School of Chemistry and Environmental Engineering, Hubei Key Laboratory of Novel Reactor and Green Chemical Technology, Key Laboratory for Green Chemical Process of Ministry of Education, Wuhan Institute of Technology, Wuhan, 430205, China.
School of Chemical Engineering and Pharmacy, Hubei Key Laboratory of Novel Reactor and Green Chemical Technology, Key Laboratory for Green Chemical Process of Ministry of Education, Wuhan Institute of Technology, Wuhan, 430205, China.
Anal Chim Acta. 2022 May 8;1206:339772. doi: 10.1016/j.aca.2022.339772. Epub 2022 Mar 26.
In this study, a novel core-shell structured magnetic metal-organic framework nanospheres (FeO@PD@BA-Zr-MOF) were fabricated by in-situ growth of boronic acid-decorated porphyrin-based metal-organic frameworks on polydopamine (PD) functionalized FeO nanospheres for highly efficient enrichment of cis-diol containing nucleosides by magnetic solid phase extraction (MSPE). PD as a molecular linker promotes the nucleation and crystal growth of boronic acid-decorated porphyrin-based metal-organic framework (BA-Zr-MOF), which was synthesized via a dual-ligand strategy by using Zr as a metal unit as well as meso-tetra (4-carboxylphenyl) porphyrin (TCPP) and 1, 4-phenylenebisboronic acid (BA) as dual organic ligands. It is worth noting that the nitrogen-rich skeleton of TCPP and abundant boric acid groups in MOF allows for effective and selective enrichment of cis-diol containing compounds by hydrophilic interaction and boron affinity. Also, Zr well assembled into the MOF is beneficial to extraction via metal oxide affinity interaction due to reversible covalent complex formation/dissociation between Zr and cis-diol compounds. The morphology, structure and saturation magnetization of FeO@PD@BA-Zr-MOF were systematically characterized. The as-prepared adsorbent coupled with high performance liquid chromatography was used for analysis of four nucleosides including cytidine, uridine, guanosine, and adenosine in urine sample with the detection limits in range of 0.002-0.005 μg mL and the quantitative limits in range of 0.008-0.018 μg mL. The as-fabricated FeO@PD@BA-Zr-MOF nanospheres shows high selectivity, low detection limit, excellent reusability and reproducibility for nucleosides enrichment. The large specific surface area and quick magnetic response performance endow the affinity magnetic nanospheres with outstanding enrichment capability for rapid extraction. The adsorbent of FeO@PD@BA-Zr-MOF nanospheres has great potential for identification and analysis of trace cis-diol containing nucleosides in biological samples.
在这项研究中，通过在聚多巴胺 (PD) 功能化的 FeO 纳米球上原位生长硼酸修饰的卟啉基金属有机骨架，制备了一种新型核壳结构的磁性金属有机骨架纳米球 (FeO@PD@BA-Zr-MOF)，用于通过磁性固相萃取 (MSPE) 高效富集顺式二醇含核苷。PD 作为分子连接剂促进了硼酸修饰的卟啉基金属有机骨架 (BA-Zr-MOF) 的成核和晶体生长，该骨架是通过双配体策略合成的，使用 Zr 作为金属单元，以及间四 (4-羧基苯基) 卟啉 (TCPP) 和 1,4-苯二硼酸 (BA) 作为双有机配体。值得注意的是，TCPP 的富氮骨架和 MOF 中的丰富硼酸基团允许通过亲水性相互作用和硼酸亲和力有效地和选择性地富集顺式二醇化合物。此外，Zr 很好地组装到 MOF 中有利于通过金属氧化物亲和力相互作用进行提取，因为 Zr 和顺式二醇化合物之间存在可逆的共价络合形成/解离。系统地表征了 FeO@PD@BA-Zr-MOF 的形态、结构和饱和磁化强度。所制备的吸附剂与高效液相色谱法相结合，用于分析尿液样品中的四种核苷，包括胞苷、尿苷、鸟苷和腺苷，检测限在 0.002-0.005μg mL 范围内，定量限在 0.008-0.018μg mL 范围内。所制备的 FeO@PD@BA-Zr-MOF 纳米球具有高选择性、低检测限、优异的可重复使用性和再生性，用于核苷的富集。大的比表面积和快速的磁响应性能使亲和磁性纳米球具有快速提取的出色富集能力。FeO@PD@BA-Zr-MOF 纳米球的吸附剂在生物样品中痕量顺式二醇含核苷的鉴定和分析方面具有很大的潜力。
