Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Role of CaCO₃° Neutral Pair in Calcium Carbonate Crystallization.

ABSTRACT: The molecular structure of the units that get incorporated into the nuclei of the crystalline phase and sustain their growth is a fundamental issue in the pathway from a supersaturated solution to the formation of crystals. Using a fluorescent dye we have recorded the variation of the pH value in time along a gel where CaCl₂ and NaHCO₃ counter-diffuse to crystallize CaCO₃. The same pH-space-time distribution maps were also computationally obtained using a chemical speciation code (phreeqc). Using data arising from this model we investigated the space-time evolution of the activity of the single species (ions and ion pairs) involved in the crystallization process. Our combined results suggest that, whatever the pathway from solution to crystals, the neutral pair CaCO₃° is a key species in the CaCO₃ precipitation system.

SUBMITTER: Genovese D

PROVIDER: S-EPMC4974600 | biostudies-literature | 2016 Aug

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Role of CaCO3° Neutral Pair in Calcium Carbonate Crystallization.

Genovese Damiano D Montalti Marco M Otálora Fermín F Gómez-Morales Jaime J Sancho-Tomás María M Falini Giuseppe G García-Ruiz Juan Manuel JM

Crystal growth & design 20160708 8

The molecular structure of the units that get incorporated into the nuclei of the crystalline phase and sustain their growth is a fundamental issue in the pathway from a supersaturated solution to the formation of crystals. Using a fluorescent dye we have recorded the variation of the pH value in time along a gel where CaCl2 and NaHCO3 counter-diffuse to crystallize CaCO3. The same pH-space-time distribution maps were also computationally obtained using a chemica ...[more]

PMID: 27512345

Similar Datasets

Uncovering the Role of Bicarbonate in Calcium Carbonate Formation at Near-Neutral pH.

Project description:Mechanistic pathways relevant to mineralization are not well-understood fundamentally, let alone in the context of their biological and geological environments. Through quantitative analysis of ion association at near-neutral pH, we identify the involvement of HCO3 - ions in CaCO3 nucleation. Incorporation of HCO3 - ions into the structure of amorphous intermediates is corroborated by solid-state nuclear magnetic resonance spectroscopy, complemented by quantum mechanical calculations and molecular dynamics simulations. We identify the roles of HCO3 - ions as being through (i) competition for ion association during the formation of ion pairs and ion clusters prior to nucleation and (ii) incorporation as a significant structural component of amorphous mineral particles. The roles of HCO3 - ions as active soluble species and structural constituents in CaCO3 formation are of fundamental importance and provide a basis for a better understanding of physiological and geological mineralization.

| S-EPMC8362096 | biostudies-literature

Crystallization kinetics of amorphous calcium carbonate in confinement.

Project description:Phase transformations of carbonates are relevant to a wide range of biological, environmental, and industrial processes. Over the past decade, it emerged that crystallization pathways in these systems can be quite complex. Metastable intermediates such as amorphous calcium carbonate (ACC) were found to greatly impact composition, structure, and properties of more stable phases. However, it has been challenging to create predictive models. Rapid transformation of ACC in bulk has been one obstacle in the determination of nucleation rates. Herein, it is reported that confinement in microfluidic droplets allows separating in time the precipitation of ACC and subsequent nucleation and growth of crystalline CaCO3. An upper limit of 1.2 cm-3 s-1 was determined for the steady-state crystal nucleation rate in the presence of ACC at ambient conditions. This rate has implications for the formation of calcium carbonate in biomineralization, bio-inspired syntheses, and carbon sequestration.

| S-EPMC6530533 | biostudies-literature

Microbially Induced Calcium Carbonate Precipitation by Sporosarcina pasteurii: a Case Study in Optimizing Biological CaCO3 Precipitation.

Project description:Current production of traditional concrete requires enormous energy investment that accounts for approximately 5 to 8% of the world's annual CO2 production. Biocement is a building material that is already in industrial use and has the potential to rival traditional concrete as a more convenient and more environmentally friendly alternative. Biocement relies on biological structures (enzymes, cells, and/or cellular superstructures) to mineralize and bind particles in aggregate materials (e.g., sand and soil particles). Sporosarcina pasteurii is a workhorse organism for biocementation, but most research to date has focused on S. pasteurii as a building material rather than a biological system. In this review, we synthesize available materials science, microbiology, biochemistry, and cell biology evidence regarding biological CaCO3 precipitation and the role of microbes in microbially induced calcium carbonate precipitation (MICP) with a focus on S. pasteurii. Based on the available information, we provide a model that describes the molecular and cellular processes involved in converting feedstock material (urea and Ca2+) into cement. The model provides a foundational framework that we use to highlight particular targets for researchers as they proceed into optimizing the biology of MICP for biocement production.

| S-EPMC10467343 | biostudies-literature

Effect of Polymer Nano- and Microparticles on Calcium Carbonate Crystallization.

Project description:Molecular and macromolecular templates are known to affect the shape, size, and polymorph selectivity on the biomineralization of calcium carbonate (CaCO3). Micro- and nanoparticles of common polymers present in the environment are beginning to show toxicity in living organisms. In this study, the role of plastic nanoparticles in the biomineralization of CaCO3 is explored to understand the ecological impact of plastic pollution. As a model study, luminescent poly(methyl methacrylate) nanoparticles (PMMA-NPs) were prepared using the nanoprecipitation method, fully characterized, and used for the mineralization experiments to understand their influence on nucleation, morphology, and polymorph selectivity of CaCO3 crystals. The PMMA-NPs induced calcite crystal nucleation with spherical morphologies at high concentrations. Microplastic particles collected from a commercial face scrub were also used for CaCO3 nucleation to observe the nucleation of calcite crystals on the particle surface. Microscopic, spectroscopic, and X-ray diffraction data were used to characterize and identify the nucleated crystals. The data presented in this paper add more information on the impact of microplastics on the marine environment.

| S-EPMC8359134 | biostudies-literature

Functionalized Multiwalled CNTs in Classical and Nonclassical CaCO3 Crystallization.

Project description:Multiwalled carbon nanotubes (MWCNTs) are interesting high-tech nanomaterials. MWCNTs oxidized and functionalized with itaconic acid and monomethylitaconate were demonstrated to be efficient additives for controlling nucleation of calcium carbonate (CaCO3) via gas diffusion (GD) in classical as well as nonclassical crystallization, yielding aragonite and truncated calcite. For the first time, all amorphous calcium carbonate (ACC) proto-structures, such as proto calcite-ACC, proto vaterite-ACC and proto aragonite-ACC, were synthesized via prenucleation cluster (PNC) intermediates and stabilized at room temperature. The MWCNTs also showed concentration-dependent nucleation promotion and inhibition similar to biomolecules in nature. Incorporation of fluorescein-5-thiosemicarbazide (5-FTSC) dye-labeled MWCNTs into the CaCO3 lattice resulted in fluorescent hybrid nanosized CaCO3. We demonstrate that functionalized MWCNTs offer a good alternative for controlled selective crystallization and for understanding an inorganic mineralization process.

| S-EPMC6723705 | biostudies-literature

Transformation and crystallization energetics of synthetic and biogenic amorphous calcium carbonate.

Project description:Amorphous calcium carbonate (ACC) is a metastable phase often observed during low temperature inorganic synthesis and biomineralization. ACC transforms with aging or heating into a less hydrated form, and with time crystallizes to calcite or aragonite. The energetics of transformation and crystallization of synthetic and biogenic (extracted from California purple sea urchin larval spicules, Strongylocentrotus purpuratus) ACC were studied using isothermal acid solution calorimetry and differential scanning calorimetry. Transformation and crystallization of ACC can follow an energetically downhill sequence: more metastable hydrated ACC → less metastable hydrated ACC ⇒ anhydrous ACC ∼ biogenic anhydrous ACC ⇒ vaterite → aragonite → calcite. In a given reaction sequence, not all these phases need to occur. The transformations involve a series of ordering, dehydration, and crystallization processes, each lowering the enthalpy (and free energy) of the system, with crystallization of the dehydrated amorphous material lowering the enthalpy the most. ACC is much more metastable with respect to calcite than the crystalline polymorphs vaterite or aragonite. The anhydrous ACC is less metastable than the hydrated, implying that the structural reorganization during dehydration is exothermic and irreversible. Dehydrated synthetic and anhydrous biogenic ACC are similar in enthalpy. The transformation sequence observed in biomineralization could be mainly energetically driven; the first phase deposited is hydrated ACC, which then converts to anhydrous ACC, and finally crystallizes to calcite. The initial formation of ACC may be a first step in the precipitation of calcite under a wide variety of conditions, including geological CO(2) sequestration.

| S-EPMC2944757 | biostudies-literature

Dehydration and crystallization of amorphous calcium carbonate in solution and in air.

Project description:The mechanisms by which amorphous intermediates transform into crystalline materials are poorly understood. Currently, attracting enormous interest is the crystallization of amorphous calcium carbonate, a key intermediary in synthetic, biological and environmental systems. Here we attempt to unify many contrasting and apparently contradictory studies by investigating this process in detail. We show that amorphous calcium carbonate can dehydrate before crystallizing, both in solution and in air, while thermal analyses and solid-state nuclear magnetic resonance measurements reveal that its water is present in distinct environments. Loss of the final water fraction--comprising less than 15% of the total--then triggers crystallization. The high activation energy of this step suggests that it occurs by partial dissolution/recrystallization, mediated by surface water, and the majority of the particle then crystallizes by a solid-state transformation. Such mechanisms are likely to be widespread in solid-state reactions and their characterization will facilitate greater control over these processes.

| S-EPMC4085778 | biostudies-literature

Recognition and Extraction of Cesium Hydroxide and Carbonate by Using a Neutral Multitopic Ion-Pair Receptor.

Project description:Current approaches to lowering the pH of basic media rely on the addition of a proton source. An alternative approach is described herein that involves the liquid-liquid extraction-based removal of cesium salts, specifically CsOH and Cs2 CO3 , from highly basic media. A multitopic ion-pair receptor (2) is used that can recognize and extract the hydroxide and carbonate anions as their cesium salts, as confirmed by 1 H?NMR spectroscopic titrations, ICP-MS, single-crystal structural analyses, and theoretical calculations. A sharp increase in the pH and cesium concentrations in the receiving phase is observed when receptor 2 is employed as a carrier in U-tube experiments involving the transport of CsOH through an intervening chloroform layer. The pH of the source phase likewise decreases.

| S-EPMC5694431 | biostudies-literature

Role of Water in CaCO3 Biomineralization.

Project description:Biomineralization occurs in aqueous environments. Despite the ubiquity and relevance of CaCO3 biomineralization, the role of water in the biomineralization process has remained elusive. Here, we demonstrate that water reorganization accompanies CaCO3 biomineralization for sea urchin spine generation in a model system. Using surface-specific vibrational spectroscopy, we probe the water at the interface of the spine-associated protein during CaCO3 mineralization. Our results show that, while the protein structure remains unchanged, the structure of interfacial water is perturbed differently in the presence of both Ca2+ and CO32- compared to the addition of only Ca2+. This difference is attributed to the condensation of prenucleation mineral species. Our findings are consistent with a nonclassical mineralization pathway for sea urchin spine generation and highlight the importance of protein hydration in biomineralization.

| S-EPMC7877725 | biostudies-literature

Edible CaCO3 nanoparticles stabilized Pickering emulsion as calcium-fortified formulation.

Project description:BackgroundNanoparticles assembled from food-grade calcium carbonate have attracted attention because of their biocompatibility, digestibility, particle and surface features (such as size, surface area, and partial wettability), and stimuli-responsiveness offered by their acid-labile nature.ResultsHerein, a type of edible oil-in-water Pickering emulsion was structured by calcium carbonate nanoparticles (CaCO3 NPs; mean particle size: 80 nm) and medium-chain triglyceride (MCT) for delivery of lipophilic drugs and simultaneous oral supplementation of calcium. The microstructure of the as-made CaCO3 NPs stabilized Pickering emulsion can be controlled by varying the particle concentration (c) and oil volume fraction (φ). The emulsification stabilizing capability of the CaCO3 NPs also favored the formation of high internal phase emulsion at a high φ of 0.7-0.8 with excellent emulsion stability at room temperature and at 4 °C, thus protecting the encapsulated lipophilic bioactive, vitamin D3 (VD3), against degradation. Interestingly, the structured CaCO3 NP-based Pickering emulsion displayed acid-trigged demulsification because of the disintegration of the CaCO3 NPs into Ca2+ in a simulated gastric environment, followed by efficient lipolysis of the lipid in simulated intestinal fluid. With the encapsulation and delivery of the emulsion, VD3 exhibited satisfying bioavailability after simulated gastrointestinal digestion.ConclusionsTaken together, the rationally designed CaCO3 NP emulsion system holds potential as a calcium-fortified formulation for food, pharmaceutical and biomedical applications.

| S-EPMC7934247 | biostudies-literature