An electrochemically fabricated ZIF-67/[HOEMIM]BF4 coating for the solid-phase microextraction and detection of polycyclic aromatic hydrocarbons.

Coatings are considered to play a crucial role in solid-phase microextraction (SPME). In this work, a novel coating named ZIF-67/[HOEMIM]BF4 was fabricated through in situ potentiostatic electrodeposition in methanol solutions containing ZIF-67 precursors and 1-(2'-hydroxyethyl)-3-methylimidazolium tetrafluoroborate ([HOEMIM]BF4). Compared with the traditional solvothermal method, this method reduced the synthesis time and enabled ZIF-67 to grow directly on the surface of stainless-steel wire, effectively simplifying the preparation process and improving the coating reproducibility. Owing to the inherent characteristics such as high porosity and high thermal and mechanical stability, and the impressive morphological regulation and extraction function of [HOEMIM]BF4, the developed coating exhibited a prolonged service life and a better extraction capacity for trace polycyclic aromatic hydrocarbons (PAHs) compared to single ZIF-67 and commercial fibers. Under the optimal conditions, the linear range of the ZIF-67/[HOEMIM]BF4-based SPME-GC method was 0.01-500 µg L-1, and the detection limit was 0.27-5.2 ng L-1. When applied in the determination of PAHs in a real water sample, recoveries between 85.6-117.3% were obtained, indicating the potential of ZIF-67/[HOEMIM]BF4 in the high efficiency SPME and GC analysis of PAHs.

A New Approach Utilizing Aza-Michael Addition for Hydrolysis-Resistance Non-Ionic Waterborne Polyester.

This work first synthesized a series of linear polyesters by step-growth polycondensation, then an amino-terminated hydrophilic polyether was grafted to the polyester as side-chains through aza-Michael addition to prepare a self-dispersible, non-ionic waterborne comb-like polyester (NWCPE). In contrast to traditional functionalization methods that usually require harsh reaction conditions and complex catalysts, the aza-Michael addition proceeds efficiently at room temperature without a catalyst. In this facile and mild way, the NWCPE samples with number-average molecular weight (Mn) of about 8000 g mol-1 were obtained. All dispersions showed excellent storage stability, reflected by no delamination observed after 6 months of storage. The NWCPE dispersion displayed better hydrolysis resistance than an ionic waterborne polyester, as was indicated by a more slight change in pH value and Mn after a period of storage. In addition, the film obtained after the NWCPE dispersion was cross-linked with the curing agent, it exhibited good water resistance, adhesion, and mechanical properties.