ß-Cyclodextrin/calix[4]arene hybrid porous organic polymer membrane for synergistic extraction of fluorescent whitening agents migrating from food contact materials.

Acurate and sensitive determination of hazards from food contact materials is important to monitor food safety. It is necessary to excavate efficient adsorbent for simultaneous recognition and adsorption of food hazards of trace level for sample preparation. In this work, ß-cyclodextrin and calix[4]arene were employed as hybrid functional monomers to prepare macrocyclic porous organic polymer (ß-CD-CX4 POP). It was proved that the supramolecular cavities of ß-CD-CX4 POP could form inclusion complexes with fluorescent whitening agents (FWAs) through host-guest recognition, which greatly improved the adsorption performance. The hydrophobic cavities of ß-cyclodextrin and calix[4]arene of ß-CD-CX4 POP exhibited synergistic effect for simultaneous recognition of FWAs. The high-throughput enrichment of FWAs was realized by ß-CD-CX4 POP membranes coupled with a multiple-channel syringe pump. Based on membrane-based solid-phase extraction combined with UHPLC-MS/MS, a sensitive analytical method was established to determine six FWAs. The LODs was in range of 3-50 ng/L with the linear range of 0.02-100 µg/L. The developed method was used to quantify FWAs in bread wrapper and bread, and the spiked recoveries ranged from 78.1%-119% with RSD of 2.3%-9.7%. This work indicated that ß-CD-CX4 POP was promising for the simultaneous recognition and adsorption of FWAs migrating from food contact materials.

Primary amide-functionalized cyclotricatechylene covalent organic frameworks membrane for efficient enrichment of melamine and its derivatives in migration solution of food contact materials.

A highly chemically stable primary amide-functionalized cyclotricatechylene covalent organic framework was synthesized by an irreversible reaction and a post-synthetic modification. It possessed a rod-like morphology and exhibited strong solvent stability owing to the polyether bonds. The material showed good adsorption performance for melamine and its derivatives and adsorption mechanism was investigated by molecular simulations. The adsorbent was coated on the nylon-66 membrane to prepare the enrichment membrane. Under optimized conditions, an in-syringe membrane-based extraction method, combined with ultra-high performance liquid chromatography-tandem mass spectrometry was developed for the analysis of melamine and six melamine derivatives in the migration solution. A good linearity was obtained with correlation coefficients ranging from 0.9924 to 0.9995. The limits of detection were 1-200 ng/L and the limits of quantification were 3-500 ng/L. This method was successfully applied to the migration solution of sushi bamboo rolling mats with spiked recoveries of 73.2%-115% and relative standard deviations of 0.9%-9.9%. This work shows a practical and perspective approach for the efficient enrichment of food contact material hazards.

Integrated sample-pretreatment strategy for separation and enrichment of microplastics and primary aromatic amines in the migration of teabag.

In this work, an integrated sample-pretreatment strategy for the separation and enrichment of microplastics and primary aromatic amines from the migration of teabag was developed. The migration solution of teabag was passed through a homemade device. The microplastics were firstly captured by a silver membrane, and then the primary aromatic amines were enriched by a solid-phase extraction column. The microplastics migrated from teabag were detected by attenuated total reflection-Fourier transform infrared spectrometer and Raman spectroscopy. The data showed the character, the number of particles, area ratio, and morphology of microplastics migrated from the teabag. Subsequently, after the enrichment procedure, a sensitive analytical method for primary aromatic amines was established followed by ultra-high performance liquid chromatography-tandem mass spectrometry. The method showed wide linear ranges with R2 greater than 0.9915, low limits of detection (2-18 ng/L), and low limits of quantification (8-50 ng/L). The developed method was adopted to analyze microplastics and primary aromatic amines migrated from nylon and polyethylene terephthalate teabag under different temperatures and times. The integrated sample-pretreatment strategy displayed promising potentials in the one-step preparation of the microplastics and hazardous molecules in the sample of environment and food security.

Hollow tube covalent organic framework for syringe filter-based extraction of ultraviolet stabilizer in food contact materials.

In this work, a novel hollow tube covalent organic framework constructed by cyclotricatechylene and tetrafluoroterephthalonitrile (CTC-TFPN-COF) with polyether bond was synthesized, and it was coated on filter membrane for extraction of ultraviolet stabilizer in migration from food contact materials. Since the monomers of the polymer were linked by polyether bond, the CTC-TFPN-COF exhibited strong chemical stability in severe conditions such as acid, alkali and various organic solvent. The excellent features of high porosity and robust structure endowed the CTC-TFPN-COF good candidate as adsorbent for extraction of ultraviolet stabilizer. Moreover, the CTC-TFPN-COF coated membranes were immobilized on syringe filter and coupled with multiple channel injection pump to realize high throughput sample pretreatment strategy. Subsequently, a sensitive analytical method for ultraviolet stabilizer was established followed by ultra-high performance liquid chromatography-tandem mass spectrometry. The flow rate of extraction and desorption, elution solvent and the volume of desorption solvent were optimized. The method was assessed, which showed wide linear ranges with R2 greater than 0.99, low limits of detection (0.9-91 ng L-1) and low limits of quantification (3-300 ng L-1). The developed method was successfully applied to determine trace ultraviolet stabilizer in the migration of food contact materials with different simulated solution, which demonstrated its promising potential in practical analysis.

Research progress on sample pretreatment methods for migrating substances from food contact materials.

Excessive absorption of migrating substances from food contact materials can affect human health. Thus, it is essential to analyze the migration of contaminant from food contact materials. However, comprehensive analysis has been challenged by low concentration of migrating substances, manifold and complex matrix interference of food contact materials. Therefore, appropriate sample pretreatment methods should be applied before instrumental detection, which is essential to improve the analytical efficiency, sensitivity, and reliability. This paper systematically reviews the development of sample pretreatment methods for analysis of migrating substances from food contact materials in the past decade. To extract volatile and semi-volatile substances, headspace extraction, headspace solid phase microextraction, and purge and trap technique are discussed. For non-volatile substances, solid-liquid extraction and field-assisted extraction are usually used to extract them from food contact materials, while liquid-liquid extraction, solid phase extraction, and their corresponding microextraction techniques play important roles on enrichment process. In addition, new progress in developments of sample pretreatment methods of food contact materials is summarized, covering new devices, specific adsorbents, and sample preparation methods for rapid detection. An outlook of future prospect of sample pretreatment, especially for non-targeted analysis of non-intentionally added substances is briefly discussed.

Study on the Release Potential of BPA and Steroid Estrogens in the Sediments of Erhai Lake, a Typical Plateau Lake of China.

On-site sampling analysis and laboratory-scale experiments were conducted to study the pollution status and release potential of EDCs in Erhai Lake. We found that nitrogen and phosphorus pollution in Erhai Lake sediment were both at a high level, as well as EDCs pollution. The concentrations of BPA, E2α, E1, E2ß, EE2, and E3 were 36.84 ng/g(DW), 13.04 ng/g(DW), 128.97 ng/g(DW), 52.57 ng/g(DW), 18.48 ng/g(DW) and 5.36 ng/g(DW), respectively. The concentrations of E2α, E1, E2ß and EE2 in the bottom water were higher than the surface water due to the impact of sediment release. The results of the 20 days release test indicated that BPA release from the sediment had a greater correlation with the original concentration and the particle size of sediment, while the steroid EDCs had no obvious correlation with these two factors, probably due to the difference in hydrophobicity between them. Under hydraulic disturbance and aerobic conditions, the release process of EDCs was accompanied by a large amount of microbial degradation, and degradation amount > released amount. BPA was released quickly, 9.56% was released in 20 days, but only 3.37% of steroid EDCs released. In comparison, the release process of steroids was longer and posed a greater threat to aquatic ecology.

Thin-layer chromatography combined with surface-enhanced Raman scattering for rapid detection of benzidine and 4-aminobiphenyl in migration from food contact materials based on gold nanoparticle doped metal-organic framework.

In this work, a rapid and sensitive thin-layer chromatography combined with surface-enhanced Raman spectroscopy method was established for rapid detection of benzidine and 4-aminobiphenyl in migration from food contact materials based on Au nanoparticle doped metal-organic framework. Benzidine and 4-aminobiphenyl were firstly separated by thin-layer chromatography to solve the limitation of their overlapping Raman peaks. Then the target molecules were monitored by adding AuNPs/MIL-101(Cr) on the sample spots. Under the optimum conditions, the concentration of benzidine and 4-aminobiphenyl can be quantitatively measured in the range of 2.0-20.0 and1.0-15.0 µg/L, respectively with good linear relationship, and the limits of detection were 0.21 and 0.23 µg/L, respectively. Furthermore, the developed method was applied to analyze benzidine and 4-aminobiphenyl in migration of different food contact materials. The recoveries of benzidine and 4-aminobiphenyl for migration of food contact materials, including paper cups, polypropylene food containers, and polyethylene glycol terephthalate bottles, were 80.6-116.0 and 80.7-118% with relative standard deviations of 1.1-9.1 and 3.1-9.9%, respectively. Surface-enhanced Raman scattering detection was performed conveniently in the on-plate mode without additional elution process. The method shows great potential in rapid monitoring of hazardous substances with overlapping characteristic Raman peaks in food contact materials.