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Advances in the synthesis and structure of α-canaphite: a multitool and multiscale study

Advances in the synthesis and structure of α-canaphite: a multitool and multiscale study
Advances in the synthesis and structure of α-canaphite: a multitool and multiscale study
α-Canaphite (CaNa2P2O7·4H2O) is a layered calcium disodium pyrophosphate tetrahydrate phase of significant geological and potential biological interest. This study overcomes the lack of a reliable protocol to synthesize pure α-canaphite by using a novel simple and reproducible approach of double decomposition in solution at room temperature. The pure α-canaphite is then characterized from the atomic to the macroscopic level using a multitool and multiscale advanced characterization strategy, providing for the first time full resolution of the α-canaphite monoclinic structure, including the hydrogen bonding network. Synchrotron X-ray diffraction and neutron diffraction are combined with multinuclear solid state NMR experimental data and computational modeling via DFT/GIPAW calculations. Among the main characteristics of the α-canaphite structure are some strong hydrogen bonds and one of the four water molecules showing a different coordination scheme. This peculiar water molecule could be the last to leave the collapsed structure on heating, leading eventually to anhydrous α-CaNa2P2O7 and could also be involved in the internal hydrolysis of pyrophosphate ions as it is the closest water molecule to the pyrophosphate ions. Relating such detailed structural data on α-canaphite to its physico-chemical properties is of major interest considering the possible roles of canaphite for biomedical applications. The vibrational spectra of α-canaphite (deuterated or not) are analyzed and Raman spectroscopy appears to be a promising tool for the identification/diagnosis of such microcrystals in vitro, in vivo or ex vivo.
Calcium pyrophosphates, DFT, NMR, Synchrotron X-ray and neutron diffraction, Synthesis, canaphite, dehydration, structure refinement
1466-8033
3130-3143
Mayen, Laëtitia
b455345a-4069-4943-8804-8ceabf7ce9f7
Jensen, Nicholai D.
554e7450-3d45-4fcf-b115-97157dc392ab
Desbord, Maximilien
76077ab5-d0b0-46cd-bc8b-91afd787da28
Laurencin, Danielle
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Bonhomme, Christian
ad2f73dc-f57e-4448-850b-652e370e2df0
Smith, Mark
abd04fbf-5f56-459d-89ec-e51ab2598c09
Porcher, Florence
a202d7bd-8004-4820-8369-e9fe6f7cfdd7
Elkaim, Erik
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Charvillat, Cédric
fd3bae0b-cd11-4f76-932c-fc25d166f54d
Gras, Pierre
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Rey, Christian
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Soulié, Jérémy
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Combes, Christèle
46d772de-42a1-4b9f-8c23-bad2aa1e9f0b
Mayen, Laëtitia
b455345a-4069-4943-8804-8ceabf7ce9f7
Jensen, Nicholai D.
554e7450-3d45-4fcf-b115-97157dc392ab
Desbord, Maximilien
76077ab5-d0b0-46cd-bc8b-91afd787da28
Laurencin, Danielle
5f5fceb8-0be6-4a68-abf6-7dc66068db63
Bonhomme, Christian
ad2f73dc-f57e-4448-850b-652e370e2df0
Smith, Mark
abd04fbf-5f56-459d-89ec-e51ab2598c09
Porcher, Florence
a202d7bd-8004-4820-8369-e9fe6f7cfdd7
Elkaim, Erik
3ad29ffe-b22f-4267-9d17-8fd8297beec3
Charvillat, Cédric
fd3bae0b-cd11-4f76-932c-fc25d166f54d
Gras, Pierre
585f1506-e1f3-4a55-9117-3d50431e1621
Rey, Christian
27dfc805-1567-434b-b64f-b3c8a9441f1f
Soulié, Jérémy
1eb6332f-46c4-4118-8540-fb74bd94eaa6
Combes, Christèle
46d772de-42a1-4b9f-8c23-bad2aa1e9f0b

Mayen, Laëtitia, Jensen, Nicholai D., Desbord, Maximilien, Laurencin, Danielle, Bonhomme, Christian, Smith, Mark, Porcher, Florence, Elkaim, Erik, Charvillat, Cédric, Gras, Pierre, Rey, Christian, Soulié, Jérémy and Combes, Christèle (2020) Advances in the synthesis and structure of α-canaphite: a multitool and multiscale study. CrystEngComm, 22 (18), 3130-3143. (doi:10.1039/D0CE00132E).

Record type: Article

Abstract

α-Canaphite (CaNa2P2O7·4H2O) is a layered calcium disodium pyrophosphate tetrahydrate phase of significant geological and potential biological interest. This study overcomes the lack of a reliable protocol to synthesize pure α-canaphite by using a novel simple and reproducible approach of double decomposition in solution at room temperature. The pure α-canaphite is then characterized from the atomic to the macroscopic level using a multitool and multiscale advanced characterization strategy, providing for the first time full resolution of the α-canaphite monoclinic structure, including the hydrogen bonding network. Synchrotron X-ray diffraction and neutron diffraction are combined with multinuclear solid state NMR experimental data and computational modeling via DFT/GIPAW calculations. Among the main characteristics of the α-canaphite structure are some strong hydrogen bonds and one of the four water molecules showing a different coordination scheme. This peculiar water molecule could be the last to leave the collapsed structure on heating, leading eventually to anhydrous α-CaNa2P2O7 and could also be involved in the internal hydrolysis of pyrophosphate ions as it is the closest water molecule to the pyrophosphate ions. Relating such detailed structural data on α-canaphite to its physico-chemical properties is of major interest considering the possible roles of canaphite for biomedical applications. The vibrational spectra of α-canaphite (deuterated or not) are analyzed and Raman spectroscopy appears to be a promising tool for the identification/diagnosis of such microcrystals in vitro, in vivo or ex vivo.

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ARTICLE_CANAPHITE_accepted - Accepted Manuscript
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Accepted/In Press date: 10 March 2020
e-pub ahead of print date: 23 April 2020
Published date: 14 May 2020
Keywords: Calcium pyrophosphates, DFT, NMR, Synchrotron X-ray and neutron diffraction, Synthesis, canaphite, dehydration, structure refinement

Identifiers

Local EPrints ID: 441505
URI: http://eprints.soton.ac.uk/id/eprint/441505
ISSN: 1466-8033
PURE UUID: 97d0821f-ee51-4dbe-8dbe-6545e467e3c7

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Date deposited: 16 Jun 2020 16:31
Last modified: 28 Oct 2020 18:03

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Contributors

Author: Laëtitia Mayen
Author: Nicholai D. Jensen
Author: Maximilien Desbord
Author: Danielle Laurencin
Author: Christian Bonhomme
Author: Mark Smith
Author: Florence Porcher
Author: Erik Elkaim
Author: Cédric Charvillat
Author: Pierre Gras
Author: Christian Rey
Author: Jérémy Soulié
Author: Christèle Combes

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