Facile preparation of covalent-organic framework composites for magnetic solid-phase extraction of naphthaleneacetic acid in food prior to HPLC-UV analysis.

Novel magnetic covalent organic frameworks (COFs) were prepared by one-pot synthetic strategy and employed as an efficient adsorbent for magnetic solid-phase extraction (MSPE) of naphthaleneacetic acid (NAA) in food samples. Depending on the predesigned the hydrogen bonding, π-π and hydrophobic interactions of magnetic COFs, the efficient and selective extraction process for NAA was achieved within 15 min. The magnetic COFs adsorbent combined with HPLC-UV was devoted to develop a novel quantitative method for NAA in complex food. The method afforded good coefficient in range of 0.002-10.0 µg mL-1 and low limit of detection was 0.0006 µg mL-1. And the newly established method afforded less adsorbent consumption, wider linearity and lower LODs than the reported analytical methods. Ultimately, the method was successfully applied to determine NAA in fresh pear, tomato and peach juice. The magnetic COFs based MSPE coupled with HPLC-UV method provided a simple, efficient and dependable alternative to monitor trace NAA in food samples.

Amide and carboxyl dual-functionalized magnetic microporous organic networks for efficient extraction of cephalosporins.

Cephalosporins (CEFs) are a class of widely used toxic antibiotics. Development of a rapid and sensitive method for detecting trace CEF residues in food samples is still challenging. Herein, we report preparation of an amide and carboxyl groups dual-functionalized core-shelled magnetic microporous organic network MMON-COOH-2CONH for efficient magnetic solid-phase extraction (MSPE) of CEFs from milk powder samples. Under optimal conditions, the established MMON-COOH-2CONH-MSPE-HPLC-UV method owns wide linear range (3-10000 µg kg-1), low limits of detection (1-3 µg kg-1), large enrichment factors (93.9-99.4), low adsorbent consumption (3 mg), and short extraction time (6 min). Synergistic extraction mechanisms of ionic bonding, hydrogen bonding, π-π, and hydrophobic interactions were elucidated by both theoretical density functional theory calculations and experimental data. This study confirms that preparation of dual-functionalized MMONs and introduction of ionic groups are feasible to promote MMONs application in sample pretreatment.

Construction of an ultra-small hydrazone-linked covalent organic polymer for selective fluorescent detection of ferric ion in aqueous solution.

A novel ultra-small hydrazone-linked covalent organic polymer (UHCOP) was synthesized based on the Schiff-base reaction between 2,4,6-trihydroxy-1,3,5-benzenetricarbaldehyde and 1,4-benzenedicarbohydrazide at room temperature and utilized as a sensitive fluorescent sensor for rapid (<2 min) and selective detection of Fe3+ in aqueous solution. The prepared UHCOP displayed ultra-small size with the diameter of 7.98 ± 0.97 nm and gave a stable fluorescent emission at 510 nm. UHCOP exhibited good sensitivity and highly selectivity towards Fe3+. The coordination interaction between UHCOP and Fe3+ resulted in the obviously aggregation-caused quenching response of UHCOP. The linear range was from 5.0 µM to 1.4 mM (R2 = 0.999) with the detection limit of 2.5 µM. Finally, UHCOP has been successfully applied in the detection of Fe3+ in real water samples, proving the fabricated UHCOP is promising as a sensitive fluorescent sensor for selective detection of Fe3+ in aqueous solution.

Fabrication of magnetic covalent organic framework for effective and selective solid-phase extraction of propylparaben from food samples.

Efficient magnetic solid phase extraction using crystalline porous polymers can find important applications in food safety. Herein, the core-shell Fe3O4@COFs nanospheres were synthesized by one-pot method and characterized in detail. The porous COF shell with large surface area had fast and selective adsorption for propylparaben via π-π, hydrogen bonding and hydrophobic interactions. The extraction and desorption parameters were evaluated in detail. Under the optimized conditions, the extraction equilibrium was reached only in 5 min, the maximum adsorption capacity for propylparaben was 500 mg g-1 and the proposed Fe3O4@DhaTab-based-MSPE-HPLC-UV method afforded good linearity (4-20000 µg mL-1) with R2 (0.997), low limits of detection (0.55 µg L-1) and limits of quantification (1.5 µg L-1). Furthermore, the developed method was applied to determine propylparaben in soft drinks with the recoveries (97.0-98.3%) and relative standard deviations (0.61 to 3.75%). These results revealed the potential of Fe3O4@DhaTab as efficient adsorbents for parabens in food samples.

Cationic Surfactant-Modified Covalent Organic Frameworks for Nitrate Removal from Aqueous Solution: Synthesis by Free-Radical Polymerization.

Development of efficient adsorbents for nitrate removal is vital for tackling increasing nitrate contamination. We report a free-radical polymerization strategy to prepare a cationic surfactant-modified covalent organic framework (DhaTab-S) for removing nitrate ions from aqueous solution. DhaTab-S was prepared by grafting a cationic surfactant diallyldimethylammonium chloride solution on vinyl-containing COF (DhaTab-V). The adsorption capacity for nitrate was pH-dependent with the maximum at pH 6, and the adsorption process was largely influenced by ionic strength. The adsorption equilibrium for nitrate on DhaTab-S was reached within 40 minutes and followed pseudo-second-order kinetics. DhaTab-S showed a nitrate adsorption capacity of 108.8 mg g-1 , which is about 15 times that of COF before surfactant modification. The large adsorption capacity makes DhaTab-S a promising candidate for nitrate removal from aqueous media.

Thiol-Ene Click Synthesis of Phenylboronic Acid-Functionalized Covalent Organic Framework for Selective Catechol Removal from Aqueous Medium.

We report a thiol-ene click strategy for the preparation of a novel phenylboronic acid-functionalized covalent organic framework (COF) for selective removal of catechol in aqueous solution. Vinyl-functionalized 2,5-diallyloxyterephthalaldehyde (Da-V) was prepared as a building ligand. Da-V was then condensed with 1,3,5-tris(4-aminophenyl)benzene (Tab) to give a vinyl-functionalized COF DhaTab-V. Subsequently, 4-mercaptophenylboronic acid (4-MPBA) was covalently linked on DhaTab-V via thiol-ene click reaction to give phenylboronic acid-functionalized COF DhaTab-PBA. The adsorption isotherms, energetics and kinetics, and reusability of DhaTab-PBA for the adsorption and removal of catechol from aqueous solution were investigated in detail. This phenylboronic acid-functionalized COF is promising as sorbent for selective removal of catechol from aqueous medium with large adsorption capacity and good reusability.