,N'-dioctylhexylethoxymalonamide (DMDOHEMA). This simplified model LLE system enables systematic investigation of the role of dipole-dipole and alkyl tail steric interactions in amphiphile aggregation. Small-angle X-ray scattering (SAXS) profiles computed from molecular dynamics trajectories are in good agreement with experimental SAXS data. Molecular dynamics simulations show that malonamide aggregation results from dipole-driven self-association and lacks characteristic aggregate sizes. Mid-q correlation peaks in the SAXS profiles emerge at high concentration for each malonamide. In those densely packed solutions, the correlation peaks are observed to result from alkyl tail-induced spacing between electron-rich polar head groups, with peak positions determined by the different alkyl tail lengths present in the malonamide molecule. This explanation of the SAXS correlation peaks contrasts with the prevailing literature, which attributes mesoscale features observed in small-angle scattering to the formation of microemulsions. Instead, this work finds that these features are present in the absence of water or any reverse micellar organization of the malonamides. As such, molecular-scale malonamide self-association and packing, rather than microemulsion-based colloidal-scale descriptions, is a more appropriate framework for these LLE systems.},
doi = {10.1021/acs.jpcb.0c07080},
journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
number = 47,
volume = 124,
place = {United States},
year = {Tue Nov 17 00:00:00 EST 2020},
month = {Tue Nov 17 00:00:00 EST 2020}
}
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Works referenced in this record:

Microscopic Structures of Tri- n -butyl Phosphate/ n -Octane Mixtures by X-ray and Neutron Scattering in a Wide q Range
journal, January 2012

  • Motokawa, Ryuhei; Suzuki, Shinichi; Ogawa, Hiroki
  • The Journal of Physical Chemistry B, Vol. 116, Issue 4
  • DOI: 10.1021/jp210808r

Recycling metals by controlled transfer of ionic species between complex fluids: en route to “ienaics”
journal, November 2014

  • Zemb, Thomas; Bauer, Caroline; Bauduin, Pierre
  • Colloid and Polymer Science, Vol. 293, Issue 1
  • DOI: 10.1007/s00396-014-3447-x

Depletion of water-in-oil aggregates from poor solvents: Transition from weak aggregates towards reverse micelles
journal, February 2015

A Novel Microemulsion Phase Transition: Toward the Elucidation of Third-Phase Formation in Spent Nuclear Fuel Reprocessing
journal, January 2018

  • Mu, Junju; Motokawa, Ryuhei; Akutsu, Kazuhiro
  • The Journal of Physical Chemistry B, Vol. 122, Issue 4
  • DOI: 10.1021/acs.jpcb.7b08515

Origin of the scattering peak in microemulsions
journal, September 1987

  • Teubner, M.; Strey, R.
  • The Journal of Chemical Physics, Vol. 87, Issue 5
  • DOI: 10.1063/1.453006

Nature of Mesoscopic Organization in Protic Ionic Liquid–Alcohol Mixtures
journal, February 2016

  • Schroer, Wolffram; Triolo, Alessandro; Russina, Olga
  • The Journal of Physical Chemistry B, Vol. 120, Issue 9
  • DOI: 10.1021/acs.jpcb.6b01422

Molecular Thermodynamic Modeling of Reverse Micelles and Water-in-Oil Microemulsions
journal, March 2016

Reverse aggregate nucleation induced by acids in liquid–liquid extraction processes
journal, January 2014

  • Déjugnat, Christophe; Dourdain, Sandrine; Dubois, Véronique
  • Physical Chemistry Chemical Physics, Vol. 16, Issue 16
  • DOI: 10.1039/c4cp00073k

Colloidal Model for the Prediction of the Extraction of Rare Earths Assisted by the Acidic Extractant
journal, January 2019

A model for molecular emulsions: Water and “weak water” mixtures
journal, February 2013

  • Kežić, B.; Mazighi, R.; Perera, A.
  • Physica A: Statistical Mechanics and its Applications, Vol. 392, Issue 4
  • DOI: 10.1016/j.physa.2012.10.027

The role of solvent and neutral organophosphorus extractant structure in their organization and association
journal, March 2018

Synergistic Solvent Extraction Is Driven by Entropy
journal, November 2019

Aspects of the percolation process for hydrogen‐bond networks in water
journal, May 1979

  • Geiger, A.; Stillinger, F. H.; Rahman, A.
  • The Journal of Chemical Physics, Vol. 70, Issue 9
  • DOI: 10.1063/1.438042

Metal Recognition Driven by Weak Interactions: A Case Study in Solvent Extraction
journal, May 2016

Aggregation, reversed micelles, and microemulsions in liquid-liquid extraction: the tri-n-butyl phosphatediluent-water-electrolyte system
journal, November 1991

Characterisation of the supramolecular structure of malonamides by application of pulsed field gradients in NMR spectroscopy
journal, January 2007

  • Dozol, Hélène; Berthon, Claude
  • Physical Chemistry Chemical Physics, Vol. 9, Issue 37
  • DOI: 10.1039/b707897h

GROMACS: High performance molecular simulations through multi-level parallelism from laptops to supercomputers
journal, September 2015

Micro-heterogeneity versus clustering in binary mixtures of ethanol with water or alkanes
journal, January 2016

  • Požar, Martina; Lovrinčević, Bernarda; Zoranić, Larisa
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 34
  • DOI: 10.1039/C6CP04676B

Polar Solvents Trigger Formation of Reverse Micelles
journal, May 2015

  • Khoshnood, Atefeh; Firoozabadi, Abbas
  • Langmuir, Vol. 31, Issue 22
  • DOI: 10.1021/la504658u

Relation between the hydrophile/hydrophobe ratio of malonamide extractants and the stability of the organic phase: investigation at high extractant concentrations
journal, January 2007

  • Bauduin, P.; Testard, F.; Berthon, L.
  • Physical Chemistry Chemical Physics, Vol. 9, Issue 28
  • DOI: 10.1039/b701479a

Morphology of 1-alkyl-3-methylimidazolium hexafluorophosphate room temperature ionic liquids
journal, May 2008

Computational Study of Molecular Structure and Self-Association of Tri- n -butyl Phosphates in n -Dodecane
journal, January 2015

  • Vo, Quynh N.; Hawkins, Cory A.; Dang, Liem X.
  • The Journal of Physical Chemistry B, Vol. 119, Issue 4
  • DOI: 10.1021/jp510365c

Network analysis and percolation transition in hydrogen bonded clusters: nitric acid and water extracted by tributyl phosphate
journal, January 2017

  • Servis, Michael J.; Wu, David T.; Braley, Jenifer C.
  • Physical Chemistry Chemical Physics, Vol. 19, Issue 18
  • DOI: 10.1039/C7CP01845B

Development and testing of a general amber force field
journal, January 2004

  • Wang, Junmei; Wolf, Romain M.; Caldwell, James W.
  • Journal of Computational Chemistry, Vol. 25, Issue 9
  • DOI: 10.1002/jcc.20035

An Analysis of Some Graph Theoretical Cluster Techniques
journal, October 1970

Random Connected Cylinders: a New Structure in Three-Component Microemulsions
journal, September 1987

Fast, efficient generation of high-quality atomic charges. AM1-BCC model: II. Parameterization and validation
journal, October 2002

  • Jakalian, Araz; Jack, David B.; Bayly, Christopher I.
  • Journal of Computational Chemistry, Vol. 23, Issue 16
  • DOI: 10.1002/jcc.10128

A Molecular Dynamics Study of Tributyl Phosphate and Diamyl Amyl Phosphonate Self-Aggregation in Dodecane and Octane
journal, March 2016

  • Servis, Michael J.; Tormey, Caleb A.; Wu, David T.
  • The Journal of Physical Chemistry B, Vol. 120, Issue 10
  • DOI: 10.1021/acs.jpcb.5b08579

Multicomponent Model for the Prediction of Nuclear Waste/Rare-Earth Extraction Processes
journal, August 2018

Aerosol-OT Surfactant Forms Stable Reverse Micelles in Apolar Solvent in the Absence of Water
journal, January 2019

  • Urano, Ryo; Pantelopulos, George A.; Straub, John E.
  • The Journal of Physical Chemistry B, Vol. 123, Issue 11
  • DOI: 10.1021/acs.jpcb.8b07847

X-ray and Neutron Scattering of Water
journal, April 2016

  • Amann-Winkel, Katrin; Bellissent-Funel, Marie-Claire; Bove, Livia E.
  • Chemical Reviews, Vol. 116, Issue 13
  • DOI: 10.1021/acs.chemrev.5b00663

Aggregation in Organic Solutions of Malonamides: Consequences for Water Extraction
journal, December 2009

  • Meridiano, Y.; Berthon, L.; Crozes, X.
  • Solvent Extraction and Ion Exchange, Vol. 27, Issue 5-6
  • DOI: 10.1080/07366290903270148

A Pictorial View of Viscosity in Ionic Liquids and the Link to Nanostructural Heterogeneity
journal, February 2020

  • Amith, Weththasinghage D.; Araque, Juan C.; Margulis, Claudio J.
  • The Journal of Physical Chemistry Letters, Vol. 11, Issue 6
  • DOI: 10.1021/acs.jpclett.0c00170

Emerging Evidences of Mesoscopic-Scale Complexity in Neat Ionic Liquids and Their Mixtures
journal, February 2017

  • Russina, Olga; Lo Celso, Fabrizio; Plechkova, Natalia V.
  • The Journal of Physical Chemistry Letters, Vol. 8, Issue 6
  • DOI: 10.1021/acs.jpclett.6b02811

LINCS: A linear constraint solver for molecular simulations
journal, September 1997

Particle mesh Ewald: An N ⋅log( N ) method for Ewald sums in large systems
journal, June 1993

  • Darden, Tom; York, Darrin; Pedersen, Lee
  • The Journal of Chemical Physics, Vol. 98, Issue 12
  • DOI: 10.1063/1.464397

Revisiting aqueous-acetone mixtures through the concept of molecular emulsions
journal, October 2012

  • Kežić, Bernarda; Perera, Aurélien
  • The Journal of Chemical Physics, Vol. 137, Issue 13
  • DOI: 10.1063/1.4755816

Attractive Interactions between Reverse Aggregates and Phase Separation in Concentrated Malonamide Extractant Solutions
journal, March 1999

  • Erlinger, C.; Belloni, L.; Zemb, Th.
  • Langmuir, Vol. 15, Issue 7
  • DOI: 10.1021/la980313w

Quiet high-resolution computer models of a plasma
journal, February 1974

Aggregation of amphiphiles in nonaqueous media
journal, May 1980

  • Ruckenstein, E.; Nagarajan, R.
  • The Journal of Physical Chemistry, Vol. 84, Issue 11
  • DOI: 10.1021/j100448a013

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

The science and applications of emulsions — an overview
journal, November 1994

A small-angle neutron scattering study of nonionic surfactant molecules at the water–oil interface: Area per molecule, microemulsion domain size, and rigidity
journal, April 1997

  • Sottmann, T.; Strey, R.; Chen, S. -H.
  • The Journal of Chemical Physics, Vol. 106, Issue 15
  • DOI: 10.1063/1.473638

Aggregation in Solvent Extraction Systems Containing a Malonamide, a Dialkylphosphoric Acid and their Mixtures
journal, July 2008

  • Antonio, M. R.; Chiarizia, R.; Gannaz, B.
  • Separation Science and Technology, Vol. 43, Issue 9-10
  • DOI: 10.1080/01496390802121537

A Telescoping View of Solute Architectures in a Complex Fluid System
journal, December 2018

Fluctuations and micro-heterogeneity in mixtures of complex liquids
journal, January 2013

  • Perera, Aurélien; Kežić, Bernarda
  • Faraday Discussions, Vol. 167
  • DOI: 10.1039/c3fd00072a

The structure of tributyl phosphate solutions: Nitric acid, uranium (VI), and zirconium (IV)
journal, November 2017

Molecular segregation observed in a concentrated alcohol–water solution
journal, April 2002

  • Dixit, S.; Crain, J.; Poon, W. C. K.
  • Nature, Vol. 416, Issue 6883
  • DOI: 10.1038/416829a

Importance of weak interactions in the formulation of organic phases for efficient liquid/liquid extraction of metals
journal, April 2020

  • Bourgeois, Damien; El Maangar, Asmae; Dourdain, Sandrine
  • Current Opinion in Colloid & Interface Science, Vol. 46
  • DOI: 10.1016/j.cocis.2020.03.004

Liquid-Liquid Extraction of Acids and Water by a Malonamide: I-Anion Specific Effects on the Polar Core Microstructure of the Aggregated Malonamide
journal, July 2014

  • Déjugnat, Christophe; Berthon, Laurence; Dubois, Véronique
  • Solvent Extraction and Ion Exchange, Vol. 32, Issue 6
  • DOI: 10.1080/07366299.2014.940229

Critical Exponents for Solvent Extraction Resolved Using SAXS
journal, December 2013

  • Ellis, Ross J.
  • The Journal of Physical Chemistry B, Vol. 118, Issue 1
  • DOI: 10.1021/jp408078v

Organic and Third Phase in HNO 3 /TBP/ n -Dodecane System: No Reverse Micelles
journal, June 2017

The role of curvature effects in liquid–liquid extraction: assessing organic phase mesoscopic properties from MD simulations
journal, January 2017

  • Duvail, Magali; van Damme, Steven; Guilbaud, Philippe
  • Soft Matter, Vol. 13, Issue 33
  • DOI: 10.1039/C7SM00733G

Canonical dynamics: Equilibrium phase-space distributions
journal, March 1985

PACKMOL: A package for building initial configurations for molecular dynamics simulations
journal, October 2009

  • Martínez, L.; Andrade, R.; Birgin, E. G.
  • Journal of Computational Chemistry, Vol. 30, Issue 13
  • DOI: 10.1002/jcc.21224

Molecular emulsions: from charge order to domain order
journal, January 2017

Aqueous tert -butanol mixtures: A model for molecular-emulsions
journal, July 2012

  • Kežić, Bernarda; Perera, Aurélien
  • The Journal of Chemical Physics, Vol. 137, Issue 1
  • DOI: 10.1063/1.4730524

Elucidation of the Structure of Organic Solutions in Solvent Extraction by Combining Molecular Dynamics and X-ray Scattering
journal, April 2014

  • Ferru, Geoffroy; Gomes Rodrigues, Donatien; Berthon, Laurence
  • Angewandte Chemie International Edition, Vol. 53, Issue 21
  • DOI: 10.1002/anie.201402677

Solute-Induced Microstructural Transition from Weak Aggregates towards a Curved Film of Surface-Active Extractants
journal, January 2012

Derivation of micelle size-dependent free energies of aggregation for octyl phosphocholine from molecular dynamics simulation
journal, April 2019

Comparative Molecular Dynamics Study on Tri- n -butyl Phosphate in Organic and Aqueous Environments and Its Relevance to Nuclear Extraction Processes
journal, May 2016

  • Mu, Junju; Motokawa, Ryuhei; Williams, Christopher D.
  • The Journal of Physical Chemistry B, Vol. 120, Issue 23
  • DOI: 10.1021/acs.jpcb.6b00781

From Order to Disorder: Computational Design of Triblock Amphiphiles with 1 nm Domains
journal, May 2020

  • Shen, Zhengyuan; Chen, Jingyi L.; Vernadskaia, Viktoriia
  • Journal of the American Chemical Society, Vol. 142, Issue 20
  • DOI: 10.1021/jacs.0c01829

How Different Are the Characteristics of Aqueous Solutions of tert -Butyl Alcohol and Trimethylamine- N -Oxide? A Molecular Dynamics Simulation Study
journal, August 2018

  • Bandyopadhyay, Dibyendu; Kamble, Yash; Choudhury, Niharendu
  • The Journal of Physical Chemistry B, Vol. 122, Issue 34
  • DOI: 10.1021/acs.jpcb.8b02411
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