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Amorphous Calcium Carbonate Constructed from Nanoparticle Aggregates with Unprecedented Surface Area and Mesoporosity
Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials. (Nanoteknologi och funktionella material)
Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials. Department of Materials and Environmental Chemistry, Stockholm University, Stockholm, Sweden. (Nanotechnology and Functional Materials)
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2018 (English)In: ACS Applied Materials and Interfaces, ISSN 1944-8244, E-ISSN 1944-8252, Vol. 10, no 25, p. 21556-21564Article in journal (Refereed) Published
Abstract [en]

Amorphous calcium carbonate (ACC), with the highest reported specific surface area of all current forms of calcium carbonate (over 350 m2 g-1), was synthesized using a surfactant-free, one-pot method. Electron microscopy, helium pycnometry, and nitrogen sorption analysis revealed that this highly mesoporous ACC, with a pore volume of ∼0.86 cm3 g-1 and a pore-size distribution centered at 8-9 nm, is constructed from aggregated ACC nanoparticles with an estimated average diameter of 7.3 nm. The porous ACC remained amorphous and retained its high porosity for over 3 weeks under semi-air-tight storage conditions. Powder X-ray diffraction, large-angle X-ray scattering, infrared spectroscopy, and electron diffraction exposed that the porous ACC did not resemble any of the known CaCO3 structures. The atomic order of porous ACC diminished at interatomic distances over 8 Å. Porous ACC was evaluated as a potential drug carrier of poorly soluble substances in vitro. Itraconazole and celecoxib remained stable in their amorphous forms within the pores of the material. Drug release rates were significantly enhanced for both drugs (up to 65 times the dissolution rates for the crystalline forms), and supersaturation release of celecoxib was also demonstrated. Citric acid was used to enhance the stability of the ACC nanoparticles within the aggregates, which increased the surface area of the material to over 600 m2 g-1. This porous ACC has potential for use in various applications where surface area is important, including adsorption, catalysis, medication, and bone regeneration.

Place, publisher, year, edition, pages
2018. Vol. 10, no 25, p. 21556-21564
Keywords [en]
amorphous calcium carbonate, drug delivery, large-angle X-ray scattering, nanoparticles, porous materials
National Category
Nano Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
URN: urn:nbn:se:uu:diva-358032DOI: 10.1021/acsami.8b03939ISI: 000437811400059PubMedID: 29862822OAI: oai:DiVA.org:uu-358032DiVA, id: diva2:1241385
Funder
Knut and Alice Wallenberg FoundationSwedish Research Council, 2014-3929Available from: 2018-08-23 Created: 2018-08-23 Last updated: 2019-08-21Bibliographically approved
In thesis
1. Porous Amorphous Calcium Carbonate and Phosphate: Synthesis and Application
Open this publication in new window or tab >>Porous Amorphous Calcium Carbonate and Phosphate: Synthesis and Application
2019 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The synthesis of porous amorphous calcium carbonate (ACC) and porous amorphous calcium phosphate (ACP) was developed in this thesis. Porous ACC with specific Brunauer–Emmett–Teller (BET) surface area of >350 m2/g was synthesized using a surfactant free approach. The high surface area of porous ACC was related to its nanostructure. Porous ACC was constructed with aggregated ACC nanoparticles that were less than 10 nm in diameter. The porosity and stability of porous ACC could be enhanced by introducing additives in the synthesis steps. The use of additives could also be used to control the crystallization of ACC to form vaterite particles with controllable morphologies. Porous ACC was tested as a drug carrier for two poorly soluble drugs (itraconazole and celecoxib). The porous ACC carrier was able to stabilize these drugs in their amorphous forms and enhance their release rate significantly when compared with the crystalline drug. Furthermore, porous ACC could also be used as a precursor/template for the synthesis of porous carbon. A porous carbon adsorbent with high uptake and high selectivity for greenhouse gases was produced. Porous ACP with a specific BET surface area of >400 m2/g was obtained by introducing phosphoric acid to the ACC suspension obtained during the synthesis of porous ACC. Similar to porous ACC, porous ACP was constructed of aggregated nanoparticles. ACP was found to be stable in ambient conditions for over 12 months and the stability could also be tailored by adjusting its composition. Porous ACP was cytocompatible and an effective drug carrier for alendronate - a bisphosphate drug for treatment of osteoporosis. The development of porous ACC and porous ACP as functional porous materials is summarized in this thesis.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2019. p. 71
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1844
Keywords
amorphous calcium carbonate, amorphous calcium phosphate, stabilization, crystallization, porous material, drug delivery, gas adsorption
National Category
Nano Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
urn:nbn:se:uu:diva-391172 (URN)978-91-513-0727-5 (ISBN)
Public defence
2019-10-09, Häggsalen, Ångströmlaboratoriet, Lägerhyddsvägen 1, Uppsala, 09:15 (English)
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Available from: 2019-09-18 Created: 2019-08-21 Last updated: 2019-10-15

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Sun, RuiZhang, PengStrömme, MariaCheung, Ocean

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