BACKGROUND: Nanozymes, a new class of nanomaterials, have emerged as promising substitutes for enzymes in biosensor design due to their exceptional stability, affordability, and ready availability. While nanozymes address many limitations of natural enzymes, they still face challenges, particularly in achieving the catalytic activity levels of their natural counterparts. This indicates the need for enhancing the sensitivity of biosensors based on nanozymes. The catalytic activity of nanozyme can be significantly improved by regulating its size, morphology, and surface composition of nanomaterial.
RESULTS: In this work, a kind of hollow core-shell structure was designed to enhance the catalytic activity of nanozymes. The hollow core-shell structure material consists of a nanozymes core layer, a hollow layer, and a MOF shell layer. Taking the classic peroxidase like Fe3O4 as an example, the development of a novel nanozyme@MOF, specifically p-Fe3O4@PDA@ZIF-67, is detailed, showcasing its application in enhancing the sensitivity of sensors based on Fe3O4 nanozymes. This innovative nanocomposite, featuring that MOF layer was designed to adsorb the signal molecules of the sensor to improve the utilization rate of reactive oxygen species generated by the nanozymes catalyzed reactions and the hollow layer was designed to prevent the active sites of nanozymes from being cover by the MOF layer. The manuscript emphasizes the nanocomposite\'s remarkable sensitivity in detecting hydrogen peroxide (H2O2), coupled with high specificity and reproducibility, even in complex environments like milk samples.
UNASSIGNED: This work firstly proposed and proved that Fe3O4 nanozyme@MOF with hollow layer structure was designed to improve the catalytic activity of the Fe3O4 nanozyme and the sensitivity of the sensors based on Fe3O4 nanozyme. This research marks a significant advancement in nanozyme technology, demonstrating the potential of structural innovation in creating high-performance, sensitive, and stable biosensors for various applications.

Encapsulating enzymes in metal-organic frameworks is a common practice to improve enzyme stability against harsh conditions. However, the synthesis of enzyme@MOFs has been primarily limited to small-scale laboratory settings, hampering their industrial applications. Spray drying is a scalable and cost-effective technology, which has been frequently used in industry for large-scale productions. Despite these advantages, its potential for encapsulating enzymes in MOFs remains largely unexplored, due to challenges such as nozzle clogging from MOF particle formation, utilization of toxic organic solvents, controlled release of encapsulated enzymes, and high temperatures that could compromise enzyme activity. Herein, we present a novel approach for preparing phytase@MIL-88 A using solvent-free spray drying. This involves atomizing two MOF precursor solutions separately using a three-fluid nozzle, with enzyme release controlled by manipulating defects within the MOFs. The physicochemical properties of the spray dried particles are characterized using X-ray diffraction, Fourier-transform infrared spectroscopy, and scanning electron microscopy. Leveraging the efficiency and scalability of spray drying in industrial production, this scalable encapsulation technique holds considerable promise for broad industrial applications.

The quantitative measurement of adsorbed guest species within metal-organic framework (MOF) pores is of fundamental importance for evaluating the adsorption performance of MOFs. However, routine analytic techniques such as thermogravimetric analysis cannot distinguish the contribution from species adsorbed within pores, species adsorbed on the surface, and gas phase or liquid phase encapsulated in the inter-crystalline space. Herein, we developed a new quantification method based on the cross-polarization (CP) solid-state nuclear magnetic resonance (ssNMR) technique, in which only the species within MOF pores are selectively probed due to the dramatically reduced mobility. Using the commercialized MOF α-Mg3(HCOO)6 as an example, a good linear correlation between Areaguest/Areaframework (i. e., the integrated area of guest and framework 13C NMR signals) and guest loading can be observed for several representative molecules such as benzene, tetrahydrofuran (THF), and 1,4-dioxane, clearly revealing the feasibility of CP quantification approach. The effects of guest molecule and corresponding residual mobility on the CP quantification are further discussed by varying the geometry and size of guest molecules. This methodology thus provides an effective and irreplaceable route to evaluate the adsorption performance of porous materials in-depth, especially for liquid-phase adsorption and gas-phase adsorption in which the capillary condensation is not negligible.

The Dean Flow, a physics phenomenon that accounts for the impact of channel curvature on fluid dynamics, has great potential to be used in microfluidic synthesis of nanoparticles. This study explores the impact of the Dean Flow on the synthesis of ZIF-8 particles. Several variables that influence the Dean Equation (the mathematical expression of Dean Flow) are tested to validate the applicability of this expression in microfluidic synthesis, including the flow rate, radius of curvature, channel cross sectional area, and reagent concentration. It is demonstrated that the current standard of reporting, providing only the flow rate and crucially not the radius of curvature, is an incomplete description that will invariably lead to irreproducible syntheses across different laboratories. An alternative standard of reporting is presented and it is demonstrated how the sleek and simple math of the Dean Equation can be used to precisely tune the final dimensions of high quality, monodisperse ZIF-8 nanoparticles between 40 and 700 nm.

Preconcentration for on-site detection or subsequent determination is a promising technique for selective sensing explosive markers at low concentrations. Here, we report divinylbenzene monolithic polymer in its blank form (neat-DVB) and as a composite incorporated with sodalite topology zeolite-like metal-organic frameworks (3-ZMOF@DVB), as a sensitive, selective, and cost-effective porous preconcentrator for aliphatic nitroalkanes in the vapor phase as explosive markers at infinite dilution. The developed materials were fabricated as 18 cm gas chromatography (GC) monolithic capillary columns to study their separation performance of nitroalkane mixture and the subsequent physicochemical study of adsorption using the inverse gas chromatography (IGC) technique. A strong preconcentration effect was indicated by a specific retention volume adsorption/desorption ratio equal to 3 for nitromethane on the neat-DVB monolith host-guest interaction, and a 14% higher ratio was observed using the 3-ZMOF@DVB monolithic composite despite the low percentage of 0.7 wt.% of sod-ZMOF added. Furthermore, Incorporating ZMOF resulted in a higher percentage of micropores, increasing the degree of freedom more than bringing stronger adsorption and entropic-driven interaction more than enthalpic. The specific free energy of adsorption (ΔGS) values increased for polar probes and nitroalkanes, denoting that adding ZMOFs earned the DVB monolithic matrix a more specific character. Afterward, Lewis acid-base properties were calculated, estimating the electron acceptor (KA) and electron donor (KB) constants. The neat-DVB was found to have a Lewis basic character with KB/KA = 7.71, and the 3-ZMOF@DVB had a less Lewis basic character with KB/KA = 3.82. An increased electron-accepting nature can be directly related to incorporating sod-ZMOF into the DVB monolithic matrix. This work considers the initial step in presenting a portable explosives detector or preconcentrating explosive markers trace prior to more sophisticated analysis. Additionally, the IGC technique allows for understanding the factors that led to the superior adsorption of nitroalkanes for the developed materials.

Herein, we demonstrate the successful utilization of reticular chemistry as an excellent designing strategy for the deliberate construction of a zirconium-tetracarboxylate metal-organic framework (MOF) inspired by the Olympic rings. HIAM-4017, with an unprecedented (4,8)-c underlying net topology termed jcs, was developed via insightful reconstruction of the rings and judicious design of a nonsymmetric organic linker. HIAM-4017 exhibits high porosity and excellent chemical and thermal stability. Furthermore, excited-state intramolecular proton transfer (ESIPT) was achieved in an isoreticular MOF, HIAM-4018, with a large Stokes shift of 155 nm as a result of introducing the hydroxyl group to the linker skeleton to induce OH···N interactions. Such interactions were analyzed thoroughly by employing the time-dependent density functional theory (TD-DFT). Because of their good thermal and chemical stability, and strong luminescence, nanosized HIAM-4017 and HIAM-4018 were fabricated and used for Cr2O72- detection. Both MOFs demonstrate excellent sensitivity and selectivity. This work represents a neat example of building structure- and property-specific MOFs guided by reticular chemistry.

Inspired by the highly efficient water oxidation of Mn4CaO5 in natural photosynthesis, development of novel artificial water oxidation catalysts (WOCs) with structure and function mimicked has inspired extensive interests. A novel 3D cobalt-based MOF (GXY-L8-Co) was synthesized for promising artificial water oxidation by employing the Co4O4 quasi-cubane motifs with a similar structure as the Mn4CaO5 as the core. The GXY-L8-Co not only shows good chemical stability in common organic solvents or water for up to 10 days but also exhibits oxygen evolution performance. It has been demonstrated that the uniform distribution of Co4O4 catalytic active sites confined in the MOF framework should be responsible for the good robustness and catalytic performance.

The removal of low concentrations of acetic acid from indoor air at museums poses serious preservation problems that the current adsorbents cannot easily address owing to their poor affinity for acetic acid and/or their low adsorption selectivity versus water. In this context, a series of topical water-stable metal-organic frameworks (MOFs) with different pore sizes, topologies, hydrophobic characters, and functional groups was explored through a joint experimental-computational exploration. We demonstrate how a subtle combination of sufficient hydrophobicity and optimized host-guest interactions allows one to overcome the challenge of capturing traces of this very polar volatile organic compound in the presence of humidity. The optimal capture of acetic acid was accomplished with MOFs that do not show polar groups in the inorganic node or have lipophilic but polar (e.g., perfluoro) groups functionalized to the organic linkers, that is, the best candidates from the list of explored MOFs are MIL-140B and UiO-66-2CF3. These two MOFs present the appropriate pore size to favor a high degree of confinement, together with organic spacers that allow an enhancement of the van der Waals interactions with the acetic acid. We establish in this work that MOFs can be a viable solution to this highly challenging problem in cultural heritage protection, which is a new field of application for this type of hybrid materials.

A highly effective and facile synthesis route is developed to create and tailor metal-decorated and nitrogen-functionalized active microporous carbon materials from ZIF-8. Clear metal- and pyrrolic-N-induced enhancements of the cyclic CO2 uptake capacities and binding energies are achieved, particularly at a much lower carbonization temperature of 700 °C than those often reported (1000 °C). The high-temperature carbonization can enhance the porosity but only at the expense of considerable losses of sample yield and metal and N functional sites. The findings are comparatively discussed with carbons derived from metal-organic frameworks (MOFs) reported previously. Furthermore, the porosity of the MOF-derived carbon is critically dependent on the structure of the precursor MOF and the crystal growth. The current strategy offers a new and effective route for the creation and tuning of highly active and functionalized carbon structures in high yields and with low energy consumption.

M-doped NH2-MIL-125(Ti) (M=Pt and Au) were prepared by using the wetness impregnation method followed by a treatment with H2 flow. The resultant samples were characterized by powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), X-ray absorption fine structure (XAFS) analyses, N2-sorption BET surface area, and UV/Vis diffuse reflectance spectroscopy (DRS). The photocatalytic reaction carried out in saturated CO2 with triethanolamine (TEOA) as sacrificial agent under visible-light irradiations showed that the noble metal-doping on NH2-MIL-125(Ti) promoted the photocatalytic hydrogen evolution. Unlike that over pure NH2-MIL-125(Ti), in which only formate was produced, both hydrogen and formate were formed over Pt- and Au-loaded NH2-MIL-125(Ti). However, Pt and Au have different effects on the photocatalytic performance for formate production. Compared with pure NH2-MIL-125(Ti), Pt/NH2-MIL-125(Ti) showed an enhanced activity for photocatalytic formate formation, whereas Au has a negative effect on this reaction. To elucidate the origin of the different photocatalytic performance, electron spin resonance (ESR) analyses and density functional theory (DFT) calculations were carried out over M/NH2-MIL-125(Ti).The photocatalytic mechanisms over M/NH2-MIL-125(Ti) (M=Pt and Au) were proposed. For the first time, the hydrogen spillover from the noble metal Pt to the framework of NH2-MIL-125(Ti) and its promoting effect on the photocatalytic CO2 reduction is revealed. The elucidation of the mechanism on the photocatalysis over M/NH2-MIL-125(Ti) can provide some guidance in the development of new photocatalysts based on MOF materials. This study also demonstrates the potential of using noble metal-doped MOFs in photocatalytic reactions involving hydrogen as a reactant, like hydrogenation reactions.