danДоклады Национальной академии наук БеларусиDoklady of the National Academy of Sciences of Belarus1561-83232524-2431The Republican Unitary Enterprise Publishing House "Belaruskaya Navuka"10.29235/1561-8323-2022-66-5-501-508dan-1089Research ArticleХИМИЯCHEMISTRYСтабилизация аморфного состояния карбонат-фосфатов кальция фосфат-ионамиStabilization of the amorphous state of calcium carbonate-phosphates with phosphate ionsГлазовИ. Е.GlazovI. E.

Глазов Илья Евгеньевич – мл. науч. сотрудник

ул.Сурганова, 9/1, 220072, Минск

 

Glazov Ilya E. – Junior Researcher

9/1, Surganov Str., 220072, Minsk

che.glazov@mail.ruКрутькоВ. К.Krut’koV. K.

Крутько Валентина Константиновна – канд. хим. наук, доцент, заведующий лабораторией

ул. Сурганова, 9/1, 220072, Минск

Krut’ko Valentina K. – Ph. D. (Chemistry), AssociateProfessor, Head of the Laboratory

9/1, Surganov Str., 220072, Minsk

tsuber@igic.bas-net.byМусскаяО. Н.MusskayaO. N.

Мусская Ольга Николаевна – канд. хим. наук, доцент, вед. науч. сотрудник

ул. Сурганова, 9/1, 220072, Минск

 

Musskaya Olga N. – Ph. D. (Chemistry), Associate Professor, Leading Researcher

9/1, Surganov Str., 220072, Minsk

musskaja@igic.bas-net.byКулакА. И.KulakA. I.

Кулак Анатолий Иосифович – академик, д-р хим. наук,профессор, директор

ул. Сурганова, 9/1, 220072, Минск 

Kulak Anatoly I. – Academician, D. Sc. (Chemistry), Professor, Director

9/1, Surganov Str., 220072, Minsk

kulak@igic.bas-net.byИнститут общей и неорганической химии Национальной академии наук БеларусиInstitute of General and Inorganic Chemistry of the National Academy of Sciences of Belarus202203112022665501508Copyright © Глазов И.Е., Крутько В.К., Мусская О.Н., Кулак А.И., 20222022Глазов И.Е., Крутько В.К., Мусская О.Н., Кулак А.И.Glazov I.E., Krut’ko V.K., Musskaya O.N., Kulak A.I.Данная работа распространяется под лицензией Creative Commons Attribution 4.0.This work is licensed under a Creative Commons Attribution 4.0 License.https://doklady.belnauka.by/jour/article/view/1089

Аморфный карбонат-фосфат кальция с отношением Ca/P 1,83 получен жидкофазным осаждением из Ca2+, PO3–4, CO2-3  - содержащих растворов при pH 10 и стабилизирован дегидратацией этанолом с последующим прогревом при 400 °C. Присутствие PO3–4-ионов в структуре аморфного карбонат-фосфата кальция обуславливает его повышенную устойчивость к превращению в кристаллические фазы. Созревание в Ca2+, PO3–4 , CO2-3  − -содержащем маточном растворе при pH 10 в течение 4 сут способствует превращению аморфного карбонат-фосфата кальция в аморфный карбонат-фосфат кальция / карбонат-гидроксиапатит / кальцит. Совместное влияние PO3–4 и CO2-3  − - ионов в водной среде на превращение аморфного карбонат-фосфата кальция в карбонат-гидроксиапатит позволяет максимально стабилизировать аморфное состояние, обеспечивающее высокую степень биоактивности.

Amorphous calcium carbonate-phosphate with a Ca/P ratio of 1.83 was precipitated from Ca2+, Ca2+, PO3–4, CO2-3  − containing solutions at pH 10 and stabilized by ethanol dehydration and followed by heating at 400 °C. The presence of PO3–4 ions in the structure of amorphous calcium carbonate-phosphate provides its increased resistance to transformation into crystalline phases. Aging in a Ca2+, PO3–4 , CO2-3  − containing mother solution at pH 10 for 4 days promotes the transformation of amorphous calcium carbonate-phosphate into amorphous calcium carbonate-phosphate / carbonated hydroxyapatite / calcite. The combined effect of PO3–4 и CO2-3  − ions in the aquatic environment on the crystallization of amorphous calcium carbonate-phosphate into carbonated hydroxyapatite contributes to a maximum stabilization of the amorphous state that provides a high extent of bioactivity.

стабилизация аморфного состоянияаморфный карбонат-фосфат кальцияаморфный карбонат кальциякальциткарбонат-гидроксиапатитamorphous state stabilizationamorphous calcium carbonate phosphateamorphous calcium carbonatecalcitecarbonated hydroxyapatiteReferencesUskoković, V. Disordering the disorder as the route to a higher order: incoherent crystallization of calcium phosphate through amorphous precursors / V. Uskoković // Cryst. Gr. Des. – 2019. – Vol. 19, N 8. – P. 4340–4357. https://doi.org/10.1021/ acs.cgd.9b00061Uskoković V. Disordering the disorder as the route to a higher order: incoherent crystallization of calcium phosphate through amorphous precursors. Crystal Growth & Design, 2019, vol. 19, no. 8, pp. 4340–4357. https://doi.org/10.1021/acs. cgd.9b00061Introducing the crystalline phase of dicalcium phosphate monohydrate / B. Q. Lu [et al.] // Nature Comm. – 2020. – Vol. 11, N 1. – P. 1–8. https://doi.org/10.1038/s41467-020-15333-6Lu B. Q., Willhammar T., Sun B. B., Hedin N., Gale J. D., Gebauer D. Introducing the crystalline phase of dicalcium phosphate monohydrate. Nature Communications, 2020, vol. 11, no. 1, pp. 1–8. https://doi.org/10.1038/s41467-020-15333-6Additives control the stability of amorphous calcium carbonate via two different mechanisms: Surface adsorption versus bulk incorporation / Z. Zou [et al.] // Adv. Funct. Mater. – 2020. – Vol. 30, N 23. – Art. 2000003. https://doi.org/10.1002/ adfm.202000003Zou Z., Yang X., Albéric M., Heil T., Wang Q., Pokroy B., Politi Y., Bertinetti L. Additives control the stability of amorphous calcium carbonate via two different mechanisms: Surface adsorption versus bulk incorporation. Advanced Functional Materials, 2020, vol. 30, no. 23, art. 2000003. https://doi.org/10.1002/adfm.202000003Use of amorphous calcium carbonate for the design of new materials / B. Cantaert [et al.] // ChemPlusChem. – 2017. – Vol. 82, N 1. – P. 107–120. https://doi.org/10.1002/cplu.201600457Cantaert B., Kuo D., Matsumura S., Nishimura T., Sakamoto T., Kato T. Use of amorphous calcium carbonate for the design of new materials. ChemPlusChem, 2017, vol. 82, no. 1, pp. 107–120. https://doi.org/10.1002/cplu.201600457Combes, C. Amorphous calcium phosphates: synthesis, properties and uses in biomaterials / C. Combes, C. Rey // Acta Biomater. – 2010. – Vol. 6, N 9. – P. 3362–3378. https://doi.org/10.1016/j.actbio.2010.02.017Combes C., Rey C. Amorphous calcium phosphates: synthesis, properties and uses in biomaterials. Acta Biomaterialia, 2010, vol. 6, no. 9, pp. 3362–3378. https://doi.org/10.1016/j.actbio.2010.02.017Ibsen, C. J. S. Apatite formation from amorphous calcium phosphate and mixed amorphous calcium phosphate/amorphous calcium carbonate / C. J. S. Ibsen, D. Chernyshov, H. Birkedal // Chem. Europ. J. – 2016. – Vol. 22, N 35. – P. 12347–12357. https://doi.org/10.1002/chem.201601280Ibsen C. J. S., Chernyshov D., Birkedal H. Apatite formation from amorphous calcium phosphate and mixed amorphous calcium phosphate/amorphous calcium carbonate. Chemistry – A European Journal, 2016, vol. 22, no. 35, pp. 12347–12357. https://doi.org/10.1002/chem.201601280Sakae, T. Historical review of biological apatite crystallography / T. Sakae, H. Nakada, J. P. LeGeros // J. Hard Tiss. Biol. – 2015. – Vol. 24, N 2. – P. 111–122. https://doi.org/10.2485/jhtb.24.111Sakae T., Nakada H., LeGeros J. P. Historical review of biological apatite crystallography. Journal of Hard Tissue Biology, 2015, vol. 24, no. 2, pp. 111–122. https://doi.org/10.2485/jhtb.24.111Dorozhkin, S. V. Multiphasic calcium orthophosphate (CaPO4) bioceramics and their biomedical applications / S. V. Dorozhkin // Ceram. Intern. – 2016. – Vol. 42, N 6. – P. 6529–6554. https://doi.org/10.1016/j.ceramint.2016.01.062Dorozhkin S. V. Multiphasic calcium orthophosphate (CaPO4) bioceramics and their biomedical applications. Ceramics International, 2016, vol. 42, no. 6, pp. 6529–6554. https://doi.org/10.1016/j.ceramint.2016.01.062Низкотемпературное формирование и идентификация двухфазных карбонат-фосфатов кальция / И. Е. Глазов [и др.] // Журн. неорган. химии. – 2022. – Т. 67, № 11. – С. 1–13. https://doi.org/ 10.31857/S0044457X22600876Glazov I. E., Krut’ko V. K., Musskaya O. N., Kulak A. I. Low-temperature formation and identification of biphasic calcium carbonate-phosphates. Zhurnal neorganicheskoj himii = Journal of Inorganic Chemistry, 2022, vol. 67, no. 2, pp. 1–13 (in Russian). https://doi.org/10.31857/S0044457X22600876Жидкофазный синтез карбонат-гидроксиапатита / И. Е. Глазов [и др.] // Вес. Нац. акад. навук Беларусi. Сер. хiм. навук. – 2019. – Т. 55, № 4. – С. 391–399. https://doi.org/10.29235/1561-8331-2019-55-4-391-399Glazov I.E., Krut’koV. K.,Musskaya O. N., KulakA.I.Wetsynthesis of carbonated hydroxyapatite.Vestsi Natsyyanal’nai akademii navuk Belarusi. Seryya khimichnykh navuk = Proceedings of the National Academy of Sciences of Belarus. Chemical series, 2019, vol. 55, no. 4, pp. 391–399 (in Russian). https://doi.org/10.29235/1561-8331-2019-55-4-391-399Structural role and spatial distribution of carbonate ions in amorphous calcium phosphate / O. F. Yasar [et al.] // J. Phys. Chem. – 2021. – Vol. 125, N 8. – P. 4675–4693. https://doi.org/10.1021/acs.jpcc.0c10355Yasar O. F., Liao W.-C., Stevensson B., Edén M. Structural role and spatial distribution of carbonate ions in amorphous calcium phosphate. Journal of Physical Chemistry C, 2021, vol. 125, no. 8, pp. 4675–4693. https://doi.org/10.1021/acs.jpcc.0c10355Апатитные фосфаты кальция: жидкофазное формирование, термические превращения, терминология и идентификация / И.Е. Глазов [и др.] // Журн. неорган. химии. – 2022. – Т. 67, № 2. – С. 193–202. https://doi.org/10.31857/s0044457x22020040Glazov I. E., Krut’ko V. K., Musskaya O. N., Kulak A. I. Calcium Phosphate Apatites: Wet Formation, Thermal Transformations, Terminology, and Identification. Russian Journal of Inorganic Chemistry, 2022, vol. 67, no. 2, pp. 173–182. https://doi.org/10.1134/s0036023622020048Nanoscale Ion Dynamics Control on Amorphous Calcium Carbonate Crystallization: Precise Control of Calcite Crystal Sizes / M. P. Asta [et al.] // J. Phys. Chem. C. – 2020. – Vol. 124, N 46. – P. 25645–25656. https://doi.org/10.1021/acs.jpcc.0c08670Asta M. P., Fernandez-Martinez A., Alonso J., Charlet L., Findling N., Magnin V., Ruta B., Sprung M., Westermeier F. Nanoscale Ion Dynamics Control on Amorphous Calcium Carbonate Crystallization: Precise Control of Calcite Crystal Sizes. Journal of Physical Chemistry C, 2020, vol. 124, no. 46, pp. 25645–25656. https://doi.org/10.1021/acs.jpcc.0c08670Koga, N. Thermally induced transformations of calcium carbonate polymorphs precipitated selectively in ethanol/water solutions / N. Koga, Y. Yamane, T. Kimura // Thermochim. Acta. – 2011. – Vol. 512, N 1–2. – P. 13–21. https://doi.org/10.1016/j. tca.2010.08.016Koga N., Yamane Y., Kimura T. Thermally induced transformations of calcium carbonate polymorphs precipitated selectively in ethanol/water solutions. Thermochimica Acta, 2011, vol. 512, no. 1–2, pp. 13–21. https://doi.org/10.1016/j. tca.2010.08.016High surface area calcite / L. N. Schultz [et al.] // J. Cryst. Gr. – 2013. – Vol. 371. – P. 34–38. https://doi.org/10.1016/j. jcrysgro.2013.01.049Schultz L. N., Andersson M. P., Dalby K. N., Müter D., Okhrimenko D. V., Fordsmand H., Stipp S. L. S. High surface area calcite. Journal of Crystal Growth, 2013, vol. 371, pp. 34–38. https://doi.org/10.1016/j.jcrysgro.2013.01.049

The authors declare that there are no conflicts of interest present.