Gao Shengnan, Zhu Jiang, Zhang Yifu, Wang Qiushi, Jing Xuyang, Meng Changgong
School of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029, People's Republic of China.
School of Chemistry, Dalian University of Technology, Dalian 116024, People's Republic of China.
R Soc Open Sci. 2017 Nov 29;4(11):171258. doi: 10.1098/rsos.171258. eCollection 2017 Nov.
Calcein-Ca (II), Zn (II) and Al (III) complexes were successfully intercalated into interlayer surfaces of layered silicate magadiite and fluorescence properties of organic metal-chelates in the confined spaces were investigated. Structures, compositions and morphologies of the intercalated magadiites were adequately studied by tests, including X-ray diffraction, energy-dispersive X-ray spectrometer, elemental mapping, X-ray photoelectron spectroscopy, inductively coupled plasma atomic emission spectroscopy, Fourier-transform infrared spectra, ultraviolet-visible spectroscopy, thermo-gravimetric analysis, differential thermal analysis and scanning electron microscopy. Results confirmed that metal-organic chelate species were immobilized onto the silicate sheets via solid-state interaction. Basal spacings between silicate layers decreased by exchanged metal ions and increased after intercalation of calcein into the interlayer spaces of cation-exchanged magadiites. The encapsulation was obtained by a flexible solid-solid reaction, and the present reaction and products had a potential of application to industrial uses. A speculative mechanism was proposed for reaction by solid-state intercalation. Furthermore, it was found that the complexes in the interlayer space also exhibited special fluorescence properties. The significance of this current work was that it provided a possible route for synthesizing metal-organic complexes that encapsulated in phyllosilicate.
钙黄绿素与钙（II）、锌（II）和铝（III）的配合物成功插层到层状硅酸盐辉沸石的层间表面，并对受限空间内有机金属螯合物的荧光性质进行了研究。通过X射线衍射、能量色散X射线光谱仪、元素映射、X射线光电子能谱、电感耦合等离子体原子发射光谱、傅里叶变换红外光谱、紫外可见光谱、热重分析、差示热分析和扫描电子显微镜等测试手段，对插层辉沸石的结构、组成和形态进行了充分研究。结果证实，金属有机螯合物通过固态相互作用固定在硅酸盐片层上。硅酸盐层间间距因交换的金属离子而减小，在将钙黄绿素插入阳离子交换辉沸石的层间空间后增大。通过柔性固-固反应实现了包封，且当前的反应和产物具有工业应用潜力。提出了一种通过固态插层反应的推测机理。此外，还发现层间空间中的配合物也表现出特殊的荧光性质。当前这项工作的意义在于，它为合成封装在层状硅酸盐中的金属有机配合物提供了一条可能的途径。
