Study of Adsorption and Desorption Performances of Zr-Based Metal–Organic Frameworks Using Paper Spray Mass Spectrometry

Abstract

The dynamic pore systems and high surface areas of flexible metal–organic framework materials make them excellent candidates to be used in different kinds of adsorption processes. However, the adsorption and desorption behaviors of therapeutic drugs on metal–organic frameworks in solution are not fully developed. Here, we systematically investigated the adsorption and desorption behaviors of a typical therapeutic drug, verapamil, over several Zr-based metal–organic frameworks [e.g., Zr-FUM, UiO-66(Zr), UiO-66(Zr)-NH2 and UiO-66(Zr)-2COOH] as well as ZrO2 in an acetonitrile solution by using paper spray mass spectrometry. In contrast to other materials, UiO-66(Zr)-2COOH demonstrated a superior adsorption performance to verapamil due to their strong acid-base and/or hydrogen-bond interactions, and the adsorption process fitted well with the pseudo-second-order kinetic model. As verapamil-adsorbed materials were used for desorption experiments, ZrO2 demonstrated the most favorable desorption performance, whereas UiO-66(Zr)-2COOH yielded the poorest desorption capability. These Zr-based materials had also been coated at the surface with filter papers for the analysis of various drugs and proteins in the process of paper spray mass spectrometry. The results demonstrated that among the studied materials, ZrO2-coated paper gave the most favorable desorption performance as a pure drug solution, whereas the paper from UiO-66(Zr) demonstrated the optimal capability in the analyses of therapeutic drugs in a complex matrix (e.g., blood) and a protein (e.g., myoglobin).

Emerging trends in paper spray mass spectrometry: Microsampling, storage, direct analysis, and applications

“…The chosen material is suspended into an aqueous starch solution, sonicated, possibly heated to boiling (Wang et al, ), and then added to the Buchner funnel containing a filter paper. Coating materials of silica particles (Wang et al, ), metal organic frameworks (MOFs) (Wang et al, ; Dhummakupt et al, ), metal oxides (Zheng et al, ,b), and polystyrene (Wang et al, ; Li et al, ) were studied. Silica particles were observed to fill pores and rest on the paper surface, adhered by the starch (Zheng et al, ).…”

“…Zirconium‐ and aluminum‐based MOF were vacuum‐coated onto paper to extract drugs from DBSs (Wang et al, ). Results showed that MOF contributed to a matrix suppression effect and a weaker interaction between analyte and the MOF surface compared to the normal analyte‐paper interaction, increasing the sensitivity of verapamil detection in DBSs 3.5–7.8‐fold.…”

New Efficient Adsorbent Materials for the Removal of Cd(II) from Aqueous Solutions

“…Phosphonate coordination networks are fast gaining an essential position amongst the families of CNs materials. To expand the adsorption capacity of CNs in a quite large range of pH, it is suggested to choose CNs which are stable in water media [5]. Compared with other adsorbent materials, the main advantages of MOFs and CNs in adsorption processes are their large specific surface area, well ordered unique structures, stable and homogeneous pores of specific sizes.…”

On‐substrate derivatization for detection of highly volatile G‐series chemical warfare agents via paper spray mass spectrometry

“…More relevantly, explosives, herbicides from aqueous matrices, pesticides, and CWA simulants from biofluids have been shown to be effectively analyzed via paper spray mass spectrometry (PS‐MS). The spray substrate has been subjected to a multitude of modifications including the addition of metal–organic‐frameworks (MOFs), carbon nanotubes, silica, urea, silanes, molecularly imprinted polymer (MIPs), and wax printing, with each resulting in a specialized system catering to a specific matrix or target chemistry. For example, these innovative modifications have allowed for sub‐parts‐per‐trillion detections of therapeutic drugs .…”