Electrochemical Impedimetric Platform Based on Con A@MIL-101 for Glycoprotein Detection.

An electrochemical impedimetric biosensing platform with lectin as a molecular recognition element has been established for the sensitive detection of glycoproteins, a class of important biomarkers in clinical diagnosis. One of the representative metal-organic framework materials, MIL-101(Cr)-NH2, was utilized as the supporting matrix, and its amino groups served as the anchors to immobilize the lectins of concanavalin A (Con A), constituting Con A@MIL-101(Cr)-NH2 for the determination of invertase (INV) as a model glycoprotein. The Con A concentration, immobilization time, and incubation time with INV were optimized. Under the optimal conditions, the degree of impedance increase was linearly proportional to the logarithm of INV concentration between 1.0 × 10-16 and 1.0 × 10-11 M, affording a limit of detection as low as 3.98 × 10-18 M. Good specificity, stability, reproducibility, and repeatability were demonstrated for the fabricated biosensing platform. Moreover, real mouse serum samples were spiked with different concentrations of INV. Excellent recoveries were obtained, which demonstrated the biosensing platform's capability of analyzing glycoproteins within a complex matrix.

Nickel-cobalt metal-organic frameworks based flexible hydrogel as a wearable contact lens for electrochemical sensing of urea in tear samples.

A flexible, wearable, non-invasive contact lens sensor utilizing nickel-cobalt metal-organic framework (Ni-Co-MOF) based hydrogel is introduced for urea monitoring in tear samples. The synthesized Ni-Co-MOF hydrogel exhibits a porous structure with interconnected voids, as visualized by Scanning Electron Microscopy (SEM). Detailed structural and vibrational properties of the material were characterized using X-ray Diffraction (XRD), Fourier Transform Infrared (FTIR) spectroscopy, and Raman spectroscopy. The developed Ni-Co-MOF hydrogel sensor showcases a detection limit of 0.445 mM for urea within a linear range of 0.5-70 mM. Notably, it demonstrates exceptional selectivity, effectively distinguishing against interfering species like UA, AA, glucose, dopamine, Cl-, K+, Na+, Ca2+, and IgG. The enhanced electrocatalytic performance of the Ni-Co-MOF hydrogel electrode is attributed to the presence of Ni and Co, fostering Ni2+ oxidation on the surface and forming a Co2+ complex that acts as a catalyst for urea oxidation. The fabricated sensor exhibits successful detection and retrieval of urea in simulated tear samples, showcasing promising potential for bioanalytical applications. The binder-free, non-toxic nature of the Ni-Co-MOF hydrogel sensor presents exciting avenues for future utilization in non-enzymatic electrochemical sensing, including applications in wearable devices, point-of-care diagnostics, and personalized healthcare monitoring.

Two-dimensional metal-organic framework nanozyme-mediated portable paper-based analytical device for dichlorophen assay.

The metal-organic frameworks (MOFs) nanozyme-mediated paper-based analytical devices (PADs) have shown great potential in portable visual determination of phenolic compounds in the environment. However, most MOF nanozymes suffer from poor dispersibility and block-like structure, which often prompts deposition and results in diminished enzymatic activity, severely hindering their environmental applications. Here, we proposed colorimetric PADs for the visual detection of dichlorophen (Dcp) based on its significant inhibitory effect on the two-dimensional (2D) MOF nanozyme activity. Specifically, we synthesized a 2D Cu TCPP (Fe) (defined as 2D-CTF) MOF nanozyme exhibiting excellent dispersibility and remarkable peroxidase-like (POD-like) activity, which could catalyze the oxidation and subsequent color change of 3,3',5,5'-tetramethylbenzidine even under neutral conditions. Notably, the POD-like activity of 2D-CTF demonstrated a unique response to Dcp because of the occupation of Fe-N4 active sites on the 2D-CTF. This property enables the use of 2D-CTF as a highly efficient catalyst to develop colorimetric PADs for naked-eye and portable detection of Dcp. We believe that the proposed colorimetric PADs offer an efficient method for Dcp assay and open fresh avenues for the advancement of colorimetric sensors for analyzing of phenolic toxic substances in real samples.

Dual-functional porphyrinic zirconium-based metal-organic framework for the fluorescent sensing of histidine enantiomers and Hg2.

A novel fluorescence sensor based on a porphyrinic zirconium-based metal-organic framework, L-cysteine-modified PCN-222 (L-Cys/PCN-222), was developed to selectively recognize histidine enantiomers and sensitively detect Hg2+. The dual-functional sensor was successfully prepared via the solvent-assisted ligand incorporation method and characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), 1H nuclear magnetic resonance (1H NMR) spectroscopy, Fourier transform infrared (FT-IR) spectroscopy, circular dichroism (CD), X-ray photoelectron spectroscopy (XPS), and nitrogen adsorption-desorption analyses. L-Cys/PCN-222 not only showed a higher quenching response for L-histidine than that for D-histidine with a fast fluorescent response rate of <40 s but also exhibited low detection limits for L- and D-histidine (2.48 µmol L-1 and 3.85 µmol L-1, respectively). Moreover, L-Cys/PCN-222 was employed as a fluorescent and visual sensor for the highly sensitive detection of Hg2+ in the linear range of 10-500 µmol L-1, and the detection limit was calculated to be 2.79 µmol L-1 in surface water. The specific and selective recognition of chiral compounds and metal ions by our probe make it suitable for real field applications.

Colorimetric and SERS dual-mode detection of GSH in human serum based on AuNPs@Cu-porphyrin MOF nanozyme.

BACKGROUND: Rapid and accurate detection of glutathione content in human blood plays an important role in real-time tracking of related diseases. Currently, surface-enhanced Raman scattering/spectroscopy (SERS) combined with nanozyme material has been proven to have excellent properties in the detection applications compared to many other methods because of it combines the advantages of trace detection capability of SERS and efficient catalytic activity of nanozymes. However, there are still existing problems in real sample detection, and to achieve quantitative detection is still challenging. RESULTS: In this study, gold nanoparticles (AuNPs) were synthesized in situ on the surface of two-dimensional Cu-porphyrin metal-organic framework (MOF) nanosheets to produce the AuNPs@Cu-porphyrin MOF nanozyme, which exhibited both oxidase-like activity and SERS detection ability. On one hand, the intrinsic oxidase-like activity of the nanozyme could be inhibited due to the chelation of glutathione (GSH) and Cu, which thus led to the visual color change of the solution. On the other hand, the abundant Raman "hot spots" at the nanogap generated by Au NPs and the internal standard (IS) signal provided by Cu-meso-tetra (4-carboxyphenyl) porphine (Cu-TCPP) MOF improved the sensitivity and quantitative accuracy of detection. SIGNIFICANCE AND NOVELTY: A dual-mode signal output sensor based on the nanozyme was thus established, which could be used in the trace detection of GSH. Such a dual-mode sensor possesses excellent detection performance, with the advantage of both wide detection range from 1 to 300 µM in the colorimetric detection mode and high sensitivity with LOD of 5 nM in the SERS detection mode, and can be applied to GSH detection in actual serum samples with reliable results.

SU-101 for the removal of pharmaceutical active compounds by the combination of adsorption/photocatalytic processes.

Pharmaceutical active compounds (PhACs) are some of the most recalcitrant water pollutants causing undesired environmental and human effects. In absence of adapted decontamination technologies, there is an urgent need to develop efficient and sustainable alternatives for water remediation. Metal-organic frameworks (MOFs) have recently emerged as promising candidates for adsorbing contaminants as well as providing photoactive sites, as they possess exceptional porosity and chemical versatility. To date, the reported studies using MOFs in water remediation have been mainly focused on the removal of a single type of PhACs and rarely on the combined elimination of PhACs mixtures. Herein, the eco-friendly bismuth-based MOF, SU-101, has been originally proposed as an efficient adsorbent-photocatalyst for the elimination of a mixture of three challenging persistent PhACs, frequently detected in wastewater and surface water in ng L-1 to mg·L-1 concentrations: the antibiotic sulfamethazine (SMT), the anti-inflammatory diclofenac (DCF), and the antihypertensive atenolol (At). Adsorption experiments of the mixture revealed that SU-101 exhibited a great adsorption capacity towards At, resulting in an almost complete removal (94.1 ± 0.8% for combined adsorption) in only 5 h. Also, SU-101 demonstrated a remarkable photocatalytic activity under visible light to simultaneously degrade DCF and SMT (99.6 ± 0.4% and 89.2 ± 1.4%, respectively). In addition, MOF-contaminant interactions, the photocatalytic mechanism and degradation pathways were investigated, also assessing the toxicity of the resulting degradation products. Even further, recycling and regeneration studies were performed, demonstrating its efficient reuse for 4 consecutive cycles without further treatment, and its subsequent successful regeneration by simply washing the material with a NaCl solution.

A novel laccase-like Cu-MOF for colorimetric differentiation and detection of phenolic compounds.

The development of convenient, fast, and cost-effective methods for differentiating and detecting common organic pollutant phenols has become increasingly important for environmental and food safety. In this study, a copper metal-organic framework (Cu-MOF) with flower-like morphology was synthesized using 2-methylimidazole (2-MI) as ligands. The Cu-MOF was designed to mimic the natural laccase active site and proved demonstrated excellent mimicry of enzyme-like activity. Leveraging the superior properties of the constructed Cu-MOF, a colorimetric method was developed for analyzing phenolic compounds. This method exhibited a wide linear range from 0.1 to 100 µM with a low limit of detection (LOD) of 0.068 µM. Besides, by employing principal component analysis (PCA), nine kinds of phenols was successfully distinguished and identified. Moreover, the combination of smartphones with RGB profiling enabled real-time, quantitative, and high-throughput detection of phenols. Therefore, this work presents a paradigm and offers guidance for the differentiation and detection of phenolic pollutants in the environment.

Nanocluster/metal-organic framework nanosheet-based confined ECL enhancement biosensor for the extracellular vesicle detection.

Gastric cancer (GC) was one of the most common cancers with high mortality. The detection of GC peritoneal metastasis had important significance. In this work, we have developed the novel electrochemiluminescence (ECL) biosensor to detect microRNA in GC extracellular vesicle (EV). Firstly, in situ growth of Cu nanocluster (Cu NC) on the metal-organic frameworks (MOFs) nanosheet was achieved successfully. Due to the confinement effect, Cu NCs in the porous structure of Zn MOF possessed the high quantum yield and good stability. Meanwhile, Zn MOF provided good electrochemical activity for the ECL reaction. Furthermore, the nanosized MOFs did not only act as sensing platform to load Cu NCs and link biomolecules, but also reduce steric hindrance effect for biomolecular recognition. Additionally, Au NPs/MXene and phospholipid layer were prepared and modified on the electrode, which can regulate electron transfer and improve the target recognition efficiency. The Cu NCs/Zn MOF nanosheet-based ECL sensor was employed to detect miRNA-421 from 1 fM to 1 nM with a detection limit of 0.5 fM. Finally, extracellular vesicles form clinic GC patient ascites were extracted and analyzed. The results showed that the constructed biosensor can be used for the GC peritoneal metastasis diagnosis.

Advanced Characterization Methodology to Unravel the Biodegradability of Metal-Organic Framework Nanoparticles in Extremely Diluted Conditions.

Porous iron(III) carboxylate metal-organic frameworks (MIL-100; MIL stands for Material of Institute Lavoisier) of submicronic size (nanoMOFs) have attracted a growing interest in the field of drug delivery due to their high drug payloads, excellent entrapment efficiencies, biodegradable character, and poor toxicity. However, only a few studies have dealt with the nanoMOF degradation mechanism, which is key to their biological applications. Complementary methods have been used here to investigate the degradation mechanism of Fe-based nanoMOFs under neutral or acidic conditions and in the presence of albumin. High-resolution STEM-HAADF coupled with energy-dispersive X-ray spectroscopy enabled the monitoring of the crystalline organization and elemental distribution during degradation. NanoMOFs were also deposited onto silicon substrates by dip-coating, forming stable thin films of high optical quality. The mean film thickness and structural changes were further monitored by IR ellipsometry, approaching the "sink conditions" occurring in vivo. This approach is essential for the successful design of biocompatible nano-vectors under extreme diluted conditions. It was revealed that while the presence of a protein coating layer did not impede the degradation process, the pH of the medium in contact with the nanoMOFs played a major role. The degradation of nanoMOFs occurred to a larger extent under neutral conditions, rapidly and homogeneously within the crystalline matrices, and was associated with the departure of their constitutive organic ligand. Remarkably, the nanoMOFs' particles maintained their global morphology during degradation.

A sensitive immunosensing platform based on the high cathodic photoelectrochemical activity of Zr-MOF and dual-signal amplification of peroxidase-mimetic Fe-MOF.

Cathodic photoelectrochemical (PEC) analysis has received special concerns because of its outstanding anti-interference capability toward reductive substances in samples, so it is highly desirable to develop high-performance photocathodic materials for PEC analysis. Herein, a Zr-based metal-organic framework (Zr-MOF), MOF-525, is explored as a photoactive material in aqueous solution for the first time, which shows a narrow band-gap of 1.82 eV, excellent visible-light absorption, and high cathodic PEC activity. A sandwiched-type PEC immunosensor for detecting prostate-specific antigen (PSA) is fabricated by using MIL-101-NH2(Fe) label and MOF-525 photoactive material. MIL-101-NH2(Fe) as a typical Fe-MOF can serve as a peroxidase mimic to catalyze the production of precipitates on the photoelectrode. Both the produced precipitates and the MIL-101-NH2(Fe) labels can quench the photocathodic current, enabling "signal-off" immunosensing of PSA. The detection limit is 3 fg mL-1, and the linear range is between 10 fg mL-1 and 100 ng mL-1 for detecting PSA. The present study not only develops a high-performance Zr-MOF photoactive material for cathodic PEC analysis but also constructs a sensitive PEC immunosensing platform based on the dual-signal amplification of peroxidase-mimetic Fe-MOF.

MOF-derived NiCo hydroxide for highly efficient non-enzymatic glucose biosensing.

An efficient and robust electrocatalyst is significant for glucose biosensing. The emergence of metal-organic framework (MOF) derived materials opens up new avenues for the development of high-performance glucose sensing catalysts. Herein, MOF derived nickel-cobalt hydroxide supported on conductive copper sheet (NiCo-OH/Cu sheet) is prepared at room temperature. The as-obtained NiCo-OH is endowed with three-dimensional network structure which enables the effective exposure of active materials, sufficient contact between glucose molecule and catalyst. The NiCo-OH/Cu sheet is revealed as good glucose electrochemical sensing material with a wide linear range of 0.05∼6.0 mM and a high sensitivity of 1340µA mM-1cm-2. Additionally, the as-fabricated NiCo-OH/Cu sheet displays good anti-interference ability and long-term stability.

MXene-supported MIL-88A(Fe) as persulfate activator for removal of tetracycline.

The poor conductivity, poor stability, and agglomeration of iron-based metal organic framework MIL-88A(Fe) limit its application as persulfate (PS) activator in water purification. Herein, MXene-supported MIL-88A(Fe) composites (M88A/MX) were synthesized to enhance its adsorption and catalytic capability for tetracycline (TC) removal. Scanning electron microscope (SEM), X-ray diffractometer (XRD), Fourier transform infrared spectrometer (FT-IR), and X-ray photoelectron spectroscopy (XPS) were used to characterize prepared materials, confirming the successful attachment of MIL-88A(Fe) to the surface of MXene. M88A/MX-0.2 composites, prepared with 0.2 g MXene addition, exhibit optimal degradation efficiency, reaching 98% under conditions of 0.2 g/L M88A/MX-0.2, 1.0 mM PS, 20 ppm TC, and pH 5. The degradation rate constants of M88A/MX-0.2 were 0.03217 min-1, which was much higher than that of MIL-88A(Fe) (0.00159 min-1) and MXene (0.00626 min-1). The removal effects of reaction parameters, such as dosage of M88A/MX-0.2 and PS; initial solution pH; and the presence of the common co-existing constituents (humic acid and the inorganic anions) were investigated in detail. Additionally, the reuse of M88A/MX-0.2 showed that the composites had good cycling stability by recurrent experiments. The results of electron paramagnetic resonance (EPR) and quenching experiments indicated that ·OH, ·SO4-, and ·O2- were involved in the M88A/MX-0.2/PS system where persulfate oxidation process was activated with prepared M88A/MX-0.2. In addition, the intermediates of photocatalytic degradation were determined by HPLC-MS, and the possible degradation pathways of the target molecules were inferred. This study offered a new avenue for sulfate-based degradation of Fe-based metal organic framework.

Molecularly imprinted metal-organic frameworks assisted cloth and paper hybrid microfluidic devices for visual detection of gonyautoxin.

Marine algal toxin contamination is a major threat to human health. Thus, it is crucial to develop rapid and on-site techniques for detecting algal toxins. In this work, we developed colorimetric cloth and paper hybrid microfluidic devices (µCPADs) for rapid detection of gonyautoxin (GTX1/4) combined with molecularly imprinted polymers. In addition, the metal-organic frameworks (MOFs) composites were applied for this approach by their unique features. Guanosine serves as a dummy template for surface imprinting and has certain structural advantages in recognizing gonyautoxin. MOF@MIPs composites were able to perform a catalytic color reaction using hydrogen peroxide-tetramethylbenzidine for the detection of GTX1/4. The cloth-based sensing substrates were assembled on origami µPADs to form user-friendly, miniaturized colorimetric µCPADs. Combined with a smartphone, the proposed colorimetric µCPADs successfully achieved a low limit of detection of 0.65 µg/L within the range of 1-200 µg/L for rapid visual detection of GTX1/4. Moreover, the GTX1/4 of real shellfish and seawater samples were satisfactorily detected to indicate the application prospect of the µCPADs. The proposed method shows good potential in the low-cost, stable establishment of assays for the rapid detection of environmental biotoxins.

Metal-Organic Framework Induced Stabilization of Proteins in Polymeric Nanoparticles.

Developing protein confinement platforms is an attractive research area that not only promotes protein delivery but also can result in artificial environment mimicking of the cellular one, impacting both the controlled release of proteins and the fundamental protein biophysics. Polymeric nanoparticles (PNPs) are attractive platforms to confine proteins due to their superior biocompatibility, low cytotoxicity, and controllable release under external stimuli. However, loading proteins into PNPs can be challenging due to the potential protein structural perturbation upon contacting the interior of PNPs. In this work, we developed a novel approach to encapsulate proteins in PNPs with the assistance of the zeolitic imidazolate framework (ZIF). Here, ZIF offers an additional protection layer to the target protein by forming the protein@ZIF composite via aqueous-phase cocrystallization. We demonstrated our platform using a model protein, lysozyme, and a widely studied PNP composed of poly(ethylene glycol)-poly(lactic-co-glycolic acid) (PEG-PLGA). A comprehensive study via standard loading and release tests as well as various spectroscopic techniques was carried out on lysozyme loaded onto PEG-PLGA with and without ZIF protection. As compared with the direct protein encapsulation, an additional layer with ZIF prior to loading offered enhanced loading capacity, reduced leaching, especially in the initial stage, led to slower release kinetics, and reduced secondary structural perturbation. Meanwhile, the function, cytotoxicity, and cellular uptake of proteins encapsulated within the ZIF-bound systems are decent. Our results demonstrated the use of ZIF in assisting in protein encapsulation in PNPs and established the basis for developing more sophisticated protein encapsulation platforms using a combination of materials of diverse molecular architectures and disciplines. As such, we anticipate that the protein-encapsulated ZIF systems will serve as future polymer protein confinement and delivery platforms for both fundamental biophysics and biochemistry research and biomedical applications where protein delivery is needed to support therapeutics and/or nutrients.

Fabrication of a novel HKUST-1/CoFe2O4/g-C3N4 electrode for the electrochemical detection of ciprofloxacin in physiological samples.

In this work, a novel HKUST-1/CoFe2O4/g-C3N4 electrode was successfully prepared via the hydrothermal method and the high-temperature calcination method, which can be applied as an electrochemical sensor for the precise detection of ciprofloxacin (CIP) in physiological samples. The novel electrode was characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and Fourier-transform infrared spectroscopy (FT-IR), and its electrochemical performance was further evaluated via the cyclic voltammetry (CV) and differential pulse voltammetry (DPV) techniques. The results demonstrated that the HKUST-1/CoFe2O4/g-C3N4 electrode exhibited an optimal linear range of 0.05-180 µmol L-1 for the CIP detection, which demonstrated a low limit of detection (LOD) of 0.0026 µmol L-1 and a low limit of quantitation (LOQ) of 0.0087 µmol L-1, respectively. Additionally, the novel semiconductor sensors exhibited exceptional selectivity, stability and repeatability in the determination of CIP. The recovery rate of CIP was found to range from 98.00% to 104.00% in serum, with the relative standard deviations (RSD) below 2.62% (n = 5), while the recovery rate of CIP was found to range from 96.00% to 105.00%, with the RSD less than 3.23% (n = 5) in urine. The current study extends to the application of the semiconductor-based electrochemical sensors and offers a new approach for the clinical pharmaceutical analysis to ensure medication safety, which could provide valuable insights into the potential of semiconductor sensors for future clinical applications.

Rapidly enrichment and detection of per-and polyfluoroalkyl substances in foods using a novel bifunctional covalent organic framework.

Per- and polyfluoroalkyl substances (PFASs) are extensively found in foods, posing potential toxicity to humans. Therefore, rapid analysis and monitoring of PFASs in foods are crucial for public health and also a challenge. To detect trace PFASs in foods, construction of sorbents with multiple interactions could be an effective approach. Herein, a cationic-fluorinated covalent organic framework (CF-COF) was prepared by post-modification and used as a magnetic solid-phase extraction adsorbent for adsorption of PFASs. By combining magnetic solid-phase extraction based on CF-COF with liquid chromatography-tandem mass spectrometry (LC - MS/MS), a novel method was developed for determination of eight long-chain PFASs in foods. Under optimized conditions, the method exhibited low detection limits (0.003-0.019 ng/g) and satisfactory recovery rates (73.5-118%) for PFASs. This study introduces a novel idea for the development of adsorbents targeting PFASs, along with a new analytical method for monitoring of PFASs in foods.

Bifunctional MNPs@UIO-66-Arg core-shell-satellite nanocomposites for enrichment of phosphopeptides.

A facile and mild method based on self-assembled lysozyme (LYZ) to fabricate bifunctional MNPs@UIO-66-Arg core-shell-satellite nanocomposites (CSSNCs) is reported for the high-efficiency enrichment of phosphopeptides. Under physiological conditions, LYZ rapidly self-assembled into a robust coating on Fe3O4@SiO2 magnetic nanoparticles (MNPs) with abundant surface functional groups, which effectively mediate heterogeneous nucleation and growth of UIO-66 nanocrystals. Well-defined MNPs@UIO-66 CSSNCs with stacked pores, showing high specific surface area (333.65 m2 g- 1) and low mass transfer resistance, were successfully fabricated by fine-tuning of the reaction conditions including reaction time and acetic acid content. Furthermore, the UIO-66 shells were further modified with arginine to obtain bifunctional MNPs@UIO-66-Arg CSSNCs. Thanks to the unique morphology and synergistic effect of Zr-O clusters and guanidine groups, the bifunctional MNPs@UIO-66-Arg CSSNCs exhibited outstanding enrichment performance for phosphopeptides, delivering a low limit of detection (0.1 fmol), high selectivity (ß-casein/BSA, mass ratio 1:2000), and good capture capacity (120 mg g- 1). The mechanism for phosphopeptides capture may attribute to the hydrogen bonds, electrostatic interactions, and Zr-O-P bonds between phosphate groups in peptides and guanidyl/Zr-O clusters on bifunctional MNPs@UIO-66-Arg CSSNCs. In addition, the small stacking pores on the core-shell-satellite architecture may selectively capture phosphopeptides with low molecular weight, eliminating interference of other large molecular proteins in complex biological samples.

Amino-functional magnetic covalent organic framework as an effective adsorbent for the determination of neonicotinoids in food samples.

Recently, covalent organic frameworks have gained popularity in sample pretreatment. However, the application of covalent organic frameworks in the enrichment of hydrophilic compounds remains a challenge. Thus, a functionalized magnetic covalent organic framework equipped with amino groups was constructed using a bottom-up functionalization strategy. Considering the advantages of this novel adsorbent such as high porosity, large adsorption capacity, and hydrophilic surface, a sensitive magnetic solid-phase extraction coupled with high-performance liquid chromatography-tandem mass spectrometry method was established for the effective determination of neonicotinoids. This method exhibited good linearities with correlation coefficients ranging from 0.9983 to 0.9995, low detection limits in the range 0.003-0.009 ng g-1 and 0.001-0.013 ng mL-1, and limits of quantification in the range 0.010-0.031 ng g-1 and 0.004-0.044 ng mL-1. Furthermore, satisfactory repeatability with relative standard deviations ≤ 6.7% and spiked recoveries between 82.3 and 99.8% were obtained. This work not only provided a promising adsorbent for the sensitive determination of trace-level neonicotinoids but also represented a unique insight for effective enrichment of super hydrophilic hazards.

Pore Size Adjustment Strategy for the Fabrication of Molecularly Imprinted Covalent Organic Framework Nanospheres at Room Temperature for Selective Extraction of Zearalenone in Cereal Samples.

Covalent organic frameworks (COFs) are attractive adsorbents for sample pretreatment due to their unique structure and properties. However, the selectivity of COFs for the extraction of hazardous compounds is still limited due to the lack of specific interactions between COFs and targets. Herein, we report a pore size adjustment strategy for room-temperature synthesis of molecularly imprinted COF (MICOF) for selective extraction of zearalenone (ZEN) in complex food samples. The three-dimensional building block tetra(4-aminophenyl) methane was used as a functional monomer, while dialdehyde monomers with different numbers of benzene ring were used to adjust the pore size of MICOF to match with the size of ZEN molecules. The prepared MICOF gave the largest adsorption capacity of 177.2 mg g-1 and the highest imprinting factor of 10.1 for ZEN so far. MICOF was used as the adsorbent for dispersed solid-phase extraction in combination with high-performance liquid chromatography for the determination of trace ZEN in cereals. The high selectivity of the developed method allows simple aqueous standard calibration for the matrix effect-free determination of ZEN in food samples. The limit of detection and the recoveries of the developed method were 0.21 µg kg-1 and 93.7-101.4%, respectively. The precision for the determination of ZEN was less than 3.8% (RSD, n = 6). The developed method is promising for the selective determination of ZEN in complex matrices.

Combination of click chemistry and Schiff base reaction: Post-synthesis of covalent organic frameworks as an immobilized metal ion affinity chromatography platform for efficient capture of global phosphopeptides in serum with chronic obstructive pulmonary disease.

Reasonable design and construction of functionalized materials are of great importance for the enrichment of global phosphopeptides. In this work, Ti4+ functionalized hydrophilic covalent organic frameworks by introducing glutathione (GSH) and 2,3,4-trihydroxy benzaldehyde (THBA) via click chemistry and Schiff base reaction (COF-V@GSH-THBA-Ti4+ ) was constructed and applied for selective enrichment of phosphopeptides in serum. Benefit from the high surface area, excellent hydrophilicity as well as regular mesoporous structure, COF-V@GSH-THBA-Ti4+ displayed high selectivity (molar ratio of 2000:1), low limit of detection (0.5 fmol), high load capacity (100.0 mg/g) and excellent size-exclusion effect (1:10000) for enrichment of phosphopeptides. For actual bio-sample analysis, 15 phosphopeptides assigned to 10 phosphoproteins with 16 phosphorylated sites and 33 phosphopeptides assigned to 25 phosphoproteins with 34 phosphorylated sites were detected from the serum of patients with chronic obstructive pulmonary disease (COPD), and normal controls. Biological processes and molecular functions analysis further disclosed the difference of serums with phosphoproteomics between COPD and normal controls.