Water-Stable Ln-MOF as a multi-emitting luminescent sensor for the detection of metal ions and pharmaceuticals.

The development of innovative multi-emission sensors for the rapid and accurate detection of contaminants is both vital and challenging. In this study, utilizing two rigid ligands (H3ICA and H4BTEC), a series of water-stable bimetallic organic frameworks (EuTb-MOFs) were synthesized. Luminescent investigations have revealed that EuTb-MOF-1 exhibits prominent multiple emission peaks, attributed to the distinctive fluorescence characteristics of Eu(III) and Tb(III) ions. Therefore, EuTb-MOF-1 efficiently recognized various metal ions and pharmaceutical compounds through 2D decoded maps. Fe3+ and Pb2+ exhibited significant quenching effects on the luminescence of EuTb-MOF-1, which were attributed to the internal filtering effect and the interaction between Lewis basic sites within EuTb-MOF-1 and Pb2+ ions, respectively. Furthermore, EuTb-MOF-1 demonstrated high sensitivity to sulfonamide antibiotics, with detection limits of 0.037 µM for SMZ and 0.041 µM for SDZ, respectively. In addition, EuTb-MOF-1 was immobilized to prepare MOF-based test strips, enabling direct visual detection of sulfonamides as a portable sensor. With excellent water stability, multi-responsive recognition capabilities, and high sensitivity to specific analytes, EuTb-MOF-1 is a promising candidate for environmental contaminant detection in aquatic systems.

Synthesis, Characterization and Photophysical Properties of a New Family of Rare-earth Cluster-based Metal-organic Frameworks.

In this work, nine new rare-earth metal-organic frameworks (RE-MOFs, where RE = Lu(III), Yb(III), Tm(III), Er(III), Ho(III), Dy(III), Tb(III), Gd(III), and Eu(III)) isostructural to Zr-MOF-808 are synthesized, characterized, and studied regarding their photophysical properties. Materials with high crystallinity and surface area are obtained from a reproducible synthetic procedure that involves the use of two fluorinated modulators. At the same time, these new RE-MOFs display tunable photoluminescent properties due to efficient linker-to-metal energy transfer promoted by the antenna effect, resulting in a series of RE-MOFs displaying lanthanoid-based emissions spanning the visible and near-infrared regions of the electromagnetic spectrum.

Advancing Anode Performance in Aqueous Zinc-Ion Batteries: A Review of Metal-Organic Framework-Based Strategies.

Aqueous zinc-ion batteries (AZIBs) are garnering substantial research interest in electric vehicles, energy storage systems, and portable electronics, primarily for the reason that the inexpensive cost, high theoretical specific capacity, and environmental sustainability of zinc metal anodes, which are an essential component to their design. Nonetheless, the progress of AZIBs is hindered by significant obstacles, such as the occurrence of anodic side reactions (SR) and the formation of zinc dendrites. Metal-organic framework (MOF)-based materials are being explored as promising alternatives owing to homogeneous porous structure and large specific surface areas. There has been a rare overview and discussion on strategies for protecting anodes using MOF-based materials. This review specifically aims to investigate cutting-edge strategies for the design of highly stable MOF-based anodes in AZIBs. Firstly, the mechanisms of dendrites and SR are summarized. Secondly, the recent advances in MOF-based anodic protection including those of pristine MOFs, MOF composites, and MOF derivatives are reviewed. Furthermore, the strategies involving MOF-based materials for zinc anode stabilization are presented, including the engineering of surface coatings, three-dimensional zinc structures, artificial solid electrolyte interfaces, separators, and electrolytes. Finally, the ongoing challenges and prospective directions for further enhancement of MOF-based anodic protection technologies in AZIBs are highlighted.

MIL-88A(Al)/chitosan/graphene oxide composite aerogel with hierarchical porosity for enhanced radioactive iodine adsorption.

To ensure the sustainable development of the nuclear industry, the effective capture of radioiodine from nuclear wastewater has attracted much attention. Herein, a novel MIL-88A(Al)/chitosan/graphene oxide (MCG) composite aerogel was prepared by using crosslinked chitosan and graphene oxide as the 3D network skeleton, and MIL-88A(Al) nanocrystalline particles were introduced into the skeleton by freeze-drying method. MIL-88A(Al) adsorption capacities for volatile and soluble iodine were 2.02 g g-1 and 850.00 mg g-1, respectively. Owing to the synergistic effect of MIL-88A(Al), GO, CS, and the hierarchically porous structures of the MCG aerogel, the adsorption capacities for volatile and soluble iodine by the MCG aerogel were increased to 2.62 g g-1 and 1072.60 mg g-1, respectively. Furthermore, the adsorption performance of the MCG aerogel for volatile and soluble iodine could be maintained at 83 % and 82 % after 5 cycles, suggesting excellent recoverability. Meanwhile, the adsorption mechanism studies showed the interactions between iodine and NH, AlO, and CO in MCG aerogel. Furthermore, the adsorption process is consistent with the Elovich kinetic and Sips isotherm models. MCG aerogels are potential candidates for enhanced radioiodine adsorption due to their high radioiodine capture performance and excellent recyclability.

Optimization of the Synthesis and Radiolabeling of ZIF-8 Nanoparticles.

Background: Lately, there has been increasing interest in the benefits of metal-organic frameworks, and among them, zeolitic imidazolate frameworks (ZIF - 8) stand out as one of the most commonly employed systems owing to their unique characteristics. Objectives: Given that properties like particle size play a key role in biomedical applications of nanoparticles, optimizing the synthesis conditions becomes crucial. Additionally, it is essential to label these nanoparticles to track them effectively within the body. Methods: Zeolitic imidazolate frameworks nanoparticles were synthesized under various conditions, including high and room temperature, using two different solvents: Water and methanol. Modifications were made to the reaction temperature and the ratio of reactants to improve the outcomes. Particle size and size distribution were assessed in all conditions. Additionally, the radiolabeling of nanoparticles was examined using four different methods to identify the method with the highest efficiency and radiochemical purity. Results: The optimum conditions for ZIF-8 synthesis were determined at 50°C using methanol as the solvent. A reactant weight ratio of 1: 2 (zinc nitrate to 2-methylimidazole) was utilized. The most effective radiolabeling approach involved using tin chloride as a reducing agent, with the reaction mixture maintained at a temperature of 70°C for 30 minutes. Conclusions: In this study, the optimum conditions were successfully identified for synthesizing and labeling ZIF-8 nanoparticles. These nanoparticles have the potential to serve as effective carriers for diagnostic and therapeutic agents.

In Situ Defect Engineering of Fe-MIL for Self-Enhanced Peroxidase-Like Activity.

Defect engineering is an effective strategy to enhance the enzyme-like activity of nanozymes. However, previous efforts have primarily focused on introducing defects via de novo synthesis and post-synthetic treatment, overlooking the dynamic evolution of defects during the catalytic process involving highly reactive oxygen species. Herein, a defect-engineered metal-organic framework (MOF) nanozyme with mixed linkers is reported. Over twofold peroxidase (POD)-like activity enhancement compared with unmodified nanozyme highlights the critical role of in situ defect formation in enhancing the catalytic performance of nanozyme. Experimental results reveal that highly active hydroxyl radical (•OH) generated in the catalytic process etches the 2,5-dihydroxyterephthalic acid ligands, contributing to electronic structure modulation of metal sites and enlarged pore sizes in the framework. The self-enhanced POD-like activity induced by in situ defect engineering promotes the generation of •OH, holding promise in colorimetric sensing for detecting dichlorvos. Utilizing smartphone photography for RGB value extraction, the resultant sensing platform achieves the detection for dichlorvos ranging from 5 to 300 ng mL-1 with a low detection limit of 2.06 ng mL-1. This pioneering work in creating in situ defects in MOFs to improve catalytic activity offers a novel perspective on traditional defect engineering.

Constructing Metal-Organic Framework Films with Adjustable Electronic Properties on Hematite Photoanode for Boosting Photogenerated Carrier Transport.

Hematite (α-Fe2O3) has become a research hotspot in the field of photoelectrochemical water splitting (PEC-WS), but the low photogenerated carrier separation efficiency limits further application. The electronic structure regulation, such as element doping and organic functional groups with different electrical properties, is applied to alleviate the problems of poor electrical conductivity, interface defects, and band mismatch. Herein, α-Fe2O3 photoanodes are modified to regulate their electric structures and improve photogenerated carrier transport by the bimetallic metal-organic frameworks (MOFs), which are constructed with Fe/Ni and terephthalate (BDC) with 2-substitution of different organic functional groups (─H, ─Br, ─NO2 and ─NH2). The α-Fe2O3 photoanode loaded with FeNi-NH2BDC MOF catalyst exhibits the optimal photocurrent density (2 mA cm-2) at 1.23 VRHE, which is 2.33 times that of the pure α-Fe2O3 photoanode. The detailed PEC analyses demonstrate that the bimetallic synergistic effect between Fe and Ni can improve the conductivity and inhibit the photogenerated carrier recombination of α-Fe2O3 photoanodes. The ─NH2 group as an electron-donor group can effectively regulate the electron distribution and band structure of α-Fe2O3 photoanodes to prolong the lifetime of photogenerated holes, which facilitates photogenerated carrier transport and further enhances the PEC-WS performance of α-Fe2O3 photoanode.

A new UiO-66-NH2 MOF-based nano-immobilized DFR enzyme as a biocatalyst for the synthesis of anthocyanidins.

Anthocyanidins and anthocyanins are one subclass of flavonoids in plants with diverse biological functions and have health-promoting effects. Dihydroflavonol 4-reductase (DFR) is one of the important enzymes involved in the biosynthesis of anthocyanidins and other flavonoids. Here, a new MOF-based nano-immobilized DFR enzyme acting as a nano-biocatalyst for the production of anthocyanidins in vitro was designed. We prepared UiO-66-NH2 MOF nano-carrier and recombinant DFR enzyme from genetic engineering. DFR@UiO-66-NH2 nano-immobilized enzyme was constructed based on covalent bonding under the optimum immobilization conditions of the enzyme/carrier ratio of 250 mg/g, 37 °C, pH 6.5 and fixation time of 10 min. DFR@UiO-66-NH2 was characterized and its catalytic function for the synthesis of anthocyanidins in vitro was testified using UPLC-QQQ-MS analysis. Compared with free DFR enzyme, the enzymatic reaction catalyzed by DFR@UiO-66-NH2 was more easily for manipulation in a wide range of reaction temperatures and pH values. DFR@UiO-66-NH2 had better thermal stability, enhanced adaptability, longer-term storage, outstanding tolerances to the influences of several organic reagents and Zn2+, Cu2+ and Fe2+ ions, and relatively good reusability. This work developed a new MOF-based nano-immobilized biocatalyst that had a good prospect of application in the green synthesis of anthocyanins in the future.

Metal-Organic Frameworks (MOFs): Classification, Synthesis, Modification, and Biomedical Applications.

Metal-organic frameworks (MOFs) are a new variety of solid crystalline porous functional materials. As an extension of inorganic porous materials, it has made important progress in preparation and application. MOFs are widely used in various fields such as gas adsorption storage, drug delivery, sensing, and biological imaging due to their high specific surface area, porosity, adjustable pore size, abundant active sites, and functional modification by introducing groups. In this paper, the types of MOFs are classified, and the synthesis methods and functional modification mechanisms of MOFs materials are summarized. Finally, the application prospects and challenges of metal-organic framework materials in the biomedical field are discussed, hoping to promote their application in multidisciplinary fields.

Optical-Propulsion Metastructures.

Pulsed laser micropropulsion (PLMP) offers a promising avenue for miniature space craft, yet conventional propellants face challenges in balancing efficiency and stability. An optical-propulsion metastructure strategy using metal-organic frameworks (MOFs) is presented to generate graphene-metal metastructures (GMM), specifically GMM-(HKUST-1), which significantly enhances PLMP performance. This novel approach leverages the unique interaction between pulsed lasers and the precisely engineered GMMs-comprising optimized metal nanoparticle size, graphene layers, and inter-particle gaps-to boost both propulsion efficiency and stability. Experimental and numerical analyses reveal that GMM-(HKUST-1) achieves aspecific impulse of 1072.94 s, ablation efficiency of 51.22%, and impulse thrust per mass of 105.15 µN µg-1, surpassing traditional propellants. With an average particle size of ≈12 nm and a density of 0.958 g cm-3, these metastructures exhibit 99% light absorption efficiency and maintain stability under atmospheric and humid conditions. The graphene nanolayer efficiently absorbs and converts laser energy, while the metal nanostructures enhance light-matter interactions, promoting energy transfer and material stability. These findings suggest that this GMM-based optical-propulsion strategy can revolutionize microspacecraft propulsion and energy systems, offering significant advancements across various domains.

Linking mechanochemistry with the green chemistry principles: Review article.

The need to explore contemporary alternatives for industrial production has driven the development of innovative techniques that address critical limitations linked to traditional batch mechanochemistry. One particularly promising strategy involves the integration of flow processes with mechanochemistry. Three noteworthy technologies in this domain are single-screw extrusion (SSE) and twin-screw extrusion (TSE) and Impact (Induction) in Continuous-flow Heated Mechanochemistry (ICHeM). These technologies go beyond the industrial production of polymers, extending to the synthesis of active pharmaceutical ingredients, the fabrication of (nano)materials, and the extraction of high-added value products through the valorisation of biomass and waste materials. In accordance with the principles of green chemistry, ball milling processes are generally considered greener compared to conventional solvothermal processes. In fact, ball milling processes require less solvent, enhance reaction rates and reaction conversion by increasing surface area and substituting thermal energy with mechanochemical energy, among others. Special attention will be given to the types of products, reactants, size of the milling balls and reaction conditions, selecting 60 articles after applying a screening methodology during the period 2020-2022. This paper aims to compile and analyze the cutting edge of research in utilizing mechanochemistry for green chemistry applications.

A Computation-guided Design of Highly Defined and Dense Bimetallic Active Sites on a Two-dimensional Conductive Metal-organic Framework for Efficient H2O2 Electrosynthesis.

Electrochemical synthesis of hydrogen peroxide (H2O2) via the two-electron oxygen reduction reaction (2e--ORR) provides an alternative method to the energy-intensive anthraquinone method. Metal macrocycles with precise coordination are widely used for 2e--ORR electrocatalysis, but they have to be commonly loaded on conductive substrates, thus exposing a large number of 2e--ORR-inactive sites that result in poor H2O2 production rate and efficiency. Herein, guided by first-principle predictions, a substrate-free and two-dimensional conductive metal-organic framework (Ni-TCPP(Co)), composed of Co-N4 sites in porphine(Co) centers and Ni2O8 nodes, is designed as a multi-site catalyst for H2O2 electrosynthesis. The approperiate distance between the CoN4 and Ni2O8 sites in Ni-TCPP(Co) weakens the electron transfer between them, thus ensuring their inherent activities and creating high-density active sites. Meanwhile, the intrinsic electronic conductivity and porosity of Ni-TCPP(Co) further facilitate rapid reaction kinetics. Therefore, outstanding 2e--ORR electrocatalytic performance has been achieved in both alkaline and neutral electrolytes (>90%/85% H2O2 selectivity within 0-0.8 V vs. RHE and >18.2/18.0 mol g-1 h-1 H2O2 yield under alkaline/neutral conditions), with confirmed feasibility for water purification and disinfection applications. This strategy thus provides a new avenue for designing catalysts with precise coordination and high-density active sites, promoting high-efficiency electrosynthesis of H2O2 and beyond.

A novel hybrid lanthanide metal-organic frameworks based on porphyrin for rapid detection of iron ions.

BACKGROUND: Iron ion (Fe3+) is essential for the environment and human health. Detecting Fe3+ in water is crucial, making high-performance detection a key objective. Lanthanide metal-organic frameworks with abundant functional sites have been deemed a promising fluorescence sensor for Fe3+ detection. Currently, most metal-organic framework-based sensors for Fe3+ detection have cumbersome and time-consuming synthesis procedures and long detection times, which greatly limits their practical application. This study aims to construct a hybrid lanthanide metal-organic frameworks-based fluorescence sensor for Fe3+ detection that promises simple and rapid iron ion quantification in water. RESULTS: A novel hybrid lanthanide metal-organic frameworks (ECTMNs) was synthesized in one step using a solvothermal method with only 4 h. The frameworks comprise two metal ions, cerium and europium, serving as metal centers, and 4,4,4,4-(Porphine-5,10,15,20-tetrayl) tetrakis (TCPP) as an organic ligand. With the addition of Fe3+, the host-guest reaction occurred between Fe3+ and ECTMNs probe, leading to the gradual fluorescence burst of ECTMNs probe. A strong linear correlation between ECTMNs fluorescence intensity and Fe3+ concentration (1-90 µM) makes it a reliable sensor for Fe3+ monitoring with a detection limit of 0.3 µM. Moreover, the method was used to analyze real samples (tap water and river water), showing good recoveries (92-98 %) and low relative standard deviations (3.96-6.11 %), making it a promising option for rapidly detecting Fe3+. SIGNIFICANCE AND NOVELTY: A rapid synthesis protocol for hybrid lanthanide metal-organic frameworks is proposed in this study. The obtained ECTMNs exhibits good water solubility, high stability, and specificity for Fe3+. Based on ECTMNs, an innovative fluorescence sensor is established for selectively detecting Fe3+ in water, which is a simple operation method with a low detection limit and short sensing time. It provides a novel method for accurately and rapidly detecting Fe3+ in environmental pollution and water safety monitoring.

Modification of metals and ligands in two-dimensional conjugated metal-organic frameworks for CO2 electroreduction: A combined density functional theory and machine learning study.

Electrochemical carbon dioxide reduction reaction (CO2RR) is a promising technology to establish an artificial carbon cycle. Two-dimensional conjugated metal-organic frameworks (2D c-MOFs) with high electrical conductivity have great potential as catalysts. Herein, we designed a range of 2D c-MOFs with different transition metal atoms and organic ligands, TMNxO4-x-HDQ (TM = Cr∼Cu, Mo, Ru∼Ag, W∼Au; x  = 0, 2, 4; HDQ = hexadipyrazinoquinoxaline), and systematically studied their catalytic performance using density functional theory (DFT). Calculation results indicated that all of TMNxO4-x-HDQ structures possess good thermodynamic and electrochemical stability. Notably, among the examined 37 MOFs, 6 catalysts outperformed the Cu(211) surface in terms of catalytic activity and product selectivity. Specifically, NiN4-HDQ emerged as an exceptional electrocatalyst for CO production in CO2RR, yielding a remarkable low limiting potential (UL) of -0.04 V. CuN4-HDQ, NiN2O2-HDQ, and PtN2O2-HDQ also exhibited high activity for HCOOH production, with UL values of -0.27, -0.29, and -0.27 V, respectively, while MnN4-HDQ, and NiO4-HDQ mainly produced CH4 with UL values of -0.58 and -0.24 V, respectively. Furthermore, these 6 catalysts efficiently suppressed the competitive hydrogen evolution reaction. Machine learning (ML) analysis revealed that the key intrinsic factors influencing CO2RR performance of these 2D c-MOFs include electron affinity (EA), electronegativity (χ), the first ionization energy (Ie), p-band center of the coordinated N/O atom (εp), the radius of metal atom (r), and d-band center (εd). Our findings may provide valuable insights for the exploration of highly active and selective CO2RR electrocatalysts.

Polypyrrole deposited on the core-shell structured nitrogen-doped porous carbon@Ag-MOF for signal amplification detection of chloride ions.

An electrochemical platform for signal amplification probing chloride ions (Cl-) is constructed by the composite integrating core-shell structured nitrogen-doped porous carbon@Ag-based metal-organic frameworks (NC@Ag-MOF) with polypyrrole (PPy). It is based on the signal of solid-state AgCl derived from Ag-MOF, since both NC and PPy have good electrical conductivity and promote the electron transport capacity of solid-state AgCl. NC@Ag-MOF was firstly synthesized with NC as the scaffold and then, PPy was anchored on NC@Ag-MOF by chemical polymerization. The composite NC@Ag-MOF-PPy was utilized to modify the electrode, which exhibited a higher peak current and lower peak potential during Ag oxidation compared with those of Ag-MOF and NC@Ag-MOF-modified electrodes. More importantly, in the coexistence of chloride (Cl-) ions in solution, the NC@Ag-MOF-PPy-modified electrode displayed a fairly stable and sharp peak of solid-state AgCl with the peak potentials gradually approaching zero, which might effectively overcome the background interference caused by electroactive substances. The oxidation peak currents of solid-state AgCl increased linearly with the concentration of  Cl- ions in a broad range of 0.15 µM-40 mM and 40-250 mM, with detection limits of 0.10 µM and 40 mM, respectively. The practical applicability for Cl- ions determination was demonstrated using human serum and urine samples. The results suggest that NC@Ag-MOF-PPy composite could be a promising candidate for the construction of the electrochemical sensor.

Counterintuitive Trend of Intrusion Pressure with Temperature in the Hydrophobic Cu2(tebpz) MOF.

Liquid porosimetry experiments reveal a peculiar trend of the intrusion pressure of water in hydrophobic Cu2(3,3',5,5'-tetraethyl-4,4'-bipyrazolate) MOF. At lower temperature (T) range, the intrusion pressure (Pi) increases with T. For higher T values, Pi first reaches a maximum and then decreases. This is at odds with the Young-Laplace law, which for systems showing a continuous decrease of contact angle with T predicts a corresponding reduction of the intrusion pressure. Though the Young-Laplace law is not expected to provide quantitative predictions at the subnanoscale of Cu2(tebpz) pores, the physical intuition suggests that to a reduction of their hydrophobicity corresponds a reduction of the Pi. Molecular dynamics simulations and sychrothron experiments allowed to clarify the mechanism of the peculiar trend of Pi with T. At increasing temperatures the vapor density within the MOF' pores grows significantly, bringing the corresponding partial pressure to ≈5 MPa. This pressure, which is consistent with the shift of Pi observed in liquid porosimetry, represents a threshold to be overcame before intrusion takes place. Beyond some value of temperature, the phenomenon of reduction of hydrophobicity (and water surface tension) dominated over the opposite effect of increase of vapor pressure and Pi inverts its trend with T.

Recent Advances of Carbon Capture in Metal-Organic Frameworks: A Comprehensive Review.

The excessive emission of greenhouse gases, which leads to global warming and alarms the world, has triggered a global campaign for carbon neutrality. Carbon capture and sequestration (CCS) technology has aroused wide research interest as a versatile emission mitigation technology. Metal-organic frameworks (MOFs), as a new class of high-performance adsorbents, hold great potential for CO2 capture from large point sources and ambient air due to their ultra-high specific surface area as well as pore structure. In recent years, MOFs have made great progress in the field of CO2 capture and separation, and have published a number of important results, which have greatly promoted the development of MOF materials for practical carbon capture applications. This review summarizes the most recent advanced research on MOF materials for carbon capture in various application scenarios over the past six years. The strategies for enhancing CO2 selective adsorption and separation of MOFs are described in detail, along with the development of MOF-based composites. Moreover, this review also systematically summarizes the highly concerned issues of MOF materials in practical applications of carbon capture. Finally, future research on CO2 capture by MOF materials is prospected.

Selective detection of food contaminants using engineered gallium-organic frameworks with MD and metadynamics simulations.

The exclusion mechanism of food contaminants such as bisphenol A (BPA), Flavonoids (FLA), and Goitrin (GOI) onto the novel gallium-metal organic framework (MOF) and functionalized MOF with oxalamide group (MOF-OX) is evaluated by utilizing molecular dynamics (MD) and Metadynamics simulations. The atoms in molecules (AIM) analysis detected different types of atomic interactions between contaminant molecules and substrates. To assess this procedure, a range of descriptors including interaction energies, root mean square displacement, radial distribution function (RDF), density, hydrogen bond count (HB), and contact numbers are examined across the simulation trajectories. The most important elements in the stability of the systems under examination are found to be stacking π-π and HB interactions. It was confirmed by a significant value of total interaction energy for BPA/MOF-OX (- 338.21 kJ mol-1) and BPA/MOF (- 389.95 kJ mol-1) complexes. Evaluation of interaction energies reveals that L-J interaction plays an essential role in the adsorption of food contaminants on the substrates. The free energy values for the stability systems of BPA/MOF and BPA/MOF-OX complexes at their global minima reached about BPA/MOF = - 254.29 kJ mol-1 and BPA/MOF-OX = - 187.62 kJ mol-1, respectively. Nevertheless, this work provides a new strategy for the preparation of a new hierarchical tree-dimensional of the Ga-MOF hybrid material for the adsorption and exclusion of food contaminates and their effect on human health.

Self-Assembled Carbon Metal-Organic Framework Oxides Derived from Two Calcination Temperatures as Anode Material for Lithium-Ion Batteries.

Owing to their structural diversity and mesoporous construction, metal-organic frameworks (MOFs) have been used as templates to prepare mesoporous metal oxides, which show excellent performance as anode materials for lithium-ion batteries (LIBs). Co-ZnO/C and Co-Co3O4/C nanohybrids were successfully synthesized based on a precursor of Co-doped MOF-5 by accurately controlling the annealing temperature and atmosphere. Experimental data proved that their electrochemical performance was closely associated with the material phase, especially for Co-ZnO/C, indicating that carbon skeleton materials can maintain a good restoration rate of over 99% after undergoing high-current density cycling. Meanwhile, Co-Co3O4/C nanohybrids showed an exceedingly high reversible capacity of 898 mAh∙g-1 at a current density of 0.1 C after 100 cycles. Their improved coulombic efficiency and superior rate capability contribute to a mesoporous structure, which provides pathways allowing for rapid Li+ diffusion and regulates volume change during charge and discharge processes.

Signal-On Detection of Caspase-3 with Methylene Blue-Loaded Metal-Organic Frameworks as Signal Reporters.

In this work, we report on an electrochemical method for the signal-on detection of caspase-3 and the evaluation of apoptosis based on the biotinylation reaction and the signal amplification of methylene blue (MB)-loaded metal-organic frameworks (MOFs). Zr-based UiO-66-NH2 MOFs were used as the nanocarriers to load electroactive MB molecules. Recombinant hexahistidine (His6)-tagged streptavidin (rSA) was attached to the MOFs through the coordination interaction between the His6 tag in rSA and the metal ions on the surface of the MOFs. The acetylated peptide substrate Ac-GDEVDGGGPPPPC was immobilized on the gold electrode. In the presence of caspase-3, the peptide was specifically cleaved, leading to the release of the Ac-GDEVD sequence. A N-terminal amine group was generated and then biotinylated in the presence of biotin-NHS. Based on the strong interaction between rSA and biotin, rSA@MOF@MB was captured by the biotinylated peptide-modified electrode, producing a significantly amplified electrochemical signal. Caspase-3 was sensitively determined with a linear range from 0.1 to 25 pg/mL and a limit of detection down to 0.04 pg/mL. Further, the active caspase-3 in apoptosis inducer-treated HeLa cells was further quantified by this method. The proposed signal-on biosensor is compatible with the complex biological samples and shows great potential for apoptosis-related diagnosis and the screening of caspase-targeting drugs.