Controlled Encapsulation of Gold Nanoparticles into Zr-Metal-Organic Frameworks with Improved Detection Limitation of Volatile Organic Compounds via Surface-Enhanced Raman Scattering.

Volatile organic compounds (VOCs) have harmful effects on human health and the environment but detecting low levels of VOCs is challenging due to a lack of reliable biomarkers. However, incorporating gold nanoparticles (Au NPs) into metal-organic frameworks (MOFs) shows promise for VOC detection. In this study, we developed nanoscale Au@UiO-66 that exhibited surface-enhanced Raman scattering (SERS) activity even at very low levels of toluene vapors (down to 1.0 ppm) due to the thickness of the shell and strong π-π interactions between benzenyl-type linkers and toluene. The UiO-66 shell also increased the thermal stability of the Au NPs, preventing aggregation up to 550 °C. This development may be useful for sensitive detection of VOCs for environmental protection purposes.

One-step Fabrication of Physical Eutectogel with Recyclability: Crystalline Domain Regulation Induced by Microgels.

HYPOTHESIS: Despite their non-volatility, low cost, and recyclability, physical eutectogels' appeal is hindered by the intricate fabrication process and the involvement of hazardous chemicals. The network of polyvinyl alcohol (PVA) in deep eutectic solvent (choline chloride and glycerol) might be developed by the addition of microgels of polyacrylic acid (Carbopol). EXPERIMENTS: Hydrogen-bond interactions between Carbopol and PVA are revealed through Fourier-transform infrared spectroscopy. The impact of microgels on crystalline domains and the polymer network can be observed using X-ray diffraction and scanning electron microscopy. The physical properties of the eutectogel, including mechanical strength and ionic conductivity, are investigated as well. Finally, the strain-sensing ability and remarkable recyclability of the eutectogel are demonstrated. FINDINGS: The physical eutectogel can be obtained through a one-step fabrication process using only green and low-cost materials. It demonstrates robust strength (1.02 MPa) and remarkable stretchability (1000 % strain). This is attributed to the uniform dispersion of PVA crystalline domains within the deep eutectic solvent, facilitated by the hydrogen bonds and space restriction effects between PVA and Carbopol. Furthermore, the physical eutectogel with recyclability can consistently generate electrical resistance signals, highlighting its potential as a reliable strain sensor.

Decoding the Biomimetic Mineralization of Metal-Organic Frameworks in Water.

This study unveils the "green" metal-organic framework (MOF) structuring mechanism by decoding proton transfer in water during ZIF-8 synthesis. Combining in situ small- to wide-angle X-ray scattering, multiscale simulations, and quantum calculations, we reveal that the ZIF-8 early-stage nucleation and crystallization process in aqueous solution unfolds in three distinct stages. In stage I, imidazole ligands replace water in zinc-water cages, triggering an "acidity flip" that promotes proton transfer. This leads to the assembly of structures from single zinc ions to 3D amorphous cluster nuclei. In stage II, amorphous nuclei undergo a critical transformation, evolving into crystalline nuclei and subsequently forming mesoscale-ordered structures and crystallites. The process proceeds until the amorphous precursors are completely consumed, with the transformation kinetics governed by an energy barrier that determines the rate-limiting step. In stage III, stable crystallite nanoparticles form in solution, characterized by a temperature-dependent thermal equilibrium of molecular interactions at the crystal-solution interface. Beyond these core advancements, we explore the influence of encapsulated pepsin and nonencapsulated lysozyme on ZIF-8 formation, finding that their amino acid proton transfer capacity and concentration influence the resulting biomolecule-MOF composite's shape and encapsulation efficiency. The findings contribute to understanding the molecular mechanisms behind biomimetic mineralization and have potential implications for engineering proteins within amorphous MOF nuclei as protein embryo growth sites.

Exploring Enzyme Encapsulation Efficiency in MOFs Using Eco-friendly Approaches.

The encapsulation of protein enzymes in metal-organic frameworks (MOFs) has been recognized as an effective enzyme immobilization approach. In this study, we demonstrated the influence of enzyme amount and the isoelectric points (pI) of different enzymes on the enzyme loading capacity in both mechanochemical (ball-milling) and water-based approaches. We found that increasing enzyme amounts enhances MOF enzyme loading without compromising activity, while the MOF shell protects encapsulated enzymes from proteinase K degradation through its size-sheltering mechanism. However, an excess of enzymes can hinder the formation of ZIF-90. Moreover, enzymes with low pI values (e.g., catalase, pI 5.4) facilitate encapsulation in MOFs, whereas enzymes with high pI values (e.g., lysozyme, pI 11.35) are more challenging to encapsulate. The simulation results revealed that increasing the enzyme amounts and pI values raises the activation energy necessary for MOF formation. This study highlights the crucial role of enzyme properties in the encapsulation process within MOFs, providing valuable insights for fabricating enzyme-MOF biocomposites for diverse applications, such as protein drug delivery.

Jammed Microgels in Deep Eutectic Solvents as a Green and Low-Cost Ink for 3D Printing of Reliable Auxetic Strain Sensors.

Additive manufacturing is a promising technique for offering novel functionality to various materials by creating three-dimensional (3D) structures. However, the development of sustainable synthesis processes for 3D printing inks or 3D-printed materials remains a major challenge. In this work, a simple two-step mixing approach is developed to prepare a 3D printing ink from green, low-cost, and low-toxicity materials [commercial Carbopol and deep eutectic solvents (DESs)]. A small weight fraction of Carbopol can impart desired rheological properties to the DES used in the 3D printing ink and also can significantly enhance the stretchability of eutectogels up to 2500% strain. The 3D-printed auxetic structure shows a negative Poisson's ratio (within 100% strain), high stretchability (300%), high sensitivity (gauge factor of 3.1), good moisture resistance, and sufficient transparency. It can detect human motion with high skin comfort and breathability. The results of this work highlight a green, low-cost, and energy-saving strategy to fabricate conductive microgel-based inks for 3D printing of wearable devices.

Triboelectric behaviour of selected MOFs in contact with metals.

MOFs have been effectively used to magnify the triboelectric charge of polymers. However, so far the individual triboelectric properties and charge transfer mechanisms of MOFs haven't been reported. Triboelectric property investigation for selected MOFs show that the main mechanism for MOF triboelectrification in contact with metals is electron transfer.

Rapid Fabrication of Biocomposites by Encapsulating Enzymes into Zn-MOF-74 via a Mild Water-Based Approach.

A zinc-based metal organic framework, Zn-MOF-74, which has a unique one-dimensional (1D) channel and nanoscale aperture size, was rapidly obtained in 10 min using a de novo mild water-based system at room temperature, which is an example of green and sustainable chemistry. First, catalase (CAT) enzyme was encapsulated into Zn-MOF-74 (denoted as CAT@Zn-MOF-74), and comparative assays of biocatalysis, size-selective protection, and framework-confined effects were investigated. Electron microscopy and powder X-ray diffraction were used for characterization, while electrophoresis and confocal microscopy confirmed the immobilization of CAT molecules inside the single hexagonal MOF crystals at loading of ∼15 wt %. Furthermore, the CAT@Zn-MOF-74 hybrid was exposed to a denaturing reagent (urea) and proteolytic conditions (proteinase K) to evaluate its efficacy. The encapsulated CAT maintained its catalytic activity in the decomposition of hydrogen peroxide (H2O2), even when exposed to 0.05 M urea and proteinase K, yielding an apparent observed rate constant (kobs) of 6.0 × 10-2 and 6.6 × 10-2 s-1, respectively. In contrast, free CAT exhibited sharply decreased activity under these conditions. Additionally, the bioactivity of CAT@Zn-MOF-74 for H2O2 decomposition was over three times better than that of the biocomposites based on zeolitic imidazolate framework 90 (ZIF-90) owing to the nanometer-scaled apertures, 1D channel, and less confinement effects in Zn-MOF-74 crystallites. To demonstrate the general applicability of this strategy, another enzyme, α-chymotrypsin (CHT), was also encapsulated in Zn-MOF-74 (denoted as CHT@Zn-MOF-74) for action against a substrate larger than H2O2. In particular, CHT@Zn-MOF-74 demonstrated a biological function in the hydrolysis of l-phenylalanine p-nitroanilide (HPNA), the activity of ZIF-90-encapsulated CHT was undetectable due to aperture size limitations. Thus, we not only present a rapid eco-friendly approach for Zn-MOF-74 synthesis but also demonstrate the broader feasibility of enzyme encapsulation in MOFs, which may help to meet the increasing demand for their industrial applications.