Dynamics of Glyceline and Interactions of Constituents: A Multitechnique NMR Study

Fraenza, Carla C.; Elgammal, Ramez A.; Garaga, Mounesha N.; Bhattacharyya, Sahana; Zawodzinski, Thomas A.; Greenbaum, Steven G.

doi:10.1021/acs.jpcb.1c09227

Title: Dynamics of Glyceline and Interactions of Constituents: A Multitechnique NMR Study

Journal Article · 25 January 2022 · Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry

DOI: https://doi.org/10.1021/acs.jpcb.1c09227 · OSTI ID:1865385

Fraenza, Carla C. ^[1]; Elgammal, Ramez A. ^[2]; Garaga, Mounesha N. ^[3]; Bhattacharyya, Sahana ^[3];

^[2];

^[3]

Hunter College of CUNY, New York, NY (United States); Department of Physics and Astronomy, Hunter college of CUNY, New York, New York, 10065, USA
Univ. of Tennessee, Knoxville, TN (United States)
Hunter College of CUNY, New York, NY (United States)

In this work, the dynamics of the organic components of the deep eutectic solvent (DES) glyceline are analyzed using an array of complementary nuclear magnetic resonance (NMR) methods. Fast-Field Cycling ¹H relaxometry, Pulsed Field Gradient diffusion, Nuclear Overhauser Effect Spectroscopy (NOESY), ¹³C NMR relaxation and pressure dependent NMR experiments are deployed to sample a range of frequencies and modes of motion of the glycerol and choline components of the DES. Generally, translational and rotational diffusion of glycerol are more rapid than those of choline while short range rotational motions observed from ¹³C relaxation indicate slow local motion of glycerol at low choline chloride (ChCl) content. The rates of glycerol and choline local motions become more similar at higher ChCl. This result taken together with pressure dependent NMR studies show that the addition of ChCl makes it easier to disrupt glycerol packing. Finally, a relatively slow hydroxyl H-exchange process between glycerol and choline protons is deduced from the data. Consistent with this, NOESY results indicate relatively little direct H-bonding between glycerol and choline. These results suggest that the glycerol H-bonding network is disrupted as choline is added, but primarily in regions where there is intimate mixing of the two components. Thus, the local dynamics of most of the glycerol, resembles that of pure glycerol until substantial choline chloride is present.

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Research Organization:: Case Western Reserve Univ., Cleveland, OH (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0019409

OSTI ID:: 1865385

Journal Information:: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry, Journal Name: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry Journal Issue: 4 Vol. 126; ISSN 1520-6106

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (62)

Fast-field-cycling NMR: Applications and instrumentation Anoardo, E.; Galli, G.; Ferrante, G. Applied Magnetic Resonance, Vol. 20, Issue 3 https://doi.org/10.1007/BF03162287	journal	April 2001
Potential use of deep eutectic solvents to facilitate lignocellulosic biomass utilization and conversion Loow, Yu-Loong; New, Eng Kein; Yang, Ge Hoa Cellulose, Vol. 24, Issue 9 https://doi.org/10.1007/s10570-017-1358-y	journal	June 2017
The electrochemical stability of ionic liquids and deep eutectic solvents Li, Qingbo; Jiang, Jingyun; Li, Guofeng Science China Chemistry, Vol. 59, Issue 5 https://doi.org/10.1007/s11426-016-5566-3	journal	March 2016
A1H NMR study of glycerol at high pressure Marzke, R. F.; Raffaelle, D. P.; Halvorson, K. E. Journal of Non-Crystalline Solids, Vol. 172-174 https://doi.org/10.1016/0022-3093(94)90464-2	journal	September 1994
New horizons in the extraction of bioactive compounds using deep eutectic solvents: A review Zainal-Abidin, Mohamad Hamdi; Hayyan, Maan; Hayyan, Adeeb Analytica Chimica Acta, Vol. 979 https://doi.org/10.1016/j.aca.2017.05.012	journal	August 2017
Deep eutectic solvents for the production and application of new materials Tomé, Luciana I. N.; Baião, Vanessa; da Silva, Wanderson Applied Materials Today, Vol. 10 https://doi.org/10.1016/j.apmt.2017.11.005	journal	March 2018
Natural deep eutectic solvents for lignocellulosic biomass pretreatment: Recent developments, challenges and novel opportunities Satlewal, Alok; Agrawal, Ruchi; Bhagia, Samarthya Biotechnology Advances, Vol. 36, Issue 8 https://doi.org/10.1016/j.biotechadv.2018.08.009	journal	December 2018
Dynamical regimes of lipids in additivated liposomes with enhanced elasticity: A field-cycling NMR relaxometry approach Fraenza, Carla C.; Anoardo, Esteban Biophysical Chemistry, Vol. 228 https://doi.org/10.1016/j.bpc.2017.06.007	journal	September 2017
Formation of type III Deep Eutectic Solvents and effect of water on their intermolecular interactions Zhekenov, Temirlan; Toksanbayev, Nursultan; Kazakbayeva, Zhanna Fluid Phase Equilibria, Vol. 441 https://doi.org/10.1016/j.fluid.2017.01.022	journal	June 2017
Physicochemical properties of choline chloride-based deep eutectic solvents and excess properties of their pseudo-binary mixtures with 1-butanol Gajardo-Parra, Nicolás F.; Lubben, Michael J.; Winnert, Joshua M. The Journal of Chemical Thermodynamics, Vol. 133 https://doi.org/10.1016/j.jct.2019.02.010	journal	June 2019
Application of deep eutectic solvents in analytical chemistry. A review Shishov, Andrey; Bulatov, Andrey; Locatelli, Marcello Microchemical Journal, Vol. 135 https://doi.org/10.1016/j.microc.2017.07.015	journal	November 2017
Zinc (II) chloride-based deep eutectic solvents for application as electrolytes: Preparation and characterization Ghareh Bagh, Fatemeh S.; Shahbaz, Kaveh; Mjalli, Farouq S. Journal of Molecular Liquids, Vol. 204 https://doi.org/10.1016/j.molliq.2015.01.025	journal	April 2015
Glycerol-based deep eutectic solvents: Physical properties AlOmar, Mohamed Khalid; Hayyan, Maan; Alsaadi, Mohammed Abdulhakim Journal of Molecular Liquids, Vol. 215 https://doi.org/10.1016/j.molliq.2015.11.032	journal	March 2016
NMR study of choline chloride-based deep eutectic solvents Delso, Ignacio; Lafuente, Carlos; Muñoz-Embid, José Journal of Molecular Liquids, Vol. 290 https://doi.org/10.1016/j.molliq.2019.111236	journal	September 2019
Field-cycling NMR relaxometry of viscous liquids and polymers Kruk, D.; Herrmann, A.; Rössler, E. A. Progress in Nuclear Magnetic Resonance Spectroscopy, Vol. 63 https://doi.org/10.1016/j.pnmrs.2011.08.001	journal	May 2012
Conversion of sunflower stalk based cellulose to the valuable products using choline chloride based deep eutectic solvents Sert, Murat; Arslanoğlu, Alparslan; Ballice, Levent Renewable Energy, Vol. 118 https://doi.org/10.1016/j.renene.2017.10.083	journal	April 2018
NMR Relaxometry and Diffusometry Analysis of Dynamics in Ionic Liquids and Ionogels for Use in Lithium-Ion Batteries Jayakody, Nishani Kanchana; Fraenza, Carla C.; Greenbaum, Steven G. The Journal of Physical Chemistry B, Vol. 124, Issue 31 https://doi.org/10.1021/acs.jpcb.0c02755	journal	July 2020
Nanoscale Spatial Heterogeneity in Deep Eutectic Solvents Kaur, Supreet; Gupta, Aditya; Kashyap, Hemant K. The Journal of Physical Chemistry B, Vol. 120, Issue 27 https://doi.org/10.1021/acs.jpcb.6b04187	journal	June 2016
Glycerol Hydrogen-Bonding Network Dominates Structure and Collective Dynamics in a Deep Eutectic Solvent Faraone, A.; Wagle, D. V.; Baker, G. A. The Journal of Physical Chemistry B, Vol. 122, Issue 3 https://doi.org/10.1021/acs.jpcb.7b11224	journal	January 2018
NMR Relaxometry: The Canonical Case Glycerol Flämig, M.; Hofmann, M.; Fatkullin, N. The Journal of Physical Chemistry B, Vol. 124, Issue 8 https://doi.org/10.1021/acs.jpcb.9b11770	journal	January 2020
Differential Microscopic Mobility of Components within a Deep Eutectic Solvent Wagle, Durgesh V.; Baker, Gary A.; Mamontov, Eugene The Journal of Physical Chemistry Letters, Vol. 6, Issue 15 https://doi.org/10.1021/acs.jpclett.5b01192	journal	July 2015
Insights into the Hydrogen Bond Interactions in Deep Eutectic Solvents Composed of Choline Chloride and Polyols Wang, Huiyong; Liu, Shuyan; Zhao, Yuling ACS Sustainable Chemistry & Engineering, Vol. 7, Issue 8 https://doi.org/10.1021/acssuschemeng.8b06676	journal	March 2019
Deep Eutectic Solvents: Sustainable Media for Nanoscale and Functional Materials Wagle, Durgesh V.; Zhao, Hua; Baker, Gary A. Accounts of Chemical Research, Vol. 47, Issue 8 https://doi.org/10.1021/ar5000488	journal	June 2014
Deep Eutectic Solvents (DESs) and Their Applications Smith, Emma L.; Abbott, Andrew P.; Ryder, Karl S. Chemical Reviews, Vol. 114, Issue 21 https://doi.org/10.1021/cr300162p	journal	October 2014
Deep Eutectic Solvents: Physicochemical Properties and Gas Separation Applications García, Gregorio; Aparicio, Santiago; Ullah, Ruh Energy & Fuels, Vol. 29, Issue 4 https://doi.org/10.1021/ef5028873	journal	March 2015
Deep Eutectic Solvents Formed between Choline Chloride and Carboxylic Acids: Versatile Alternatives to Ionic Liquids Abbott, Andrew P.; Boothby, David; Capper, Glen Journal of the American Chemical Society, Vol. 126, Issue 29 https://doi.org/10.1021/ja048266j	journal	July 2004
Experimental and Computational Studies of Choline Chloride-Based Deep Eutectic Solvents Perkins, Sasha L.; Painter, Paul; Colina, Coray M. Journal of Chemical & Engineering Data, Vol. 59, Issue 11 https://doi.org/10.1021/je500520h	journal	August 2014
Application of Hole Theory to Define Ionic Liquids by their Transport Properties ^† Abbott, Andrew P.; Harris, Robert C.; Ryder, Karl S. The Journal of Physical Chemistry B, Vol. 111, Issue 18 https://doi.org/10.1021/jp0671998	journal	May 2007
Electrochemistry in Deep Eutectic Solvents Nkuku, Chiemela A.; LeSuer, Robert J. The Journal of Physical Chemistry B, Vol. 111, Issue 46 https://doi.org/10.1021/jp075794j	journal	November 2007
Translational and Rotational Diffusion of Glycerol by Means of Field Cycling ¹ H NMR Relaxometry Kruk, D.; Meier, R.; Rössler, E. A. The Journal of Physical Chemistry B, Vol. 115, Issue 5 https://doi.org/10.1021/jp110514r	journal	February 2011
Mesoscopic Structuring and Dynamics of Alcohol/Water Solutions Probed by Terahertz Time-Domain Spectroscopy and Pulsed Field Gradient Nuclear Magnetic Resonance Li, Ruoyu; D’Agostino, Carmine; McGregor, James The Journal of Physical Chemistry B, Vol. 118, Issue 34 https://doi.org/10.1021/jp502799x	journal	August 2014
Molecular Motions and Ion Diffusions of the Room-Temperature Ionic Liquid 1,2-Dimethyl-3-propylimidazolium Bis(trifluoromethylsulfonyl)amide (DMPImTFSA) Studied by ¹ H, ¹³ C, and ¹⁹ F NMR Hayamizu, Kikuko; Tsuzuki, Seiji; Seki, Shiro The Journal of Physical Chemistry A, Vol. 112, Issue 47 https://doi.org/10.1021/jp802392t	journal	November 2008
Natural Deep Eutectic Solvents – Solvents for the 21st Century Paiva, Alexandre; Craveiro, Rita; Aroso, Ivo ACS Sustainable Chemistry & Engineering, Vol. 2, Issue 5 https://doi.org/10.1021/sc500096j	journal	March 2014
Glycerol eutectics as sustainable solvent systems Abbott, Andrew P.; Harris, Robert C.; Ryder, Karl S. Green Chem., Vol. 13, Issue 1 https://doi.org/10.1039/C0GC00395F	journal	January 2011
Dynamics of the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulphonyl)imide studied by nuclear magnetic resonance dispersion and diffusion Ordikhani Seyedlar, Amin; Stapf, Siegfried; Mattea, Carlos Physical Chemistry Chemical Physics, Vol. 17, Issue 3 https://doi.org/10.1039/C4CP04178J	journal	January 2015
Molecular and ionic diffusion in aqueous – deep eutectic solvent mixtures: probing inter-molecular interactions using PFG NMR D’Agostino, Carmine; Gladden, Lynn F.; Mantle, Mick D. Physical Chemistry Chemical Physics, Vol. 17, Issue 23 https://doi.org/10.1039/C5CP01493J	journal	January 2015
Liquid structure of the choline chloride-urea deep eutectic solvent (reline) from neutron diffraction and atomistic modelling Hammond, Oliver S.; Bowron, Daniel T.; Edler, Karen J. Green Chemistry, Vol. 18, Issue 9 https://doi.org/10.1039/C5GC02914G	journal	January 2016
Dynamics of ionic liquids in bulk and in confinement by means of ¹ H NMR relaxometry – BMIM-OcSO ₄ in an SiO ₂ matrix as an example Kruk, Danuta; Wojciechowski, Milosz; Brym, Szczepan Physical Chemistry Chemical Physics, Vol. 18, Issue 33 https://doi.org/10.1039/C6CP02377K	journal	January 2016
Nanostructure, hydrogen bonding and rheology in choline chloride deep eutectic solvents as a function of the hydrogen bond donor Stefanovic, Ryan; Ludwig, Michael; Webber, Grant B. Physical Chemistry Chemical Physics, Vol. 19, Issue 4 https://doi.org/10.1039/C6CP07932F	journal	January 2017
Dynamical properties of EMIM-SCN confined in a SiO ₂ matrix by means of ¹ H NMR relaxometry Kruk, Danuta; Wojciechowski, Milosz; Verma, Yogendra Lal Physical Chemistry Chemical Physics, Vol. 19, Issue 48 https://doi.org/10.1039/C7CP06174A	journal	January 2017
Thermophysical properties of glyceline–water mixtures investigated by molecular modelling Baz, Jörg; Held, Christoph; Pleiss, Jürgen Physical Chemistry Chemical Physics, Vol. 21, Issue 12 https://doi.org/10.1039/C9CP00036D	journal	January 2019
Ionic conductivity of deep eutectic solvents: the role of orientational dynamics and glassy freezing Reuter, Daniel; Binder, Catharina; Lunkenheimer, Peter Physical Chemistry Chemical Physics, Vol. 21, Issue 13 https://doi.org/10.1039/C9CP00742C	journal	January 2019
Investigation of glycerol hydrogen-bonding networks in choline chloride/glycerol eutectic-forming liquids using neutron diffraction Turner, Adam H.; Holbrey, John D. Physical Chemistry Chemical Physics, Vol. 21, Issue 39 https://doi.org/10.1039/C9CP04343H	journal	January 2019
Deep eutectic solvents: alternative reaction media for organic oxidation reactions Di Carmine, Graziano; Abbott, Andrew P.; D'Agostino, Carmine Reaction Chemistry & Engineering, Vol. 6, Issue 4 https://doi.org/10.1039/D0RE00458H	journal	January 2021
Molecular motion and ion diffusion in choline chloride based deep eutectic solvents studied by 1H pulsed field gradient NMR spectroscopy D'Agostino, Carmine; Harris, Robert C.; Abbott, Andrew P. Physical Chemistry Chemical Physics, Vol. 13, Issue 48 https://doi.org/10.1039/c1cp22554e	journal	January 2011
Deep eutectic solvents: syntheses, properties and applications Zhang, Qinghua; De Oliveira Vigier, Karine; Royer, Sébastien Chemical Society Reviews, Vol. 41, Issue 21 https://doi.org/10.1039/c2cs35178a	journal	January 2012
Calcul des densités spectrales résultant d'un mouvement aléatoire de translation en relaxation par interaction dipolaire magnétique dans les liquides Ayant, Y.; Belorizky, E.; Aluzon, J. Journal de Physique, Vol. 36, Issue 10 https://doi.org/10.1051/jphys:019750036010099100	journal	January 1975
Spin Diffusion Measurements: Spin Echoes in the Presence of a Time‐Dependent Field Gradient Stejskal, E. O.; Tanner, J. E. The Journal of Chemical Physics, Vol. 42, Issue 1 https://doi.org/10.1063/1.1695690	journal	January 1965
Dielectric Relaxation in Glycerol, Propylene Glycol, and n ‐Propanol Davidson, D. W.; Cole, R. H. The Journal of Chemical Physics, Vol. 19, Issue 12 https://doi.org/10.1063/1.1748105	journal	December 1951
Dynamic effects of pair correlation functions on spin relaxation by translational diffusion in liquids Hwang, Lian-Pin; Freed, Jack H. The Journal of Chemical Physics, Vol. 63, Issue 9 https://doi.org/10.1063/1.431841	journal	January 1975
Dynamic effects of pair correlation functions on spin relaxation by translational diffusion in liquids. II. Finite jumps and independent T ₁ processes Freed, Jack H. The Journal of Chemical Physics, Vol. 68, Issue 9 https://doi.org/10.1063/1.436302	journal	May 1978
Reorientational motions in compressed viscous fluids: Selectively deuterated glycerol Wolfe, M.; Jonas, J. The Journal of Chemical Physics, Vol. 71, Issue 8 https://doi.org/10.1063/1.438754	journal	October 1979
Effects of eccentricity on nuclear magnetic relaxation by intermolecular dipole–dipole interactions: ¹³ C relaxation of neopentane Albrand, J. P.; Taieb, M. C.; Fries, P. The Journal of Chemical Physics, Vol. 75, Issue 5 https://doi.org/10.1063/1.442318	journal	September 1981
Determining diffusion coefficients of ionic liquids by means of field cycling nuclear magnetic resonance relaxometry Kruk, D.; Meier, R.; Rachocki, A. The Journal of Chemical Physics, Vol. 140, Issue 24 https://doi.org/10.1063/1.4882064	journal	June 2014
Translational and reorientational dynamics in deep eutectic solvents Reuter, D.; Münzner, P.; Gainaru, C. The Journal of Chemical Physics, Vol. 154, Issue 15 https://doi.org/10.1063/5.0045448	journal	April 2021
Molecular dynamics simulations vs field-cycling NMR relaxometry: Structural relaxation mechanisms in the glass-former glycerol revisited Becher, M.; Wohlfromm, T.; Rössler, E. A. The Journal of Chemical Physics, Vol. 154, Issue 12 https://doi.org/10.1063/5.0048131	journal	March 2021
Deep eutectic solvent formation: a structural view using molecular dynamics simulations with classical force fields Mainberger, Sebastian; Kindlein, Moritz; Bezold, Franziska Molecular Physics, Vol. 115, Issue 9-12 https://doi.org/10.1080/00268976.2017.1288936	journal	February 2017
Comment on nuclear spin relaxation by translational diffusion in liquids: effects of the eccentricity of the nuclei Belorizky, E.; Fries, P. H. Journal of Physics C: Solid State Physics, Vol. 14, Issue 19 https://doi.org/10.1088/0022-3719/14/19/001	journal	July 1981
Nuclear spin relaxation by translational diffusion in liquids and solids: high- and low-frequency limits Sholl, C. A. Journal of Physics C: Solid State Physics, Vol. 14, Issue 4 https://doi.org/10.1088/0022-3719/14/4/018	journal	February 1981
Relaxation Effects in Nuclear Magnetic Resonance Absorption Bloembergen, N.; Purcell, E. M.; Pound, R. V. Physical Review, Vol. 73, Issue 7 https://doi.org/10.1103/PhysRev.73.679	journal	April 1948
Insights into the Properties of Deep Eutectic Solvent Based on Reline for Ga-Controllable CIGS Solar Cell in One-Step Electrodeposition Zhang, Yongzheng; Han, Junfeng; Liao, Cheng Journal of The Electrochemical Society, Vol. 163, Issue 13 https://doi.org/10.1149/2.0611613jes	journal	January 2016
Recent progress on deep eutectic solvents in biocatalysis Xu, Pei; Zheng, Gao-Wei; Zong, Min-Hua Bioresources and Bioprocessing, Vol. 4, Issue 1 https://doi.org/10.1186/s40643-017-0165-5	journal	July 2017

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