Insights into Paraben Adsorption by Metal-Organic Frameworks for Analytical Applications.

Metal-organic frameworks (MOFs) are attractive materials used as sorbents in analytical microextraction applications for contaminants of emerging concern (CECs) from environmental liquid matrices. The demanding specs for a sorbent in the analytical application can be comprehensively studied by considering the interactions of the target analytes with the frameworks by the use of single-crystal X-ray diffraction, computational analysis, and adsorption studies, including the kinetic ones. The current study intends a better understanding of the interactions of target CECs (particularly, propylparaben (PPB) as a model) and three Zn-based layered pillared MOFs: [Zn(tz)(bdc)] (Htz = 1,2,4-triazole and Hbdc = 1,4-benzenedicarboxylic acid) and their amino derivatives [Zn(NH-tz)(bdc)] and [Zn(tz)(NH-bdc)] (NH-Htz = 3-amino-1,2,4-triazole and NH-Hbdc = 2-amino-1,4-benzenedicarboxylic acid).

Using Design of Experiments to Optimize a Screening Analytical Methodology Based on Solid-Phase Microextraction/Gas Chromatography for the Determination of Volatile Methylsiloxanes in Water.

Volatile methylsiloxanes (VMSs) constitute a group of compounds used in a great variety of products, particularly personal care products. Due to their massive use, they are continually discharged into wastewater treatment plants and are increasingly being detected in wastewater and in the environment at low concentrations. The aim of this work was to develop and validate a fast and reliable methodology to screen seven VMSs in water samples, by headspace solid-phase microextraction (HS-SPME) followed by gas chromatography with flame ionization detection (GC-FID).

Headspace solid-phase microextraction based on the metal-organic framework CIM-80(Al) coating to determine volatile methylsiloxanes and musk fragrances in water samples using gas chromatography and mass spectrometry.

A headspace solid-phase microextraction (HS-SPME) method was developed using the metal-organic framework (MOF) CIM-80(Al) as extraction phase and in combination with gas chromatography-mass spectrometry (GC-MS) for the simultaneous determination of 6 methylsiloxanes and 7 musk fragrances in different environmental waters. The chromatographic separation was optimized in different GC instruments equipped with different detectors, allowing the correct separation and identification of the compounds. The HS-SPME method was optimized using a Box-Behnken experimental design, while the validation was carried out together with the most suitable commercial fiber (divinylbenzene/polydimethylsiloxane) for comparison purposes.

Application of a Pillared-Layer Zn-Triazolate Metal-Organic Framework in the Dispersive Miniaturized Solid-Phase Extraction of Personal Care Products from Wastewater Samples.

The pillared-layer Zn-triazolate metal-organic framework (CIM-81) was synthesized, characterized, and used for the first time as a sorbent in a dispersive micro-solid phase extraction method. The method involves the determination of a variety of personal care products in wastewaters, including four preservatives, four UV-filters, and one disinfectant, in combination with ultra-high performance liquid chromatography and UV detection. The CIM-81 MOF, constructed with an interesting mixed-ligand synthetic strategy, demonstrated a better extraction performance than other widely used MOFs in D-µSPE such as UiO-66, HKUST-1, and MIL-53(Al).

Monitoring trihalomethanes and nitrogenous disinfection by-products in blending desalinated waters using solid-phase microextraction and gas chromatography.

A simple and efficient method has been developed for the extraction and determination of 16 common volatile halogenated disinfection by-products (DBPs) (four trihalomethanes, six haloacetonitriles, and six halonitromethanes) in blending desalinated waters, using headspace solid-phase microextraction and gas chromatography with flame ionization detector (HS-SPME/GC-FID). After the optimization using factorial designs of the HS-SPME parameters (optimum: carboxen/polydimethylsiloxane such as fiber, extraction time of 60 min at 30°C, pH 7, addition of 40% (w/v) of sodium chloride, and desorption time of 2 min at 250°C), quantification limits ranged from 3.03 to 40.