Rights statement: This is the author’s version of a work that was accepted for publication in Acta Biomaterialia. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in Acta Biomaterialia, 31, 2016 DOI: 10.1016/j.actbio.2015.10.016
Accepted author manuscript, 1.23 MB, PDF document
Available under license: CC BY-NC-ND: Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License
Rights statement: This is the author’s version of a work that was accepted for publication in Acta Biomaterialia. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in Acta Biomaterialia, 31, 2016 DOI: 10.1016/j.actbio.2015.10.016
Accepted author manuscript, 1.73 MB, PDF document
Available under license: CC BY-NC-ND: Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License
Final published version
Research output: Contribution to Journal/Magazine › Journal article › peer-review
Research output: Contribution to Journal/Magazine › Journal article › peer-review
}
TY - JOUR
T1 - From crystalline to amorphous calcium pyrophosphates
T2 - a solid state Nuclear Magnetic Resonance perspective
AU - Gras, Pierre
AU - Baker, Annabelle
AU - Combes, Christèle
AU - Rey, Christian
AU - Sarda, Stéphanie
AU - Wright, Adrian J.
AU - Smith, Mark Edmund
AU - Hanna, John V.
AU - Gervais, Christel
AU - Laurencin, Danielle
AU - Bonhomme, Christian
N1 - D. Laurencin and M. E. Smith thank the Royal Society for funding collaborative research (Warwick-Montpellier JP090313 partnership) as well as the UK 850 MHz solid-state NMR Facility used in this research was funded by EPSRC, BBSRC and Birmingham University. This is the author’s version of a work that was accepted for publication in Acta Biomaterialia. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in Acta Biomaterialia, 31, 2016 DOI: 10.1016/j.actbio.2015.10.016
PY - 2016/2
Y1 - 2016/2
N2 - Hydrated calcium pyrophosphates (CPP, Ca2P2O7·nH2O) are a fundamental family of materials among osteoarticular pathologic calcifications. In this contribution, a comprehensive multinuclear NMR (Nuclear Magnetic Resonance) study of four crystalline and two amorphous phases of this family is presented. 1H, 31P and 43Ca MAS (Magic Angle Spinning) NMR spectra were recorded, leading to informative fingerprints characterizing each compound. In particular, different 1H and 43Ca solid state NMR signatures were observed for the amorphous phases, depending on the synthetic procedure used. The NMR parameters of the crystalline phases were determined using the GIPAW (Gauge Including Projected Augmented Wave) DFT approach, based on first-principles calculations. In some cases, relaxed structures were found to improve the agreement between experimental and calculated values, demonstrating the importance of proton positions and pyrophosphate local geometry in this particular NMR crystallography approach. Such calculations serve as a basis for the future ab initio modeling of the amorphous CPP phases.Statement of significanceThe general concept of NMR crystallography is applied to the detailed study of calcium pyrophosphates (CPP), whether hydrated or not, and whether crystalline or amorphous. CPP are a fundamental family of materials among osteoarticular pathologic calcifications. Their prevalence increases with age, impacting on 17.5% of the population after the age of 80. They are frequently involved or associated with acute articular arthritis such as pseudogout. Current treatments are mainly directed at relieving the symptoms of joint inflammation but not at inhibiting CPP formation nor at dissolving these crystals. The combination of advanced NMR techniques, modeling and DFT based calculation of NMR parameters allows new original insights in the detailed structural description of this important class of biomaterials.
AB - Hydrated calcium pyrophosphates (CPP, Ca2P2O7·nH2O) are a fundamental family of materials among osteoarticular pathologic calcifications. In this contribution, a comprehensive multinuclear NMR (Nuclear Magnetic Resonance) study of four crystalline and two amorphous phases of this family is presented. 1H, 31P and 43Ca MAS (Magic Angle Spinning) NMR spectra were recorded, leading to informative fingerprints characterizing each compound. In particular, different 1H and 43Ca solid state NMR signatures were observed for the amorphous phases, depending on the synthetic procedure used. The NMR parameters of the crystalline phases were determined using the GIPAW (Gauge Including Projected Augmented Wave) DFT approach, based on first-principles calculations. In some cases, relaxed structures were found to improve the agreement between experimental and calculated values, demonstrating the importance of proton positions and pyrophosphate local geometry in this particular NMR crystallography approach. Such calculations serve as a basis for the future ab initio modeling of the amorphous CPP phases.Statement of significanceThe general concept of NMR crystallography is applied to the detailed study of calcium pyrophosphates (CPP), whether hydrated or not, and whether crystalline or amorphous. CPP are a fundamental family of materials among osteoarticular pathologic calcifications. Their prevalence increases with age, impacting on 17.5% of the population after the age of 80. They are frequently involved or associated with acute articular arthritis such as pseudogout. Current treatments are mainly directed at relieving the symptoms of joint inflammation but not at inhibiting CPP formation nor at dissolving these crystals. The combination of advanced NMR techniques, modeling and DFT based calculation of NMR parameters allows new original insights in the detailed structural description of this important class of biomaterials.
KW - Crystalline calcium pyrophosphates
KW - Amorphous calcium pyrophosphates
KW - 1H
KW - 31P
KW - 43Ca solid state NMR
KW - First principles GIPAW calculations
U2 - 10.1016/j.actbio.2015.10.016
DO - 10.1016/j.actbio.2015.10.016
M3 - Journal article
VL - 31
SP - 348
EP - 357
JO - Acta Biomaterialia
JF - Acta Biomaterialia
SN - 1742-7061
ER -