Zairov Rustem, Dovzhenko Alexey, Terekhova Natalia, Kornev Timur, Zhou Ying, Huang Zeai, Tatarinov Dmitry, Nizameeva Guliya, Fayzullin Robert R, Gubaidullin Aidar T, Salikhova Taliya, Enrichi Francesco, Mironov Vladimir F, Mustafina Asiya
Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, 8 Arbuzov Str., 420088 Kazan, Russia.
Institute of Chemistry, Kazan Federal University, Kremlevskaya Str. 18, 420008 Kazan, Russia.
Nanomaterials (Basel). 2023 Jan 21;13(3):438. doi: 10.3390/nano13030438.
The present work demonstrates the optimization of the ligand structure in the series of bis(phosphine oxide) and β-ketophosphine oxide representatives for efficient coordination of Tb and Eu ions with the formation of the complexes exhibiting high Tb- and Eu-centered luminescence. The analysis of the stoichiometry and structure of the lanthanide complexes obtained using the XRD method reveals the great impact of the bridging group nature between two phosphine oxide moieties on the coordination mode of the ligands with Tb and Eu ions. The bridging imido-group facilitates the deprotonation of the imido- bis(phosphine oxide) ligand followed by the formation of tris-complexes. The spectral and PXRD analysis of the separated colloids indicates that the high stability of the tris-complexes provides their safe conversion into polystyrenesulfonate-stabilized colloids using the solvent exchange method. The red Eu-centered luminescence of the tris-complex exhibits the same specificity in the solutions and the colloids. The pronounced luminescent response on the antibiotic ceftriaxone allows for sensing the latter in aqueous solutions with an LOD value equal to 0.974 μM.
本工作展示了双（氧化膦）和β-酮氧化膦系列中配体结构的优化，以实现铽（Tb）和铕（Eu）离子的有效配位，形成具有高Tb和Eu中心发光的配合物。使用X射线衍射（XRD）方法对所得镧系配合物的化学计量和结构进行分析，结果表明两个氧化膦部分之间桥连基团的性质对配体与Tb和Eu离子的配位模式有很大影响。桥连亚氨基基团促进了亚氨基双（氧化膦）配体的去质子化，随后形成三配合物。对分离出的胶体进行光谱和粉末X射线衍射（PXRD）分析表明，三配合物的高稳定性使得它们能够通过溶剂交换法安全地转化为聚苯乙烯磺酸盐稳定的胶体。三配合物以Eu为中心的红色发光在溶液和胶体中表现出相同的特异性。对抗生素头孢曲松有明显的发光响应，能够在水溶液中检测到该抗生素，检测限（LOD）值为0.974 μM。
