Role of Magnesium Ion in the Stabilization of Biogenic Amorphous Calcium Carbonate: A Structure−Function Investigation

Politi, Yael; Batchelor, David; Zaslansky, Paul; Chmelka, Bradley F.; Weaver, James C.; Sagi, Irit; Weiner, Steve; Addadi, Lia

doi:10.1021/cm902674h

Cited by 225 publications

(204 citation statements)

References 36 publications

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“…Indeed, just like calcium, Mg 2+ is a closed shell diamagnetic cation, and magnesium-25, the NMR active isotope, is a spin-5/2 low-nucleus of low natural abundance (~10.0%), [38] with a relatively large quadrupole moment, meaning that the NMR signals can be very broad. Although techniques like 25 Mg solid state NMR [38,39,76,88] and Mg K-edge EXAFS and XANES [89][90][91] are being developed to help investigate the local structure around magnesium, they cannot be used routinely, because they require access to ultra-high field magnets or soft X-ray synchrotron sources. Furthermore, these experiments can be very time-consuming, especially for samples in which the Mg content is low.…”

Section: D Towards the Analysis Of The Local Environment Of The Magmentioning

confidence: 99%

Magnesium incorporation into hydroxyapatite

Laurencin¹,

Almora‐Barrios²,

Leeuw³

et al. 2011

Biomaterials

315

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: D Towards the Analysis Of The Local Environment Of The Magmentioning

confidence: 99%

Magnesium incorporation into hydroxyapatite

Laurencin¹,

Almora‐Barrios²,

Leeuw³

et al. 2011

Biomaterials

315

190

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“…This is in contrast to the calcium and calcium-magnesium carbonate systems, where the transformation of the amorphous precursors at equivalent conditions in solution has been shown to be much faster: the transformation of ACC to crystalline CaCO 3 in solution occurs in 1-2 min at ambient temperature (Ogino et al 1987) and is considered to involve a dehydration process (Rodriguez-Blanco et al 2011a, b). The crystallization of Mg-doped ACC although it occurs at a slower pace compared to ACC (Rodriguez-Blanco et al 2011a, b;Politi et al 2010) it is still much faster than ADC. Furthermore, in the presence of Mg the energy needed to dehydrate the Mg ion is higher compared to the Ca ion (Di Tommaso and de Leeuw 2010).…”

Section: Is Amorphous Dysprosium Carbonate Special?mentioning

confidence: 99%

Amorphous dysprosium carbonate: characterization, stability, and crystallization pathways

et al. 2013

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The crystallization of amorphous dysprosium carbonate (ADC) has been studied in air (21-750°C) and in solution (21-250°C). This poorly ordered precursor, Dy 2 (CO 3 ) 3 Á4H 2 O, was synthesized in solution at ambient temperature. Its properties and crystallization pathways were studied by powder X-ray diffraction, Fourier transform infrared spectroscopy, scanning and transmission electron microscopy, thermogravimetric analysis, and magnetic techniques. ADC consists of highly hydrated spherical nanoparticles of 10-20 nm diameter that are exceptionally stable under dry treatment at ambient and high temperatures (\550°C). However, ADC transforms in solution to a variety of Dy-carbonates, depending on the temperature and reaction times. The transformation sequence is (a) poorly crystalline metastable tengerite-type phase, Dy 2 (CO 3 ) 3 Á2-3H 2 O; and (b) the orthorhombic kozoite-type phase DyCO 3 (OH) at 165°C after prolonged times (15 days) or faster (12 h) at 220°C. Both the amorphous phase and the kozoite-type phase DyCO 3 (OH) are paramagnetic in the range of temperatures measured from 1.8 to 300 K.

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“…Observation of deposits of ACP indicates that the presence of Mg 2+ is able to stabilize this phase. A very recent study showed that although the short-range structure around the Mg 2+ ion is different in the various minerals studied, they all involve a shortening of the Mg−O bond length, and the compact structure around magnesium introduces distortion in the host mineral, thus inhibiting its crystallization [12]. The apparent stabilization of ACP may be because of the binding of Mg 2+ to newly formed nuclei, not only preventing these from reaching a critical growth size and subsequent Ostwald maturation, but also leading to redissolution [13].…”

Section: Nucleation and Growth Of Calcium Orthophosphate Crystals Fromentioning

confidence: 99%

Dynamics of crystallization and dissolution of calcium orthophosphates at the near-molecular level

Wang

et al. 2011

Chin. Sci. Bull.

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Although extensive investigations of biogenic and geological calcium phosphate crystallization/dissolution and their phase transformations have been performed, the mechanisms of crystallization and dissolution of sparingly soluble calcium phosphates in geological settings have not been completely determined at the near-molecular level. In particular, an understanding of the physical-chemical processes at the earliest nucleation stage and the subsequent crystal surface dynamics in soil solutions is lacking. This review focuses on the earliest events in homo/heterogeneous nucleation from an initial supersaturated solution phase, the subsequent growth of calcium phosphate phases, and the relevant influences of the presence of additional inorganic and organic molecules in both geological and biological settings. These studies have implications for the understanding of the complex processes of calcium phosphate transformations in soils, and provide possible physical-chemical mechanisms for the biogeochemical behavior of phosphorus at the near-molecular level. calcium orthophosphates, crystallization, dissolution, AFM Citation:Wang L J, Lu J W, Xu F S, et al. Dynamics of crystallization and dissolution of calcium orthophosphates at the near-molecular level.

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Role of Magnesium Ion in the Stabilization of Biogenic Amorphous Calcium Carbonate: A Structure−Function Investigation

Cited by 225 publications

References 36 publications

Magnesium incorporation into hydroxyapatite

Magnesium incorporation into hydroxyapatite

Amorphous dysprosium carbonate: characterization, stability, and crystallization pathways

Dynamics of crystallization and dissolution of calcium orthophosphates at the near-molecular level

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