Accelerating the Phosphatase-like Activity of Uio-66-NH2 by Catalytically Inactive Metal Ions and Its Application for Improved Fluorescence Detection of Cardiac Troponin I.

Compared with natural enzymes, nanozymes usually exhibit much lower catalytic activities, which limit the sensitivities of nanozyme-based immunoassays. Herein, several metal ions without enzyme-like activities were engineered onto Uio-66-NH2 nanozyme through postsynthetic modification. The obtained Mn+@Uio-66-NH2 (Mn+ = Zn2+, Cd2+, Co2+, Ca2+and Ni2+) exhibited improved phosphatase-like catalytic activities. In particular, a 12-fold increase in the catalytic efficiency (kcat/Km) of Uio-66-NH2 was observed after the modification with Zn2+. Mechanism investigations indicate that both the amino groups and oxygen-containing functional groups in Uio-66-NH2 are the binding sites of Zn2+, and the modified Zn2+ ions on Uio-66-NH2 serve as the additional catalytic sites for improving the catalytic performance. Furthermore, the highly active Zn2+@Uio-66-NH2 was used as a nanozyme label to develop a fluorescence immunoassay method for the detection of cardiac troponin I (cTnI). Compared with pristine Uio-66-NH2, Zn2+@Uio-66-NH2 can widen the linear range by 1 order of magnitude (from 10 pg/mL-1 µg/mL to 1 pg/mL-1 µg/mL) and also lower the detection limit by 5 times (from 4.7 pg/mL to 0.9 pg/mL).

Study on the Selectivity of Molecular Imprinting Materials Determined through Hydrogen Bonding on Template Molecular Structures of Flavonoids.

Molecular imprinting technology is widely used for the specific identification of compounds, but the selective recognition mechanisms of the same compounds still need to be further studied. Based on differences in hydrogen bond size and orientation, molecularly imprinted polymers (MIPs) were designed to adsorb flavonols with the same parent core and different hydroxyl groups. A surface-imprinted material was designed with silicon dioxide as the carrier, myricetin as the template molecule, and methacrylic acid (MAA) as the functional monomer. Scanning electron microscopy (SEM), Brunauer-Emmett-Teller surface area (BET) analyses, Fourier-transform infrared spectroscopy (FT-IR), and other characterization experiments were carried out. The intrinsic mechanism of the MIPs was also explored. The MIPs showed good adsorption of myricetin and other flavonoids through hydrogen bonding and steric hindrance. The adsorption capacity was 3.12-9.04 mg/g, and the imprinting factor was 1.78-3.37. Flavonoids with different hydroxyl groups in different numbers and directions had different hydrogen bond strengths with functional monomers. R2, R4, and R1 on 2-phenylchromogenone had stronger electronegativity, and the hydroxyl group was also more likely to form and have stronger hydrogen bonds. The hydroxyl negativity and the degree of steric hindrance of flavonoids played a major role in the recognition of molecularly imprinted materials. This study is of great significance for the synthesis of and selection of templates for analogous molecular imprinting materials.

Sulfonic Functionalized Polydopamine Coatings with pH-Independent Surface Charge for Optimizing Capillary Electrophoretic Separations.

Enhancing the pH-independence and controlling the magnitude of electroosmotic flow (EOF) are critical for highly efficient and reproducible capillary electrophoresis (CE) separations. Herein, we present a novel capillary modification method utilizing sulfonated periodate-induced polydopamine (SPD) coating to achieve pH-independent and highly reproducible cathodic EOF in CE. The SPD-coated capillaries were obtained through post-sulfonation treatment of periodate-induced PDA (PDA-SP) coatings adhered on the capillary inner surface. The successful immobilization of the SPD coating and the substantial grafting of sulfonic acid groups were confirmed by a series of characterization techniques. The excellent capability of PDA-SP@capillary in masking silanol groups and maintaining a highly robust EOF mobility was verified. Additionally, the parameters of sulfonation affecting the EOF mobilities were thoroughly examined. The obtained optimum SPD-coated column offered the anticipated highly pH-independent and high-strength cathodic EOF, which is essential for enhancing the CE separation performance and improving analysis efficiency. Consequently, the developed SPD-coated capillaries enabled successful high-efficiency separation of aromatic acids and nucleosides and rapid cyclodextrin-based chiral analysis of racemic drugs. Moreover, the SPD-coated columns exhibited a long lifetime and demonstrated good intra-day, inter-day, and column-to-column repeatability.

Strategy of Choosing Templates in Molecular Imprinting to Expand the Recognition Width for Family-Selectivity.

The class-selective molecular-imprinted polymers (MIPs) have shown the recognition ability to multiple targeted molecules through using one or multiple templates. However, choosing the right templates, the core problem, still lacks a systemic guide and decision-making. In this work, we propose a strategy of selecting templates through expanding the recognition width for the improvement of class-selectivity. First, three families of genotoxic impurity (GTI) were selected as model objects, and the spatial size and binding energy of each GTI-monomer complexes were obtained and compared by computational simulation. The two indexes of energy width (WE) and size width (WL) were introduced to compare the similarity and differences on the two recognition factors, binding strength and spatial size, among these GTIs in each family. Through shortening the width to increase similarity on binding energy and size, the dual templates in the aromatic amines (AI) family and sulfonic acid esters (SI) family were successfully selected. Correspondingly, the prepared dual-template MIPs in the two GTI families can simultaneously recognize all the GTIs comparing with that of single template MIP, respectively. Meanwhile, through comparing the adsorption capacity of the selected template and its analogues in one GTI family, the recognition efficiency of the dual-template MIPs was higher than that of the single-template MIP. This indicates that though using the selected right templates, the higher class-selectivity and the larger recognition width can be realized. Thus, this work can solve the problem of blind template selection, and provide the useful theoretical guidance for designing family-selective molecular imprinting.

Protein Recognition Based on Temperature-Stimulated Multiparameter Response Virtual Array Sensing Strategy.

In the field of array sensing, researchers are committed to miniaturizing array sensing systems while ensuring the acquisition of multiple sensing information. Here, a new strategy called "stimulus responsive array sensing" was presented to obtain virtual multiple sensing without constructing multiple physical sensing units. Based on bioluminescence resonance energy transfer, where luciferase acts as the donor and temperature stimulus response polymers act as the receptors, by using only one sensing unit to output multiple stimulus responsive sensing signals in temperature dimension, an equivalent array sensing could be achieved. This strategy can distinguish and quantify a variety of proteins. More importantly, glucose responsive monomers were doped in polymers; thus, more virtual sensing units can be further increased to obtain more sensing signals, greatly increasing the accuracy of protein recognition, and it can also be used to differentiate several compositions of protein under different glucose concentrations in urine caused by different renal diseases. The results show the potential of the "stimulus responsive array sensing" for analyzing molecular compositions in complex biological systems and show a new tack in array sensing.

Improved selectivity of molecularly imprinted polymers based on the synergistic action of hydrogen bond and electrostatic interaction.

Based on the synergistic action of hydrogen bond and electrostatic interaction, provided by methacrylic acid and 2-aminoethyl ester hydrochloride (FM2), respectively, novel molecularly imprinted polymers (SA-MIPs) were designed to improve its selective recognition ability. Diclofenac sodium (DFC) was chosen as the template molecule of this study. The interaction and their recognition sites between two functional monomers and templates were confirmed by nuclear magnetic resonance hydrogen spectroscopy. Because of the synergistic action of hydrogen bond and electrostatic interaction, the imprinting factor (IF) of SA-MIPs (IF = 2.26) is superior to the corresponding monofunctional monomer imprinting materials (IF = 1.52, 1.20) and the materials using two functional monomers with an only single type of interaction (IF = 1.54, 1.75). The results of selective adsorption experiments indicate that the selective recognition ability of SA-MIPs is significantly better than that of the other four MIPs, and the difference in selectivity coefficient for methyl orange is the largest between SA-MIPs and the MIPs only using FM2, which is about 70 times. In addition, x-ray photoelectron spectroscopy was used to verify the interaction between SA-MIPs and the template. This work and its explanation of the interaction mechanism at the molecular level will be helpful for the rational design of novel MIPs with higher selectivity. Besides, SA-MIPs have good adsorption performance (37.75 mg/g) for DFC in aqueous solutions, which could be used as potential adsorption materials for the effective removal of DFC in the aquatic environment.

Metal-Organic Frameworks-Based Immobilized Enzyme Microreactors Integrated with Capillary Electrochromatography for High-Efficiency Enzyme Assay.

Enzyme assays are important for studying enzyme-mediated biochemical reactions and for clinical diagnosis and drug development. The technique of an immobilized enzyme microreactor (IMER) integrated with capillary electrophoresis (CE) has been frequently utilized in online enzyme assays. However, the traditional approaches for IMER-CE enzyme analysis have some defects such as low loading capacity and poor stability. Herein, metal-organic frameworks (MOFs), which have enormous potential in the fields of enzyme immobilization and capillary electrochromatographic (CEC) separation, were first explored as novel support materials with good enzyme immobilization performance and stationary phases with excellent separation abilities to construct an integrated MOFs-IMER-CEC microanalysis system for a high-efficiency online enzyme assay. As a proof-of-concept demonstration, acetylcholinesterase (AChE) was immobilized on a densely packed UiO-66-NH2 nanocrystal coating on a capillary inner surface with abundant intercrystalline mesoporosity and was employed as a highly effective and robust IMER for CEC-integrated online enzyme analysis. The excellent separation performance of the UiO-66-NH2-modified capillary was verified by high-efficiency separation of three types of neutral, acidic, and basic compounds. The Michaelis-Menten constant and enzyme inhibition kinetics of UiO-66-NH2-IMER were systematically assessed, exhibiting distinct advantages such as remarkably increased enzyme loadability, superior affinity for substrates, and greatly improved stability and repeatability compared to CE-integrated IMERs prepared by the traditional covalent bonding method. Furthermore, the developed method was successfully utilized for detecting organophosphorus pesticides in leguminous vegetable samples, demonstrating its strong practicality. The study not only proposed a novel support material and construction strategy for a high-performance microchannel-based IMER but also can be widely used in bioanalysis and biosensing research.

Homomesoporous Metal-Organic Framework for High-Performance Electrochromatographic Separation.

Metal-organic frameworks (MOFs) have exhibited tremendous potential in the area of separation science. However, most of the developed MOF-based stationary phases contained only microporous structures and suffer from limited separation performance. Herein, homomesoporous MOFs with excellent mass transfer capability and strong thermodynamic interactions are first explored as the novel stationary phase for high-performance capillary electrochromatographic separations. As a proof of concept, noninterpenetrated mesoMOF-1 with uniform mesopore sizes (22.5 × 26.1 Å) and good stability was facilely grown on the inner surface of capillaries and applied as a homomesoporous MOF coating-based stationary phase for high-efficiency electrochromatographic separation. Seven types of analytes with different molecular dimensions were all baseline separated on a mesoMOF-1 coated column with high theoretical plate numbers and excellent repeatability, exhibiting significantly improved separation selectivity and column efficiency in comparison to a microporous HKUST-1 coated column. The maximum column efficiencies of the mesoMOF-1 coated column for substituted benzenes and halobenzenes reached up to 1.4 × 105 plates/m, and its mass loadability was also much higher than that of the HKUST-1 coated column. In addition, based on the analysis of adsorption kinetics and chromatographic retention behaviors, the interaction and retention mechanisms of different molecular-weight analytes on mesoMOF-1 coated stationary phases were systematically explored and disclosed in detail. These results indicate that the homomesoporous MOF-based stationary phase can effectively balance the kinetic diffusion (mass transfer capability) and thermodynamic interactions (the strength of adsorption interaction), having great potential for high-performance chromatographic separation.

Microorganisms as Bio-SPE Materials for Extraction of Pharmaceutical Drugs: Mechanism of Extraction.

In solid-phase extraction (SPE), the extraction materials depend on the physicochemical interactions to obtain the target analytes from complex systems. However, many matrix interferences existing in real samples influence the extraction efficiency through these common interactions. Therefore, extraction materials based on more special interactions for biological systems need to be developed. In this work, live microorganisms including Escherichia coli and Staphylococcus aureus were considered as the potential biological SPE (bio-SPE) materials with their biological functions in the live state. To study the enrichment and selectivity of the bio-SPE, four antibacterial drugs and two non-antibacterial drugs were employed as the target analytes. The enrichment factor (EF) was used as the evaluation index. The results showed that when using chlorpheniramine (CPM) and ofloxacin (OFLO), the enrichment capacity of E. coli was better than that of S. aureus. When extracting a single analyte, the enrichment ability of E. coli for CPM was significantly higher than other analytes, and the EF was 8.5. In a mixture solution of antibacterial analytes, OFLO could be enriched mostly by E. coli. However, in the mixture solution of antibacterial and non-antibacterial analytes, CPM was enriched more than that of antibacterial analytes. In real rat plasma, bio-SPE using live E. coli could obviously extract CPM, while traditional liquid-liquid extraction could not. The confocal microscopy results showed that the extraction mechanism may not only depend on the surface adsorption of bacteria with analytes but also on the uptake into bacteria. This provides a valuable basis for the development of more biological separation materials based on biological interactions.

Effects of repeated drought stress on the physiological characteristics and lipid metabolism of Bombax ceiba L. during subsequent drought and heat stresses.

BACKGROUND: Trees of Bombax ceiba L. could produce a large number of viable seeds in the dry-hot valleys. However, the seedling regeneration of the species is difficult in these areas as mild drought often occur repeatedly which might be followed by heat stress. However, how the repeated drought affects the subsequent drought and heat tolerance of B. ceiba is not clear. In this study, chlorophyll fluorescence, soluble sugar content and lipid metabolism were measured for the drought-treated seedlings and heat-treated seedlings with or without drought hardening. RESULTS: Neither the first nor third dehydration treatments affected the photosynthetic activity and soluble sugar content of B. ceiba seedlings. However, they differentially affected the fluidity of the local membranes and the levels of diacylglycerol and phosphatidic acid. Heat shock severely decreased the photosynthetic efficiency but drought priming reduced the effects of heat shock. Moreover, heat shock with or without drought priming had differential effects on the metabolism of soluble sugars and some lipids. In addition, the unsaturation level of membrane glycerolipids increased following heat shock for non-drought-hardened seedlings which, however, maintained for drought-hardened seedlings. CONCLUSIONS: The results suggest that two cycles of dehydration/recovery can affect the metabolism of some lipids during the third drought stress and may enhance the heat tolerance of B. ceiba by adjusting lipid composition and membrane fluidity.

In vitro evaluation of intestinal absorption of tiliroside from Edgeworthia gardneri (Wall.) Meisn.

Although Edgeworthia gardneri (Wall.) Meisn and its main component tiliroside (TIL) show good bioactivity, its intestinal absorption data supporting its low bioavailability have not been reported.The evaluation results of three absorption models in vitro and in vivo indicated that the results of the Ussing chamber model were basically consistent with the results of in vivo experiments. It was thus applied to investigate the characteristics of TIL across various intestinal regions and the interaction between TIL and adenosine triphosphate (ATP)-binding cassette family proteins (ABC) including, P-glycoprotein (P-gp), multidrug resistance-associated protein 2 (MRP2), and breast cancer resistance protein (BCRP).The data of the bi-directional transport showed that the ileum had the higher apparent permeability coefficient (Papp) of TIL than duodenum and jejunum, suggesting the best absorption of TIL in the ileum.In the presence of the MRP2 inhibitor, the absorption of TIL from water extracts of E. gardneri (Wall.) Meisn (WAE) was improved, indicating that MRP2 other than P-gp and BCRP affected the absorption of TIL and might be responsible for its low bioavailability. This study laid the foundation for enhancing the bioavailability of TIL and highlighted the influences of efflux transporters on bioavailability.

Nanoscale Hierarchically Micro- and Mesoporous Metal-Organic Frameworks for High-Resolution and High-Efficiency Capillary Electrochromatographic Separation.

Metal-organic frameworks (MOFs) have been widely applied in a variety of fields. However, most of the developed MOFs are micrometer scale in crystal size and contain only micropores, which will limit the mass transport and diffusion of various analytes into their internal interaction sites, severely restricting the potential of MOFs in separation science. Herein, nanoscale hierarchically porous MOFs (NHP-MOFs) were first explored as a novel MOF-based stationary phase with excellent mass transfer performance and abundant accessible interaction sites for high-performance chromatographic separation. As a proof-of-concept demonstration, the nanoscale hierarchically micro- and mesoporous UiO-66 (NHP-UiO-66) was firmly immobilized on the capillary inner surface and utilized as the porous stationary phase for high-resolution and high-efficiency electrochromatographic separation. A wide range of low-, medium-, and high-molecular-weight analytes, including substituted benzenes, chlorobenzenes, polycyclic aromatic hydrocarbons, nucleosides, polypeptides, and proteins were all separated well on a NHP-UiO-66-coated column with excellent resolution and repeatability, exhibiting significantly improved column efficiency and separation ability compared to those of a microporous UiO-66-modified column. The maximum column efficiencies for all the six kinds of analytes reached up to 1.2 × 105 plates/m, and the relative standard deviations of the migration times of substituted benzenes for intraday, interday, and column-to-column were all lower than 5.8%. These results reveal that NHP-MOFs can effectively combine the advantages of the high specific surface area of microporous MOFs and the excellent mass transfer performance and abundant accessible interaction sites of NHP materials, possessing great prospect for high-performance chromatographic separation.

Preparation and evaluation of a molybdenum disulfide quantum dots embedded C18 mixed-mode chromatographic stationary phase.

Molybdenum disulfide quantum dots (MoS2 QDs) were chosen as a functional two-dimensional material to improve the separation performance of a traditional C18 column. In this work, MoS2 QDs were synthesized by the combination of sonication and solvothermal treatment of bulk MoS2. The prepared MoS2 QDs were characterized by transmission electron microscope (TEM), Zeta potential measurement, UV-visible absorption and fluorescence spectroscopy. Then, a novel MoS2 QDs embedded C18 (Sil-MoS2-C18) stationary phase was prepared for performing mixed-mode liquid chromatography. The results of elemental analysis (EA), thermogravimetric analysis (TGA), Fourier transform infrared spectrometry (FT-IR), X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM) and Brunauer-Emmett-Teller (BET) measurements indicated the stationary phase was prepared successfully. Five types of compounds including alkylbenzenes, polycyclic aromatic hydrocarbons (PAHs), nucleosides and nucleobases, anilines and flavonoids were utilized to evaluate reversed phase, weak cation exchange and hydrophilic interaction of the new column. To a certain extent, the column could achieve separation for different properties of samples on one column, with less organic solvent and shorter time than conventional alkyl and amino columns. Furthermore, the mechanism for separation was studied by investigating effects of mobile phase composition and pH on retentions. In summary, the Sil-MoS2-C18 stationary phase was deemed able to serve the performance of various types of phases, which revealed the prepared mixed-mode column could be potentially applied for the analysis of complex samples. Graphical abstract.

A SPE Method with Two MIPs in Two Steps for Improving the Selectivity of MIPs.

Molecular imprinted polymers (MIPs) have been widely applied in the separation of compounds in complex matrixes due to the high selectivity for molecular recognition. However, MIPs not only adsorb the targeted molecule but also adsorb structurally similar analogues, which leads to some loss of selectivity. In this work, for improvement of selectivity of MIPs, a novel solid-phase extraction method with two MIPs in two steps (TMIPs-TSPE) was established. As a demonstration, two MIPs were prepared by using quercetin as the template and 4-vinylypyridine (4VP) and acrylamide (AM) as representative functional monomers, respectively. The adsorption properties and kinetic characteristics of the two MIPs showed that they had a distinct adsorption capacity and adsorption mechanism, which is the basis for establishment of TMIPs-TSPE. The TMIPs-TSPE method first used one of the two MIPs as adsorbent to extract molecules from a solution mixture containing quercetin and three analogues. Then the other MIP was used to achieve a second extraction of the extracted molecules from the first step. The results showed that the unique targeted molecule quercetin was extracted, which illustrates that TMIPs-TSPE improved the specificity of the MIPs. The process of molecular recognition can be influenced by the intensity of binding sites between MIPs and molecules. Moreover, it may also depend on the spatial orientation of molecules entering the cavities of MIPs, which deserves more attention as one important property for the development of molecular imprinting. These results demonstrated that the novel TMIPs-TSPE method contributes to the improved selectivity of MIPs.

Green synthesis of carbon dots using the flowers of Osmanthus fragrans (Thunb.) Lour. as precursors: application in Fe3+ and ascorbic acid determination and cell imaging.

In this work, dried flowers of Osmanthus fragrans Lour. were applied as green precursors to synthesize carbon dots (CDs) by a green hydrothermal method for the first time. The CDs showed strong blue fluorescence at 410 nm under 340-nm excitation with a quantum yield of approximately 18.53%. Furthermore, the CDs were applied for the sensitive detection of Fe3+. The linear response of Fe3+ ranged from 10 nM to 50 µM with a limit of detection as low as 5 nM. In addition, other ions were used as competitive substances to explore the selectivity of CDs for Fe3+. The fluorescence quenching effect of Fe3+ was much stronger, which demonstrated that the CDs had high selectivity for Fe3+ and they can be employed for the selective detection of Fe3+. The potential fluorescence quenching mechanism between CDs and Fe3+ was identified as the inner filter effect. The CDs were then used as a fluorescent sensor for the detection of Fe3+ in water samples and human serum; the recovery range was 93.76-113.80% (relative standard deviation less than 0.79%). These results indicate that the CDs can be applied for the sensitive and selective detection of Fe3+ in real samples. Moreover, on the basis of the redox reaction between Fe3+ and ascorbic acid (AA), the CD-Fe3+ system can be used as a fluorescent "off-on" sensor for the detection of AA with a limit of detection of 5 µM. What is more, because of their low toxicity and biocompatibility, the CDs can also be used for cell imaging and acted as a fluorescent probe for fluorescence imaging of Fe3+ and AA in living cells. These results demonstrate that the CDs have great potential for application in the fields of sensing, bioimaging, and even disease diagnosis.

Structure and non-covalent interactions of 1,3-difluoropropane and its complex with water explored by rotational spectroscopy and quantum chemical calculations.

1,3-difluoropropane and its complex with water were characterized by using Fourier transform microwave spectroscopy with the aid of quantum chemical calculations. Rotational spectra of the monomer were extended to the 13C isotopologues which lead to a precise structural determination of the two observed conformers. For the 1,3-difluoropropane-water complex, the most stable isomer has been observed and assigned in the supersonic jet expansion. In the observed isomer, water acts as a proton donor and a proton acceptor forming one O-H⋯F weak hydrogen bond and two C-H⋯O weak hydrogen bonds, respectively. The measurements on the three 13C, 18O, and deuterated water allowed determination of the skeleton structure and evaluation of the weak hydrogen bond parameters. Quantum theory of atoms in molecules, non-covalent interaction, and symmetry-adapted perturbation theory analyses were performed to reveal the nature of the intermolecular non-covalent interactions.

Rotational spectrum, internal dynamics, and molecular structure of methylphenylsilane.

The rotational spectra of two isotopologues of methylphenylsilane were measured and assigned by using the supersonic-jet Fourier transform microwave spectroscopic technique in the 2.0-20.5 GHz range. The feature of rotational spectra of methylphenylsilane indicates that the doublets of rotational transitions in methylphenylsilane are contributable to the methyl internal rotation with a V3 barrier of 559 (25) cm-1. No splitting has been observed due to the methyl internal rotation in its carbon analog, ethylbenzene, which indicated that the barrier to such motion should be higher than 700 cm-1. Silicon incorporation of the ethyl group in ethylbenzene leads to a much lower barrier to the methyl internal rotation.

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.