Complementary Homogeneous Electrochemical and Photothermal Dual-Modal Sensor for Highly Sensitive Detection of Organophosphorus Pesticides via Stimuli-Responsive COF/Methylene Blue@MnO2 Composite.

Credible and on-site detection of organophosphorus pesticides (OPs) in complex matrixes is significant for food security and environmental monitoring. Herein, a novel COF/methylene blue@MnO2 (COF/MB@MnO2) composite featured abundant signal loading, a specific recognition unit, and robust oxidase-like activity was successfully prepared through facile assembly processes. The multifunctional composite acted as a homogeneous electrochemical and photothermal dual-mode sensing platform for OPs detection through stimuli-responsive regulation. Without the presence of OPs, the surface MnO2 coating could recognize thiocholine (TCh), originating from acetylcholinesterase (AChE)-catalyzed hydrolysis of acetylthiocholine (ATCh), and exhibited a distinctly amplified diffusion current due to the release of plentiful MB; while the residual MnO2 nanosheets could only catalyze less TMB into oxidized TMB (oxTMB) with a typical near-infrared (NIR) absorption, enabling NIR-driven photothermal assay with a low temperature using a portable thermometer. Based on the inhibitory effect of OPs on AChE activity and OP-regulated generation of TCh, chlorpyrifos as a model target can be accurately detected with a low limit of detection of 0.0632 and 0.108 ng/mL by complementary electrochemical and photothermal measurements, respectively. The present dual-mode sensor was demonstrated to be excellent for application to the reliable detection of OPs in complex environmental and food samples. This work can not only provide a complementary dual-mode method for convenient and on-site detection of OPs in different scenarios but also expand the application scope of the COF-based multifunctional composite in multimodal sensors.

A carbon dots-enhanced laccase-based electrochemical sensor for highly sensitive detection of dopamine in human serum.

Enzyme-based electrochemical sensor possesses a significant advantage in the highly efficient detection of small molecules, however, the poor electron transport efficiency limits their wide application. In this study, taking advantage of the distinct biocatalytic activity of laccase and the excellent electroconductibility of carbon dots, a carbon dots-enhanced laccase-based electrochemical sensor for the detection of dopamine (DA) is established. Thereinto, laccase can specifically recognize DA and promote its electrocatalytic oxidation on the electrode, while, the carbon dots can be used as the immobilization substrate of laccase and enhance its electron transfer efficiency, thus achieving the highly sensitive detection of dopamine. The electrochemical performance of the modified electrode interface is studied by electrochemical impedance spectroscopy and differential pulse voltammetry. As demonstrated, the electrocatalytic activity of the proposed electrochemical sensor for DA is significantly improved and exhibits a low detection limit (0.08 µM) and a wide linear range (0.25 µM-76.81 µM). The excellent selectivity allows the sensor has the capacity for specific discrimination the DA from other interferents. Furthermore, by analyzing the DA in human serum verifies the practicability of this assay in real sample analysis.

Colorimetric and electrochemical arsenate assays by exploiting the peroxidase-like activity of FeOOH nanorods.

The authors describe an electrochemical and an optical method for the determination of As(V) by using iron oxyhydroxide (FeOOH) nanorods that display peroxidase-mimicking activity. The nanorods catalyze the oxidation of substrate ABTS by H2O2 to form a green product with an absorption maximum at 418 nm. If, however, As(V) is electrostatically adsorbed on the nanorods, the oxidation is gradually inhibited. A colorimetric assay was worked out based on these findings. Response is linear in the 0 to 8 ppb and 8 to 200 ppb As(V) concentration range, and the detection limit is 0.1 ppb. Even higher sensitivity is achieved in an electrochemical method which is based on the excellent electrical conductivity of FeOOH nanorods. Electrochemical analysis of As(V) was achieved by first adsorbing As(V) on the nanorods. This inhibits the ABTS reduction current signal, best measured at a potential of 150 mV (vs. Ag/AgCl). The linear range extends from 0.04 to 200 ppb, and the detection limit is as low as 12 ppt. Graphical abstract Schematic representation of FeOOH nanorod-based colorimetric and electrochemical assays for arsenate (As(V)). As(V) adsorbed on FeOOH nanorods inhibits the peroxidase-mimicking activity of nanorods, and a colorimetric and electrochemical dual-signal assay was constructed to achieve sensitive determination of As(V).

Colorimetric Assay Conversion to Highly Sensitive Electrochemical Assay for Bimodal Detection of Arsenate Based on Cobalt Oxyhydroxide Nanozyme via Arsenate Absorption.

This study reports a novel and convenient bimodal method for label-free and signal-off detection of arsenate in environmental samples. Cobalt oxyhydroxide (CoOOH) nanoflakes with facile preparation and intrinsic peroxidase-like activity as nanozyme can efficiently catalyze the conversion of chromogenic substrate such as 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) with the presence of H2O2 into green-colored oxidation products. CoOOH nanoflakes can specifically bind with arsenate via electrostatic attraction and As-O bond interaction, which gives rise to inhibition of the peroxidase-like activity of CoOOH. Thus, through arsenate specific inhibition of CoOOH nanozyme toward ABTS catalysis, a simple colorimetric method was developed for arsenate detection with a detection limit of 3.72 ppb. Based on the system of CoOOH nanozyme and ABTS substrate, this colorimetric method can be converted into an electrochemical sensor for arsenate assay by the utilization of CoOOH nanoflake-modified electrode. The electrochemical measurement can be realized by chronoamperometry, which showed more sensitive and a lower limit of detection as low as 56.1 ppt. The applicability of this bimodal method was demonstrated by measuring arsenate and total arsenic in different real samples such as natural waters and soil extracted solutions, and the results are of satisfactory accuracy as confirmed by inductively coupled plasma mass spectrometry analysis. The bimodal strategy offers obvious advantages including a label-free step, convenient operation, on-site assay, low cost, and high sensitivity, which is promising for reliable detection of arsenate and total arsenic in environmental samples.

CdSe/ZnS quantum dots coated with carboxy-PEG and modified with the terbium(III) complex of guanosine 5'-monophosphate as a fluorescent nanoprobe for ratiometric determination of arsenate via its inhibition of acid phosphatase activity.

A ratiometric fluorometric method is described for the determination of arsenate via its inhibitory effect on the activity of the enzyme acid phosphatase. A nanoprobe was designed that consists of CdSe/ZnS quantum dots (QDs) coated with the terbium(III) complex of guanosine monophosphate (Tb-GMP). The nanoprobe was synthesized from carboxylated QDs, Tb(III) and GMP via binding of Tb(III) by both the carboxy and the phosphate groups. The nanoprobe, under single-wavelength excitation (at 280 nm), displays dual (red and green) emission, with peaks at around 652 nm from the QDs, and at 547 nm from the Tb-GMP coordination polymers. It is shown to be a viable nanoprobe for fluorometric determination of As(V) detection through it inhibitory action on the activity of acid phosphatase (ACP). The enzyme destroys the Tb-GMP structure via hydrolysis of GMP, and hence the fluorescence of the Tb-GMP complex is quenched. In contrast, the fluorescence of the CdSe/ZnS QDs remains inert to ACP. It therefore can serve as an internal reference signal. In the presence of arsenate (an analog of phosphate), the activity of ACP is inhibited due to competitive binding. Thus, hydrolysis of GMP is prevented. These findings were used to design a ratiometric fluorometric method for the quantification of As(V). The ratio of fluorescences at 547 and 652 nm increases linearly in the 0.5 to 200 ppb As(V) concentation range, and the limit of detection is 0.39 ppb. Under a UV lamp, the probe shows distinguishable color from green to red on increasing the concentration of As(V). Graphical abstract Schematic illustration of CdSe/ZnS quantum dot coated with carboxy-PEG and modified with the terbium(III)-GMP complex as a fluorescent nanoprobe for ratiometric determination of arsenate via its inhibition of ACP activity.

An ultratrace assay of arsenite based on the synergistic quenching effect of Ru(bpy)32+ and arsenite on the electrochemiluminescence of Au-g-C3N4 nanosheets.

A novel ratiometric electrochemiluminescence (ECL) indicator has been constructed for ultratrace As(iii) detection based on the synergistic quenching of ECL emission of Au-g-C3N4 NSs using As(iii) and Ru(bpy)32+, meanwhile generating a new ECL signal of Ru(bpy)32+ with an increased intensity. Due to the dual quenching effect of As(iii) and Ru(bpy)32+ coupled with the generation of the second ECL signal of Ru(bpy)32+, the sensitivity and selectivity for detecting As(iii) are vastly enhanced.

Electrochemical sensor for arsenite detection using graphene oxide assisted generation of prussian blue nanoparticles as enhanced signal label.

An electrochemical sensor was fabricated for arsenite detection using graphene oxide-assisted generation of prussian blue nanoparticles as enhanced redox signal label. The 5'-thiolate-labeled (GT)21-ssDNA was first self-assembled on a gold electrode surface via Au-S bond. Graphene oxide can interact with ssDNA through π-π stacking interaction and facilitate the generation of prussian blue nanoparticles on its surface as an electrochemically active indicator. In the absence of arsenite, plenty of graphene oxide/prussian blue nanoparticles can be adsorbed on the electrode surface to produce a stronger redox signal of prussian blue nanoparticles. While in the presence of arsenite, (GT)21-ssDNA can recognize and combine with arsenite via hydrogen bonds to form (GT)21-ssDNA/arsenite complex with a frizzy structure. The conformational change of (GT)21-ssDNA led to less adsorption of graphene oxide/prussian blue nanoparticles on the electrode surface, resulting in a reduced redox response. The arsenite-induced (GT)21-ssDNA structure switching can be used for sensitive detection of arsenite with a linear range from 0.2 to 500 ppb and a detection limit down to 0.058 ppb. Benefiting from (GT)21-ssDNA containing arsenite recognition sequence, the proposed sensor exhibited excellent specificity against other heavy metal ions. The applicability of the electrochemical biosensor for arsenite assay in real water samples demonstrated the great potential of this strategy for trace arsenite detection in environment.

Ratiometric electrochemical assay for sensitive detecting microRNA based on dual-amplification mechanism of duplex-specific nuclease and hybridization chain reaction.

We propose a ratiometric electrochemical assay for detecting microRNA (miRNA) on the basis of dual-amplification mechanism by using distinguishable electrochemical signals from thionine (Thi) and ferrocene (Fc). The thiol-modified and ferrocene-labeled hairpin capture probes (CP) are first immobilized on an Au electrode via Au-S reaction. The target miRNA hybridizes with CP and unfolding the hairpin structure of CP to form miRNA-DNA duplexes. Then, kamchatka crab duplex specific nuclease (DSN) specifically cleaves the DNA in miRNA-DNA duplexes, leading to the release of miRNA and another cleaves cycle, meanwhile, numerous Fc leaves away from the electrode surface and leads to the signal-off of Fc. The residual fragment on electrode surface acts as a HCR primer to form dsDNA polymers through in situ HCR with the presence of the primer and two probes (HDNA and HDNA'), resulting in the capture of numerous DNA/Au NPs/Thi and the signal-on of Thi. The dual-amplification mechanism significantly amplifies the decrease of Fc signal and the increase of Thi signal for ratiometric readout (IThi/IFc), thus providing a sensitive method for the selective detection of miR-141 with a detection limit down to 11aM. The dual-signal ratiometric outputs have an intrinsic self-calibration to the effects from system, which is promising to be applied in biosensing and clinical diagnosis.

Simultaneously electrochemical detection of microRNAs based on multifunctional magnetic nanoparticles probe coupling with hybridization chain reaction.

We report a sensor combining two distinguishable magnetic nanoprobes (DNA1/Fe3O4 NPs/Thi and DNA2/Fe3O4 NPs/Fc) with target-triggered hybridization chain reaction (HCR) strategy for the simultaneous detection of microRNA-141 (miR-141) and microRNA-21 (miR-21). In the presence of targets, the thiol-modified hairpin capture probes (HCP1 and HCP2) specifically hybridize with miR-141 and miR-21 on a gold electrode, leading to the conformation change of HCP1 and HCP2, respectively. The conformation change subsequently triggers HCR to generate plentiful bonding sequences of magnetic nanoprobes. Thus, numerous thionine (Thi) modified DNA1/Fe3O4 NPs/Thi and ferrocene carboxaldehyde (Fc-CHO) modified DNA2/Fe3O4 NPs/Fc are captured by the well-designed HCR, via DNA hybridization respectively, giving rise to the dual magnified response of currents. The increase in the electrochemical currents at different potentials of the two magnetic nanoprobes enables us to simultaneously and quantitatively detect miR-141 and miR-21. Target-triggered HCR increases the amount of captured nanoprobes due to the increasing number of bonding sequences, greatly amplifying the currents of the two magnetic nanoprobes in the presence of targets, and ultimately realizing the dual signal amplification with increased sensitivity. The sensor can be applied for detecting miRNAs in cell lysates, thus, promising to be a clinic diagnosis of cancers by means of simultaneous detection of a variety of miRNA biomarkers.

How effectively do parents discern their children's cognitive deficits at a preschool age?

BACKGROUND: This hospital-based study explored how effectively parents discern their children's cognitive deficits at a preschool age since few studies have addressed preschool children's cognitive problems. METHODS: One hundred and forty-six preschool children suspected of possessing a cognitive deficit were recruited and subjected to further cognitive assessments. All parental concerns for their children were elicited and categorized into various child developmental domains. The cognitive performances amongst children whose parents expressed specific concerns were compared. RESULTS: With regard to the children whose parents expressed multiple concerns about their child's developmental problems, the Performance Intelligence Quotient (PIQ), Verbal Intelligence Quotient (VIQ) and Full Scale Intelligence Quotient (FSIQ) scores were significantly lower than they were for the children whose parents had behavior concerns (p < 0.01). For children whose parents had raised concerns about their child's speech developmental problems, the VIQ and FSIQ scores were found to be significantly lower than they were for the children whose parents had raised behavior concerns (p < 0.01). In addition, it was found that parental concerns about multiple domains of developmental problems could produce relatively higher sensitivity and positive predictive value in the deficits of both verbal and non-verbal cognitive abilities. Parental concerns about only speech developmental problems were noted to yield high positive predictive value regarding verbal-cognitive deficits. CONCLUSION: The results indicate that parents' initial concerns about their children's multiple or speech developmental problems were relatively highly correlated with cognitive deficits. It is recommended that clinicians should guide parents to voice and organize their concerns regarding the perception of their children's developmental progress, and further precisely analyze and utilize significant information.