Engineering "three-in-one" fluorescent nanozyme of Ce-Au NCs for on-site visual detection of Hg2.

Hg2+ contamination poses a serious threat to the environment and human health. Although gold nanoclusters (Au NCs) have been utilized as fluorescence probes or colorimetric nanozymes for performing Hg2+ assays by using a single method, designing multifunctional nanoclusters as fluorescent nanozyme remains challenging. Herein, Ce-aggregated gold nanoclusters (Ce-Au NCs) were reported with "three in one" functions to generate strong fluorescence, excellent peroxidase-like activity, and the highly specific recognition of Hg2+ via its metallophilic interaction. A portable fluorescence and colorimetric dual-mode sensing device based on Ce-Au NCs was developed for on-site visual analysis of Hg2+. In the presence of Hg2+, fluorescence was effectively quenched and the paper-based chips gradually darkened from green till they became completely absent, while peroxidase-like activity was significantly enhanced. Two independent signals were captured by one identification unit, which provided self-validation to improve reliability and accuracy. Therefore, this work presents a simple synthesis of a multifunctional fluorescent nanozyme, and the developed portable device for on-site visual detection has considerable potential for application in the rapid on-site analysis of heavy metal ions in the environment.

Loading of AuNCs with AIE effect onto cerium-based MOFs to boost fluorescence for sensitive detection of Hg2.

Ligand-protected gold nanoclusters (AuNCs) have become promising nanomaterials in fluorescence (FL) methods for mercury ions (Hg2+) monitoring, but low FL efficiency hinders their widespread application. Herein, AuNCs/cerium-based metal-organic frameworks (AuNCs/Ce-MOFs) were prepared by loading 6-aza-2-thiothymine-protected AuNCs (ATT-AuNCs) with aggregation-induced emission (AIE) effect on the surface of Ce-MOFs by electrostatic attraction. This strategy improved the FL intensity of AuNCs through two aspects: (i) the AIE effect of ATT-AuNCs and (ii) the confinement effect of Ce-MOFs, which improved the restriction of intramolecular motion (RIM) of ATT-AuNCs. In addition, Ce-MOFs could adsorb and aggregate Hg2+ during detection, which might increase the local concentration. Therefore, based on the high FL signal of AuNCs/Ce-MOFs and enriched Hg2+, sensitive detection of Hg2+ could be achieved. More importantly, the strong specific recognition between AuNCs and Hg2+ could guarantee selectivity. The developed FL sensor exhibited superior detection performances with a wide linear range of 0.2-500 ng mL-1 and a low detection limit of 0.067 ng mL-1. Furthermore, the FL sensor used for sensitive and selective detection of Hg2+ in real samples, and the results agreed well with the standard method. In summary, this work proposed an effective and generalized strategy for improving the FL efficiency of AuNCs, which would greatly facilitate their application in pollutant monitoring.

Isolation of Sensing Units and Adsorption Groups Based on MOF-on-MOF Hierarchical Structure for Both Highly Sensitive Detection and Removal of Hg2.

Bifunctional materials have attracted ongoing interest in the field of detection and removal of contaminants because of their integration of two functions, but they exhibit commonly exceptional performance in only one of these two aspects. The interaction between the two functional units of the bifunctional materials may compromise their sensing and adsorption abilities. Guided by the concept of domain building blocks (DBBs), a hierarchical metal-organic framework (MOF)-on-MOF hybrid was designed by growing gold nanoclusters (AuNCs)-embedded zeolitic imidazolate framework 8 (AuNCs/ZIF-8) on the surface of Zr-MOF (UiO-66-NH2) for the simultaneous detection and removal of Hg2+. In the hybrid, the amino groups (-NH2) and AuNCs─which were the adsorption groups and sensing units, respectively, were isolated from each other. Specifically, the adsorption groups (-NH2) were assembled in the inner UiO-66-NH2 layer, while the sensing units (AuNCs) were confined in the outer ZIF-8 layer. This hierarchical structure not only spatially hindered the electron transfer between these two units but also triggered the aggregation-induced emission of AuNCs because of the confinement of ZIF-8 on the AuNCs, thus changing the fluorescence of AuNCs from quenching to enhancement. The newly prepared UiO-66-NH2@AuNCs/ZIF-8 hybrid, as expected, showed an ultralow detection limit (0.42 ppb) and a high adsorption capacity (129.9 mg·g-1) for Hg2+. Overall, this work provides a feasible approach to improve the integrated performance of MOF-based composites based on DBBs.

Simple and sensitive fluorescence sensing of methyl parathion based on the inner filter effect of p-nitrophenol on nitrogen-doped titanium carbide quantum dots.

It is of great significance to develop an effective method for methyl parathion (MP) detection. Herein, a novel nitrogen-doped titanium carbide quantum dots (N-Ti3 C2 QDs) was prepared and used to construct a simple and sensitive fluorescence sensing platform of MP by making use of inner filter effect (IFE). The prepared N-Ti3 C2 QDs can exhibit strong blue fluorescence at 434 nm. Meanwhile, MP could hydrolyze to produce p-nitrophenol (p-NP) under alkaline conditions, which showed a characteristic ultraviolet-visible (UV-visible) absorption peak at 405 nm, resulting in the fluorescence of N-Ti3 C2 QDs is effectively quenched by p-NP. In addition, the investigation of time-resolved fluorescence decays indicated that the corresponding quenching mechanism of p-NP on N-Ti3 C2 QDs is due to the IFE. After optimizing the conditions, the as-developed fluorescence sensing platform displayed wide detection range (0.1-30 µg mL-1 ) and low detection limit (0.036 µg mL-1 ) for MP, and it was also successfully applied for MP analysis in real water samples, thus it is expected that this simple, sensitive and enzyme-free sensing platform shows great applications.

Advances in the application of metal-organic framework nanozymes in colorimetric sensing of heavy metal ions.

Nanozymes, which can be defined as nanomaterials with excellent catalytic function, are well known to the scientific community due to their distinct merits, such as low cost and high stability, which render them preferable to natural enzymes. As porous organic-inorganic coordination materials, metal-organic frameworks (MOFs) possess a large number of active sites and thus can effectively mimic the properties of natural enzymes. Recently, MOF-based nanozymes have also exhibited good application potential for the analysis of heavy metal ions. In comparison to the traditional detection methods for heavy metal ions, nanozyme-based colorimetric sensing permits intuitive visual analysis by using relatively simple instruments, facilitating rapid and simple on-site screening. In this minireview, the preparation of MOF-based nanozymes and the different nanozyme activity types are briefly described, such as peroxidase-like and oxidase-like, and the relevant catalytic mechanisms are elaborated. Based on this, different response mechanisms of MOF-based colorimetric methods to heavy metal ions, such as turn-off, turn-on, and turn-off-on, are discussed. In addition, the colorimetric sensing applications of MOF-based nanozymes for the detection of heavy metal ions are summarized. Finally, the current research status of MOF-based nanozymes and the future development direction are discussed.

Gold nanocluster-confined covalent organic frameworks as bifunctional probes for electrochemiluminescence and colorimetric dual-response sensing of Pb2.

The development of bifunctional signal probes based on a single component is highly desirable for sensitive and simple dual-mode detection of Pb2+. Here, novel gold nanocluster-confined covalent organic frameworks (AuNCs@COFs) were fabricated as a bisignal generator to enable electrochemiluminescence (ECL) and colorimetric dual-response sensing. AuNCs with both intrinsic ECL and peroxidase-like activity were confined into the ultrasmall pores of the COFs via an in situ growth method. On the one hand, the space-confinement effect of the COFs closed the ligand motion-induced nonradiative transition channels of the AuNCs. As a result, the AuNCs@COFs exhibited a 3.3-fold enhancement in anodic ECL efficiency compared to the solid-state aggregated AuNCs using triethylamine as the coreactant. On the other hand, due to the outstanding spatial dispersibility of the AuNCs in the structurally ordered COFs, a high density of active catalytic sites and accelerated electron transfer were obtained, leading to the promotion of the enzyme-like catalytic capacity of the composite. To validate its practical applicability, a Pb2+-triggered dual-response sensing system was proposed based on the aptamer-regulated ECL and peroxidase-like activity of the AuNCs@COFs. Sensitive determinations down to 7.9 pM for the ECL mode and 0.56 nM for the colorimetric mode were obtained. This work provides an approach for designing single element-based bifunctional signal probes for dual-mode detection of Pb2+.

Highly Fluorescent Magnetic ATT-AuNCs@ZIF-8 for All-in-One Detection and Removal of Hg2+: An Ultrasensitive Probe to Evaluate Its Removal Efficiency.

The development of multifunctional materials for the synchronous detection and removal of mercury ions (Hg2+) is in high demand. Although a few multifunctional materials as a fluorescent indicator and adsorbent have achieved this aim, the feedback of their removal efficiency still depends on other methods. Herein, magnetic Fe3O4 nanoparticles (MNPs) and 6-aza-2-thiothymine-protected gold nanoclusters (ATT-AuNCs) were rationally assembled into a zeolitic imidazolate framework 8 (ZIF-8) structure via a one-pot method. The coordination assembly of ATT-AuNCs and ZIF-8 not only strengthened the aurophilic interactions of adjacent ATT-AuNCs but also induced the restriction of intramolecular motion of ATT with a six-membered heterocyclic structure. As a consequence, the fluorescence (FL) quantum yield of MNPs/ATT-AuNCs@ZIF-8 was 12.5-fold higher than that of pristine ATT-AuNCs. Benefiting from the enhanced FL emission, MNPs/ATT-AuNCs@ZIF-8 showed improved sensitivity for Hg2+ detection and therefore could evaluate the removal efficiency via FL detection, without relying on another detection method. Additionally, the nanocomposite also displayed a satisfactory removal capability for Hg2+, including a short capture time (20 min), a high removal efficiency (>96.9%), and excellent reusability (10 cycles). This work provides an approach for customizing functional nanocomposites to concurrently detect and remove Hg2+ with superior performance, especially for high detection sensitivity.

Dual-quenching effects of methylene blue on the luminophore and co-reactant: Application for electrochemiluminescent-electrochemical ratiometric zearalenone detection.

Methylene blue (MB) is a common multifunctional indicator, which can be applied as a quencher for electrochemiluminescence (ECL) analysis as well as a classical redox probe. Although it is relatively prevalent for MB to study the mechanism with Ru-based luminophores in ECL systems, there are few studies on the effects between MB and co-reactants. In this work, we proposed the first investigation of MB on the luminophore and co-reactant of the self-enhanced ECL composites (nitrogen-doped graphene quantum dots on Ru(bpy)32+-doped silica nanoparticles, NGQDs-Ru@SiO2), respectively. The relatively narrow ECL spectrum of luminophore (Ru@SiO2) and the suitable ultraviolet-visible absorption spectrum of MB led to the ECL resonance energy transfer between them, meanwhile the appropriate energy levels among them facilitated the electron transfer, resulting in a decreased ECL signal (quench mode I). Additionally, the co-reactant (NGQDs) was prone to π-π conjugation with MB due to its abundant π-electrons, which reduced the concentration of NGQDs' intermediates and triggered a weakened ECL signal (quench mode II). Therefore, the dual-quenching effects are ingeniously integrated and designed in one ECL-electrochemical (ECL-EC) ratiometric aptasensor for zearalenone detection, for demonstrating its efficacy in enhancing the sensitivity, which is 4.8-fold higher than Ru@SiO2 alone. This innovative ratiometric aptasensor achieved a relatively wide linear range from 1.0 × 10-15 to 5.0 × 10-8 g mL-1, and obtained a low detection limit of 8.5 × 10-16 g mL-1. Our proposed dual-quenching interactions between MB and NGQDs-Ru@SiO2 will open a new prospective for ECL-EC ratiometric aptasensor, which further broaden the application in sensitive and precise analysis of mycotoxins.

A ratiometric fluorescence aptasensor based on photoinduced electron transfer from CdTe QDs to WS2 NTs for the sensitive detection of zearalenone in cereal crops.

Semiconductor quantum dots (QDs) and tungsten disulfide nanosheets (WS2 NTs) have been widely studied in photocatalysis and photoelectrochemistry as representative electron donor-acceptor pairs but rarely in fluorescence sensing. In this study, we investigated the effect of WS2 NTs on the fluorescence signal of cadmium telluride (CdTe) QDs by grafting an aptamer as a bridge between them. The corresponding quenching mechanism was systematically explored, and results described the photoinduced electron transfer (PET) from excited CdTe QDs to WS2 NTs. Based on these results, a novel ratiometric fluorescence aptasensor was developed for zearalenone (ZEN) determination by innovatively introducing exonuclease I to digest the aptamer of ZEN and control the PET between CdTe QDs and WS2 NTs. The designed aptasensor exhibited an acceptable linear range and detection limit (0.1 pg mL-1), and superior accuracy and selectivity. This ratiometric fluorescence aptasensor was also used to monitor ZEN in rice and corn flour.

An ultra-high-sensitivity electrochemiluminescence aptasensor for Pb2+ detection based on the synergistic signal-amplification strategy of quencher abscission and G-quadruplex generation.

Signal amplification provides an effective way to improve detection performance. Herein, an ultrasensitive electrochemiluminescence (ECL) aptasensor for Pb2+ detection was developed based on a dual signal-amplification strategy of the abscission of a quencher and the generation of a G-quadruplex by one-step and simultaneous way. Nitrogen-doped carbon quantum dots linked with complementary DNA (cDNA-NCQDs) at the sensing interface was applied as the quencher of a tris(4,4'-dicarboxylic acid-2,2'-bipyridyl)ruthenium(II) (Ru(dcbpy)32+)/tripropylamine system to minimize the ECL signal due to the intermolecular hydrogen bond-induced energy-transfer process. Upon the addition of Pb2+, its specific binding with the aptamer triggered the abscission of cDNA-NCQDs, accompanied by the formation of G-quadruplex on the surface of the electrode, both of which amplified the intensity of the light emission. The ECL amplification efficiency induced by the above two mechanisms (78.6%) was valuably greater than that of their sum value (69.3%). This synergistic effect resulted in high detection sensitivity of the ECL aptasensor, which allowed to thereby obtain Pb2+ measurements in the range of 1 fM - 10 nM with an ultra-low detection limit of 0.19 fM. The Pb2+-mediated synergistic signal-amplification ECL strategy can provide a new approach for integrating various amplification strategies.

An intermolecular hydrogen-bond-induced quench-type Ru(dcbpy)32+/TPA electrochemiluminescence system by nitrogen-doped carbon quantum dots.

Here, we show that nitrogen-doped carbon quantum dots (NCQDs) strongly inhibits the anodic electrochemiluminescence (ECL) signal of a tris(4,4'-dicarboxylic acid-2,2'-bipyridyl) ruthenium(II) (Ru(dcbpy)32+)/tripropylamine (TPA) aqueous system. To determine the ECL-quenching mechanism, we used photoluminescence spectroscopy, UV-Visible absorption spectroscopy and dynamic simulation technology. Quenching of the ECL signal of Ru(dcbpy)32+/TPA by NCQDs was predominantly attributed to the interaction between Ru(dcbpy)32+ and NCQDs rather than that between TPA and NCQDs. Specifically, when Ru(dcbpy)32+ and NCQDs were in aqueous solution together, the carboxyl (-COOH) groups of Ru(dcbpy)32+ were in contact with oxygen- and nitrogen-containing groups on the surface of NCQDs and formed intermolecular hydrogen bonds. This process involved energy transfer from the excited-state Ru(dcbpy)32+ to the intermolecular hydrogen bonds, thus resulting in a decrease in the Ru(dcbpy)32+ ECL signal. On this basis, a quenching-type ECL sensor for the quantification of NCQDs was fabricated. The sensor had a wide linear range and an estimated detection limit of 0.0012 mg mL-1, as well as excellent stability and selectivity. Satisfactory recoveries of 97.0-99.5% were obtained using the ECL sensor to quantify NCQDs in tap water. NCQDs could potentially be used as a quenching probe of Ru(dcbpy)32+ to construct various biosensors with widespread applications in the sensing field.

Inner filter effect-modulated ratiometric fluorescence aptasensor based on competition strategy for zearalenone detection in cereal crops: Using mitoxantrone as quencher of CdTe QDs@SiO2.

Herein, an innovative ratiometric fluorescence (FL) aptasensor was successfully fabricated for the accurate analysis of zearalenone (ZEN) in corn and barley flour. The ZEN aptamer-modified nitrogen doped graphene quantum dots (NGQDs-apt) and silica sphere-encapsulated cadmium telluride quantum dots (CdTe QDs@SiO2) were directly mixed and applied as ratiometric probes. In the absence of ZEN, mitoxantrone (MTX), which was innovatively introduced as quencher, was captured by NGQDs-apt and its inner filter effect (IFE) on CdTe QDs@SiO2 was inhibited. When ZEN existed, MTX separated from NGQDs-apt and re-dispersed around CdTe QDs@SiO2 owing to the competitive binding of ZEN with its aptamer. As the IFE of free MTX on CdTe QDs@SiO2 recovering, the FL intensity of CdTe QDs@SiO2 was quenched, while the FL intensity of NGQDs-apt was nearly invariant. On this basis, a ratiometric FL aptasensor for ZEN was fabricated, which exhibited outstanding detection performances with a desirable detection limit of 0.32 pg mL-1.

Sensitive and selective detection of Hg2+ in tap and canal water via self-enhanced ECL aptasensor based on NH2-Ru@SiO2-NGQDs.

In the present study, a novel self-enhanced electrochemiluminescence (ECL) aptasensor which combined self-enhanced ECL composite as signal response element and aptamer as the specific recognition element was firstly proposed for the sensitive and selective detection of Hg2+. Innovatively, the luminophore Ru(bpy)32+-doped silica nanoparticles functionalized with 3-aminopropyltriethoxysilane (NH2-Ru@SiO2) and the co-reactant nitrogen doped graphene quantum dots (NGQDs) were bound together to form the self-enhanced ECL composite, NH2-Ru@SiO2-NGQDs, by electrostatic adsorption. Satisfactorily, high and stable luminous efficiency of NH2-Ru@SiO2-NGQDs was obtained benefited from the short electron transfer distance and low energy loss of self-enhanced-typal ECL composite. For the fabrication of the self-enhanced ECL aptasensor for Hg2+ detection, the Hg2+ aptamer, of which one end was connected to NH2-Ru@SiO2-NGQDs, and the other end was fixed on glass carbon electrode (GCE) surface through Au-S bond, was served as a bridge. Upon the addition of Hg2+, the aptamer was bent due to the formation of thymine-Hg2+-thymine (T-Hg2+-T) specific structure, which caused the self-enhanced ECL composite was close to the GCE surface. On this basis, a linearly enhanced ECL signal was acquired with the concentration of Hg2+ in the range of 5.0 × 10-11 M - 1.0 × 10-6 M with excellent selectivity, repeatability and stability in 3 min for each assay. In addition, the proposed aptasensor showed satisfying accuracy and practicability for Hg2+ analysis in tap and canal water verified by the inductively coupled plasma-mass spectrometry (ICP-MS) method.

Induced self-enhanced electrochemiluminescence aptamer sensor for 17ß-estradiol detection based on nitrogen-doped carbon quantum dots as Ru(dcbpy)32+ coreactant: What role of intermolecular hydrogen bonds play in the system?

Herein, an induced self-enhanced electrochemiluminescence (ECL) sensor with superior ECL performances was simply fabricated by just dropping the ECL reagent (tris(4,4'-dicarboxylicacid-2,2'-bipyridyl) ruthenium (II) dichloride, Ru(dcbpy)3Cl2) and coreactant (nitrogen-doped carbon quantum dots, NCQDs) pair onto the surface of glassy carbon electrode. In this strategy, based on the carboxyl (-COOH) groups in Ru(dcbpy)32+ and oxygen, nitrogen-containing groups on NCQDs surface, an intermolecular hydrogen bonds-induced self-enhanced ECL composite was generated in the solid contact layer for the first time. Since Ru(dcbpy)32+ and NCQDs were co-existing in the same composite, the electron-transfer distance between them was shortened and the energy loss was decreased, thereby higher ECL efficiency was acquired. This working process greatly avoided the introduction of signal amplifier and simplified the experimental operation. On this basis, 17ß-estradiol (E2) was selected as a target model to fabricate a self-enhanced ECL aptamer sensor for the investigation of its analytical performances. Resultantly, excellent detection properties of E2, including wider linear range of 1.0 × 10-14 - 1.0 × 10-6 mol L-1 and lower detection limit of 1.0 × 10-15 mol L-1 with superior selectivity, were successfully achieved. Finally, E2 spiked into milk powder was quantified to assess the practicability of this sensor. Prospectively, this strategy could be extensively applied for other analytes determination by adjusting the corresponding target aptamers.

A FRET-based aptasensor for ochratoxin A detection using graphitic carbon nitride quantum dots and CoOOH nanosheets as donor-acceptor pair.

A new fluorescence aptasensor for Ochratoxin A (OTA) analysis in corn and barley flour was developed owing to the favourable quenching function of cobalt oxyhydroxide (CoOOH) nanosheets. The first combination of graphitic carbon nitride quantum dots (g-CNQDs) and CoOOH nanosheets as efficient energy donor-acceptor pair was reported, and the quenching mechanism was proved by investigating the fluorescence lifetime of g-CNQDs. The aptamer-modified g-CNQDs (g-CNQDs-apt) were adsorbed onto CoOOH nanosheets surface by van der Waals force. Consequently, the Förster resonance energy transfer (FRET) from g-CNQDs-apt to CoOOH nanosheets was initiated, leading to quenched fluorescence. With the addition of OTA, the linear aptamer specifically bound with OTA to form G-quadruplex, which had relatively weak interaction with the CoOOH nanosheets and separated from the nanosheets surface. Thus, the FRET process between g-CNQDs-apt and CoOOH nanosheets was hindered, leading to the fluorescence of g-CNQDs-apt recovered clearly. The developed aptasensor exhibited acceptable detection limit with 0.5 nM and desirable linear relationship from 1 nM to 140 nM. Meanwhile, the aptasensor possessed multiple advantages, including easy operation, rapid detection and high selectivity. Moreover, the aptamer sensing platform was favorably applied for OTA determination in cereal (barley and corn flour), in which the recoveries varied from 94.5% to 101% with the relative standard deviation under 2.24%.