skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: X-ray Raman scattering: a new in situ probe of molecular structure during nucleation and crystallization from liquid solutions

Abstract

X-ray Raman scattering (XRS) has been used for in situ probing of solute molecule speciation in solution during cooling crystallization. The C and N K-edges of aqueous imidazole were measured as a function of temperature to monitor the transition from the undersaturated state through supersaturation to crystallization. A new jacketed-vessel crystallizer with internal flow was used, which enables thermal control and minimizes radiation damage. We have demonstrated that the C and N K-edges of imidazole are sensitive to changes in local bonding. In line with this, an abrupt change in the N K-edge fine structure indicates the onset of desolvation and crystallization from the supersaturated solution. In contrast, negligible changes are observed in the C and N K-edge spectra acquired during cooling, indicating that the average solvation structure around imidazole molecules does not change significantly while traversing the thermodynamically metastable supersaturated zone. To the best of our knowledge this is the first time X-ray Raman scattering has been used for studying molecular speciation in organic aqueous solutions during crystallization. Time-dependent density functional theory (TD-DFT) calculations of the near-edge spectra were performed using implicit, explicit and combined solvation models to elucidate the likely binding sites of the water molecules. An explicitmore » solvation model with one water molecule coordinating each nitrogen moiety in the imidazole ring accurately reproduces the peak positions and intensities of the XRS spectra of aqueous imidazole solution.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3];  [2]; ORCiD logo [2];  [4];  [5]; ORCiD logo [1]
  1. School of Chemical and Process Engineering, University of Leeds, Leeds LS2 9JT, UK, Diamond Light Source Ltd.
  2. Diamond Light Source Ltd., Didcot, UK
  3. Advanced Photon Source, Argonne National Laboratory, Argonne, USA
  4. School of Design, The University of Leeds, Leeds LS2 9JT, UK
  5. School of Chemical and Process Engineering, University of Leeds, Leeds LS2 9JT, UK, Department of Physics
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE; AstraZeneca PLC.; Diamond Light Source, UK
OSTI Identifier:
1474755
Alternate Identifier(s):
OSTI ID: 1486882
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Published Article
Journal Name:
CrystEngComm
Additional Journal Information:
Journal Name: CrystEngComm Journal Volume: 20 Journal Issue: 43; Journal ID: ISSN 1466-8033
Publisher:
Royal Society of Chemistry (RSC)
Country of Publication:
United Kingdom
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS

Citation Formats

Al-Madhagi, Laila H., Chang, Sin-Yuen, Balasubramanian, Mahalingam, Kroner, Anna B., Shotton, Elizabeth J., Willneff, Elizabeth A., Mishra, Bhoopesh, and Schroeder, Sven L. M. X-ray Raman scattering: a new in situ probe of molecular structure during nucleation and crystallization from liquid solutions. United Kingdom: N. p., 2018. Web. doi:10.1039/C8CE00929E.
Al-Madhagi, Laila H., Chang, Sin-Yuen, Balasubramanian, Mahalingam, Kroner, Anna B., Shotton, Elizabeth J., Willneff, Elizabeth A., Mishra, Bhoopesh, & Schroeder, Sven L. M. X-ray Raman scattering: a new in situ probe of molecular structure during nucleation and crystallization from liquid solutions. United Kingdom. doi:10.1039/C8CE00929E.
Al-Madhagi, Laila H., Chang, Sin-Yuen, Balasubramanian, Mahalingam, Kroner, Anna B., Shotton, Elizabeth J., Willneff, Elizabeth A., Mishra, Bhoopesh, and Schroeder, Sven L. M. Mon . "X-ray Raman scattering: a new in situ probe of molecular structure during nucleation and crystallization from liquid solutions". United Kingdom. doi:10.1039/C8CE00929E.
@article{osti_1474755,
title = {X-ray Raman scattering: a new in situ probe of molecular structure during nucleation and crystallization from liquid solutions},
author = {Al-Madhagi, Laila H. and Chang, Sin-Yuen and Balasubramanian, Mahalingam and Kroner, Anna B. and Shotton, Elizabeth J. and Willneff, Elizabeth A. and Mishra, Bhoopesh and Schroeder, Sven L. M.},
abstractNote = {X-ray Raman scattering (XRS) has been used for in situ probing of solute molecule speciation in solution during cooling crystallization. The C and N K-edges of aqueous imidazole were measured as a function of temperature to monitor the transition from the undersaturated state through supersaturation to crystallization. A new jacketed-vessel crystallizer with internal flow was used, which enables thermal control and minimizes radiation damage. We have demonstrated that the C and N K-edges of imidazole are sensitive to changes in local bonding. In line with this, an abrupt change in the N K-edge fine structure indicates the onset of desolvation and crystallization from the supersaturated solution. In contrast, negligible changes are observed in the C and N K-edge spectra acquired during cooling, indicating that the average solvation structure around imidazole molecules does not change significantly while traversing the thermodynamically metastable supersaturated zone. To the best of our knowledge this is the first time X-ray Raman scattering has been used for studying molecular speciation in organic aqueous solutions during crystallization. Time-dependent density functional theory (TD-DFT) calculations of the near-edge spectra were performed using implicit, explicit and combined solvation models to elucidate the likely binding sites of the water molecules. An explicit solvation model with one water molecule coordinating each nitrogen moiety in the imidazole ring accurately reproduces the peak positions and intensities of the XRS spectra of aqueous imidazole solution.},
doi = {10.1039/C8CE00929E},
journal = {CrystEngComm},
number = 43,
volume = 20,
place = {United Kingdom},
year = {2018},
month = {11}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1039/C8CE00929E

Citation Metrics:
Cited by: 2 works
Citation information provided by
Web of Science

Figures / Tables:

Fig. 1 Fig. 1: The flow cell crystallizer used for XRS measurements of solution phase samples. The shaded grey area is encapsulated in He gas.

Save / Share:

Works referenced in this record:

The Relationship between Solution Structure and Crystal Nucleation: A Neutron Scattering Study of Supersaturated Methanolic Solutions of Benzoic Acid
journal, July 2010

  • Burton, R. C.; Ferrari, E. S.; Davey, R. J.
  • The Journal of Physical Chemistry B, Vol. 114, Issue 26
  • DOI: 10.1021/jp103099j

ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005


Imidazole, a New Tunable Reagent for Producing Nanocellulose, Part I: Xylan-Coated CNCs and CNFs
journal, September 2017

  • Mao, Jia; Abushammala, Hatem; Hettegger, Hubert
  • Polymers, Vol. 9, Issue 12
  • DOI: 10.3390/polym9100473

Nucleation of NaCl from Aqueous Solution: Critical Sizes, Ion-Attachment Kinetics, and Rates
journal, October 2015

  • Zimmermann, Nils E. R.; Vorselaars, Bart; Quigley, David
  • Journal of the American Chemical Society, Vol. 137, Issue 41
  • DOI: 10.1021/jacs.5b08098

Self-association of organic solutes in solution: a NEXAFS study of aqueous imidazole
journal, January 2015

  • Thomason, M. J.; Seabourne, C. R.; Sattelle, B. M.
  • Faraday Discussions, Vol. 179
  • DOI: 10.1039/C5FD00005J

X-Ray Raman Spectroscopic Study of Water in the Condensed Phases
journal, March 2008


The ORCA program system: The ORCA program system
journal, June 2011

  • Neese, Frank
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 1
  • DOI: 10.1002/wcms.81

Molecular aggregation phenomena in solution: an energy dispersive X-ray diffraction study of concentrated imidazole water solutions
journal, February 1999


Detection and characterisation of sub-critical nuclei during reactive Pd metal nucleation by X-ray absorption spectroscopy
journal, January 2016

  • Chang, S. -Y.; Gründer, Y.; Booth, S. G.
  • CrystEngComm, Vol. 18, Issue 5
  • DOI: 10.1039/C5CE01883H

NEXAFS Sensitivity to Bond Lengths in Complex Molecular Materials: A Study of Crystalline Saccharides
journal, November 2015

  • Gainar, Adrian; Stevens, Joanna S.; Jaye, Cherno
  • The Journal of Physical Chemistry B, Vol. 119, Issue 45
  • DOI: 10.1021/acs.jpcb.5b07159

The LERIX User Facility
conference, January 2007

  • Seidler, G. T.; Fister, T. T.; Cross, J. O.
  • X-RAY ABSORPTION FINE STRUCTURE - XAFS13: 13th International Conference, AIP Conference Proceedings
  • DOI: 10.1063/1.2644702

In situ XAFS Study of Palladium Electrodeposition at the Liquid/Liquid Interface
journal, May 2017


Intermolecular bonding of hemin in solution and in solid state probed by N K-edge X-ray spectroscopies
journal, January 2015

  • Golnak, Ronny; Xiao, Jie; Atak, Kaan
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 43
  • DOI: 10.1039/C5CP04529K

Solubilities, Partition Coefficients, Density, and Surface Tension for Imidazoles + Octan-1-ol or + Water or + n -Decane
journal, May 2002

  • Domańska, Urszula; Kozłowska, Marta Karolina; Rogalski, Marek
  • Journal of Chemical & Engineering Data, Vol. 47, Issue 3
  • DOI: 10.1021/je0103014

Pseudoequivalent Nitrogen Atoms in Aqueous Imidazole Distinguished by Chemical Shifts in Photoelectron Spectroscopy
journal, July 2008

  • Nolting, Dirk; Ottosson, Niklas; Faubel, Manfred
  • Journal of the American Chemical Society, Vol. 130, Issue 26
  • DOI: 10.1021/ja8022384

Femtosecond X-ray protein nanocrystallography
journal, February 2011

  • Chapman, Henry N.; Fromme, Petra; Barty, Anton
  • Nature, Vol. 470, Issue 7332, p. 73-77
  • DOI: 10.1038/nature09750

Determination of intramolecular bond lengths in gas phase molecules from K shell shape resonances
journal, December 1984

  • Sette, F.; Stöhr, J.; Hitchcock, A. P.
  • The Journal of Chemical Physics, Vol. 81, Issue 11
  • DOI: 10.1063/1.447528

Die Kristallstruktur von Imidazol, C 3 N 2 H 4 , bei Zimmertemperatur
journal, May 1969


Prenucleation clusters and non-classical nucleation
journal, December 2011


Self-association of imidazole and its methyl derivatives in aqueous solution. A study by ultraviolet spectroscopy
journal, August 1997


X-ray Absorption Spectroscopy Study of the Hydrogen Bond Network in the Bulk Water of Aqueous Solutions
journal, July 2005

  • Näslund, Lars-Åke; Edwards, David C.; Wernet, Philippe
  • The Journal of Physical Chemistry A, Vol. 109, Issue 27
  • DOI: 10.1021/jp050413s

Identification of Protonation State by XPS, Solid-State NMR, and DFT: Characterization of the Nature of a New Theophylline Complex by Experimental and Computational Methods
journal, November 2010

  • Stevens, Joanna S.; Byard, Stephen J.; Muryn, Christopher A.
  • The Journal of Physical Chemistry B, Vol. 114, Issue 44
  • DOI: 10.1021/jp106465u

Water ordering around methane during hydrate formation
journal, October 2000

  • Koh, Carolyn A.; Wisbey, Robert P.; Wu, Xiaoping
  • The Journal of Chemical Physics, Vol. 113, Issue 15
  • DOI: 10.1063/1.1288818

The Electronic Structure and Adsorption Geometry of l -Histidine on Cu(110)
journal, October 2008

  • Feyer, Vitaliy; Plekan, Oksana; Skála, Tomáš
  • The Journal of Physical Chemistry B, Vol. 112, Issue 43
  • DOI: 10.1021/jp805671h

A new imidazolylquinoline for organic thin film transistor
journal, February 2005


Site-specific electronic structure of imidazole and imidazolium in aqueous solutions
journal, January 2018

  • Meyer, F.; Blum, M.; Benkert, A.
  • Physical Chemistry Chemical Physics, Vol. 20, Issue 12
  • DOI: 10.1039/C7CP07885D

Mode Recognition in UV Resonance Raman Spectra of Imidazole: Histidine Monitoring in Proteins
journal, July 2012

  • Balakrishnan, Gurusamy; Jarzecki, Andrzej A.; Wu, Qiang
  • The Journal of Physical Chemistry B, Vol. 116, Issue 31
  • DOI: 10.1021/jp305083t

Investigation of volatile liquid surfaces by synchrotron x-ray spectroscopy of liquid microjets
journal, March 2004

  • Wilson, Kevin R.; Rude, Bruce S.; Smith, Jared
  • Review of Scientific Instruments, Vol. 75, Issue 3
  • DOI: 10.1063/1.1645656

The nucleation of inosine: the impact of solution chemistry on the appearance of polymorphic and hydrated crystal forms
journal, January 2007

  • Chiarella, Renato A.; Gillon, Amy L.; Burton, Rebecca C.
  • Faraday Discussions, Vol. 136
  • DOI: 10.1039/b616164m

Solution crystallisation via a submerged liquid–liquid phase boundary: oiling out
journal, February 2003

  • Bonnett, P. E.; Carpenter, K. J.; Dawson, S.
  • Chemical Communications, Issue 6
  • DOI: 10.1039/b212062c

Photoemission from Liquid Aqueous Solutions
journal, April 2006

  • Winter, Bernd; Faubel, Manfred
  • Chemical Reviews, Vol. 106, Issue 4
  • DOI: 10.1021/cr040381p

Solvent structure and perturbations in solutions of chemical and biological importance
journal, January 1994


A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010

  • Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
  • The Journal of Chemical Physics, Vol. 132, Issue 15
  • DOI: 10.1063/1.3382344

Uncovering Molecular Processes in Crystal Nucleation and Growth by Using Molecular Simulation
journal, January 2011

  • Anwar, Jamshed; Zahn, Dirk
  • Angewandte Chemie International Edition, Vol. 50, Issue 9
  • DOI: 10.1002/anie.201000463

Crystal nucleation in the presence of a metastable critical point
journal, July 1998

  • Talanquer, V.; Oxtoby, David W.
  • The Journal of Chemical Physics, Vol. 109, Issue 1
  • DOI: 10.1063/1.476554

Quantitative analysis of complex amino acids and RGD peptides by X-ray photoelectron spectroscopy (XPS): Quantitative XPS analysis of amino acids and RGD peptides
journal, April 2013

  • Stevens, Joanna S.; de Luca, Alba C.; Pelendritis, Michalis
  • Surface and Interface Analysis, Vol. 45, Issue 8
  • DOI: 10.1002/sia.5261

A molecular beam study of the evaporation of water from a liquid jet
journal, June 1988

  • Faubel, M.; Schlemmer, S.; Toennies, J. P.
  • Zeitschrift f�r Physik D Atoms, Molecules and Clusters, Vol. 10, Issue 2-3
  • DOI: 10.1007/BF01384861

X-ray excited optical luminescence (XEOL) detection of x-ray absorption fine structure (XAFS)
journal, October 1998

  • Soderholm, L.; Liu, G. K.; Antonio, Mark R.
  • The Journal of Chemical Physics, Vol. 109, Issue 16
  • DOI: 10.1063/1.477320

Enhancement of Protein Crystal Nucleation by Critical Density Fluctuations
journal, September 1997


X-ray Spectroscopy of Liquid Water Microjets
journal, May 2001

  • Wilson, Kevin R.; Rude, Bruce S.; Catalano, Tony
  • The Journal of Physical Chemistry B, Vol. 105, Issue 17
  • DOI: 10.1021/jp010132u

The crystal structure of imidazole at –150°C
journal, November 1966


A 1H NMR study of crystal nucleation in solution
journal, January 2004

  • Spitaleri, Andrea; Hunter, Christopher A.; McCabe, James F.
  • CrystEngComm, Vol. 6, Issue 80
  • DOI: 10.1039/b407163h

Universal Signature of Hydrogen Bonding in the Oxygen K -Edge Spectrum of Alcohols
journal, October 2010

  • Pylkkänen, T.; Lehtola, J.; Hakala, M.
  • The Journal of Physical Chemistry B, Vol. 114, Issue 41
  • DOI: 10.1021/jp106479a

Isotope effects in liquid water probed by x-ray Raman spectroscopy
journal, July 2007


Minimally augmented Karlsruhe basis sets
journal, December 2010

  • Zheng, Jingjing; Xu, Xuefei; Truhlar, Donald G.
  • Theoretical Chemistry Accounts, Vol. 128, Issue 3
  • DOI: 10.1007/s00214-010-0846-z

Ionization of Imidazole in the Gas Phase, Microhydrated Environments, and in Aqueous Solution
journal, April 2008

  • Jagoda-Cwiklik, Barbara; Slavíček, Petr; Cwiklik, Lukasz
  • The Journal of Physical Chemistry A, Vol. 112, Issue 16
  • DOI: 10.1021/jp711476g

Nucleation
journal, December 2010

  • Vekilov, Peter G.
  • Crystal Growth & Design, Vol. 10, Issue 12
  • DOI: 10.1021/cg1011633

Using a novel plug flow reactor for the in situ, simultaneous, monitoring of SAXS and WAXD during crystallisation from solution
journal, January 2003

  • Alison, Harvey G.; Davey, Roger J.; Garside, John
  • Physical Chemistry Chemical Physics, Vol. 5, Issue 22
  • DOI: 10.1039/b309309c

The crystal structure of imidazole by neutron diffraction at 20°C and –150°C
journal, August 1977

  • Craven, B. M.; McMullan, R. K.; Bell, J. D.
  • Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 33, Issue 8
  • DOI: 10.1107/S0567740877008954

Experimental studies of the core excitation of imidazole, 4,5-dicyanoimidazole, and s-triazine
journal, July 1993

  • Apen, Elizabeth; Hitchcock, Adam P.; Gland, John L.
  • The Journal of Physical Chemistry, Vol. 97, Issue 26
  • DOI: 10.1021/j100128a019

Chemical Speciation and Bond Lengths of Organic Solutes by Core-Level Spectroscopy: pH and Solvent Influence on p -Aminobenzoic Acid
journal, March 2015

  • Stevens, Joanna S.; Gainar, Adrian; Suljoti, Edlira
  • Chemistry - A European Journal, Vol. 21, Issue 19
  • DOI: 10.1002/chem.201405635

Quantum Calculation of Molecular Energies and Energy Gradients in Solution by a Conductor Solvent Model
journal, March 1998

  • Barone, Vincenzo; Cossi, Maurizio
  • The Journal of Physical Chemistry A, Vol. 102, Issue 11
  • DOI: 10.1021/jp9716997

Nucleation of First-Order Phase Transitions
journal, February 1998

  • Oxtoby, David W.
  • Accounts of Chemical Research, Vol. 31, Issue 2
  • DOI: 10.1021/ar9702278

Adsorption of Histidine and Histidine-Containing Peptides on Au(111)
journal, June 2010

  • Feyer, Vitaliy; Plekan, Oksana; Tsud, Nataliya
  • Langmuir, Vol. 26, Issue 11
  • DOI: 10.1021/la904684e

Aqueous Imidazole Solutions: A Structural Perspective from Simulations with High-Rank Electrostatic Multipole Moments
journal, October 2011

  • Liem, Steven Y.; Shaik, Majeed S.; Popelier, Paul L. A.
  • The Journal of Physical Chemistry B, Vol. 115, Issue 39
  • DOI: 10.1021/jp2053234

Nucleation of Organic Crystals-A Molecular Perspective
journal, January 2013

  • Davey, Roger J.; Schroeder, Sven L. M.; ter Horst, Joop H.
  • Angewandte Chemie International Edition, Vol. 52, Issue 8
  • DOI: 10.1002/anie.201204824

Bonding of Histidine to Cerium Oxide
journal, July 2013

  • Tsud, Nataliya; Acres, Robert G.; Iakhnenko, Marianna
  • The Journal of Physical Chemistry B, Vol. 117, Issue 31
  • DOI: 10.1021/jp404385h

Influence of TMAO and urea on the structure of water studied by inelastic X-ray scattering
journal, January 2016

  • Sahle, Christoph J.; Schroer, Martin A.; Juurinen, Iina
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 24
  • DOI: 10.1039/C6CP01922F

Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields
journal, November 1994

  • Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F.
  • The Journal of Physical Chemistry, Vol. 98, Issue 45, p. 11623-11627
  • DOI: 10.1021/j100096a001

X-ray Absorption Spectroscopy Measurements of Liquid Water
journal, July 2005

  • Näslund, L. -Å.; Lüning, J.; Ufuktepe, Y.
  • The Journal of Physical Chemistry B, Vol. 109, Issue 28
  • DOI: 10.1021/jp052046q

X-ray Raman spectroscopy at the oxygen K edge of water and ice:  Implications on local structure models
journal, September 2002


Multielement spectrometer for efficient measurement of the momentum transfer dependence of inelastic x-ray scattering
journal, June 2006

  • Fister, T. T.; Seidler, G. T.; Wharton, L.
  • Review of Scientific Instruments, Vol. 77, Issue 6
  • DOI: 10.1063/1.2204581

Simulation of liquid imidazole using a high-rank quantum topological electrostatic potential
journal, January 2010

  • Shaik, Majeed S.; Liem, Steven Y.; Yuan, Yongna
  • Physical Chemistry Chemical Physics, Vol. 12, Issue 45
  • DOI: 10.1039/c0cp00417k

Fityk : a general-purpose peak fitting program
journal, September 2010


A miniature closed-circle flow cell for high photon flux X-ray scattering experiments
journal, September 2015

  • Sahle, Ch. J.; Henriquet, C.; Schroer, M. A.
  • Journal of Synchrotron Radiation, Vol. 22, Issue 6
  • DOI: 10.1107/S1600577515016331

Saturation Behavior in X-ray Raman Scattering Spectra of Aqueous LiCl
journal, December 2013

  • Juurinen, Iina; Pylkkänen, Tuomas; Ruotsalainen, Kari O.
  • The Journal of Physical Chemistry B, Vol. 117, Issue 51
  • DOI: 10.1021/jp409528r