Bimetallic Ag/Fe-MOG derived flake-like Ag2O/Fe2O3 p-n heterojunction for efficient photodegradation organic pollutants within a wide pH range.

In this paper, we reported a facile and clean strategy to prepare the flake-like Ag2O/Fe2O3 bimetallic p-n heterojunction composites for photodegradation organic pollutants. The surface morphology, crystal structure, chemical composition and optical properties of Ag2O/Fe2O3 were characterized by SEM, high-resolution TEM images with EDX spectra, XRD, XPS, FT-IR and UV-vis DRS spectra respectively. The formation of Ag2O/Fe2O3 p-n heterojunction facilitated the interfacial transfer of electrons as well as the separation of charge carries. Hence, the as-synthesized Ag2O/Fe2O3-3 composites exhibited ultra-high photocatalytic activity. Under the experimental conditions of catalyst dosage of 0.4 mg mL-1 and irradiation time of 60 min, the degradation conversion rate of rhodamine B reached 96.1 %, which was 5.0 and 2.8 times of pure phase Ag2O and Fe2O3, respectively. Meanwhile, the degradation performance of Ag2O/Fe2O3-3 was not limited by pH, and it can achieve high degradation efficiency under 3-11. In addition, Ag2O/Fe2O3-3 also showed superb degradation ability for other common anionic dyes, cationic dyes and antibiotics. XPS and FT-IR spectra showed that Ag2O/Fe2O3-3 retained a carbon skeleton that facilitated electron transport and light absorption conversion. And the analyses of quenching experiment and EPR demonstrated •O2-, •OH and h+ were crucial reactive oxidant species contributing to the rapid organic pollutant degradation. This work provides new insights into obtaining p-n photocatalysts heterojunction with excellent catalytic activity for removing organic pollutants from wastewater.

Coreactant-Free Zirconium Metal-Organic Framework with Dual Emission for Ratiometric Electrochemiluminescence Detection of HIV DNA.

Owing to the limitations of dual-signal luminescent materials and coreactants, constructing a ratiometric electrochemiluminescence (ECL) biosensor based on a single luminophore is a huge challenge. This work developed an excellent zirconium metal-organic framework (MOF) Zr-TBAPY as a single ECL luminophore, which simultaneously exhibited cathodic and anodic ECL without any additional coreactants. First, Zr-TBAPY was successfully prepared by a solvothermal method with 1,3,6,8-tetra(4-carboxyphenyl)pyrene (TBAPY) as the organic ligand and Zr4+ cluster as the metal node. The exploration of ECL mechanisms confirmed that the cathodic ECL of Zr-TBAPY originated from the pathway of reactive oxygen species (ROS) as the cathodic coreactant, which is generated by dissolved oxygen (O2), while the anodic ECL stemmed from the pathway of generated Zr-TBAPY radical itself as the anodic coreactant. Besides, N,N-diethylethylenediamine (DEDA) was developed as a regulator to ECL signals, which quenched the cathodic ECL and enhanced the anodic ECL, and the specific mechanisms of its dual action were also investigated. DEDA can act as the anodic coreactant while consuming the cathodic coreactant ROS. Therefore, the coreactant-free ratiometric ECL biosensor was skillfully constructed by combining the regulatory role of DEDA with the signal amplification reaction of catalytic hairpin assembly (CHA). The ECL biosensor realized the ultrasensitive ratio detection of HIV DNA. The linear range was 1 fM to 100 pM, and the limit of detection (LOD) was as low as 550 aM. The outstanding characteristic of Zr-TBAPY provided new thoughts for the development of ECL materials and developed a new way of fabricating the coreactant-free and single-luminophore ratiometric ECL platform.

Dual-emission Tb-based coordination polymer as a ratiometric fluorescence probe for the detection of phosphate.

A simple, sensitive dual-emission probe was developed for the detection of phosphate (Pi). The probe Tb-BTB/DPA was synthesized by mixing dual-ligand, 1,3,5-tri(4-carboxyphenyl) benzene (H3BTB) and dipicolinic acid (DPA), with metal ions Tb3+ in ethanol-water solution at 40℃ for 2 h. Tb-BTB/DPA exhibits two emission peaks, the emission at 362 nm is attributed to H3BTB, an energy transfer between Tb3+ nodes, and DPA further enhances the fluorescence of Tb3+ at 544 nm. Pi competes with ligand H3BTB to coordinate Tb3+, resulting in partial collapse of the Tb-BTB/DPA structure and interrupting the electron transfer between H3BTB and Tb3+. Therefore, the emission at 362 nm is enhanced, while the emission at 544 nm is unchanged, and a ratiometric fluorescence method is developed to detect Pi. Tb-BTB/DPA exhibits good linearity within the Pi concentration range (0.1-50 µmol/L), and the detection limit was 25.8 nmol/L. This study provides a new way to prepare probes with dual emission sensing properties.

Coreactant-free aggregation-induced electrochemiluminescence system based on the novel zinc-luminol metal-organic gel for ultrasensitive detection of PiRNA-823.

Aggregation-induced electrochemiluminescence (AIECL) technology has aroused widespread interest due to the significant improve in ECL response by solving the problems of aggregation-caused quenching and poor water solubility of the luminophore. However, the existing AIECL emitters still suffer from low ECL efficiency, additional coreactants and complex synthesis steps, which greatly limit their applications. Herein, luminol, as a kind of AIE molecule, was assembled with Zn2+ nodes to obtain a novel microflower-like Zinc-luminol metal-organic gel (Zn-MOG) by one-step method. In the light of the strong affinity of N atoms in luminol ligand to Zn2+, Zn-MOG with vigorous viscosity and stability can be formed immediately after vortex oscillation, overcoming the main difficulties of the complicated synthesis steps and poor film-forming performance encountered in current AIECL materials. Impressively, an AIECL resonance energy transfer (RET) biosensor was constructed using Zn-MOG as a donor and Alexa Fluor 430 as an acceptor in combination with DNA-Fuel-driven target recycling amplification for the ultrasensitive detection of PiRNA-823. The fabricated biosensor exhibited a wide linear relationship in the range of 100 aM to 100 pM and a detection limit as low as 60.0 aM. This work is the first to realize the construction of ECL emitters using the AIE effect of luminol, which provides inspiration for the design of AIECL systems without adding coreactants.

Ratiometric Electrochemiluminescence of Zirconium Metal-Organic Framework as a Single Luminophore for Sensitive Detection of HPV-16 DNA.

This study developed a new zirconium metal-organic framework (MOF) luminophore named Zr-DPA@TCPP with dual-emission electrochemiluminescence (ECL) characteristics at a resolved potential. First, Zr-DPA@TCPP with a core-shell structure was effectively synthesized through the self-assembly of 9,10-di(p-carboxyphenyl)anthracene (DPA) and 5,10,15,20-tetra(4-carboxyphenyl)porphyrin (TCPP) as the respective organic ligands and the Zr cluster as the metal node. The reasonable integration of the two organic ligands DPA and TCPP with ECL properties into a single monomer, Zr-DPA@TCPP, successfully exhibited synchronous anodic and cathodic ECL signals. Besides, due to the impressively unique property of ferrocene (Fc), which can quench the anodic ECL but cannot affect the cathodic ECL signal, the ratiometric ECL biosensor was cleverly designed by using the cathode signal as an internal reference. Thus, combined with DNA recycle amplification reactions, the ECL biosensor realized sensitive ratiometric detection of HPV-16 DNA with the linear range of 1 fM-100 pM and the limit of detection (LOD) of 596 aM. The distinctive dual-emission properties of Zr-DPA@TCPP provided a new idea for the development of ECL luminophores and opened up an innovative avenue of fabricating the ratiometric ECL platform.

Dual-ligand two-dimensional terbium-organic frameworks nanosheets for ratiometric fluorescence detection of phosphate.

Here, we reported a ratiometric fluorescence strategy for the detection of phosphate (Pi) in artificial wetland water. The strategy was based on dual-ligand two-dimensional terbium-organic frameworks nanosheets (2D Tb-NB MOFs). 2D Tb-NB MOFs were prepared through blending 5-boronoisophthalic acid (5-bop), 2-aminoterephthalic acid (NH2-BDC) and Tb3+ ions at room temperature in the presence of triethylamine (TEA). The dual-ligand strategy realized dual emission originated from ligand NH2-BDC and Tb3+ ions at 424 and 544 nm, respectively. Pi could compete with ligands to coordinate Tb3+ due to the strong binding ability between Pi and Tb3+, resulting in structural destruction of 2D Tb-NB MOFs, so static quenching and antenna effect between ligands and metal ions were interrupted, and emission at 424 nm was enhanced and emission at 544 nm was weakened. This novel probe had excellent linearity with Pi concentrations from 1 to 50 µmol/L; the detection limit was 0.16 µmol/L. This work revealed that mixed ligands improved sensing efficiency of MOFs by enhancing the sensitivity of the coordination between the analyte and MOFs.

A novel luminol-coordinated silver(I) organic gel with self-enhanced chemiluminescence applied for uric acid detection.

A novel silver(I)-based metal-organic gel (AgMOG) consisting of luminol as the ligand was synthesized by a facile strategy, which was found to exhibit self-enhancing chemiluminescence (CL) property. Based on this, a new AgMOG-K2S2O8 CL system without additional catalyst was established. According to the results of CL spectra, electron spin resonance (ESR) spectra as well as the influence of radical scavengers to AgMOG-K2S2O8 system, the possible CL mechanism of this system was discussed. In this CL system, AgMOG exhibited the dual properties of catalysis and luminescence. On the one hand, AgMOG can catalyze K2S2O8 to produce SO4•-. The generated SO4•- can be converted to hydroxyl radical (OH•) under alkaline condition, and further converted to other radical oxygen species (ROS, such as 1O2 and O2•-). Furthermore, the reaction between the K2S2O8 and H2O can form H2O2, which also can be catalyzed by AgMOG to produce ROS. On the other hand, the AgMOG can be oxidized by ROS to emit strong CL signal. Then, based on the quenching effect of uric acid (UA) to this CL system, a method for UA detection was established with a good linearity over the range from 0.08 to 10 µmol·L-1. In this work, a new CL luminant with catalytic property was synthesized by a simple method, and a self-enhancing AgMOG-K2S2O8 CL system was developed for the first time, providing a novel direction for the application of MOG in the CL field.

Skeleton-coated CoCu-Based bimetal hollow nanoprisms as High-Performance electrocatalysts for oxygen evolution reaction.

CoSx materials with high catalytic activity are considered as promising HER electrocatalysts, but their inherent low electrical conductivity and easy loss of active sites have greatly limited their applications in OER electrocatalysis. Herein, we present a convenient method to synthesize Co-Cu hollow nanoprisms after wrapping and calcining with trithiocyanuric acid (C3H3N3S3) (denoted N-Co-Cu-S-x HNs). The results showed that Cu doping modified the charge density of Co center, leading to the enhancement of the intrinsic activity of the Co3S4 active center, meanwhile wrapping trithiocyanuric acid on the surfaces and calcinating to form N-containing C skeleton as a flexible substrate to encapsulate the catalysts, which effectively protected the active sites inside the catalysts. Notably, the OER catalyst that was optimized by adjusting the metal ratio and controlling the trithiocyanuric acid incorporation exhibited a low overpotential of 306 mV under a current density of 10 mA cm-2 and showed a superior durability of more than 27 h. This work may provide some insights into the preparation of oxygen evolution reaction catalysts with excellent performance through doping transition metals and protecting the internal active sites strategies.

Controlled synthesis of zinc-metal organic framework microflower with high efficiency electrochemiluminescence for miR-21 detection.

In this study, as the self-enhanced electrochemiluminescence (ECL) emitter, the dual ligand metal-organic framework microflower was successfully synthesized via a facile one-pot method by integrating 9,10-di(pcarboxyphenyl) anthracene (DPA) ligand and N, N-Diethylethylenediamine (DEAEA) ligand into zinc ions metal node, denoted as Zn-DPA/DEAEA (d-MOF). The DPA ligand was a typical ECL luminophore. The DEAEA ligand not only could be used as an effective co-reactant but also a morphologic regulator. The morphology of d-MOF changed from a thick sheet to a thin sheet and finally a microflower by controlling the dosage of DEAEA. Linking emitter and co-reactant in a MOF structure, the d-MOF exhibited an efficient intramolecular electron transfer process, with a strong and ultra-stable ECL performance without any extra co-reactants compared with the DPA ligand or the Zn-DPA single ligand MOF (s-MOF). Furthermore, an ECL resonance energy transfer (ECL-RET) biosensor was fabricated using d-MOF as donor, and 6-carboxy-4', 5'-dichloro-2', 7'-dimethoxyfluorescein (JOE) as accepter for the ultra-sensitive detection of miR-21 without additional co-reactant. And with a detection linear range of miR-21 was 100.0 aM to 10.0 pM, with a detection limit of 61.7 aM. This work offers a new perspective for the future design of stable self-enhanced ECL materials.

Efficient and Sustainable in†situ Photo-Fenton Reaction to Remove Phenolic Pollutants by NH2 -MIL-101(Fe)/Ti3 C2 Tx Schottky-Heterojunctions.

Metal-organic frameworks (MOFs) with abundant active sites, a class of materials composed of metal nodes and organic ligands, is widely used for photocatalytic degradation of pollutants. However, the rapid recombination of photoinduced carriers of MOFs limits its photocatalytic degradation performance. Herein, Ti3 C2 Tx nanosheets-based NH2 -MIL-101(Fe) hybrids with Schottky-heterojunctions were fabricated by in situ hydrothermal assembly for improved photocatalytic activity. The photodegradation efficiencies of the NH2 -MIL-101(Fe)/Ti3 C2 Tx (N-M/T) hybrids for phenol and chlorophenol were 96.36 % and 99.83 % within 60 minutes, respectively. The N-M/T Schottky-heterojunction duly transferred electrons to the Ti3 C2 Tx nanosheets surface via built-in electric fields, effectively suppressing the recombination of photogenerated carriers, thereby improving the photocatalytic performance of NH2 -MIL-101(Fe). Moreover, the Fe-mixed-valence in the N-M/T led to improvement in the efficiency of the in situ generated photo-Fenton reactions, further enhancing the photocatalytic activity with more generated reactive oxygen species (ROS). The study proposes a highly effective removal of phenolic pollutants in wastewater.

Facile synthesis of dual-ligand terbium-organic gels as ratiometric fluorescence probes for efficient mercury detection.

Mercury (Hg) pollution can negatively impact ecosystems, and there is a need for simple Hg2+ monitoring platforms. Here, a dual-ligand fluorescence probe based on terbium-organic gels (Tb-L0.2P0.8 MOGs) was constructed for efficient Hg2+ detection. Tb-L0.2P0.8 MOGs were developed through a facile room-temperature gelation method, showing two emission peaks derived from luminol and Tb3+ at 424 nm and 544 nm, respectively. The aggregation-induced emission (AIE) effect between luminol and Tb3+ led to luminol with blue fluorescence. However, Hg2+ could dramatically quench the fluorescence signal of luminol at 424 nm because of the intense coordination interaction of Hg2+ with luminol and photo-induced electron transfer (PET). The Phen ligand could sensitize the luminescence of Tb3+ and offer a reference fluorescence, thus resulting in a unique ratiometric fluorescence response toward Hg2+. This novel nanoprobe had excellent linearity with Hg2+ concentrations range of 0.1-30 µM; the detection limit was 3.6 nM. The analysis of real samples showed the potential application of MOGs for measuring Hg2+ in porphyra and tap water. Mixed ligands were introduced for high-efficiency strategies to improve the analytical performance by regulating the emission behavior of MOGs.

One-component nano-metal-organic frameworks with superior multienzyme-mimic activities for 1,4-dihydropyridine metabolism.

Although a number of nanozymes have been developed, it is still difficult to develop single-component nanozyme with overall high multienzyme-like activities. In this study, the nanosized metal-organic frameworks (nano-MOFs) FePCN (PCN stands for porous coordination network) was synthesized by integrating zirconium and iron ions with different catalytic property on single-component MOFs and exhibited superior intrinsic multienzyme-like activities, namely oxidase-, peroxidase- and phosphatase-mimicking activity. The catalytic active sites of oxidase- and peroxidase-, and phosphatase-like activity of FePCN were Fe-centers and Zr-O clusters, respectively. Based on the intrinsic oxidase-like activity and the similarity of molecular structures between cytochrome P450 oxidase (CYP) cofactors and the organic linker in FePCN, FePCN exhibited high CYP-like activity to catalyze the oxidation of hypotensive drug 1,4-dihydropyridine (1,4-DHP) into diethyl 2,6-dimethylpyridine-3,5-dicarboxylate (DDPD) and the yield of DDPD reached over 80%. Moreover, as peroxidase- and phosphatase-mimics, FePCN was successfully applied to detecting H2O2 under neutral condition and catalyzing the dephosphorylation of adenosine triphosphate (ATP), respectively. This study provides a feasible way for rational design one-component nanomaterials as multienzyme-mimics.

Zinc-Metal Organic Frameworks: A Coreactant-free Electrochemiluminescence Luminophore for Ratiometric Detection of miRNA-133a.

Developing a coreactant-free ratiometric electrochemiluminescence (ECL) strategy based on a single luminophore to achieve more accurate and sensitive microRNA (miRNA) detection is highly desired. Herein, utilizing zinc-metal organic frameworks (Zn-MOFs) as the single luminophore, a novel dual-potential ratiometric ECL biosensor was constructed for ultrasensitive detection of miRNA-133a. The as-prepared Zn-MOFs exhibited simultaneous cathode and anode ECL emission. Furthermore, the Zn-MOFs were confirmed to be a multichannel ECL sensing platform with excellent annihilation and coreactant ECL emission. The corresponding ECL behaviors were investigated in detail. Benefiting from the hybridization chain reaction (HCR) amplification technology, N,N-diethylethylenediamine (DEAEA) was modified on hairpin DNA, and the gained products loaded with quantities of DEAEA enhanced the anodic ECL intensity of Zn-MOFs. In the presence of miRNA-133a, the ECL intensity ratio of anode to cathode (Ia/Ic) was significantly increased, which realized the ultrasensitive ratiometric detection of miRNA-133a. In addition, without an exogenous coreactant, the biosensor revealed superb accuracy and stability. Under optimal conditions, the detection linearity of miRNA-133a was from 50 aM to 50 fM with a low detection limit of 35.8 aM (S/N = 3). This is the first work to use Zn-MOFs as a single emitter for reliable ratiometric ECL bioanalysis, which provides a new perspective for fabricating a ratiometric ECL biosensor platform.