Extraction and determination of bioactive flavonoids from Abelmoschus manihot (Linn.) Medicus flowers using deep eutectic solvents coupled with high-performance liquid chromatography.

A highly efficient and ecofriendly extraction method using deep eutectic solvents was developed to extract bioactive flavonoids from Abelmoschus manihot (Linn.) Medicus flowers. First, a series of deep eutectic solvents using choline chloride as hydrogen bond acceptor with different hydrogen bond donors was successfully synthesized. Then, the types of deep eutectic solvents and the extraction conditions for bioactive flavonoids (hyperoside, isoquercitrin, and myricetin) were optimized based on the flavonoids extraction efficiencies. The optimized deep eutectic solvent for hyperoside and isoquercitrin extraction was composed of choline chloride and acetic acid with a molar ratio of 1:2. The optimized deep eutectic solvent for myricetin extraction was composed of one mole of choline chloride and two moles of methacrylic acid. The optimal extraction conditions were set as: solid to solvent ratio, 35:1 (mg/mL); extraction time, 30 min; extraction temperature, 30°C. Qualitative and quantitative analysis were performed using ultra high performance liquid chromatography with tandem mass spectrometry and high-performance liquid chromatography. And the extraction efficiencies of hyperoside, isoquercitrin, and myricetin under optimal extraction conditions were calculated as 11.57, 5.64, and 1.11 mg/g, much higher than those extracted by traditional extraction solvents. Therefore, the prepared deep eutectic solvents can be selected as alternative solvent to extract bioactive flavonoids.

Magnetic covalent organic frameworks with core-shell structure as sorbents for solid phase extraction of fluoroquinolones, and their quantitation by HPLC.

A core-shell structured magnetic covalent organic frameworks of the type Fe3O4@COFs was prepared by using the Fe3O4 nanoparticles as magnetic core, and 4,4"-diamino-p-terphenyl and 1,3,5-tris(p-formylphenyl)benzene as two building blocks. The Fe3O4@COFs were characterized by scanning electron microscopy, transmission electron microscopy, energy dispersive spectrum, Fourier transform infrared spectroscopy, zeta potentiometric analysis, X-ray diffraction, vibrating sample magnetometry, thermogravimetric analysis and the nitrogen adsorption-desorption isotherms. The Fe3O4@COFs have core-shell structure with average diameter of 200 ± 2.4 nm, a high specific surface area (124 m2·g-1), uniform pore size distribution (3.1 nm), good magnetic responsivity (36.8 emu·g-1), good thermal and chemical stability. They were applied as the sorbents for magnetic solid phase extraction (MSPE) for fluoroquinolones (FQs) ciprofloxacin, enrofloxacin, lomefloxacin, gatifloxacin, levofloxacin and pefloxacin. The effects of sorbent dosage, extraction time, p H value, ionic strength, desorption solvent and desorption time were investigated. By combining MSPE with HPLC-DAD analysis, a rapid and sensitive method was developed for the enrichment and determination of these FQs. The method had good linearity in the range of 2.5-1500 ng·g-1 FQ concentration range and low limits of detection (0.25-0.5 ng·g-1). The method was successfully applied to the extraction and determination of FQs in (spiked) pork, milk and human plasma samples. Recoveries ranged from 78.7-103.5% (with RSD<6.2%). Graphical abstract Schematic representation of the magnetic covalent organic frameworks which prepared by using the Fe3O4 nanoparticles as magnetic core, 4,4"-diamino-p-terphenyl and 1,3,5-tris(p-formylphenyl)benzene as two building blocks. The Fe3O4@COFs were applied as adsorbents for magnetic solid phase extraction of six fluoroquinolones (FQs) and HPLC-DAD was applied to analysis the extraction efficiencies.

A magnetic and carbon dot based molecularly imprinted composite for fluorometric detection of 2,4,6-trinitrophenol.

A magnetic molecularly imprinted composite was prepared by reverse microemulsion using carbon dots (CDs), Fe3O4 as the co-nucleus, and a molecularly imprinted polymer (MIP; with 2,4,6-trinitrophenol as the template) acting as recognition sites. The composite of type CD/Fe3O4@MIPs was characterized by transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), Fourier transform infrared spectroscopy (FT-IR), zeta potentiometric analysis, X-ray diffraction (XRD) and vibrating sample magnetometry (VSM). The results showed that the composite MIP has a spherical shape with average diameter of 200 nm. They also showed that the composite contains core-shell structures with several Fe3O4 nanoparticles and CDs embedded in each of the microsphere. The composite can extract 2,4,6-trinitrophenol (TNP) and has an imprinting factor of 3.6. It has high selectivity and sensitivity for TNP which acts as a quencher of the fluorescence of the CDs (with excitation/emission maxima at 370/470 nm). The limit of detection of this fluorometric TNP assay is 0.5 nM. The method was successfully applied to the determination of TNP in spiked tap water and river water samples, and recoveries ranged from 89.4% to 108.5% (with an RSD of <6%). Graphical abstract Schematic representation of the magnetic molecularly imprinted composite containing fluorescent carbon dots, Fe3O4 and molecularly imprinted polymer (CD/Fe3O4@MIPs). The CD/Fe3O4@MIPs were applied to the selective and sensitive detection of 2,4,6-trinitrophenol (TNP) by fluorometry.

Fabrication of covalent organic frameworks and its selective extraction of fluoronitrobenzenes from environmental samples.

In this study, porous covalent organic frameworks (COFs, named as COFs-SWMU) were synthesized for the first time via a facile approach by using 4,4',4''-methylidynetri-anilin and 2,5-dihydroxy-1,4-benzenedicarboxaldehyde as precursors under ambient temperature. The COFs-SWMU were characterized by scanning electron microscopy, Fourier-transform infrared spectroscopy, X-ray diffraction and X-ray photoelectron spectroscopy, thermogravimetric analysis, etc. The COFs-SWMU exhibited a relatively high specific surface area and desirable thermal stability. The adsorption performance of COFs-SWMU towards fluoronitrobenzenes (FNBs, including 1-fluoro-2-nitrobenzene, 1-fluoro-3-nitrobenzene, 1-fluoro-4-nitrobenzene, 2,4-difluoronitrobenzene, 3,4-difluoronitrobenzene, and 3,4-dinitrofluorobenzene) was investigated on the basis of adsorption capacity and partition coefficient (PC). The adsorption kinetics and isotherm of COFs-SWMU for FNBs were studied in detail. Further, a simple, fast and sensitive method which combined COFs-SWMU based extraction with high-performance liquid chromatography-diode array detection, was proposed for the analysis of FNBs in environmental samples. Desirable linearity (R2>0.9998) in the range of 0.1-100 µg•mL-1, low limits of detection (LODs; 0.1‒0.15 µg•mL‒1), low limits of quantitation (LOQs; 0.28‒0.40 µg•mL‒1), and desirable precision (RSDs, 0.24-2.83% for intraday and 1.13-6.92% for interday) are obtained. Finally, the COFs-SWMU were applied to the effective extraction of FNBs from environmental samples, and desirable recovery results were obtained.

Highly Crystalline Covalent Organic Frameworks Act as a Dual-Functional Fluorescent-Sensing Platform for Myricetin and Water, and Adsorbents for Myricetin.

Selective detection of active ingredients in complex samples has always been a crucial challenge because there are many disturbing compounds, especially structural analogues that interfere with the detection. In this work, a fluorescent covalent organic framework (named COF-TD), which can be used for the selective fluorescence detection and enrichment of myricetin from complex samples, was reported for the first time. The highly crystalline COF-TD with bright blue fluorescence was formed through a solution polymerization method by the condensation reaction between 4,4',4″-(1,3,5-triazine-2,4,6-triyl)trianiline and 2,5-dihydroxy-1,4-benzenedicarboxaldehyde. Due to spatial size selectivity, multisites hydrogen bonding, and π-π interaction, myricetin can quench the fluorescence of COF-TD with an inner filter effect (IFE) and static quenching mechanisms as well as can be enriched on COF-TD. Myricetin can observably eliminate the interference of other compounds and selectively quench the fluorescence of COF-TD with a limit of detection (LOD) of 0.30 µg·mL-1. The high adsorption ability of COF-TD (Q = 124.6 mg·g-1) to myricetin was also obtained. Finally, a sensing platform based on COF-TD for myricetin was successfully developed and applied for the detection of myricetin from vine teas. In addition, COF-TD also showed good water sensing ability and could be used effectively to detect water content in organic solvent (1-18% water in acetone, 0.5-5% water in acetonitrile, 1-4.5% water in ethyl acetate, v/v). To the best of our knowledge, this is the first report where COF-TD was used to detect water in a relatively wide concentration range. In all, this work provided dual-functional fluorescent COFs with the properties of an adsorbent, opening up new methodologies for the simple, selective, and enrichment detection method for myricetin.

N,Cl-Codoped Carbon Dots from Impatiens balsamina L. Stems and a Deep Eutectic Solvent and Their Applications for Gram-Positive Bacteria Identification, Antibacterial Activity, Cell Imaging, and ClO- Sensing.

In this study, we first synthesized metal-free N,Cl-doped carbon dots (N,Cl-CDs) using Impatiens balsamina L. stems as green precursors in a deep eutectic solvent (DES). The obtained N,Cl-CDs were characterized through transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Fourier-transform infrared (FT-IR) spectroscopy, fluorescence (FL) spectroscopy, and ultraviolet (UV) spectroscopy. In addition to the common features of carbon dots (CDs), such as high light stability, small size, low toxicity, good aqueous solubility, and favorable biocompatibility, these N,Cl-CDs exhibited excellent recognition and selectivity for Gram-positive bacteria by doping with N and Cl elements using DES. The N,Cl-CDs with positive charge cannot only differentiate Gram-positive bacteria by selective fluorescence imaging but also have antibacterial effects on Gram-positive bacteria. Through potential, ROS, and morphological analyses of bacteria before and after treatment with N,Cl-CDs, the antibacterial mechanisms of bacteriostasis, Enterococcus faecium, Staphylococcus aureus, Bacillus subtilis, Escherichia coli, Pseudomonas aeruginosa, and Salmonella were explored. In addition, N,Cl-CDs demonstrated low cytotoxicity and good cell imaging ability in cancer and normal cells. Moreover, they can be used as a fluorescence sensor for the detection of ClO- with a detection range from 100 nM to 40 µM and a limit of detection (LOD) of 30 nM. In summary, the prepared N,Cl-CDs could be applied as environmentally friendly Gram-positive bacterial identification and antibacterial agents. Additionally, their cell imaging and ClO- detection abilities were outstanding.

Core-shell structured magnetic covalent organic frameworks for magnetic solid-phase extraction of diphenylamine and its analogs.

Core-shell structured magnetic covalent organic frameworks (Fe3O4@COFs) were synthesized via a facile approach at room temperature using 1,3,5-tris(4-aminophenyl)benzene (TAPB) and 2,5-dibromo-1,4-benzenedicarboxaldehyde (DBDA) as two building blocks for the first time. The Fe3O4@COFs were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier-transform infrared (FT-IR) spectroscopy, powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), vibrating sample magnetometry (VSM), nitrogen adsorption-desorption isotherms, and zeta potentiometric analysis. The Fe3O4@COFs had a high specific surface area (141.94 m2·g-1) and uniform pore size distribution (average 4.53 nm). They also demonstrated good magnetic response (32.49 emu·g-1) and good thermal and chemical stabilities. Furthermore, adsorption experiments were conducted to evaluate the adsorption capacities and adsorption times of Fe3O4@COFs to diphenylamine (DPA) and its analogs, including benzidine (BZ), 1-naphthylamine (1-NA), 4-phenylphenol (4-PP), and O-tolidine (O-TD). From the experimental results, the maximum adsorption capacities of DPA, 1-NA, 4-PP, BZ, and O-TD were calculated as 246.25, 95.20, 85.85, 107.20, and 123.55 mg·g-1, respectively. A duration of 20 min was sufficient for adsorption. The Fe3O4@COFs were explored as adsorbents for magnetic solid-phase extraction (MSPE) of DPA and its analogs, and the MSPE parameters, including adsorbent dosage, extraction time, pH, ionic strength, desorption solvent, desorption time, and desorption frequency were optimized. Combined with HPLC using diode-array detection, a simple, fast, and sensitive method was proposed to detect DPA and its analogs, which exhibited good linearity (r >0.9946) in the range of 0.1-100 µg·mL-1. Moreover, the low limits of detection (ranging from 0.02 to 0.08 µg·mL-1, S/N = 3), low limits of quantitation (ranging from 0.05 to 0.30 µg·mL-1, S/N = 10), good precision with low relative SDs (<5.86% for intra-day and <6.44% for inter-day) were obtained. Finally, Fe3O4@COFs were applied to the effective MSPE of DPA and its analogs in actual samples chosen from the natural environment, and good recoveries (ranging from 79.97 to 122.52%) were observed.

Sensitivity fluorescent switching sensor for Cr (VI) and ascorbic acid detection based on orange peels-derived carbon dots modified with EDTA.

Orange peels were applied as precursors to synthesize carbon dots (CDs) via a one-step green hydrothermal method. The relationship between quantum yield and volatile oils in 14 different varieties of orange peels were investigated. The CDs showed strong blue fluorescence and were further modified with EDTA. Compared with the CDs, the CDs@EDTA exhibited higher sensitivity for Cr(VI) detection with a LOD of 10 nM. The CDs@EDTA was proved to be an effective fluorescent sensor element for Cr(VI) detection in water samples with recoveries ranged from 92.09% to 104.87% (RSD < 5%). Moreover, CDs@EDTA/Cr(VI) system was further developed as a fluorescent "off-on" sensor for ascorbic acid (AA) detection with a LOD of 0.1 µM. Further, the sensor had been successfully applied for the analysis of AA in fresh oranges and commercial orange juices. The recoveries of AA in fresh oranges and orange juices were 92.58-106.76% and 91.54-104.95%, respectively.

Facile synthesis of porous covalent organic frameworks for the effective extraction of nitroaromatic compounds from water samples.

Novel porous covalent organic frameworks (COFs) were synthesized via a facile approach at room temperature by using 1,3,5-tris(4-aminophenyl)benzene and 2,3,5,6-tetrafluoroterephthalaldehyde as two building blocks for the first time. And the COFs were applied as dispersive solid phase extraction (dSPE) adsorbents for the extraction of six nitroaromatic compounds (NACs) from diverse water samples. The COFs were characterized by scanning electron microscopy (SEM), energy dispersive spectrum (EDS), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), the nitrogen adsorption-desorption isotherms and Zeta potentiometric analysis. The results indicated that the COFs possessed high specific surface area, good thermal and chemical stability. Moreover, some parameters (including adsorbent dosage, extraction time, pH, ion strength, desorption solvent, desorption time and desorption frequency) which influenced the extraction efficiencies of NACs were investigated in details. By combining COFs-based dSPE with HPLC-DAD analysis, a simple, fast and effective method was developed for the extraction and determination of six NACs. The method demonstrated good linearity in the range of 0.01-50 µg mL-1 (R > 0.9973) with low limits of quantification (0.1-0.25 µg mL-1, S/N = 10) and low limits of detection (0.03-0.09 µg mL-1, S/N = 3). Good precision with relative standard deviations (RSD) lower than 3.56% for intra-day and 4.78% for inter-day were also obtained. Finally, COFs-based dSPE was applied to the effective extraction of six NACs from three kinds of actual water samples, and good recoveries (ranged from 84.00 to 112.29%) were observed. These results demonstrated that the COFs had promising potential to be adsorbents for dSPE of NACs in complex samples.