Formation and Stability of Calcium Oxalates, the Main Crystalline Phases of Kidney Stones

Izatulina, Alina R.; Punin, Yurii O.; Shtukenberg, Alexandr G.; Frank-Kamenetskaya, O. V.; Gurzhiy, Vladislav V.

doi:10.1007/978-3-642-20018-2_38

Cited by 5 publications

(115 citation statements)

References 9 publications

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“…Calcium oxalate monohydrate , and calcium phosphate spherulites are typically found in kidney stones and urinary sediments. Pathologists have long recognized the spherulitic character of amyloid protein deposits associated with a variety of neurodegenerative disorders. − …”

Section: Overview Of Spherulite Forming Substances and Growth Conditionsmentioning

confidence: 99%

Spherulites

et al. 2011

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Section: Overview Of Spherulite Forming Substances and Growth Conditionsmentioning

confidence: 99%

Spherulites

et al. 2011

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“…Calcium oxalates are notably common biominerals and can be found, e.g., in coal basins, bituminous shale, bottom sediments, on the contact of rocks with guano, lichens, fungi, or some higher plants, and even on a surface of monuments. − This is mostly due to the affinity of oxalates to bivalent cations, which is reflected in the ability to form insoluble precipitates, and because the sources of calcium (carbonate rocks and subfossils) interact more actively with weak organic acids. Calcium oxalates are also found among the pathogenic mineral precipitates in human bone marrow, myocardium, joints, lungs, liver, thyroid gland, intestinal mucosa, eyes, and urinary system. − Oxalates span therefore several fields (medicine, biology, mineralogy, materials science, etc. ), which is reflected in a large number of publications.…”

Section: Introductionmentioning

confidence: 99%

Hydrated Calcium Oxalates: Crystal Structures, Thermal Stability, and Phase Evolution

Izatulina

Gurzhiy

Krzhizhanovskaya

et al. 2018

Crystal Growth & Design

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Thermal stability, structural evolution pathways, and phase transition mechanisms of the calcium oxalates whewellite (CaC2O4·H2O), weddellite (CaC2O4·(2+x)H2O), and caoxite (CaC2O4·3H2O) have been analyzed using single crystal and powder X-ray diffraction (XRD). During single crystal XRD heating experiments, α-CaC2O4 and the novel calcium oxalate monohydrate have been obtained and structurally characterized for the first time. The highest thermal expansion of these compounds is observed along the direction of the hydrogen bonds, whereas the lowest expansion and even contraction of the structures occur due to the displacement of neighbor layered complexes toward each other and to an orthogonalization of the monoclinic angles. Within the calcium oxalate family, whewellite should be regarded as the most stable crystalline phase at ambient conditions. Weddellite and caoxite transform to whewellite during dehydration-driven phase transition promoted by time and/or heating.

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“…15,16 Depending upon the temperature, whewellite can adopt two structuresso-called low and high-temperature forms (denoted as LT and HT, respectively) (Figure 1). Upon further heat treatment (up to ~410 °C), several anhydrous polymorphs can also be obtained synthetically (CaC2O4, noted COA), 17,18 which are unstable under ambient laboratory conditions and rehydrate back to the COM. 18,19 The transitions between these phases lead to changes in lattice cell parameters and local environments of the oxalates (Figures S1 and S2), with notably increased dynamics around the neighboring water molecules in the HT-COM, and variations in the distances to neighboring calcium cations.…”

Section: Introductionmentioning

confidence: 99%

“…18,19 The transitions between these phases lead to changes in lattice cell parameters and local environments of the oxalates (Figures S1 and S2), with notably increased dynamics around the neighboring water molecules in the HT-COM, and variations in the distances to neighboring calcium cations. 17,20 https://doi.org/10.26434/chemrxiv-2024-rtx53-v2 ORCID: https://orcid.org/0000-0002-7445-0528 Content not peer-reviewed by ChemRxiv. License: CC BY-NC-ND 4.0 17 (b) Structural relationships between LT-COM, HT-COM and α-COA.…”

Section: Introductionmentioning

confidence: 99%

“…IR and Raman studies can give information on the coordination of oxalate ions, [21][22][23] but cannot always differentiate between different polymorphs. 24 Powder and single crystal XRD analysis can provide more structural information, 4,25 including polymorphism; 17 but is unsuitable for studying amorphous materials. Regarding ssNMR, studies on oxalate-containing materials have been carried out at natural abundance on the 13 C nucleus, 26,27 but have required isotopic enrichment for 17 O, due to its much lower natural abundance (~ 0.037% for 17 O, vs ~ 1.1% for 13 C).…”

Section: Introductionmentioning

confidence: 99%

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High-resolution 17O solid-state NMR as a unique probe for investigating oxalate binding modes in materials: The case study of calcium oxalate biominerals

Goldberga,

Hung,

Sarou-Kanian

et al. 2024

Preprint

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Oxalate ligands are found in many classes of materials, including energy-storage materials and biominerals like hydrated calcium-oxalates. Determining their local environments at the atomic scale is thus paramount to establishing the structure and properties of numerous phases. Here, we show that high-resolution 17O solid-state NMR is a valuable asset for investigating the structure of crystalline oxalate systems. First, an efficient 17O-enrichment procedure of oxalate ligands is demonstrated using mechanochemical saponification. Then, the use of 17O-enriched oxalates for the synthesis of the biologically relevant calcium-oxalate monohydrate (COM) phase is presented, enabling the analysis of its structure and heat-induced phase transitions by high-resolution 17O solid-state NMR. NMR studies of the low-temperature COM form (LT-COM), using magnetic fields varying from 9.4 to 35.2 T, as well as 13C-17O MQ/D-RINEPT and 17O{1H} MQ/REDOR experiments, enabled the 8 inequivalent oxygen sites of the oxalate ligands to be resolved, with a tentative assignment proposed. Then, the structural changes occurring upon heat treatment of COM were followed by high-resolution 17O solid-state NMR, providing new insight into the structures of the high-temperature form (HT-COM) and anhydrous calcium oxalate alpha-phase (alpha-COA), including the presence of structural disorder in the latter case. Overall, this work highlights the ease associated with 17O-isotopic enrichment of oxalate oxygens, and how it enables the study of oxalate structures (including materials of biological relevance) at high-resolution via solid-state NMR, in the frame of “NMR-crystallography” investigations.

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Formation and Stability of Calcium Oxalates, the Main Crystalline Phases of Kidney Stones

Cited by 5 publications

References 9 publications

Spherulites

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Hydrated Calcium Oxalates: Crystal Structures, Thermal Stability, and Phase Evolution

High-resolution 17O solid-state NMR as a unique probe for investigating oxalate binding modes in materials: The case study of calcium oxalate biominerals

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