Amorphous 1-D nanowires of calcium phosphate/pyrophosphate: A demonstration of oriented self-growth of amorphous minerals

Chaobo Feng; Bing Qiang Lu; Yunshan Fan; Haijian Ni; Yunfei Zhao; Shuo Tan; Zhi Zhou; Lijia Liu; Jordan A. Hachtel; Demie Kepaptsoglou; Baohu Wu; Denis Gebauer; Shisheng He; Feng Chen

doi:10.1016/j.jcis.2023.12.002

Amorphous 1-D nanowires of calcium phosphate/pyrophosphate: A demonstration of oriented self-growth of amorphous minerals

Chaobo Feng, Bing Qiang Lu, Yunshan Fan, Haijian Ni, Yunfei Zhao, Shuo Tan, Zhi Zhou, Lijia Liu, Jordan A. Hachtel, Demie Kepaptsoglou, Baohu Wu, Denis Gebauer, Shisheng He, Feng Chen

electron Microscopy and Microanalysis

Research output: Contribution to journal › Article › peer-review

5 Scopus citations

Abstract

Amorphous inorganic solids are traditionally isotropic, thus, it is believed that they only grow in a non-preferential way without the assistance of regulators, leading to the morphologies of nanospheres or irregular aggregates of nanoparticles. However, in the presence of (ortho)phosphate (Pi) and pyrophosphate ions (PPi) which have synergistic roles in biomineralization, the highly elongated amorphous nanowires (denoted ACPPNs) form in a regulator-free aqueous solution (without templates, additives, organics, etc). Based on thorough characterization and tracking of the formation process (e.g., Cryo-TEM, spherical aberration correction high resolution TEM, solid state NMR, high energy resolution monochromated STEM-EELS), the microstructure and its preferential growth behavior are elucidated. In ACPPNs, amorphous calcium orthophosphate and amorphous calcium pyrophosphate are distributed at separated but close sites. The ACPPNs grow via either the preferential attachment of ∼2 nm nanoclusters in a 1-dimension way, or the transformation of bigger nanoparticles, indicating an inherent driving force-governed process. We propose that the anisotropy of ACPPNs microstructure, which is corroborated experimentally, causes their oriented growth. This study proves that, unlike the conventional view, amorphous minerals can form via oriented growth without external regulation, demonstrating a novel insight into the structures and growth behaviors of amorphous minerals.

Original language	English
Pages (from-to)	960-970
Number of pages	11
Journal	Journal of Colloid and Interface Science
Volume	657
DOIs	https://doi.org/10.1016/j.jcis.2023.12.002
State	Published - Mar 2024

Funding

We thank Dr. Ruijuan Qi, Dr. Yanping Sui, and Dr. Chunlei Zhang for helping with TEM characterizations. EELS measurements were conducted at the Center for Nanophase Materials Sciences (CNMS), which is a DOE Office of Science User Facility using instrumentation within ORNL's Materials Characterization Core provided by UT-Battelle, LLC, under Contract No. DE-AC05-00OR22725 with the DOE and sponsored by the Laboratory Directed Research and Development Program of Oak Ridge National Laboratory, managed by UT-Battelle, LLC, for the U.S. Department of Energy. Solid state NMR was conducted by Dr. Ming Shen and supported by the Open Project of Shanghai Key Laboratory of Magnetic Resonance in East China Normal University ( SKMR2023A02 ). We also thank the China Scholarship Council for the support during Chaobo Feng's visit to Leibniz University Hannover ( 202206260260 ). This work was supported by the National Natural Science Foundation of China (Nos. 31771081 , 52272304 , 82372442 ), the Science and Technology Commission of Shanghai Municipality (Nos. 21ZR1449700 and 19441901900 ), and the SuperSTEM is the UK national facility for Advanced Electron Microscopy Funded by EPSRC ( EP/W021080/1 ).

Keywords

Amorphous inorganic solids
Calcium phosphate
Calcium pyrophosphate
Nanowires
Oriented growth

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10.1016/j.jcis.2023.12.002

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Feng, C., Lu, B. Q., Fan, Y., Ni, H., Zhao, Y., Tan, S., Zhou, Z., Liu, L., Hachtel, J. A., Kepaptsoglou, D., Wu, B., Gebauer, D., He, S., & Chen, F. (2024). Amorphous 1-D nanowires of calcium phosphate/pyrophosphate: A demonstration of oriented self-growth of amorphous minerals. Journal of Colloid and Interface Science, 657, 960-970. https://doi.org/10.1016/j.jcis.2023.12.002

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abstract = "Amorphous inorganic solids are traditionally isotropic, thus, it is believed that they only grow in a non-preferential way without the assistance of regulators, leading to the morphologies of nanospheres or irregular aggregates of nanoparticles. However, in the presence of (ortho)phosphate (Pi) and pyrophosphate ions (PPi) which have synergistic roles in biomineralization, the highly elongated amorphous nanowires (denoted ACPPNs) form in a regulator-free aqueous solution (without templates, additives, organics, etc). Based on thorough characterization and tracking of the formation process (e.g., Cryo-TEM, spherical aberration correction high resolution TEM, solid state NMR, high energy resolution monochromated STEM-EELS), the microstructure and its preferential growth behavior are elucidated. In ACPPNs, amorphous calcium orthophosphate and amorphous calcium pyrophosphate are distributed at separated but close sites. The ACPPNs grow via either the preferential attachment of ∼2 nm nanoclusters in a 1-dimension way, or the transformation of bigger nanoparticles, indicating an inherent driving force-governed process. We propose that the anisotropy of ACPPNs microstructure, which is corroborated experimentally, causes their oriented growth. This study proves that, unlike the conventional view, amorphous minerals can form via oriented growth without external regulation, demonstrating a novel insight into the structures and growth behaviors of amorphous minerals.",

keywords = "Amorphous inorganic solids, Calcium phosphate, Calcium pyrophosphate, Nanowires, Oriented growth",

author = "Chaobo Feng and Lu, {Bing Qiang} and Yunshan Fan and Haijian Ni and Yunfei Zhao and Shuo Tan and Zhi Zhou and Lijia Liu and Hachtel, {Jordan A.} and Demie Kepaptsoglou and Baohu Wu and Denis Gebauer and Shisheng He and Feng Chen",

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doi = "10.1016/j.jcis.2023.12.002",

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T2 - A demonstration of oriented self-growth of amorphous minerals

AU - Feng, Chaobo

AU - Lu, Bing Qiang

AU - Fan, Yunshan

AU - Ni, Haijian

AU - Zhao, Yunfei

AU - Tan, Shuo

AU - Zhou, Zhi

AU - Liu, Lijia

AU - Hachtel, Jordan A.

AU - Kepaptsoglou, Demie

AU - Wu, Baohu

AU - Gebauer, Denis

AU - He, Shisheng

AU - Chen, Feng

PY - 2024/3

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AB - Amorphous inorganic solids are traditionally isotropic, thus, it is believed that they only grow in a non-preferential way without the assistance of regulators, leading to the morphologies of nanospheres or irregular aggregates of nanoparticles. However, in the presence of (ortho)phosphate (Pi) and pyrophosphate ions (PPi) which have synergistic roles in biomineralization, the highly elongated amorphous nanowires (denoted ACPPNs) form in a regulator-free aqueous solution (without templates, additives, organics, etc). Based on thorough characterization and tracking of the formation process (e.g., Cryo-TEM, spherical aberration correction high resolution TEM, solid state NMR, high energy resolution monochromated STEM-EELS), the microstructure and its preferential growth behavior are elucidated. In ACPPNs, amorphous calcium orthophosphate and amorphous calcium pyrophosphate are distributed at separated but close sites. The ACPPNs grow via either the preferential attachment of ∼2 nm nanoclusters in a 1-dimension way, or the transformation of bigger nanoparticles, indicating an inherent driving force-governed process. We propose that the anisotropy of ACPPNs microstructure, which is corroborated experimentally, causes their oriented growth. This study proves that, unlike the conventional view, amorphous minerals can form via oriented growth without external regulation, demonstrating a novel insight into the structures and growth behaviors of amorphous minerals.

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ER -

Amorphous 1-D nanowires of calcium phosphate/pyrophosphate: A demonstration of oriented self-growth of amorphous minerals

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