Fabrication of highly crystalline covalent organic framework for solid-phase extraction of three dyes from food and water samples.

Herein, a covalent organic framework, which was fabricated at room temperature by using 1,3,5-tris(p-formylphenyl) benzene and 1,3,5-tris(4-aminophenyl)benzene as building blocks, was employed as an adsorbent for solid-phase extraction of dyes including congo red, methyl blue and direct red 80 for the first time. The prepared covalent organic framework was properly characterized by different techniques and the results revealed that it had a uniform spherical structure, high crystallinity, satisfactory surface area, and good thermal stability. Moreover, the adsorption performance of the material was explored by using static and dynamic adsorption experiments and the results indicated that the material showed good adsorption capacities for three dyes with adsorption capacities in the range of 55.25-284.10 mg/g and the adsorption equilibrium can be achieved in 15 min. Further, to achieve the best adsorption effects of the material, the influence parameters such as pH, ionic strength, type of desorption solvent, and the material dosage in the solid-phase extraction column, were optimized in turn. Finally, under optimal conditions, the solid-phase extraction coupled with HPLC was applied to the analysis of dyes in food and water samples. The recoveries of dyes in actual samples were satisfactory, revealing the unique applicability of the material in the sample pretreatment field.

Magnetic molecular imprinted covalent organic framework composite for the magnetic solid-phase extraction of bisphenol AF.

A magnetic molecular imprinted covalent organic framework composite (MCOF-MIP) that possessed the 'dual-selectivity' of a covalent organic framework and molecular imprinted polymer (MIP) with rapid response performance was successfully prepared for the removal of bisphenol AF (BPAF) from real water and blood samples. First, the MCOF was separately synthesized using magnetic Fe3O4 as the magnetic core, 1,3,5-triaminobenzene and 2,5-dibromobenzene-1,4-diformaldehyde as precursors and a deep eutectic solvent (DES) as the solvent using a solvothermal synthesis method. The MCOF showed high crystallinity and good adsorption capacities for BPAF (107.4 mg g-1), bisphenol A (113.6 mg g-1), bisphenol S (120.0 mg g-1) and bisphenol F (82.1 mg g-1). To further improve the selectivity for BPAF, an MIP, which uses BPAF as a template, was introduced to form the MCOF-MIP. Due to the dual selectivity of MCOF and MIP, the MCOF-MIP exhibited relatively high selective adsorption capacity to BPAF (243.1 mg g-1) compared to that for the MCOF (107.4 mg g-1), while the adsorption capacities (149.7-109.4 mg g-1) for the other three compounds were not significantly improved. Furthermore, a magnetic solid-phase extraction (MSPE) method was established, and MSPE parameters such as adsorbent dosage, adsorption time, desorption solvent and desorption time were optimized. Combined with high-performance liquid chromatography with diode-array detection (HPLC-DAD) analysis, a rapid and sensitive method was developed to detect BPAF, which showed good linearity (r > 0.9969) ranging from 0.1 to 400 µg mL-1. Low limits of detection (0.04 µg mL-1, S/N = 3) and quantitation (0.1 µg mL-1, S/N = 10) and good precision with low relative SDs (<1.2 % for intra-day and <1.1 % for inter-day) were also obtained. Finally, MSPE coupled with HPLC-DAD was employed for the analysis of BPAF in water and blood samples, and the recoveries of BPAF were satisfactory (91.1-112.6 %).

Fluorescent hydrogen-bonded organic framework act as a multifunctional platform for Fe3+ and F- sensing, and for information encryption.

Due to their exceptional optical properties and adjustable functional characteristics, hydrogen-bonded organic frameworks (HOFs) demonstrate significant potential in applications such as sensing, information encryption. However, studies on the synthesis of HOFs designed to construct multifunctional platforms are scant. In this work, we report the synthesis of a new fluorescent HOF by assembling melem and isophthalic acid (IPA), designated as HOF-IPA. HOF-IPA exhibited good selectivity and sensitivity towards Fe3+, making it suitable as a fluorescent sensor for Fe3+ detection. The sensor achieved satisfactory recoveries ranging from 97.79 % to106.42 % for Fe3+ sensing, with a low relative standard deviation (RSD) of less than 3.33 %, indicating significant application potential for HOF-IPA. Due to the ability of F- to mask the electrostatic action on the surface of Fe3+ and inhibit the photoelectron transfer (PET) of HOF-IPA, the HOF-IPA - Fe3+ system can be utilized as a fluorescent "off-on" sensor for F- detection. Additionally, owing to the colorless, transparent property of HOF-IPA in aqueous solution under sunlight and its blue fluorescence property under UV light (color) or microplate reader (fluorescence intensity), HOF-IPA based ink can be used for various types of information encryption, and all yielding favorable outcomes.

Fluorescent covalent organic frameworks for environmental pollutant detection sensors and enrichment sorbents: a mini-review.

Covalent organic frameworks (COFs) are a class of porous crystalline materials based on organic building blocks containing light elements, such as C, H, O, N, and B, interconnected by covalent bonds. Because of their regular crystal structure, high porosity, stable mechanical structure, satisfactory specific surface area, easy functionalization, and high tunability, they have important applications in several fields. Currently, most of the established methods based on COFs can only be used for individual detection or adsorption of the target. Impressively, fluorescent COFs as a special member of the COF family are able to achieve highly selective and sensitive detection of target pollutants by fluorescence enhancement or quenching. The construction of a dual-functional platform for detection and adsorption based on fluorescent COFs can enable the simultaneous realization of visual monitoring and adsorption of target pollutants. Therefore, this paper reviews the research progress of fluorescent COFs as fluorescence sensors and adsorbents. First, the fluorescent COFs were classified according to the different bonding modes between the building blocks, and then the applications of fluorescent COF-based detection and adsorption bifunctional materials for various environmental contaminants were highlighted. Finally, the challenges and future application prospects of fluorescent COFs are discussed.

Carbonized human hair derived carbon dots for detection of clozapine.

Clozapine (CLZ) is known as the most effective antipsychotic medication for schizophrenia. However, low dosage or over dosage of CLZ is adverse to the treatment of Schizophrenia. Thus, it is necessary to develop effective detection method for CLZ. Recently, due to the advantages such as excellent optical properties, good photobleachability and sensitivity, carbon dots (CDs)-based fluorescent sensors for the detection of target analytes have drawn a great deal of attention. In this work, blue fluorescent CDs (Named as B-CDs) with quantum yield (QY) as high as 38% were obtained by using carbonized human hair as source material through one-step dialysis method for the first time. B-CDs showed obvious graphite-like structure with an average of 1.76 nm, containing abundant functional groups such as -C=O, amino N and C-N on the surface of carbon cores. Optical analysis showed that the B-CDs exhibited excitation-dependent emission property with maximum emission wavelength of 450 nm. Moreover, B-CDs were further applied as a fluorescence sensor to the detection of CLZ. The B-CDs based sensor exhibited a good quenching response by CLZ through the inner filter effect and static quenching mechanism with a limit of detection of 67 ng/mL, which was much lower than the minimal effective concentration in blood (0.35 µg/mL). Finally, to test the practical application value of the developed fluorescence method, the determination of the content of CLZ in tablets and the concentration in blood was carried out. Compared with the results of high-performance liquid chromatography (HPLC) method, it can be found that the constructed fluorescence detection method showed high accuracy and had great application potential in the detection of CLZ. Additionally, the results of cytotoxicity experiment showed that B-CDs had low cytotoxicity, which laid the foundation for the subsequent application of B-CDs in biological systems.

Hydroxyl-riched covalent organic framework for solid-phase microextraction of flavonoids aglycones or their metabolites in mice's plasma: Luteolin and quercetagetin as examples.

Herein, a hydroxyl­riched covalent organic framework (named COF-DES-1) was synthesized using 1,3,5-tris(4-aminophenyl)benzene and 2,5-dihydroxyterephthalaldehyde as building blocks and employed as a coating of solid-phase microextraction (SPME) fiber. Ascribed to the advantages (e.g. suitable pore size and rich functional group characteristics) of coating, the SPME fiber showed good adsorption capacities to flavonoids aglycones including luteolin and quercetagetin, and the maximum adsorption capacities for them were 145.31 µg and 84.75 µg, respectively. Due to the size exclusion property of COF-DES-1, SPME fiber showed good protein exclusion effects on seven selected proteins with high exclusion efficiencies (>93%). Accordingly, an attractive strategy of the combination of COF-DES-1 based SPME fiber and HPLC-MS/MS was proposed for the extraction and determination of luteolin, quercetagetin or their metabolites. The results revealed that the fiber can be effectively applied to extract luteolin and its metabolites, and quercetagetin from mice's palsma. Compared with the traditional protein precipitation methods, the extraction effects of SPME fiber based extraction method were much better, indicating the promising applicability of the fiber for the enrichment of flavonoids aglycones or their metabolites in biological samples.