Enhanced peroxidase-like activity of MOF nanozymes by co-catalysis for colorimetric detection of cholesterol.

Metal-organic frameworks (MOFs) have been widely used as nanozymes with a great development prospect due to their unique advantages. It is known that the current Fe-based or Cu-based MOF, etc., exhibits the catalytic activity of nanozymes through the Fenton catalytic reaction. And the conversion efficiency of the Fe3+/Fe2+ or Cu2+/Cu+ cycle is key to the catalytic activity. Therefore, we proposed a novel co-catalytic method to promote the reaction rate of the rate-limiting step of Cu2+/Cu+ conversion in the Fenton reaction of Cu2+/H2O2 to enhance the catalytic activity of the nanozymes. As a proof of concept, the MoCu-2MI nanozyme with high catalytic activity was successfully synthesized using Mo-doped Cu-2MI (2-methylimidazole). By using 3,3',5,5'-tetramethylbenzidine (TMB) as the chromogenic substrate, MoCu-2MI exhibited higher peroxidase-like activity than pure Cu-2MI. Then, it was confirmed that the newly introduced Mo played a crucial co-catalytic role by characterizing the possible catalytic mechanism. Specifically, Mo acted as a co-catalyst to accelerate the electron transfer in the system, and then promote the Cu2+/Cu+ cycle in the Cu-Fenton reaction, which was conducive to accelerating the production of a large number of reactive oxygen species (ROS) from H2O2, and finally improve the activity. Ultimately, a biosensor platform combined with MoCu-2MI and cholesterol oxidase realized the one-step colorimetric detection of cholesterol in the range of 2-140 µM with the detection limit as low as 1.2 µM. This study provides a new strategy for regulating the activity of MOF nanozymes.

Preparation of cationic hierarchical porous covalent organic frameworks for rapid and effective enrichment of perfluorinated substances in dairy products.

Perfluorinated substances (PFASs) are harmful pollutants that have environmental persistence and high bioaccumulation. Effective sample pretreatment must be performed to detect trace or even ultra-trace PFASs in actual samples because of their extremely low contents in complex samples. In this study, a cationic hierarchical porous covalent organic frameworks (C-H-COF) were customized via a template-assisted strategy using polystyrene spheres (PS) as sacrificial materials and a post-synthetic modification method. C-H-COF showed good adsorption selectivity for PFASs owing to the dual effects of the full utilization of the internal adsorption sites and electrostatic interaction. The key role of electrostatic attraction in the extraction of PFASs using C-H-COF was further proven by density functional theory (DFT) calculations. The maximum adsorption capacity of the C-H-COF for perfluorooctanoic acid (PFOA) was 400 mg·g⁻1, which was superior to that of microporous COFs (M-COF) and hierarchical porous COFs without cationic functionalization (H-COF). Accordingly, an analytical method for sensitively detecting five PFASs was established by employing C-H-COF as a dispersive solid phase extraction (DSPE) adsorbent combined with ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS), and the limits of detection were 0.011‒0.29 ng·L⁻1. Moreover, the hierarchical porous structure of the C-H-COF accelerated the mass transfer of analytes so that the extraction process could be completed within 10 min. This method was employed to analyze PFASs in dairy products, in which the ultra-trace levels of analytes were quickly determined with spiked recoveries of 80.1‒112.6%. This work not only provides a rational synthetic strategy for novel ionic hierarchical porous COFs but also helps to expand the application of COFs in sample pretreatment.

The TanSat mission: preliminary global observations.

The Chinese global carbon dioxide monitoring satellite (TanSat) was launched successfully in December 2016 and has completed its on-orbit tests and calibration. TanSat aims to measure the atmospheric column-averaged dry air mole fractions of carbon dioxide (XCO2) with a precision of 4 ppm at the regional scale, and in addition, to derive global and regional CO2 fluxes. Progress towards these objectives is reviewed and the first scientific results from TanSat measurements are presented. TanSat on-orbit tests indicate that the Atmospheric Carbon dioxide Grating Spectrometer is in normal working status and is beginning to produce L1B products. The preliminary TanSat XCO2 products have been retrieved by an algorithm and compared to NASA Orbiting Carbon Observatory-2 (OCO-2) measurements during an overlapping observation period. Furthermore, the XCO2 retrievals have been validated against eight ground-site measurement datasets from the Total Carbon Column Observing Network, for which the preliminary conclusion is that TanSat has met the precision design requirement, with an average bias of 2.11 ppm. The first scientific observations are presented, namely, the seasonal distributions of XCO2 over land on a global scale.