Molecular‐Level StructureProperty Relationships in Biogenic Calcium Carbonates: The Unique Insights of Solid‐State NMR Spectroscopy

Shir, Ira Ben; Kababya, Shifi; Schmidt, Asher

doi:10.1002/ijch.201300121

Cited by 12 publications

(15 citation statements)

References 90 publications

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“…We applied solid-state NMR spectroscopy for identifying the bioorganic molecules that are bound to the mineral particles and, therefore, possibly responsible for the nucleation of the mineral phase. To examine these structures, we used a combination of the 1 H-13 C cross-polarization (CP) and single-pulse 13 C NMR techniques (19). The former consists of a CP magnetization transfer from 1 H nuclei to nearby 13 C nuclei and enables the detection of carbon species localized in hydrogen-rich chemical environmentsnamely, the SOM and the interfacial carbonates (i.e., those exposed to the mineral/organic interface).…”

Section: Detection Of Highly Disordered Environments In Coral Skeletonmentioning

confidence: 99%

“…S3). The spectra from the bulk of the carbonates display a single resonance; this resonance is symmetric and centered at d 13 C = 171.0 parts per million (ppm), which is characteristic of crystalline aragonitic environments (19). In contrast, the spectra from the interfacial carbonates display a much broader resonance that is asymmetric and whose maximum intensity is slightly lower (d 13 The three CRM maps for each section were generated on the basis of the relative intensity distribution of (i) two characteristic Raman bands of aragonite-namely, the translational lattice mode at 152 cm −1 (A1 and B1) and the v 1 symmetric stretching mode of the CO 3 2units at implies that the interfacial carbonates form highly disordered, amorphous environments a few nanometers thick (20) that coat the aragonite crystals.…”

Section: Detection Of Highly Disordered Environments In Coral Skeletonmentioning

confidence: 99%

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Biological control of aragonite formation in stony corals

Euw

Zhang

Manichev

et al. 2017

Science

166

149

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Little is known about how stony corals build their calcareous skeletons. There are two prevailing hypotheses: that it is a physicochemically dominated process and that it is a biologically mediated one. Using a combination of ultrahigh-resolution threedimensional imaging and two-dimensional solid-state nuclear magnetic resonance (NMR) spectroscopy, we show that mineral deposition is biologically driven. Randomly arranged, amorphous nanoparticles are initially deposited in microenvironments enriched in organic material; they then aggregate and form ordered aragonitic structures through crystal growth by particle attachment. Our NMR results are consistent with heterogeneous nucleation of the solid mineral phase driven by coral acid-rich proteins. Such a mechanism suggests that stony corals may be able to sustain calcification even under lower pH conditions that do not favor the inorganic precipitation of aragonite.

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Section: Detection Of Highly Disordered Environments In Coral Skeletonmentioning

confidence: 99%

Section: Detection Of Highly Disordered Environments In Coral Skeletonmentioning

confidence: 99%

Biological control of aragonite formation in stony corals

Euw

Zhang

Manichev

et al. 2017

Science

166

149

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“…However, they found no evidence of large scale separation of Ca 2+ and CO 3 2-as suggested by Goodwin et al 16 . The local environment of water has also been extensively studied with NMR on both biogenic 13,[19][20] and synthetic ACC 11,[21][22][23][24][25] . These studies reported both translationally restricted and mobile water as well as hydroxide ions in ACC 11,23,25 .…”

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confidence: 99%

Hydrogen Bonding in Amorphous Calcium Carbonate and Molecular Reorientation Induced by Dehydration

et al. 2018

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Amorphous calcium carbonate (ACC) is a meta-stable hydrated solid that has received great attention as a precursor in calcium carbonate crystallization in both synthetic and biological systems. In particular, the atomic structure of ACC is a matter of ongoing discussion. Some studies have pointed out similarities between the local structure of amorphous calcium carbonate and its crystalline counterparts, whereas others suggested no resemblance to any known crystalline form. Despite the large number of studies, few structural aspects have been described beyond the first Ca-O distance and coordination number. Specifically, the role of carbonate ions and water molecules in the amorphous network are poorly understood. Here we address this issue using neutron and x-ray total scattering in combination with molecular modeling on a set of well-defined synthetic CaCO 3 •nH 2 O samples, synthesized by rapid mixing of CaCl 2 and Na 2 CO 3 solutions and with two levels of hydration, n = 1.1 and n = 0.5. An atomistic model of ACC is derived based on the total scattering data and the results were substantiated by spectroscopic techniques, with particular focus on the hydrogen bonding. Our results show that the ACC studied here has a broad distribution of coordination numbers for all coordination spheres. A close structural relationship is found between water and carbonate, whereby the loss of water induces a rearrangement of the carbonate ions with negligible change in total number of oxygen atoms coordinated with the calcium ion. We find that the local environments of the ions in ACC are more similar to those of ions in solution than to any of the crystalline forms of calcium carbonate. Introduction: Amorphous precursors play a key role in mineral formation. In both biological and synthetic settings, they are either exploited for their unique properties, which are clearly distinct from their crystalline counterparts 1-4 or stored and crystallized when needed 3-6. ACC in particular, is of special interest due to its widespread occurrence in biology, where it is found in two forms; a transient and a stabilized form 3-4, 7. Transient biogenic ACCs act as precursors for crystalline biominerals and have proven difficult to study due to their short-lived nature 3, 8. Transient ACCs have been shown to exhibit different local structures 3. Moreover, they were generally found to dehydrate prior to crystallization 9-10 suggesting that dehydration may play a key role in destabilizing ACC 11. Stabilized biogenic ACC, is often hydrated with n = N H2O /N Ca ≈ 1 12 , crystallization is prevented by the presence of various additives. This type

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“…On the latter a single thin resonance at ( 13 C) = 171.5 ppm is observed that corresponds to carbonate from crystalline aragonite. 11 The resonances of the organic matrix and of -chitin in particular are not observed due to their very low proportion in the sample (less than 5 w%). Exposed carbonates, observed in the CPMAS spectrum at long contact time, exhibit a slightly shifted resonance at higher field (170.5 ppm) and of larger linewidth due to higher local disorder as compared to carbonates in crystalline environment.…”

Section: Bone Apatite Organo-mineral Interfacementioning

confidence: 99%

“…Solid-state NMR is in principle the method of choice to access a fine description of biomineralized tissues. 9,10,11 The intrinsic low sensitivity of this spectroscopy limits however its applicability to the investigation of surfaces and interfaces in materials of low specific surface area where the selective observation of surface versus bulk species is extremely challenging. In that context, Dynamic Nuclear Polarization (DNP) has recently emerged as an appealing technique to drastically enhance the sensitivity of solid-state NMR spectroscopy and, in particular, to amplify signals at surfaces in an approach called DNP SENS (DNP Surface Enhanced NMR Spectroscopy).…”

Section: Introductionmentioning

confidence: 99%

Structural description of surfaces and interfaces in biominerals by DNP SENS

Azaı̈s

Euw

Ajili

et al. 2019

Solid State Nuclear Magnetic Resonance

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Biological mineralized tissues are hybrid materials with complex hierarchical architecture composed of biominerals often embedded in an organic matrix. The atomic-scale comprehension of surfaces and organo-mineral interfaces of these biominerals is of paramount importance to understand the ultrastructure, the formation mechanisms as well as the biological functions of the related biomineralized tissue. In this communication we demonstrate the capability of DNP SENS to reveal the fine atomic structure of biominerals, and more specifically their surfaces and interfaces. For this purpose, we studied two key examples belonging to the most significant biominerals family in nature: apatite in bone and aragonite in nacreous shell. As a result, we demonstrate that DNP SENS is a powerful approach for the study of intact biomineralized tissues. Signal enhancement factors are found to be up to 40 and 100, for the organic and the inorganic fractions, respectively, as soon as impregnation time with the radical solution is long enough (between 12 and 24 h) to allow an efficient radical penetration into the calcified tissues. Moreover, ions located at the biomineral surface are readily detected and identified through 31 P or 13 C HETCOR DNP SENS experiments. Noticeably, we show that protonated anions are preponderant at the biomineral surfaces that are in the form of HPO4 2for bone apatite and HCO3 2for nacreous aragonite. Finally, we demonstrate that organo-mineral interactions can be probed at the atomic level with high sensitivity. In particular, reliable { 31 P}-13 C REDOR experiments are achieved in a few hours, leading to the determination of distances, molar proportion and binding mode of citrate bonded to bone mineral in native compact bone. According to our results, only 50% of the total amount of citrate in bone is directly interacting with bone apatite through two out of three carboxylic groups.

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Molecular‐Level StructureProperty Relationships in Biogenic Calcium Carbonates: The Unique Insights of Solid‐State NMR Spectroscopy

Cited by 12 publications

References 90 publications

Biological control of aragonite formation in stony corals

Biological control of aragonite formation in stony corals

Hydrogen Bonding in Amorphous Calcium Carbonate and Molecular Reorientation Induced by Dehydration

Structural description of surfaces and interfaces in biominerals by DNP SENS

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