A Zr-MOF@GO-Coated Fiber with High Specific Surface Areas for Efficient, Green, Long-Life Solid-Phase Microextraction of

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A Zr‑MOF@GO‑Coated Fiber with High Specific Surface Areas for Efficient, Green, Long‑Life Solid‑Phase Microextraction of Nonsteroidal Anti‑inflammatory Drugs in Water Hongmei Liu1   · Hua Fan1 · Shihao Dang1 · Mingdeng Li1 · Gu A1 · Hui Yu2 Received: 31 January 2020 / Revised: 22 June 2020 / Accepted: 25 June 2020 © Springer-Verlag GmbH Germany, part of Springer Nature 2020

Abstract A composite material featuring a zirconium-based metal–organic framework and graphene oxide (Zr-MOF@GO) was synthesized by a hydrothermal method and bonded to a stainless steel wire with an inorganic binder as a solid-phase microextraction (SPME) fiber for the derivatization-free extraction and analysis of nonsteroidal anti-inflammatory drugs (NSAIDs) coupled with gas chromatography (GC). The force between the Zr-MOF@GO and NSAIDs includes coordination action, H-bonding, and π–πconjugation effect, which results in the better extraction performance than a commercial polyamide fiber. The developed method achieved low detection limits (0.001–0.030 µg L−1, S/N = 3) and wide linear range (0.01–500 µg L−1) with good linearity (R ≥ 0.9970). The fiber coating had a high scratch resistance, which could effectively prevent coating wear and failure due to the friction between the fiber and the casing. Combined with the high thermal and chemical stability, the loss-free service life of the coating reached at least 240 extractions. Particularly, the derivatization-free extraction technique can greatly reduce the extraction time and use of organic solvents, thus maximizing the SPME technology advantages. It is evident that the analysis method is simple, environmentally friendly, and fast for detecting NSAIDs in water with high efficiency and long service life. Keywords  Solid-phase microextraction · Metal–organic frameworks · Graphene oxide · Nonsteroidal anti-inflammatory drugs · Efficient extraction · Derivatization-free extraction

Introduction Nonsteroidal anti-inflammatory drugs (NSAIDs), as an acidic compound with pKa values between 3.5 and 4.91, are one of the most frequently used pharmaceutical compounds in human and veterinary medicine for treating inflammation and pain [1]. However, excessive use of NSAIDs by humans can cause adverse health effects, such as gastrointestinal disorders and the inhibition of platelet aggregation Electronic supplementary material  The online version of this article (https​://doi.org/10.1007/s1033​7-020-03930​-y) contains supplementary material, which is available to authorized users. * Hongmei Liu [email protected] 1



School of Chemical and Biological Engineering, Lanzhou Jiaotong University, Lanzhou 730000, China



Jimo Comprehensive Inspection and Testing Center, Qingdao 266260, Shandong, China

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[2]. At the same time, drugs excreted by humans could also enter the environmental water and re-enter humans and animals through drinking water. Although the concentration of the drugs in water is very low, studies have shown that it may be potentially harmful, resulting in severe drug resistan