Facile synthesis of boronic acid-functionalized magnetic metal–organic frameworks for selective extraction and quantification of catecholamines in rat plasma

Precise determination of the endogenous catecholamines, dopamine (DA), epinephrine (E) and norepinephrine (NE) faces substantial challenges due to their low physiological concentrations in plasma. We synthesized, for the first time, a magnetic metal–organic framework (MIL-100) composite with boronic acid-functionalized pore-walls (denoted as MG@MIL-100-B composite) using a metal–ligand-fragment coassembly (MLFC) strategy. The composites were then applied as an effective magnetic solid-phase extraction (SPE) sorbent for determination of trace catecholamine concentrations in rat plasma through coupling with HPLC-MS/MS. The obtained nano-composites exhibited high magnetic responsivity, uniform mesopores, large specific surface area, and boronic acid-functionalized inner pore-walls. Catecholamines in rat plasma were extracted through interaction between the cis-diol structures and the boronic acid groups in the MG@MIL-100-B composites. Extraction conditions were optimized by studying SPE parameters including adsorption and desorption time, elution solvent type, pH conditions and adsorbent amount. With our approach, the detection limits (S/N = 3) were as low as 0.005 ng mL⁻¹ for DA and E, and 0.02 ng mL⁻¹ for NE. Intra- and inter-day precision ranged from 2.84–6.63% (n = 6) and 5.70–11.44% (n = 6), respectively. Recoveries from spiking experiments also showed satisfactory results of 94.40–109.51%. Finally, the MG@MIL-100-B composites were applied successfully to determine catecholamine concentrations in rat plasma.

MG@MIL-100-B takes magnetic Fe₃O₄ microparticles as core and coated by MIL-100-B shows great potential as a SPE absorbent material for the analysis of catecholamines, due to its rapid magnetic separation, outstanding sensitivity and selectivity.     

Fe-based metal–organic frameworks as heterogeneous catalysts for highly efficient degradation of wastewater in plasma/Fenton-like systems

Fe-based metal organic frameworks (Fe-MOFs) were successfully synthesized with the dielectric barrier discharge (DBD) plasma method and FeSO₄·7H₂O as the Fe precursor. Fe-MOFs were used as Fenton-like catalysts in DBD plasma/Fenton-like technology to treat wastewater, which addressed the issues with iron solubility. Since the valence state of iron will affect the catalytic performance, the Fe precursor FeSO₄·7H₂O was added to regulate the valence state and adjust the catalytic performance by improving the availability of active sites. The influences of discharge voltage, catalyst addition amount, H₂O₂ addition amount and pH on the degradation efficiency of methyl orange (MO) were systematically examined. Through free radical capture experiments, the reaction mechanism of the plasma/Fenton-like catalytic degradation process was deduced primarily as the coordinated oxidation process of hydroxyl radicals (·OH), photo-generated holes (h⁺) and superoxide radicals (·O₂⁻). The reusability experiments proved that the catalyst was stable and reusable. The possible degradation pathways were proposed based on the identification of intermediate products generated in the degradation process by liquid chromatography-mass spectrometry (LC-MS) analyses.

Fe-based metal organic frameworks (Fe-MOFs) were successfully synthesized with the dielectric barrier discharge (DBD) plasma method and FeSO₄·7H₂O as the Fe precursor.     

Cu-based metal–organic framework HKUST-1 as effective catalyst for highly sensitive determination of ascorbic acid

In this work, a Cu-based nanosheet metal–organic framework (MOF), HKUST-1, was synthesised using a solvent method at room temperature. Its morphology, structure and composition were characterised by scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM), powder X-ray diffraction (XRD), Fourier transform infrared (FTIR), Raman spectroscopy, nitrogen adsorption and desorption isotherms, energy dispersive X-ray spectroscopy (EDS) and elemental analysis (EA). This material was then loaded onto the surface of an indium tin oxide (ITO) electrode to catalyse the electrochemical oxidation of ascorbic acid (AA). An equal-electron-equal-proton reaction was deduced from the pH investigation, and a diffusion-controlled process was reinforced by the dynamics study. Under optimal conditions, the oxidation peak current at +0.02 V displayed a linear relationship with the concentration of AA within the ranges of 0.01–25 and 25–265 mM, respectively. The limit of detection (LOD) was 3 μM at S/N of 3. The superb response could be ascribed to the porous nanosheet structure of HKUST-1, which enhanced both the effective surface area and the electron transfer ability significantly. Moreover, the novel AA sensor demonstrated good reproducibility, favourable stability and high sensitivity towards glucose, uric acid (UA), dopamine (DA) and several amino acids. It was also successfully applied to the real sample testing of various AA-containing tablets.

In this work, a Cu-based nanosheet metal–organic framework (MOF), HKUST-1, was synthesised using a solvent method at room temperature and it demonstrated high capability and sensitivity towards the oxidation of ascorbic acid (AA).     

A new core–shell magnetic mesoporous surface molecularly imprinted composite and its application as an MSPE sorbent for determination of phthalate esters

In this study, a new core–shell magnetic mesoporous surface molecularly imprinted polymer (Fe₃O₄@SiO₂@mSiO₂-MIPs) which has specific adsorption and rapid adsorption rate for phthalate esters (PAEs) was prepared by a convenient method. Based on this composite as a magnetic solid phase extraction (MSPE) material, a rapid, efficient and sensitive matrix dispersion magnetic solid-phase extraction gas chromatography-mass spectrometry method (DMSPE-GC/MS) was developed for the determination of PAEs in multiple liquid samples. It is the first time that Fe₃O₄@SiO₂@mSiO₂-MIPs have been prepared by bonding amino groups on the surface of a double layer silicon substrate with diisononyl phthalate (DINP) as virtual template and 3-(2-aminoethyl)-aminopropyl trimethoxymethylsilane (TSD) as functional monomer. FT-IR, TEM, EDS, SEM, XRD, BET and VSM were used to characterize the composite. The adsorption isotherm and kinetics of Fe₃O₄@SiO₂@mSiO₂-MIPs showed that it possessed fast adsorption rates (approximately 5 min to reach equilibrium), high adsorption capacities (523.9 mg g⁻¹) and good recognition of PAEs. The real samples were preconcentrated by Fe₃O₄@SiO₂@mSiO₂-MIPs, under the optimum DMSPE-GC/MS conditions. Validation experiments showed that the method presented good linearity (R² > 0.9971), satisfactory precision (RSD < 5.7%) and high recovery (92.1–105.8%), and the limits of detection ranged from 1.17 ng L⁻¹ to 3.03 ng L⁻¹. The results indicated that the novel method had good sensitivity, high efficiency and wide sample application and was suitable for the determination of PAEs in liquid drink samples such as water, alcohol, beverages and so on.

A new core–shell magnetic mesoporous surface molecularly imprinted polymer (Fe3O4@SiO2@mSiO2-MIPs) which has specific adsorption for phthalate esters was synthesized by a facile and convenient method.     

Self-assembly of 2D-metal–organic framework/graphene oxide membranes as highly efficient adsorbents for the removal of Cs+ from aqueous solutions

The potential toxicity and irreversibility of radionuclide Cs place severe pressure on the natural environment, which has become one of the most forefront pollution problems in nuclear energy utilization. To solve this problem, novel self-assembled membranes consisting of two-dimensional (2D) metal–organic frameworks (MOFs) and graphene oxide (GO) were prepared by a facile filtration method, which can efficiently absorb Cs⁺ from aqueous solutions. The batch experimental results showed that the sorption of Cs⁺ on the GO/Co-MOF composite membrane was strongly dependent on the addition mass and the membrane compositions. Thus, the dominant interaction mechanism was interface or surface complexation and electrostatic interaction. The maximum sorption efficiency of Cs⁺ on GO/Co-MOF was 88.4% with 8 mg addition mass at pH = 7.0 and 299 K. Detailed FT-IR and XPS analyses suggested that the efficient synergistic effects in the unique architectures of GO/Co-MOF play an important role in the high sorption capacity of Cs⁺. The facile preparation method and the highly-efficient Cs⁺ removal behaviour of GO/Co-MOF make the novel membrane a promising candidate for the elimination of radionuclide contamination.

A 2D-metal–organic frameworks/graphene oxide membrane that combines the electrostatic self-assembly of electronegative GO sheets and electropositive MOF sheets, which exhibits high mechanical flexibility, and superior Cs⁺ sorption, is presented.