Metal-organic Gels Research Articles

Dual-source signal amplification electrochemiluminescence sensor combined with molecularly imprinted polymers for the imidacloprid detection

A novel lanthanide metal-organic-gel (MOG)-derived material/nitrogen-doped graphdiyne (Tb-Ru-MOG/CeO2/N-GDY) composite with a dual-source signal amplification strategy was prepared and used to construct a molecularly imprinted sensor based on bifunctional monomers for the detection of imidacloprid (IMI) using electrochemiluminescence (ECL). In a green reaction environment, terbium (III) (Tb3+) can undergo multiple coordination reactions with 4′-(4-carboxyphenyl)-2,2′:6′,2″-terpyridine (Hcptpy) and tris(4,4′-dicarboxylicacid-2,2′-bipyridyl) ruthenium (II) dichloride (Ru(dcbpy)32+), and combine with ceria nanoparticles (CeO2 NPs) to form Tb-Ru-MOG/CeO2. Within the Tb-Ru-MOG/CeO2 framework, energy transfer from the double ligands can sensitize the central Tb3+, triggering a distinct antenna effect and energy-transfer, and its polyporous configuration offered a nanoconfined space for Ce3+/Ce4+ to effectively catalyze coreactant radicals (S2O82−), leading to in-situ endogenous activation ECL reactions. The conductive N-GDY accelerated electron movement and increased the loading on the electrode surface, enhancing the exogenous excitation of the ECL signals. Leveraging the synergistic effect of the bifunctional monomer, the synthesized molecularly imprinted polymers (MIPs) ECL sensor demonstrated a wide detection range from 10 nM to 10,000 nM for IMI, with a limit of detection (LOD) of 1.37 nM, showcasing an innovative concept for the dual-source strategy of signal amplification in integrated ECL composites to analyze food and environmental hazards.

Renewable Electrochemiluminescence Biosensor Based on Eu-MOGs as a Highly Efficient Emitter and a DNAzyme-Mediated Dual-drive DNA Walker as a Signal Amplifier for Ultrasensitive Detection of miRNA-222.

Herein, novel europium metal-organic gels (Eu-MOGs) with excellent cathode electrochemiluminescence (ECL) emission are first used to construct biosensors for the ultrasensitive detection of miRNA-222. Impressively, N and O elements of organic ligand 2,2':6,2″-terpyridine 4,4',4″-tricarboxylic acid (H3-tctpy) can perfectly coordinate with Eu3+ to form Eu-MOGs, which not only reduce nonradiative transition caused by the intramolecular free rotation of phenyl rings in other MOGs to enhance the ECL signal with extraordinary ECL efficiency as high as 37.2% (vs the [Ru(bpy)3]2+/S2O82- ECL system) but also reinforce ligand-to-metal charge transfer (LMCT) by the strong affinity between Eu3+ and N and O elements to greatly improve the stability of ECL signals. Besides, an improved nucleic acid cascade amplification reaction is developed to greatly raise the conversion efficiency from target miRNA-222 to a DNAzyme-mediated dual-drive DNA walker as output DNA, which can simultaneously shear the specific recognition sites from two directions. In that way, the proposed biosensor can further enhance the detection sensitivity of miRNA-222 with a linear range of 10 aM-1 nM and a detection limit (LOD) of 8.5 aM, which can also achieve an accurate response in cancer cell lysates of MHCC-97L and HeLa. Additionally, the biosensor can be self-regenerated by the folding/unfolding of related triplets with pH changes to simplify experimental operations and reduce the cost. Hence, this work proposed novel MOGs with stable and intense ECL signals for the construction of a renewable ECL biosensor, supplying a reliable detection method in biomarker analysis and disease diagnosis.

Cobalt-doped iron-based metal–organic gels as efficient visible-light-driven peroxymonosulfate activators for the efficient degradation of norfloxacin with simultaneous antibacterial activity

A strategically fabricated cobalt-doped iron-based metal–organic gel (CFM) synergistically promotes peroxymonosulfate (PMS) activation and visible light-induced photocatalysis to remove norfloxacin (NOR). Cobalt incorporation into the metal–organic gel significantly optimizes its electronic structure, leading to the exceptional performance of CFM in synergistically activating PMS, amplifying visible light absorption, and enhancing photoinduced charge separation efficiency. The Vis/50 %-CFM/PMS system enables a NOR removal rate of up to 96.8 % within 60 min and a total organic carbon (TOC) removal rate of 78.3 %, signifying excellent decontamination performance. Exhibiting robust mineralization potential, the Vis/CFM/PMS system has undergone comprehensive analysis of the intermediary degradation process using Density Functional Theory (DFT) calculations. The toxicity of degradation intermediates was assessed employing the quantitative structure–activity relationship (QSAR) model. In addition, the Vis/CFM/PMS system showed antibacterial effects against E. coli and S. aureus. This investigation furnishes a novel perspective toward developing innovative PMS activation photocatalyst coupling systems for environmental remediation.

Anchoring the AIEgen by Zr clusters in metal-organic gel for efficient X-ray detection and imaging

Anchoring the AIEgen by Zr clusters in metal-organic gel for efficient X-ray detection and imaging

Unravelling co-catalyst integration methods in Ti-based metal-organic gels for photocatalytic H2 production.

The synthesis, characterization and photocatalytic hydrogen evolution reaction (HER) performance of a series of metal-organic gels (MOGs) constructed from titanium(IV)-oxo clusters and dicarboxylato linkers (benzene-1,4-dicarboxylato and 2-aminobenzene-1,4-dicarboxylato) are described. All the MOGs exhibit a microstructure comprised of metal-organic nanoparticles intertwined into a highly meso-/macroporous structure, as demonstrated by cryogenic transmission electron microscopy and gas adsorption isotherms. Comprehensive chemical characterization enabled the estimation of the complex formula for these defective materials, which exhibit low crystallinity and linker vacancies. To gain deeper insights into the local structure, X-ray absorption fine structure (XAFS) spectroscopy experiments were performed and compared to that of the analogous crystalline metal-organic framework. Additionally, the ultraviolet-visible absorption properties and optical band gaps were determined from diffuse reflectance spectroscopy data. The MOGs were studied as light absorbers for the sacrificial photocatalytic HER under simulated solar light irradiation using a platinum co-catalyst by either (1) in situ photodeposition or (2) ex situ doping process, through a post-synthetic metalation of the MOG structure. The chemical analysis of the metalation, along with high-angle annular dark-field scanning transmission electron microscopy, revealed that although the in situ addition of the co-catalyst led to greater HER rates (227 vs. 110 μmolH2 gMOG-1 h-1 for in situ and ex situ, respectively), the ex situ modification provided a finer distribution of platinum nanoparticles along the porous microstructure and, as a result, it led to a more efficient utilization of the co-catalyst (45 vs. 110 mmolH2 gPt-1 h-1).

Porous reticular Co@Fe metal-organic gel: dual-function simulated peroxidase nanozyme for both colorimetric sensing and antibacterial applications.

Constructing metal-organic gels (MOGs) with enzyme-catalyzed activity and studying their catalytic mechanism are crucial for the development of novel nanozyme materials. In this study, a Co@Fe MOG with excellent peroxidase activity was developed by a simple and mild one-pot process. The results showed that the material exhibited almost a single peroxidase activity under optimal pH conditions, which allowed it to attract and oxidize the chromogenic substrate 3,3',5,5'-tetramethylbenzidine (TMB). Based on the active electron transfer between the metal centers and the organic ligand in the synthetic material, the Co@Fe MOG-H2O2-TMB system was verified to be able to detect H2O2 and citric acid (CA). The catalytic microenvironment formed by the adsorption and the catalytic center accelerated the electron-transfer rate, which expedited the generation of hydroxyl radicals (˙OH, a kind of reactive oxygen species (ROS)) in the presence of H2O2. The persistence and high intensity of ˙OH generation were proven, which would endow Co@Fe MOG with a certain antibacterial ability, promoting the healing of bacteria-infected wounds. In conclusion, this study contributes to the development efforts toward the application systems of nanozymes for marker detection and antibacterial activity.

A wearable AuNP enhanced metal-organic gel (Au@MOG) sensor for sweat glucose detection with ultrahigh sensitivity.

The demand for sensitive and non-invasive sensors for monitoring glucose levels in sweat has grown considerably in recent years. This study presents the development of a wearable sensor for sweat glucose detection with ultrahigh sensitivity. The sensor was fabricated by embedding Au nanoparticles (AuNPs) and metal-organic gels (MOGs) on nickel foam (NF). A non-enzymatic electrocatalytic glucose sensor has been developed to combine the three-dimensional network of MOGs with more active sites favourable for glucose diffusion and the transfer of electrons from glucose to the electrode. These results show that the sensor has an ultrahigh sensitivity of 13.94 mA mM-1 cm-2, a linear detection range between 2 and 600 μM, and a lower detection limit as low as 1 μM (signal/noise = 3) with comparable accuracy and reliability under non-alkaline conditions to those of high-pressure ion chromatography (HPIC). Furthermore, a wearable sweat glucose sensor has been constructed by sputtering an Au conductive layer on a flexible polydimethylsiloxane (PDMS) substrate and coating it with Au@MOGs. Our work demonstrates that the combination of Au NPs and MOGs can enhance the sensitivity and activity of these materials, making them useful for electrocatalytic glucose monitoring with ultrahigh sensitivity.

Electrochemical reconstruction of metal-organic gels into crystalline oxy-hydroxide heterostructures for efficient oxygen evolution electrocatalysis.

Metal-organic gels (MOGs) are emerging soft materials with distinct metal active centers, multifunctional ligands and hierarchical porous structures, showing promising potential in the field of electrocatalysis. However, the reconfiguration of MOGs during the electrocatalytic process remains underexplored, with current studies in early developmental stages. To deeply investigate the application of MOG materials in electrocatalysis, the compositional transformations and structural changes under an electrochemical activation method were studied in detail, leading to high-performance OER pre-electrocatalysts. XRD and HRTEM results demonstrate the complete reconfiguration of amorphous Fe5Ni5-MOG into crystalline NiOOH/FeOOH heterostructures. The synergistic effect of the bimetallic center and the rich NiOOH-FeOOH interface in the reconstituted Re-Fe5Ni5-MOG exhibit excellent OER activity in alkaline electrolytes, with low overpotentials (205 mV at 10 mA cm-2) and a Tafel slope of 58 mV dec-1. In situ characterization during the electrocatalytic process reveals the gradual transformation of the metal center into metal hydroxyl oxides upon increasing the voltage to 1.55 V. DFT analysis suggests that in the Fe-Ni double site reaction pathway, active substances preferentially adsorb on the Fe site before the Ni sites.

AIEgen-functionalized metal-organic gel as a bifunctional platform for efficient adsorption and portable sensing of gaseous iodine.

Herein, we proposed a novel metal-organic gel (YTU-G-1) for efficient adsorption and portable sensing of gaseous iodine. YTU-G-1 exhibits an unprecedentedly high detection sensitivity (KSV = 2.21 × 106 L mol-1) and an extremely low limit of detection (LOD) down to the pmol level (481 pmol L-1). YTU-G-1 also shows a marked iodine adsorption capacity of 1.398 g g-1. A wearable membrane was successfully fabricated via the electrospinning technique, which exhibits excellent skin-compatibility and serves as a portable tool for sensitive response to potential on-site nuclear emergencies.

Photo-responsive metal-organic gels of rigid phenylene-1,3-di-substituted angular dienes with metal halides: gel-to-gel transformations triggered by [2 + 2] polymerization.

Herein, the first report on gel-to-gel transformations via [2 + 2] photopolymerization in MOGs of metal halides and rigid dienes is presented. The MOGs and their xerogels show exceptional ability to undergo [2 + 2] polymerisation upon UV irradiation. Gel-to-gel transformations are very rare as the post-modification of gelators weakens the gel and transforms it to a sol. Such transformations change the molecular assemblies into gels with altered mechanical and chemical properties. These phenomena pave the way to synthesize new MOGs with improved rigidity that cannot be synthesized otherwise.

Realization of white-light-emitting diodes from a high-brightness zirconium-based metal-organic gel driven by the AIE effect.

Developing luminescent materials with suitable correlated color temperature (CCT) and sufficient color-rendering index (CRI) is a challenging problem in the field of commercialized warm white LED lighting. Herein, a novel metal-organic gel (MOG) material named YTU-G-1(SE) was synthesized, consisting of zirconium metal coordinated with 1,1,2,2-tetrakis(4-carboxyphenyl) ethylene. YTU-G-1(SE) exhibits strong fluorescent properties with an aggregation-induced emission (AIE) effect, emitting yellow-green fluorescence at 515 nm. The internal and external quantum efficiencies (IQE/EQE) of YTU-G-1(SE) are close to unity, with values of 95.74 ± 0.5% and 88.67 ± 0.5%, respectively. Finally, we combined YTU-G-1(SE) with a commercial blue chip and a commercial red phosphor (Sr,Ca)AlSiN3:Eu2+ to fabricate a warm white light LED with a color temperature of 3736 K, a color-rendering index Ra of 88.2, and a lumen efficiency of 79.42 lm W-1. This work provides a new approach to regulating the emission of AIE and offers a novel idea for developing high-performance warm-white pc-WLEDs.

Combination of Ternary Electrochemiluminescence System of BNQDs/AgMOG-K2S2O8 and Electrochemiluminescence Resonance Energy Transfer Strategy for Ultrasensitive Immunoassay of Amyloid-β Protein.

In this work, based on boron nitride quantum dots (BNQDs) as energy donors and MnO2@MWCNTs-COOH as energy receptors, we designed an efficient electrochemiluminescence resonance energy transfer (ECL-RET) immunosensor for the detection of amyloid-β (Aβ42) protein, a biomarker of Alzheimer's disease (AD). First, the signal amplification of a ternary ECL system composed of BNQDs (as the ECL emitter), K2S2O8 (as the coreactant), and silver metal-organic gels (AgMOG, as the coreaction accelerator) was realized, and PDDA as stabilizer was added, a strong and stable initial ECL signal was obtained. AgMOG could not only support a large amount of BNQDs and Aβ42 capture antibody (Ab1) through Ag-N bond but also exhibit excellent ECL catalytic performance and enhance the luminescent intensity of BNQDs@PDDA-K2S2O8 system. In addition, due to the broad absorption spectrum of MnO2@MWCNTs-COOH and the extensive overlap with the ECL emission spectrum of BNQDs, the quenching probe Ab2-MnO2@MWCNTs-COOH could be introduced into the ternary system through a sandwich immune response. On this basis, the signal on-off ECL immunosensor was constructed to achieve the ultrasensitive detection of Aβ42 through signal transformation. Under the optimal conditions, the prepared ECL biosensor manifested a wide linear range (10 fg/mL-100 ng/mL) with a detection limit of 2.89 fg/mL and showed excellent stability, selectivity, and repeatability, which provided an effective strategy for the ultrasensitive detection of biomarkers in clinical analysis.

Unraveling the synergistic effect of adsorption-photocatalysis in magnetically recyclable Fe3O4/metal-organic gels/sodium alginate beads for chlortetracycline hydrochloride elimination

The development of highly efficient and easily recyclable materials remains at the forefront of chlortetracycline hydrochloride (CTC) remediation. Herein, two magnetic metal-organic gels (Fe3O4/Fe-MOG and Fe3O4/Al-MOG) are constituted by an ultrafast room-temperature synthesis of MOGs on the surface of carboxylated Fe3O4, affording exceptional adsorption-photocatalysis abilities towards CTC under visible light irradiation, along with favorable magnetic separation capabilities. Meanwhile, the proposed synergistic mechanisms of adsorption-photocatalysis, the probable degradation pathways of CTC, and the underlying toxicity evaluation of intermediates are expounded. More importantly, we ingeniously develop Fe3O4/MOGs/SA beads with sodium alginate (SA) as the backbone and magnetic MOGs as the reaction center, which minimizes the loss of powdered Fe3O4/MOGs and ameliorates the recyclability. Attractively, Fe3O4/MOGs/SA beads achieve long-term continuous operation for CTC degradation in various water samples under visible light irradiation. Overall, this work highlights a new possibility for devising immobilized magnetic MOGs with adsorption-photocatalysis synergies in actual and large-scale wastewater remediation.

Advancements in Exploring Metal-Organic Gels: Structure, Synthesis, and Characterization with a Focus on Preparation Conditions

Advancements in Exploring Metal-Organic Gels: Structure, Synthesis, and Characterization with a Focus on Preparation Conditions

Facile synthesis of an Ni/LaAlO3 – Perovskite via an MOF gel precursor for the dry reforming of methane

A simple strategy to prepare the pure perovskite phase of lanthanum aluminate (LaAlO3) by calcination of a highly porous, dry MOF precursor gel has been developed. This study demonstrates that the structural and textural properties, such as specific surface area, pore volumes and pore sizes, of precursor-like metal–organic gels (MOG) (MOG-Al-La) based on metal–organic framework (MOF) structures can be modulated by optimizing the solvothermal treatment time. The perovskite obtained after solvothermal treatment at 120 °C for 12 h and calcination at 750 °C maintained the mesoporous characteristics of the MOF precursor, with a small particle size due to the decrease in crystallization temperature. These properties in the support allowed a good dispersion of the active Ni sites, low reducibility, and a strong interaction between them and the support, thus suppressing sintering under the severe catalytic reaction conditions evaluated (GHSV = 120,000 cm3/g·h) for the dry reforming of methane. The resulting MOX-(12 h)-LaAlO3-750-Ni catalyst gave a CH4 average conversion of 75% and CO2 average conversion of 80% after 20 h of reaction. The improved stability of the catalyst was attributed to suppression of the formation of the dense network of carbon filaments that can stress and subsequently fracture the support, cause attrition of the catalyst granules and hinder diffusion of the reactants both through the pores of the support and the interparticle spaces.

Metal–Organic Gel Leading to Customized Magnetic-Coupling Engineering in Carbon Aerogels for Excellent Radar Stealth and Thermal Insulation Performances

HighlightsFe3+, Co2+, H3BTC, and collagen peptide are used to achieve a one-step assembly of stable FeCo-MOG/CP by manipulating the complexation effect and solution polarity.By optimizing pyrolysis, two kinds of nitrogen-doped carbon aerogels loaded with virus-shaped and nanospherical magnetic particles are obtained.FeCo/Fe3O4/NC and FeCo/NC aerogels exhibit excellent electromagnetic wave absorbing and radar stealth performances.

Facile synthesis of dual-ligand europium-metal organic gels for ratiometric electrochemiluminescence detecting I27L gene

Metal organic gels (MOGs) are a new kind of intelligent soft materials with excellent luminescence properties. However, MOGs with dual electrochemiluminescence (ECL) properties have not been reported. In this study, using Eu3+ as metal node, 4′-(4-carboxyphenyl)-2,2′:6′,2″-terpyridine (Hcptpy) and Luminol as organic ligands, a novel dual-ligand Europium-organic gels (Eu-L-H MOGs) were prepared by simple mixing at room temperature. On the one hand, Eu-L-H MOGs could exhibit strong and stable anodic ECL signals in the phosphate buffered saline (PBS) without the addition of co-reactants, which came from the blue emission of Luminol. On the other hand, using K2S2O8 as a cathodic co-reactant, Eu-L-H MOGs produced cathodic signals, which were derived from the red emission of Eu sensitized by Hcptpy through the antenna effect. Based on the independent dual ECL signals of Eu-L-H MOGs, we selected Alexa Flour 430 as the receptor and anodic ECL emission of Eu-L-H MOGs as the donor to construct the ECL resonance energy transfer (ECL-RET) ratio biosensor, which utilized exonuclease III assisted DNA cycle amplification to achieve ultrasensitive detection of the I27L gene. The detection linearity of I27L ranged from 1 fM to 10 nM, with a detection limit as low as 284 aM. This study developed a straightforward technique for obtaining a single luminescent material with dual signals, and further broadened the analytical application of MOGs in the realm of ECL.

Dual-Ligand Strategy to Construct Metal Organic Gel Catalyst with the Optimized Electronic Structure for High-Efficiency Overall Water Splitting and Flexible Metal-Air Battery.

Non-noble metal catalysts are known for their efficient catalytic performance for oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). Metal organic gels (MOGs) can be considered as a promising electrocatalyst owing to the diverse physicochemical properties but usually suffer from its poor electrical conductivity and catalytic stability. Here, a FeCo-MOG is constructed with considerable trifunctional activity. The optimal P-CoFe-H3 prepared by using phytic acid (PA) and 2,4,6-Tris[(p-carboxyphenyl)amino]-1,3,5-triazine benzoic acid (H3TATAB) as dual ligands), exhibits outstanding ORR, OER, and HER activities as well as stability, exceeding most of state-of-the-art catalysts. As expected, the flexible Zn-air battery applied with P-CoFe-H3 as air cathode displays considerable power density, discharge voltage plateau, and cycling stability. Impressively, it is also capable of driving the overall water-splitting device by applying the P-CoFe-H3 as anode and cathode. Furthermore, theoretical calculations reveal that dual ligands can optimize the coordination environment and charge density of active sites, thereby reducing the absorption energy of intermediate species and boosting the catalytic performance. This work endows the dual-ligands coordination strategy with great potentiality for MOGs-based electrocatalysts in energy conversion devices.

Electrochemical Reconstruction Engineering: Metal–Organic Gels as Pre‐Catalysts for NiOOH/FeOOH Heterostructure to Boost Oxygen Evolution Reaction

Electrochemical Reconstruction Engineering: Metal–Organic Gels as Pre‐Catalysts for NiOOH/FeOOH Heterostructure to Boost Oxygen Evolution Reaction

Water-Stable Luminescent Eu–Al-Nanoscale Metal–Organic Gels for the Detection of Doxycycline

Water-Stable Luminescent Eu–Al-Nanoscale Metal–Organic Gels for the Detection of Doxycycline