New perspectives on calcium environments in inorganic materials containing calcium–oxygen bonds: A combined computational–experimental 43Ca NMR approach

Gervais, Christel; Laurencin, Danielle; Wong, Alan; Pourpoint, Frédérique; Labram, John G.; Woodward, Bleddyn; Howes, A. P.; Pike, Kevin J.; Dupree, R.; Mauri, Francesco; Bonhomme, Christian; Smith, Mark E.

doi:10.1016/j.cplett.2008.09.004

Cited by 81 publications

(119 citation statements)

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“…43 Ca NMR chemical shifts were referenced using a 1 mol.L -1 aqueous solution of CaCl 2 (at 0 ppm). [36,37] The conclusions from the data recorded at 19.6 T were identical to those at 18.8 T.…”

Section: Solid State Nmrsupporting

confidence: 70%

Magnesium incorporation into hydroxyapatite

Laurencin¹,

Almora‐Barrios²,

Leeuw³

et al. 2011

Biomaterials

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304

190

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The incorporation of Mg in hydroxyapatite (HA) was investigated using multinuclear solid state NMR, X-ray absorption spectroscopy (XAS) and computational modeling. High magnetic field 43 Ca solid state NMR and Ca K-edge XAS of a ~10% Mg-substituted HA were performed, bringing direct evidence of the preferential substitution of Mg in the Ca(II) position. 1 H and 31 P solid state NMR show that the environment of the anions is disordered in this substituted apatite phase. Both Density Functional Theory (DFT) and interatomic potential computations of Mg-substituted HA structures are in agreement with these observations. Indeed, the incorporation of low levels of Mg in the Ca(II) site is found to be more favourable energetically, and the NMR parameters calculated from these optimized structures are consistent with the experimental data. Calculations provide direct insight in the structural modifications of the HA lattice, due to the strong contraction of the M•••O distances around Mg. Finally, extensive interatomic potential calculations also suggest that a local clustering of Mg within the HA lattice is likely to occur.

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Section: Solid State Nmrsupporting

confidence: 70%

Magnesium incorporation into hydroxyapatite

Laurencin¹,

Almora‐Barrios²,

Leeuw³

et al. 2011

Biomaterials

Self Cite

304

190

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“…The calculated chemical shifts for 43 Ca using the GIPAW method are usually accurate within AE5 ppm. 20,24 Even if we accept the upper limits of the errors, the computational results predict the spectra notably different from those reported, 42 suggesting some irregularities of the previously published 43 Ca spectrum for this mineral.…”

Section: Hydrated Cement Phasesmentioning

confidence: 79%

“…The integrated ratio of the signals is very close to 1 : 1 as expected from the structure. This is the first experimental report of 43 Ca 24 The structure of b-C 2 S is known to be built of isolated SiO 4 tetrahedra in an environment of two distinct Ca ions. 53 The calcium atom in site 1, Ca(1) (here and further we use the same notation as in the original crystallographic publications), is coordinated to six oxygen atoms with Ca (1) 56 All Ca-O distances for both Ca sites are very irregular, with no local symmetry in the oxygen environment.…”

Section: Cement Compoundsmentioning

confidence: 88%

“…The Ca(2) octahedron is less compressed than that of Ca (1), 59 which would result in a smaller C q . Considering that the average Ca-O distance in the site Ca (2) is larger than that for the Ca(1) site (2.391 Å compared to 2.338 Å ), the isotropic chemical shift of Ca (2) is expected 23,24 to be somewhat smaller than Ca (1). Combining this all together, the region D can be tentatively assigned to the Ca(2).…”

Section: Cement Compoundsmentioning

confidence: 94%

“…A few calculated C q 's are found between 4 and 7.2 MHz, which is on the upper end of known values for 43 Ca. [20][21][22][23][24] Only one of 29 sites in triclinic C 3 S shows unrealistically high calculated C q of 31.9 MHz. Due to extreme broadening it would be very difficult to verify experimentally if such site is indeed exist.…”

Section: Cement Compoundsmentioning

confidence: 99%

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Natural abundance high field 43Ca solid state NMR in cement science

Moudrakovski

Alizadeh

Beaudoin

2010

Phys. Chem. Chem. Phys.

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/npsi/ctrl?lang=en http://nparc.cisti-icist.nrc-cnrc.gc.ca/npsi/ctrl?lang=fr Access and use of this website and the material on it are subject to the Terms and Conditions set forth at http://nparc.cisti-icist.nrc-cnrc.gc.ca/npsi/jsp/nparc_cp.jsp?lang=en NRC Publications Archive Archives des publications du CNRCThis publication could be one of several versions: author's original, accepted manuscript or the publisher's version. / La version de cette publication peut être l'une des suivantes : la version prépublication de l'auteur, la version acceptée du manuscrit ou la version de l'éditeur. For the publisher's version, please access the DOI link below./ Pour consulter la version de l'éditeur, utilisez le lien DOI ci-dessous.http://dx.doi.org/10.1039/c000353kPhysical Chemistry Chemical Physics, 12, pp. 6961-6969, 2010-06-01 Natural abundance high field 43Ca NMR solid state NMR in cement science Moudrakovski, I.; Alizadeh, R.; Beaudoin, J. J. The material in this document is covered by the provisions of the Copyright Act, by Canadian laws, policies, regulations and international agreements. Such provisions serve to identify the information source and, in specific instances, to prohibit reproduction of materials without written permission. For more information visit http://laws.justice.gc.ca/en/showtdm/cs/C-42Les renseignements dans ce document sont protégés par la Loi sur le droit d'auteur, par les lois, les politiques et les règlements du Canada et des accords internationaux. Ces dispositions permettent d'identifier la source de l'information et, dans certains cas, d'interdire la copie de documents sans permission écrite. Pour obtenir de plus amples renseignements : http://lois.justice.gc.ca/fr/showtdm/cs/C-42 Natural abundance high field 43 Ca solid state NMR in cement sciencew This work is a systematic attempt to determine the possibilities and the limitations of the 43 Ca high field solid state NMR in the study of cement-based materials. The low natural abundance (0.135%) and small gyromagnetic ratio of 43 Ca present a serious challenge even in a high magnetic field. The NMR spectra of a number of cement compounds of known structure and composition are examined. The spectra of several phases important in cement science, e.g., anhydrous beta di-calcium silicate (b-C 2 S) and tri-calcium (C 3 S) silicate were obtained for the first time and the relation of spectroscopic and structural parameters is discussed. The method was also applied to the hydrated C 3 S and synthetic calcium silicate hydrates (C-S-H) of different composition in order to understand the state of calcium and transformations in the structure during hydrolysis. The spectra of hydrated C 3 S reveals a calcium environment similar to that of the C-S-H samples and 11 Å Tobermorite. These observations support the validity of using layered crystalline C-S-H systems as structural models for the C-S-H that forms in the hydration of Portland cement.

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Solution NMR of the Light Main Group Metals

Hanusa

2015

Encyclopedia of Inorganic and Bioinorganic Chemistry

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Metal‐centered NMR spectroscopy in solution has long been an important complement to the nonmetal nuclei (e.g., 1 H, 13 C, and 31 P) routinely used in the NMR characterization of organic, organometallic, and coordination compounds. The chemical shifts of metal nuclei can be sensitive to small changes in molecular geometry and coordination number, revealing subtle differences in the solution composition of complexes, and can be used to study interchange mechanisms. This article is intended as an overview of the characteristics of the NMR‐active nuclei of the seven lightest metals as measured in solution, and as studied with computational methods. All of these elements (Li, Be, Na, Mg, Al, K, and Ca) possess one or more isotopes with nuclear spins that are potentially observable with solution NMR (nuclear magnetic resonance) techniques. They all possess quadrupole moments, and their resonances are often broad in asymmetric environments. Apart from those characteristics, they constitute a varied group, with their relative receptivity (a measure of their ease of observation) varying by a factor of over 400 000 to 1. Issues of detection and characteristic chemical shift ranges are discussed, with the aim of assisting the experimentalist in deciding whether metal‐based NMR will be useful in characterizing a system of concern and what information is likely to be obtained. An emphasis is placed on spectra obtained in nonaqueous solutions; in such media, ion‐pairing effects are the greatest, and it is where the species with the largest chemical shifts are typically found. Reviews on individual nuclei are cited where available.

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New perspectives on calcium environments in inorganic materials containing calcium–oxygen bonds: A combined computational–experimental 43Ca NMR approach

Cited by 81 publications

References 39 publications

Magnesium incorporation into hydroxyapatite

Magnesium incorporation into hydroxyapatite

Natural abundance high field 43Ca solid state NMR in cement science

Solution NMR of the Light Main Group Metals

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