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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]
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  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.
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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. https://doi.org/10.1039/C8CE00929E
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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. https://doi.org/10.1039/C8CE00929E.
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@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 = {Mon Nov 05 00:00:00 EST 2018},
month = {Mon Nov 05 00:00:00 EST 2018}
}
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https://doi.org/10.1039/C8CE00929E
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Cited by: 6 works
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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.
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