[논문]비정질 칼슘 포스페이트 나노 입자의 합성과 특성

한지훈; 정성욱

doi:10.14478/ace.2018.1089

비정질 칼슘 포스페이트 나노 입자의 합성과 특성
Synthesis and Characterization of Amorphous Calcium Phosphate Nanoparticles 원문보기

공업화학 = Applied chemistry for engineering, v.29 no.6, 2018년, pp.740 - 745

한지훈 (부산대학교 화학공학.고분자공학과) , 정성욱 (부산대학교 화공생명.환경공학부)

초록
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본 연구에서는 비정질 칼슘 포스페이트(ACP) 나노 입자의 합성과 특성 분석을 진행하였다. 염화칼슘(calcium chloride ($CaCl_2$))과 아데노신 인산나트륨(disodium adenosine triphosphate ($Na_2ATP$)) 그리고 피트산 나트륨(sodium phytate) 첨가제를 열수 반응을 통해 상대적으로 단분산된 100 nm 크기 이하의 ACP 나노 입자를 성공적으로 합성하였고 나노 입자의 화학적 조성과 구조를 재료 분석을 통해 확인하였다. 피트산 나트륨 첨가제의 사용을 통해 얻은 ACP 나노 입자는 비정질성을 유지하고 결정성 하이드록시아파타이트(HAP)로의 전환을 방지하는 안정성이 향상되었음을 발견하였다. 본 연구를 통해 발견된 향상된 안정성을 가지는 ACP 나노 입자는 재생 의학 분야에서의 생체 적합 물질로의 응용에 중요한 잠재적 용도가 있을 것이라 사료된다.

Abstract ▼ AI-Helper

The synthesis and characterization of amorphous calcium phosphate (ACP) nanoparticles were reported in this work. We show that relatively monodisperse ACP nanoparticles with a size of sub-100 nm can be prepared by a hydrothermal reaction of calcium chloride ($CaCl_2$) and disodium adenosine triphosphate ($Na_2ATP$) in the presence of sodium phytate as an additive. Their compositions and structures were confirmed using a series of material characterization techniques. Our results exhibit that ACP nanoparticles synthesized using sodium phytate enhanced the stability of maintaining their amorphous nature and prevented from a conversion to crystalline hydroxyapatite (HAP). ACP nanoparticles with the improved stability have potential uses in biomaterial applications in regenerative medicine.

주제어

표/그림 (5)

그림 Figure 1. Schematic illustration of the preparation of amorphous calcium phosphate (ACP) nanoparticles via a hydrothermal method.
그림 Figure 2. FESEM images of as-synthesized ACP nanoparticles. (A) ACP nanoparticles synthesized in the presence of MgCl₂. Inset is a higher magnification FESEM image. (B) ACP nanoparticles synthesized in the presence of sodium phytate. (C) Crystalline hydroxyapatite (HAP) nanorods that were transformed from ACP nanoparticles synthesized with no additives after a short induction period. Inset is a higher magnification FESEM image.
그림 Figure 3. FESEM images and their corresponding EDS spectra of as-synthesized ACP nanoparticles. (A) ACP nanoparticles synthesized with no additives. (B) ACP nanoparticles synthesized in the presence of MgCl₂.
$Figure 4. X-ray powder diffraction (XRD) patterns of ACP nanoparticles and HAP nanorods. Blue curve (ACP1) exhibits the XRD pattern of the ACP nanoparticles synthesized in the presence of MgCl<sub>2</sub> (blue curve). Red curve (ACP<sup>2</sup>) shows the XRD pattern of the ACP particles synthesized in the presence of sodium phytate. Green curve (HAP) corresponding to the XRD pattern of HAP nanorods shows their characteristic peaks (denoted with asterisk marks) that are assigned based on JCPDS No. 09-0432 (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article).$ 그림 Figure 4. X-ray powder diffraction (XRD) patterns of ACP nanoparticles and HAP nanorods. Blue curve (ACP1) exhibits the XRD pattern of the ACP nanoparticles synthesized in the presence of MgCl₂ (blue curve). Red curve (ACP²) shows the XRD pattern of the ACP particles synthesized in the presence of sodium phytate. Green curve (HAP) corresponding to the XRD pattern of HAP nanorods shows their characteristic peaks (denoted with asterisk marks) that are assigned based on JCPDS No. 09-0432 (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article).
그림 Figure 5. FT-IR spectra of as-synthesized ACP nanoparticles and HAP nanorods. Black curve corresponds to FT-IR of Na₂ATP. Red (ACP¹) and blue (ACP²) curves correspond to the spectra from the as-synthesized ACP nanoparticles in the presence of MgCl₂ and sodium phytate, respectively. Green (HAP) curve corresponds to HAP nanorods that were transformed from ACP nanoparticles synthesized with no additive. The positions of characteristic ν₃ and ν₄ vibrations of PO₄^3- groups were embodied with the arrows in each spectrum (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article).

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제안 방법

The morphologies of ACP nanoparticles and HAP nanorods were investigated by field emission scanning electron microscopy (FESEM) (Zeiss Supra 40 FESEM) with an accelerating voltage ranged from 5 to 10 kV. Energy dispersive X-ray spectroscopy (EDS) was performed using Zeiss Supra 40 FESEM equipped with an Oxford X-ray energy dispersive spectrometer for elemental analysis. Transmission electron microscopy (TEM) of ACP nanoparticles and HAP nanorods was performed on a Hitachi H-7600 microscope operating at 80 kV.
By incorporating the additives such as MgCl₂ and sodium phytate in the aqueous mixture during the hydrothermal reaction, we were able to produce large ACP nanoparticles with ~500 nm diameter in the presence of Mg²⁺ ions from MgCl₂ and small with ~100 nm in the presence of sodium phytate with fairly narrow size distributions. The structure, morphology, and composition of the ACP nanoparticles were thoroughly characterized using FESEM and EDS measurements. Their amorphous structure was confirmed by FT-IR and XRD measurements.

이론/모형

6 kW power (40 kV, 30 mA). Fourier transform infrared spectroscopy (FT-IR) was performed by using a Spectrum GX FT-IR spectrometer with both KBr pellet and attenuated total reflection (ATR) techniques. The morphologies of ACP nanoparticles and HAP nanorods were investigated by field emission scanning electron microscopy (FESEM) (Zeiss Supra 40 FESEM) with an accelerating voltage ranged from 5 to 10 kV.

성능/효과

Our results implied that the as-synthesized nanoparticles indeed had ACP phase confirmed by the existence of the broad peak at 2θ = ~30°[18] and the overall broad shape of the patterns were clearly distinguished from XRD patterns of HAP nanorods.

후속연구

The differences in the stability of the ACP nanoparticles synthesized with or without the additives such as MgCl₂ and sodium phytate were likely in qualitative agreement with expectations based on their potential role of lowering of surface energy via passivation of the surface of ACP nanoparticles. Additional studies of characterizing the surfaces of stabilized ACP nanoparticles would be required to uncover the mechanistic role of sodium phytate as a stabilizing ligand in the near future. In summary, our results provide a facile means of producing ACP nanoparticles of relatively narrow size distributions via a hydrothermal method and improving their stability of preserving the amorphous phase by using sodium phytate.

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