Multimetal-Based Metal-Organic Framework System for the Sensitive Detection of Heart-Type Fatty Acid Binding Protein in Electrochemiluminescence Immunoassay.

In this work, an electrochemiluminescence (ECL) quenching system using multimetal-organic frameworks (MMOFs) was proposed for the sensitive and specific detection of heart-type fatty acid-binding protein (H-FABP), a marker of acute myocardial infarction (AMI). Bimetallic MOFs containing Ru and Mn as metal centers were synthesized via a one-step hydrothermal method, yielding RuMn MOFs as the ECL emitter. The RuMn MOFs not only possessed the strong ECL performance of Ru(bpy)32+ but also maintained high porosity and original metal active sites characteristic of MOFs. Moreover, under the synergistic effect of MOFs and Ru(bpy)32+, RuMn MOFs have more efficient and stable ECL emission. The trimetal-based MOF (FePtRh MOF) was used as the ECL quencher because of the electron transfer between FePtRh MOFs and RuMn MOFs. In addition, active intramolecular electron transfer from Pt to Fe or Rh atoms also occurred in FePtRh MOFs, which could promote intermolecular electron transfer and improve electron transfer efficiency to enhance the quenching efficiency. The proposed ECL immunosensor demonstrated a wide dynamic range and a low detection limit of 0.01-100 ng mL-1 and 6.8 pg mL-1, respectively, under optimal conditions. The ECL quenching system also presented good specificity, stability, and reproducibility. Therefore, an alternative method for H-FABP detection in clinical diagnosis was provided by this study, highlighting the potential of MMOFs in advancing ECL technology.

Advances in the application of metal oxide nanozymes in tumor detection and treatment.

Natural enzymes play an important role to support the regular life activities of the human body. However, the application conditions of natural enzymes are harsh and there are limitations in their use. As artificial enzymes, nanozymes possess the substrate specificity of natural enzymes. Due to the advantages of low cost, good stability and strong catalytic properties, nanozymes hold a wide range of applications in the fields of sensing, chemical, food and medicine. Some of the more common ones are noble metal nanozymes, metal oxide nanozymes and carbon-based nanozymes. Among them, metal oxide nanozymes have attracted much attention because of their decent fixity, exceedingly good physicochemical properties and other advantages. Today, malignant tumors pose a great danger to the human body and are a serious threat to human health. However, traditional treatments have more side effects, and finding new treatment modalities is particularly important for tumor treatment. For example, enzyme therapy can be used to catalyze reactions in the body to achieve tumor treatment. Nanozymes can exert enzymatic activity and effectively treat malignant tumors through catalysis and synergy, and have made certain progress. This paper reviews the detection and application of metal oxide nanozymes in tumor detection and treatment in recent years and provides an outlook on their future application and development.

Advances in the Application of Transition-Metal Composite Nanozymes in the Field of Biomedicine.

Due to the limitation that natural peroxidase enzymes can only function in relatively mild environments, nanozymes have expanded the application of enzymology in the biological field by dint of their ability to maintain catalytic oxidative activity in relatively harsh environments. At the same time, the development of new and highly efficient composite nanozymes has been a challenge due to the limitations of monometallic particles in applications and the inherently poor enzyme-mimetic activity of composite nanozymes. The inherent enzyme-mimicking activity is due to Au, Ag, and Pt, along with other transition metals. Moreover, the nanomaterials exhibit excellent enzyme-mimicking activity when composited with other materials. Therefore, this paper focuses on composite nanozymes with simulated peroxidase activity that have been prepared using noble metals such as Au, Ag, and Pt and other transition metal nanoparticles in recent years. Their simulated enzymatic activity is utilized for biomedical applications such as glucose detection, cancer cell detection and tumor treatment, and antibacterial applications.

Sulfur Quantum Dot-Based Electrochemiluminescence Resonance Energy Transfer System for a Dual-Mode Ultrasensitive Detection of MC-LR Using Ag+ as a Signal Amplification Switch.

Improving the sensitivity and accuracy of bioimmunoassays has been the focus of research into the development of electrochemiluminescence (ECL) sensing platforms, as this is a critical factor in their application to practical analysis. In this work, an electrochemiluminescence-electrochemistry (ECL-EC) dual-mode biosensing platform based on an "off-on-super on" signals pattern strategy was developed for the ultrasensitive detection of Microcystin-LR (MC-LR). In this system, sulfur quantum dots (SQDs) are a novel class of ECL cathode emitter with almost no potentially toxic effects. The sensing substrate is made from rGO/Ti3C2Tx composites, whose huge specific surface area greatly reduces the possibility of aggregation-caused quenching of SQDs. The ECL detection system was constructed based on the ECL-resonance energy transfer (ERET) strategy, where methylene blue (MB) with an ECL receptor function was bound to the aptamer of MC-LR by electrostatic adsorption and the center actual distance between the donor and the acceptor was calculated to be 3.84 nm, which was verified to be in accordance with the ERET theory. Meanwhile, the introduction of Ag+ as an ECL signal-amplifying molecule greatly improved the sensitivity of sensing analysis. Based on the specific binding of MC-LR to the aptamer, the concentration of MC-LR was found to have a positive correlation with the ECL signal. Also, EC detection was realized with the benefit of the excellent electrochemical properties of MB. The dual-mode biosensor greatly improves the confidence of the detection, examination areas of 0.001-100 pg/mL with MC-LR for ECL and EC were obtained, and the detection limits are 0.17 and 0.24 pg/mL, respectively.

Bimetallic Metal-Organic Frameworks as an Efficient Capture Probe in Signal On-Off-On Electrochemiluminescence Aptasensor for Microcystin-LR Detection.

To ensure drinking water quality, the development of rapid and accurate analytical methods is essential. Herein, a highly sensitive electrochemiluminescence (ECL) aptasensor-based on the signal on-off-on strategy was developed to detect the water pollutant microcystin-LR (MC-LR). This strategy was based on a newly prepared ruthenium-copper metal-organic framework (RuCu MOF) as the ECL signal-transmitting probe and three types of PdPt alloy core-shell nanocrystals with different crystal structures as signal-off probes. Compounding the copper-based MOF (Cu-MOF) precursor with ruthenium bipyridyl at room temperature facilitated the retention of the intrinsic crystallinity and high porosity of the MOFs as well as afforded excellent ECL performance. Since bipyridine ruthenium in RuCu MOFs could transfer energies to the organic ligand (H3BTC), the ultra-efficient ligand luminescent ECL signal probe was finally obtained, which greatly improved the sensitivity of the aptasensor. To further improve the sensitivity of the aptasensor, the quenching effects of noble metal nanoalloy particles with different crystal states were investigated, which contained PdPt octahedral (PdPtOct), PdPt rhombic dodecahedral (PdPtRD), and PdPt nanocube (PdPtNC). Among them, the PdPtRD nanocrystal exhibited higher activity and excellent durability, stemming from the charge redistribution caused by the hybridization of Pt and Pd atoms. Moreover, PdPtRD could also load more -NH2-DNA strands because it exposed more active sites with a large specific surface area. The fabricated aptasensor exhibited outstanding sensitivity and stability in MC-LR detection, with a linear detection range of 0.0001-50 ng mL-1. This study provides valuable directions for the application of alloy nanoparticles of noble metals and bimetallic MOFs in the field of ECL immunoassay.

Ultrasensitive Photoelectrochemical Immunoassay Strategy Based on Bi2S3/Ag2S for the Detection of the Inflammation Marker Procalcitonin.

As an inflammatory marker, procalcitonin (PCT) is more representative than other traditional inflammatory markers. In this work, a highly efficient photoelectrochemical (PEC) immunosensor was constructed based on the photoactive material Bi2S3/Ag2S to realize the sensitive detection of PCT. Bi2S3 was prepared by a hydrothermal method, and Ag2S quantum dots were deposited on the ITO/Bi2S3 surface via in situ reduction. Bi2S3 is a kind of admirable photoelectric semiconductor nanomaterial on account of its moderate bandgap width and low binding rate of photogenerated electron holes, which can effectively convert light energy into electrical energy. Therefore, based on the energy level matching principle of Bi2S3 and Ag2S, a labeled Bi2S3/Ag2S PEC immunosensor was constructed, and the sensitive detection of PCT was successfully established. The linear detection range of the PEC immunosensor was 0.50 pg∙mL-1 to 50 ng∙mL-1, and the minimum detection limit was 0.18 pg∙mL-1. Compared with the traditional PEC strategy, the proposed PEC immunosensor is simple, convenient, and has good anti-interference, sensitivity, and specificity, which could provide a meaningful theoretical basis and reference value for the clinical detection of PCT.

Dual-quenching mechanisms in electrochemiluminescence immunoassay based on zinc-based MOFs of ruthenium hybrid for D-dimer detection.

The successful application of electrochemiluminescence (ECL) in immunoassay for clinical diagnosis requires improving sensitivity and accuracy. Herein was reported an ECL analytical model based zinc-based metal-organic frameworks of ruthenium hybrid (RuZn MOFs) as the signal emitter. To enlarge the output difference, the quenching effect of three different noble metal nanoparticles included palladium seeds (Pdseeds), palladium octahedrons (Pdoct), and Pt-based palladium (Pd@Ptoct) core-shell were researched. Among them, Pd@Ptoct core-shell possessed higher activity and improved durability than Pd-only (NPs), they could load more protein macromolecules amicably and stabilized in the analysis system. Furthermore, since the charge redistribution owing to the hybridization of the Pt and Pd atoms in Pd@Ptoct, it could generate the electron flow maximumly from the emitter RuZn MOFs to Pd@Ptoct and result in the enhancement of quenching ECL. And the UV absorption of noble metal nanoparticles overlapped with the ECL emission of RuZn MOFs to varying degrees, which caused the behavior of resonance energy transfer (RET) reaction at the same time. This would greatly promote the sensitivity of this ECL system compared with the traditional single quenching mechanism. Based on this, a signal-off immunsensor was constructed to sensitive detection of D-dimer with linearity range from 0.001 to 200 ng mL-1, limit of detection (LOD) was 0.20 pg mL-1 and provide a further theoretical basis for the clinical application of ECL technology.

Split-Type Photoelectrochemical/Visual Sensing Platform Based on SnO2/MgIn2S4/Zn0.1Cd0.9S Composites and Au@Fe3O4 Nanoparticles for Ultrasensitive Detection of Neuron Specific Enolase.

Herein, a novel dual mode detection system of split-type photoelectrochemical (PEC) and visual immunoassay was developed to detect neuron specific enolase (NSE), which achieved simultaneous and reliable NSE detection due to the completely different signal readouts and transduction mechanism. Specifically, specific reactions of antigens and antibodies were performed in 96-microwell plates. Gold nanoparticle (Au NP)-loaded Fe3O4 (Au@Fe3O4) NPs were used as secondary antibody markers and signal regulators, which could produce a blue-colored solution in the presence of 3,3',5,5'-tetramethylbenzidine (TMB) and H2O2 because of its peroxidase-like activity. Therefore, the visual detection of NSE was realized, making the results more intuitive. Meanwhile, the above biological process could also be used as part of the split-type PEC sensing platform. Oxidized TMB and Fe3+ were consumptive agents of the electron donor, which both realized the double quenching of PEC signal generated by the SnO2/MgIn2S4/Zn0.1Cd0.9S composites. Owing to the waterfall band structure, SnO2/MgIn2S4/Zn0.1Cd0.9S composites partially absorb visible light and effectively inhibit the electron-hole recombination, thereby providing significantly enhanced and stable initial signal. On the basis of the multiple signal amplification strategy and the split-type mode, NSE could be sensitively detected with a low detection limit of 14.0 fg·mL-1 (S/N = 3) and a wide linear range from 50.0 fg·mL-1 to 50.0 ng·mL-1.

Dual-Mechanism Quenching of Electrochemiluminescence Immunosensor Based on a Novel ECL Emitter Polyoxomolybdate-Zirconia for 17ß-Estradiol Detection.

The exploration of novel electrochemiluminescence (ECL) reagents has been a breakthrough work in ECL immunoassay. In this work, the ECL properties of polyoxomolybdate-zirconia (POM-ZrO2) were discovered for the first time and their luminescence mechanism was initially explored. Virgulate POM-ZrO2 was synthesized from phosphomolybdic acid hydrate and zirconium oxychloride by solvothermal method, which achieved intense and stabilized cathode ECL emission at a negative potential. Polyaniline@Au nanocrystals (PANI@AuNPs) as the executor of the dual-mechanism quenching strategy were used to reduce the output signal. The quenching efficiency was significantly enhanced by the dual mechanisms of ECL energy transfer and electron transfer. Specifically, PANI@AuNPs can serve as an energy receptor to absorb the energy emitted by POM-ZrO2 (energy donor), while the appropriate energy level can be regarded as the condition for electron transfer to quench the ECL intensity of POM-ZrO2. Herein, the proposed dual-mechanism quenching strategy was applied to the immunoassay of 17ß-estradiol by constructing a competitive immunosensor. As expected, the immunosensor demonstrated favorable analytical performance and a wide sensing range from 0.01 pg/mL to 200 ng/mL. Hence, it provides a novel method for the sensitive analysis of other biomolecules, such as disease markers and environmental estrogens.

Oxygen Free Radical Scavenger PtPd@PDA as a Dual-Mode Quencher of Electrochemiluminescence Immunosensor for the Detection of AFB1.

Here, a dual-mode quenched electrochemiluminescence (ECL) immunosensor based on PtPd@PDA was proposed. Among them, nitrogen-doped hydrazide conjugated carbon dots (NHCDs), as an ECL emitter and a donor of resonance energy transfer, were quenched by PtPd@PDA (receptor). At the same time, PDA in PtPd@PDA, as an oxygen radical scavenger, completed the further quenching of the ECL signal by consuming O2•- generated by the decomposition of co-reactant H2O2. The dual-mode quenching from the above two channels was achieved. In addition, compared with the traditional carbon quantum dots, NHCDs as ECL emitters had lower excitation potential. Moreover, a large number of amino groups provided by aminated MWCNTs could capture more antibodies while connecting with NHCDs. Under the optimum experimental conditions, taking aflatoxin B1 as the target, the proposed sensor with good specificity, stability, and reproducibility had good linearity when the concentration of AFB1 was 0.01-100 ng/mL, with the detection limit of 2.63 pg/mL (S/N = 3). This strategy provided more possibilities for the application of dopamine metal nanocomposites in electrochemiluminescence analysis and offered a new approach to detect AFB1.

Signal-enhanced electrochemiluminescence strategy using iron-based metal-organic frameworks modified with carboxylated Ru(II) complexes for neuron-specific enolase detection.

The preparation of highly efficient electrochemiluminescence (ECL) illuminants is an effective method to improve the sensitivity and repeatability of ECL immunoassay. In this study, we prepared an ECL immunoassay for efficient and sensitive detection of neuron-specific enolase (NSE) by linking carboxylated Ru(bpy)32+ to an iron-based metal-organic framework (NH2-MIL-88 (Fe)) via an amide bond as an ECL signal probe. NH2-MIL-88 (Fe) possesses a large number of amino groups that can catalyze the co-reactant S2O82-, which generates abundant reaction intermediates SO4•- around Ru(dcbpy)32+, reduces the loss of material transport and energy transfer between SO4•- and Ru(dcbpy)32+, and significantly enhances the ECL signal. We used polyaniline-intercalating vanadium oxide (PVO) nanosheets as the substrates to capture NSE owing to the large specific surface area and extraordinary conductivity of the nanosheets. Similarly, PVO nanosheets also possess abundant amino groups, which can act as co-reaction promoters to catalyze the reaction of S2O82- to SO4•-, enhancing the ECL signal of the immunoassay. Therefore, we constructed a dual-enhanced ECL immunoassay with Ru(dcbpy)32+/NH2-MIL-88 (Fe) and PVO as the signal probe and substrate, respectively, which exhibited excellent sensitivity and selectivity for detecting NSE. This study offers an effective strategy for ultrasensitive detection of trace proteins using ECL immunoassays.

Enhancing Electrochemiluminescence Efficiency through Introducing Atomically Dispersed Ruthenium in Nickel-Based Metal-Organic Frameworks.

The successful application of electrochemiluminescence (ECL) in various fields required continuous exploration of novel ECL signal emitters. In this work, we have proposed a pristine ECL luminophor named NiRu MOFs, which owned extremely high and stable ECL transmission efficiency and was synthesized via a straightforward two-step hydrothermal pathway. The foundation framework of pure Ni-MOFs with the initial structure was layered-pillared constructed by the coordinated octahedrally divalent between nickel and terephthalic acid (BDC). The terephthalates were coordinated and pillared directly to the nickel hydroxide layers and the three-dimensional framework was formed, which had a weak ECL response strength. Then, the ruthenium pyridine complex was recombined with pure Ni-MOFs to produce NiRu MOFs and part of the introduced ruthenium was atomically dispersed in the layered-pillared structure through an ion-exchange method, which led to the ECL luminous efficiency being significantly boosted more than pure Ni-MOFs. In order to verify the superiority of this newly synthesized illuminant, an ECL immunoassay model has been designed, and the results demonstrated that it had extremely strong and steady signal output in practical application. This study realized an efficient platform in ECL immunoassay application with the limit of detection of 0.32 pg mL-1 for neuron-specific enolase (NSE). Therefore, the approach which combined the pristine pure Ni-MOFs and the star-illuminant ruthenium pyridine complex would provide a convenient and meaningful solution for exploring the next-generation ECL emitters.

Electrochemical aptasensor based on gold modified thiol graphene as sensing platform and gold-palladium modified zirconium metal-organic frameworks nanozyme as signal enhancer for ultrasensitive detection of mercury ions.

Gold modified thiol graphene (Au@HS-rGO) was prepared and applied as sensing platform for constructing the electrochemical aptasensor. While gold-palladium modified zirconium metal-organic frameworks (AuPd@UiO-67) nanozyme was employed as signal enhancer for detecting mercury ions (Hg2+) sensitively. Herein, gold nanoparticles (Au NPs) were modified on HS-rGO to form the thin Au@HS-rGO layer. Then the substrate strand (Apt1) was modified on the platform through Au-S bond. The signal strand (Apt2) was further decorated on the platform in the presence of Hg2+. Herein, the Apt2 was labeled with AuPd@UiO-67 nanozyme, which exhibited catalase-like properties to catalyze H2O2, thereby generating the electrical signal. With the concentration of Hg2+ increased, the amount of modified Apt2-AuPd@UiO-67 increased, leading to the rise of current response. Since the current responses were linear with concentration of Hg2+, the detection of Hg2+ can be achieved. Under the optimum conditions, the prepared electrochemical aptasensor exhibited wide linear range from 1.0 nmol/L to 1.0 mmol/L, along with a low detection limit of 0.16 nmol/L. Moreover, the electrochemical aptasensor showed excellent selectivity, reproducibility and stability, together with superior performance in actual water sample analysis. Therefore, this proposed electrochemical aptasensor may have promising applications and provide references for environmental monitoring and management.

Ultrasensitive Photochemical Immunosensor Based on Flowerlike SnO2/BiOI/Ag2S Composites for Detection of Procalcitonin.

Based on the necessity and urgency of detecting infectious disease marker procalcitonin (PCT), a novel unlabeled photoelectrochemical (PEC) immunosensor was prepared for the rapid and sensitive detection of PCT. Firstly, SnO2 porous nanoflowers with good photocatalytic performance were prepared by combining hydrothermal synthesis and calcining. BiOI nanoflowers were synthesized by facile ultrasonic mixed reaction. Ag2S quantum dots were deposited on SnO2/BiOI composites by in situ growth method. The SnO2/BiOI/Ag2S composites with excellent photoelectric properties were employed as substrate material, which could provide significantly enhanced and stable signal because of the energy level matching of SnO2, BiOI and Ag2S and the good light absorption performance. Accordingly, a PEC immunosensor based on SnO2/BiOI/Ag2S was constructed by using the layered modification method to achieve high sensitivity analysis of PCT. The linear dynamic range of the detection method was 0.50 pg·mL-1~100 ng·mL-1, and the detection limit was 0.14 pg·mL-1. In addition, the designed PEC immunosensor exhibited satisfactory sensitivity, selectivity, stability and repeatability, which opened up a new avenue for the analyzation of PCT and further provided guidance for antibiotic therapy.

Dual-signal electrochemiluminescence immunosensor for Neuron-specific enolase detection based on "dual-potential" emitter Ru(bpy)32+ functionalized zinc-based metal-organic frameworks.

Neuron-specific enolase (NSE) is the preferred marker for monitoring small cell lung cancer and neuroblastoma. We devised a dual-signal ratiometric electrochemiluminescence (ECL) sensing strategy for sensitive detection of NSE. In this work, Ru (bpy)32+ functionalized zinc-based metal-organic framework (Ru-MOF-5) nanoflowers (NFs) with plentiful carboxyl groups provide an excellent biocompatible sensing platform for the construction of immunosensor. Importantly, Ru-MOF-5 NFs possess stable and efficient "dual-potential" ECL emission of cathode (-1.5 V) and anode (1.5 V) in the existence of co-reactant K2S2O8. Simultaneously, the cathode ECL emitter ZnO-AgNPs are employed as the secondary antibody marker, whose participation amplify the cathode ECL signal as well attenuate the anode ECL emission of Ru-MOF-5 NFs. By monitoring the ECL dual-signal of -1.5 V and 1.5 V and calculating their ratios, a ratiometric strategy of quantified readout proportional is implemented for the proposed immunosensor to precise analyze NSE. Based on optimization conditions, the ECL immunosensor displays the wide linear range of 0.0001 ng/mL to 200 ng/mL and the minimum detection limit is 0.041 pg/mL. The "dual-potential" ratiometric ECL immunosensor effectively reduces system error or background signal by self-calibration from both emissions and improves detection reliability. The dual-signal ratiometric strategy with satisfactory reproducibility and stability provides further development possibilities for other biomolecular detection and analysis.

Self-Luminescent Lanthanide Metal-Organic Frameworks as Signal Probes in Electrochemiluminescence Immunoassay.

The successful use of electrochemiluminescence (ECL) in immunoassay for clinical diagnosis requires development of novel ECL signal probes. Herein, we report lanthanide (Ln) metal-organic frameworks (LMOFs) as ECL signal emitters in the ECL immunoassay. The LMOFs were prepared from precursors containing Eu (III) ions and 5-boronoisophthalic acid (5-bop), which could be utilized to adjust optical properties. Investigations of ECL emission mechanisms revealed that 5-bop was excited with ultraviolet photons to generate a triplet-state, which then triggered Eu (III) ions for red emission. The electron-deficient boric acid decreased the energy-transfer efficiency from the triplet-state of 5-bop to Eu (III) ions; consequently, both were excited with high-efficiency at single excitation. In addition, by progressively tailoring the atomic ratios of Ni/Fe, NiFe composites (Ni/Fe 1:1) were synthesized with more available active sites, enhanced stability, and excellent conductivity. As a result, the self-luminescent europium LMOFs displayed excellent performance characteristics in an ECL immunoassay with a minimum detectable limit of 0.126 pg mL-1, using Cytokeratins21-1 (cyfra21-1) as the target detection model. The probability of false positive/false negative was reduced dramatically by using LMOFs as signal probes. This proposed strategy provides more possibilities for the application of lanthanide metals in analytical chemistry, especially in the detection of other disease markers.

Label-free electrochemical immunosensor based on biocompatible nanoporous Fe3O4 and biotin-streptavidin system for sensitive detection of zearalenone.

In this study, a sensitive label-free electrochemical immunosensor was designed based on nanoporous Fe3O4 and a biotin-streptavidin system to specifically detect zearalenone (ZEN). Herein, nanoporous Fe3O4 was employed to carry streptavidin to prepare the highly sensitive immunosensor. The application of nanoporous Fe3O4 and the biotin-streptavidin reaction provided large amounts of antibodies on each conjugate, thus amplifying the detected signal. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were conducted to characterize the modification with ZEN. Factors which might influence the properties of the immunosensor, including concentration of nanoporous Fe3O4, pH of the buffer, incubation time and temperature were studied. Under the best conditions, the immunosensor displayed a highly sensitive response toward ZEN, ranging in concentration from 10.0 pg mL-1 to 3.00 ng mL-1 and 3.00 ng mL-1 to 12.0 ng mL-1, with a low detection limit of 3.7 pg mL-1. The results for analysis of human urine samples were satisfactory. Furthermore, this proposed method may find promising applications in the detection of other mycotoxins.

Electrochemiluminescence immunosensor of "signal-off" for ß-amyloid detection based on dual metal-organic frameworks.

In this work, a "signal-off" sandwich electrochemiluminescence (ECL) immunosensor was fabricated for ingenious detection of Alzheimer's disease marker ß-amyloid (Aß) based on dual metal-organic frameworks (dual-MOFs), which included NH2-UiO-66 and MIL-101. Dual-MOFs with high porosity and plentiful functional groups can increase the biomolecules binding rate, and through the synergy with the different materials can effectively amplify the inherent properties of the material itself. Ru(bpy)32+ was capsulated in NH2-UiO-66 as luminophor, the complex possessed steady and excellent luminescence efficiency as well as large specific surface area to load sufficient antibodies. MoS2 quantum dots (MoS2 QDs) combined with MIL-101 via Au-S bond. MIL-101@Au-MoS2 QDs was used for the label of secondary antibodies (Ab2) to quench the ECL signal of Ru(bpy)32+/NH2-UiO-66. The amount of Ab2-MIL-101@Au-MoS2 QDs bound to antigen will gradually accrue with the increase of the concentration of Aß, which led to "signal-off" for accurate estimation of Aß. Under optimal conditions, the developed assay for Aß detection demonstrated a wide linear range of 10-5 ng mL-1 to 50 ng mL-1 and the detection limit was as low as 3.32 fg mL-1 (S/N = 3). The cooperation of dual-MOFs has potential as a universal strategy for quantitative analysis of other targets.

A photoelectrochemical immunosensor based on CdS/CdTe-cosensitized SnO2 as a platform for the ultrasensitive detection of amyloid ß-protein.

An ultrasensitive label-free photoelectrochemical (PEC) immunosensor was developed to detect amyloid ß-protein (Aß) based on CdS/CdTe-cosensitized SnO2 nanoflowers. Specifically, SnO2 with a flower-like porous nanostructure was utilized as a perfect substrate for the construction of PEC immunosensors, and the SnO2-modified electrode was first coated with CdTe quantum dots (QDs) and then further deposited with CdS by successive ionic layer adsorption and reaction techniques. The formed SnO2/CdS/CdTe-cosensitized structure exhibited excellent photocurrent intensity and was employed as an excellent photoactive matrix to immobilize Aß antibody to further construct the immunosensor. Under optimal conditions, the as-constructed PEC immunosensor was used to detect Aß and exhibited a wide linear concentration range from 0.5 pg mL-1 to 10 ng mL-1, with a low limit of detection (LOD, 0.18 pg mL-1, S/N = 3). Meanwhile, it also presented good reproducibility, specificity, and stability and may open a new promising platform for the clinical detection of Aß or other biomarkers.

Electrochemiluminescence immunoassay for the N-terminal pro-B-type natriuretic peptide based on resonance energy transfer between a self-enhanced luminophore composed of silver nanocubes on gold nanoparticles and a metal-organic framework of type MIL-125.

The N-terminal pro-B-type natriuretic peptide (NT-proBNP) is a marker of heart failure. A novel sandwich type electrochemiluminescence (ECL) immunoassay is described for the NT-proBNP. The method is based on ECL resonance energy transfer (RET) between silver nanocubes that were covered with semicarbazide-modified gold nanoparticles (AgNC-sem@AuNPs) as the donor, and a Ti(IV)-based metal-organic framework of type MIL-125 as the acceptor. The ECL signal was strongly amplified by increasing the luminous efficiency. ECL-RET occurs due to the partial overlap between the ECL emission of the AgNC-sem@AuNPs (emission wavelength at 470 nm to 900 nm) and the visible absorption spectrum of MIL-125 (absorption wavelength at 406 nm to 900 nm). This results in the quenching of ECL. The AgNC-sem@AuNPs were placed on the electrode. The antibody was immobilized on AgNC-sem@AuNPs via Au-NH2 bond, and MIL-125 was utilized as a label for the secondary antibody. The assay works in the 0.25 pg mL-1 to 100 ng mL-1 concentration range and has a 0.11 pg mL-1 lower detection limit (at S/N = 3). Graphical abstract Schematic representation of self-enhanced luminescence mechanism (semicarbazide (Sem) as co-reaction accelerator) and Electrochemiluminescence resonance energy transfer (ECL-RET): silver nanocubes (AgNCs) as the energy donor and MIL-125 as the energy acceptor.