High-affinity graphene oxide-encapsulated magnetic Zr-MOF for pretreatment and rapid determination of the photosensitizers hematoporphyrin and hematoporphyrin monomethyl ether in human urine prior to UPLC-HRMS

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 0.042g/L for Hp and HMME, respectively, while limits of quantitation (LOQs) were 0.12 and 0.14g/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.