skip to main content
OSTI.GOV 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];  [4]; ORCiD logo [2]
  1. Science and Technology Facilities Council (STFC), Harwell Campus, Oxford (United Kingdom). Diamond Light Source, Ltd.; Univ. of Leeds (United Kingdom)
  2. Science and Technology Facilities Council (STFC), Harwell Campus, Oxford (United Kingdom). Diamond Light Source, Ltd.
  3. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
  4. Univ. of Leeds (United Kingdom)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
AstraZeneca PLC.; Diamond Light Source, UK; USDOE
OSTI Identifier:
1474755
Alternate Identifier(s):
OSTI ID: 1486882
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article: Published Article
Journal Name:
CrystEngComm
Additional Journal Information:
Journal Volume: 20; Journal Issue: 43; Journal ID: ISSN 1466-8033
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
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 States: 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 States. 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. Fri . "X-ray Raman scattering: a new in situ probe of molecular structure during nucleation and crystallization from liquid solutions". United States. 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 States},
year = {Fri Sep 28 00:00:00 EDT 2018},
month = {Fri Sep 28 00:00:00 EDT 2018}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1039/c8ce00929e

Save / Share:

Works referenced in this record:

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

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


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