Department of Chemistry, Faculty of Science, Ferdowsi University of Mashhad, Mashhad 9177948974, Iran.
Institute of Inorganic Chemistry I, Ulm University, Albert-Einstein-Allee 11, 89081 Ulm, Germany.
Inorg Chem. 2021 Feb 1;60(3):1472-1479. doi: 10.1021/acs.inorgchem.0c02769. Epub 2021 Jan 12.
The linkage of molecular components into functional heterogeneous framework materials has revolutionized modern materials chemistry. Here, we use this principle to design polyoxometalate-based frameworks as high affinity adsorbents for drugs of abuse, leading to their application in solid-phase extraction analysis. The frameworks are assembled by the reaction of a Keggin-type polyanion, [SiWO], with lanthanoids Dy(III), La(III), Nd(III), and Sm(III) and the multidentate linking ligand 1,10-phenanthroline-2,9-dicarboxylic acid (HPDA). Their reaction leads to the formation of crystalline 1D coordination polymers. Because of the charge mismatch between the lanthanoids (+3) and the dodecasilicotungstate (-4), we observe incorporation of the PDA ligands into crystalline materials, leading to four polyoxometalate-based frameworks where Keggin-type heteropolyanions are linked by cationic {Ln(PDA)} groups (Ln = Dy (), La (), Nd (), and Sm ()). Structural analysis of the polyoxometalate-based frameworks suggested that they might be suitable for surface binding of common drugs of abuse via supramolecular interactions. To this end, they were used for the extraction and quantitative determination of four model drugs of abuse (amphetamine, methamphetamine, codeine, and morphine) by using micro-solid-phase extraction (D-μSPE) and high-performance liquid chromatography (HPLC). The method showed wide linear ranges, low limits of detection (0.1-0.3 ng mL), high precision, and satisfactory spiked recoveries. Our results demonstrate that polyoxometalate-based frameworks are suitable sorbents in D-μSPE for molecules containing amine functionalities. The modular design of these networks could in the future be used to expand and tune their substrate binding behavior.
将分子组件连接成具有功能异质结构的框架材料已经彻底改变了现代材料化学。在这里，我们利用这一原理设计基于多金属氧酸盐的框架作为滥用药物的高亲和力吸附剂，从而将其应用于固相萃取分析中。这些框架是通过 Keggin 型多阴离子[SiWO]与镧系元素 Dy(III)、La(III)、Nd(III)和 Sm(III)以及多齿连接配体 1,10-邻菲啰啉-2,9-二羧酸（HPDA）的反应组装而成。它们的反应导致形成结晶 1D 配位聚合物。由于镧系元素（+3）与十二硅钨酸盐（-4）之间的电荷不匹配，我们观察到 PDA 配体掺入结晶材料中，从而形成四个基于多金属氧酸盐的框架，其中 Keggin 型杂多阴离子由阳离子{Ln(PDA)}基团（Ln = Dy()、La()、Nd()和 Sm()）连接。基于多金属氧酸盐的框架结构分析表明，它们可能通过超分子相互作用适合于常见滥用药物的表面结合。为此，它们被用于通过微固相萃取（D-μSPE）和高效液相色谱（HPLC）对四种模型药物（安非他命、甲基苯丙胺、可待因和吗啡）的提取和定量测定。该方法显示出宽的线性范围、低的检测限（0.1-0.3ngmL）、高的精密度和令人满意的加标回收率。我们的结果表明，基于多金属氧酸盐的框架是用于含有胺官能团的分子的 D-μSPE 中合适的吸附剂。这些网络的模块化设计将来可用于扩展和调整其基质结合行为。
