Department of Clinical Laboratory, Ningbo No. 2 Hospital, Ningbo, 315010, Zhejiang, China.
Key Laboratory of Health Risk Appraisal for Trace Toxic Chemicals of Zhejiang Province, Ningbo Municipal Center for Disease Control and Prevention, Ningbo, 315010, Zhejiang, China.
Anal Bioanal Chem. 2018 Nov;410(29):7749-7764. doi: 10.1007/s00216-018-1391-1. Epub 2018 Oct 2.
In this paper, a high-affinity graphene oxide-encapsulated magnetic Zr-MOF (GO-Mag@Zr-MOF) was synthesized and characterized by SEM, TEM, and XPS for its morphology, structure, and components. Subsequently, the as-prepared GO-Mag@Zr-MOF was, for the first time, employed as magnetic solid-phase extraction (MSPE) adsorbent for pretreatment and determination of photodynamic therapy (PDT) with the photosensitizers hematoporphyrin (Hp) and hematoporphyrin monomethyl ether (HMME) in human urine samples coupled with ultra-performance liquid chromatography-high resolution mass spectrometry (UPLC-HRMS). The synthesized GO-Mag@Zr-MOF revealed excellent adsorption efficiency for Hp and HMME in urine samples. Under optimal conditions, the spiked recoveries of the developed method were in the range of 89.5-105.6% with RSDs less than 10%. The limits of detection (LODs) were found to be 0.036 and 0.042 μg/L for Hp and HMME, respectively, while limits of quantitation (LOQs) were 0.12 and 0.14 μg/L. The proposed method was found to be rapid, effective, sensitive, and accurate for clinical analysis. Moreover, this paper, for the first time, carefully expounded the mass spectrum cracking mechanisms of Hp and HMME. Graphical abstract ᅟ.
在本文中，合成了一种高亲和力的氧化石墨烯包裹的磁性 Zr-MOF（GO-Mag@Zr-MOF），并通过 SEM、TEM 和 XPS 对其形貌、结构和成分进行了表征。随后，首次将制备的 GO-Mag@Zr-MOF 用作磁性固相萃取（MSPE）吸附剂，用于预处理和测定人尿液样品中的光动力疗法（PDT），所用光敏剂为血卟啉（Hp）和血卟啉单甲醚（HMME），并结合超高效液相色谱-高分辨质谱（UPLC-HRMS）进行分析。合成的 GO-Mag@Zr-MOF 对尿液样品中的 Hp 和 HMME 表现出优异的吸附效率。在最佳条件下，该方法的加标回收率在 89.5-105.6%范围内，相对标准偏差（RSD）小于 10%。Hp 和 HMME 的检出限（LODs）分别为 0.036 和 0.042μg/L，定量限（LOQs）分别为 0.12 和 0.14μg/L。该方法快速、有效、灵敏、准确，适用于临床分析。此外，本文首次详细阐述了 Hp 和 HMME 的质谱裂解机制。
