TY - JOUR
T1 - Preparation of calcium phosphate nanoparticles hybridized with europium(III) complex for novel luminescent organic-inorganic systems
AU - Kataoka, Takuya
AU - Shinozaki, Kenji
AU - Abe, Shigeaki
AU - Tagaya, Motohiro
N1 - Funding Information:
This study was supported by a grant from the Japan Society for the Promotion of Science KAKENHI (Grant-in-Aid for Young Scientists (A), Grant No. 17H04954 , and Challenging Research (Exploratory) , Grant No. 17K19027 ). The authors thank Analysis and Instrumentation Center in Nagaoka University of Technology for providing the analytical facilities.
Publisher Copyright:
© 2018 Elsevier Ltd
PY - 2018/11
Y1 - 2018/11
N2 - We have synthesized novel inorganic–organic hybrid systems based on the interactions between calcium phosphate (CP) and tris(2,2,6,6-tetramethyl-3,5-heptanedionato)europium (III) (EuTH) complex to clarify the states of the EuTH molecules. We achieved the nucleation and crystal growth of electronically localized of EuTH molecules using two different synthetic processes (based on the timing of the addition EuTH before and after the CP nucleation stage). The coordination environment of the Eu3+ ion inside/on the hybrids was clearly changed, having the higher spatial symmetry states in the hybrid. The aspect ratios of the hybrid crystallites were 2.5–6.0, suggesting that the EuTH molecules selectively interacted with the a–plane of the CP nuclei to induce preferential crystal growth along with the uncovered c–plane. The segregated EuTH molecules on CP surfaces suppressed Ca2+ dissolution from the hybrids in phosphate buffer saline. In the excitation spectra of the hybrids, the 7F0 → 5L6 transition appeared as a result of the interaction between the EuTH and phosphate ions, suggesting that the phosphate ions affected the coordination environment. In the luminescence spectra of the hybrids, the luminescence intensity ratio of the magnetic dipole transition (5D0 → 7F1) to electric dipole transition (5D0 → 7F2) were higher than those of EuTH and the other Eu3+-doped inorganic systems. Thus, the higher spatial symmetry states of the Eu3+ ion in the hybrids resulted in greater luminescence intensities and quantum efficiencies, which would be affected by the phosphorus anti-quenching. In the future, CP hybrids with various organic complexes will be prepared, and these could be applied in the biomedical fields such as in bio-imaging and drug delivery systems.
AB - We have synthesized novel inorganic–organic hybrid systems based on the interactions between calcium phosphate (CP) and tris(2,2,6,6-tetramethyl-3,5-heptanedionato)europium (III) (EuTH) complex to clarify the states of the EuTH molecules. We achieved the nucleation and crystal growth of electronically localized of EuTH molecules using two different synthetic processes (based on the timing of the addition EuTH before and after the CP nucleation stage). The coordination environment of the Eu3+ ion inside/on the hybrids was clearly changed, having the higher spatial symmetry states in the hybrid. The aspect ratios of the hybrid crystallites were 2.5–6.0, suggesting that the EuTH molecules selectively interacted with the a–plane of the CP nuclei to induce preferential crystal growth along with the uncovered c–plane. The segregated EuTH molecules on CP surfaces suppressed Ca2+ dissolution from the hybrids in phosphate buffer saline. In the excitation spectra of the hybrids, the 7F0 → 5L6 transition appeared as a result of the interaction between the EuTH and phosphate ions, suggesting that the phosphate ions affected the coordination environment. In the luminescence spectra of the hybrids, the luminescence intensity ratio of the magnetic dipole transition (5D0 → 7F1) to electric dipole transition (5D0 → 7F2) were higher than those of EuTH and the other Eu3+-doped inorganic systems. Thus, the higher spatial symmetry states of the Eu3+ ion in the hybrids resulted in greater luminescence intensities and quantum efficiencies, which would be affected by the phosphorus anti-quenching. In the future, CP hybrids with various organic complexes will be prepared, and these could be applied in the biomedical fields such as in bio-imaging and drug delivery systems.
KW - Calcium phosphate
KW - Europium(III) complex
KW - Luminescent nanomaterials
KW - Organic-inorganic hybrid systems
KW - Photofunctional interfaces
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U2 - 10.1016/j.jpcs.2018.06.031
DO - 10.1016/j.jpcs.2018.06.031
M3 - Article
AN - SCOPUS:85049334505
VL - 122
SP - 218
EP - 226
JO - Journal of Physics and Chemistry of Solids
JF - Journal of Physics and Chemistry of Solids
SN - 0022-3697
ER -