# Supramolecular Materials as Solid-Phase Microextraction Coatings in Environmental Analysis
## 3 Metal-Organic Frameworks
### MOFs as SPME Coatings for Environmental Applications
#### 3.3.5 Extraction of Pharmaceutical and Personal Care Products
Finally, the validated method was applied to quantify the target analytes in wastewater samples collected at different treatment stages from a wastewater treatment plant in Guangzhou, China, obtaining the highest contamination levels in the aeration unit (1.8-85.1 \(\upmu\)g/L) and barscreen (0.7-3.3 ng/L). Regarding the CIM-80(Al)-based coating, it was obtained on APTES-pretreated nitinol wires by in situ growth [78]. The fibers were used for the HS-SPME-GC-MS analysis of six linear and cyclic methylsiloxane and seven musk fragrances as model PCPs. The performance of the MOF-based coating was compared with that achieved by using the commercially available 65 \(\upmu\)m PDMS/DVB-coated fibers: the developed coating provided lower or comparable LOQs for cyclic methylsiloxane compared to the commercial one (in the 0.2-0.7 \(\upmu\)g/L vs. 0.5-0.6 \(\upmu\)g/L range), whereas an opposite behavior was observed for linear methylsiloxane (0.1-0.4 \(\upmu\)g/L vs. 0.05-0.06 \(\upmu\)g/L). As for musk fragrances, LOQs in the 1.2-3.5 \(\upmu\)g/L and 0.1-0.4 \(\upmu\)g/L ranges were obtained for the MOF-based and commercial coating, respectively. However, the CIM-80(Al)-based coating demonstrated slightly better precision, a larger linear range, and reduced cross-contamination compared to the commercial fibers. Finally, the HS-SPME-GC-MS method was applied for the analysis of three seawater and three wastewater samples, detecting cashmeran (15 \(\pm\) 2 and 1.4 \(\pm\) 0.2 \(\upmu\)g/L) and galaxolide (46.9 \(\pm\) 0.2 and 6 \(\pm\) 1 \(\upmu\)g/L) in two out of three wastewater samples, whereas no analyte could be quantified in the analyzed seawater samples. A superhydrophobic amino-functionalized UiO-66(Zr) coating was proposed by [PERSON] et al. for the extraction of semi-volatile UV filters from environmental water samples [79]. The superhydrophobic MOF was synthesized in solvothermal conditions and deposited onto SS wires by means of a neutral silicone sealant. By capping the NH\({}_{2}\)-UiO-66(Zr) MOF with phenylsilane groups, the adsorption of water molecules within the MOF lattice was strongly reduced, thus increasing the enrichment capability of the coating up to six and eight times higher compared to PDMS and unfunctionalized MOFs, respectively. After optimization and validation, the HS-SPME-GC-MS method, characterized by LOQs in the range of 0.7-7.1 ng/L and RSDs \(\leq\) 6%, was applied for the quantitation of UV filters in river and pond water samples, detecting concentration levels in the 40.1-193.7 ng/L and 26.1-250.1 ng/L ranges, respectively. A ZIF-8-based coating was developed for the in-tube (IT)-SPME-HPLC-FLD detection of five model fluoroquinolones in tap water, river water, and wastewater samples [80]. Firstly, a porous monolith was obtained by copolymerization of 4-vinylbenzoic acid with ethylenedimetacrylate in a fused silica capillary. Then, the ZIF-8 MOF was obtained by in situ layer-by-layer deposition using ZnNO\({}_{3}\) and imidazole solutions, allowing both a controlled self-assembly of the MOF and a good column-to-column reproducibility (RSDs \(<\) 10%). The IT extraction allowed for the on-line SPME-HPLC-FLD analysis of the aqueous solutions containing the analytes, obtaining LOQs in the 0.48-1.8 ng/L range and EFs in the 255-296 range. Finally, the reliability of the method was assessed by detecting low concentration levels of flexoracin, enrofloxacin, and sarafloxacin in the investigated samples.