ZIF-67 based CoS2 self-assembled on graphitic carbon nitride microtubular for sensitive electrochemical detection of paraquat in fruits.

Paraquat (PQ) is a widely used and harmful herbicide that must be detected in the environment. This study reports a novel composite (CoS2-GCN) prepared by assembling cobalt disulfide (CoS2) derived from metal-organic frameworks (MOFs) on graphitic carbon nitride (GCN). An electrochemical sensor (CoS2-GCN/ glassy carbon electrode (GCE)) was successfully prepared by modifying CoS2-GCN onto a GCE to sensitively detect PQ. Different concentrations of PQ were detected using square-wave voltammetry, and the CoS2-GCN/GCE electrochemical sensor showed remarkable response signals for PQ in the range of 20 - 1000 nM and 1 - 13 µM, with a detection limit of 4.13 nM (S/N = 3). The CoS2-GCN/GCE electrochemical sensor exhibited high stability, reproducibility, and immunity to interference, which were attributed to the synergistic effects of CoS2 and GCN. In addition, the CoS2-GCN/GCE electrochemical sensor showed high applicability for the analysis of fruit samples. Therefore, the proposed sensor has potential applications in PQ detection.

Dual-mode colorimetric determination of As(III) based on negatively-charged aptamer-mediated aggregation of positively-charged AuNPs.

The aggregation and redispersion of positively-charged AuNPs ((+)AuNPs) modified with cysteamine (CS) could be regulated by the negatively charged As(III)-specific aptamer (As(III)-apt). In general, (+)AuNPs aggregated with increasing inducer concentration. However, in the present study, it was found that (+)AuNPs re-dispersed after a certain high concentration of As(III)-apt was reached. By optimizing the concentration of As(III)-apt that resulted in the aggregation and redispersion behavior of (+)AuNPs, a dual-mode colorimetric aptasensor for As(III) determination was established. It was not only able to quantify As(III) sensitively over a ranges of As(III) concentrations, but also to selectively differentiate As(III) and eliminate false results from other control ions by dual-mode.

A Facile Aptasensor for Instantaneous Determination of Cadmium Ions Based on Fluorescence Amplification Effect of MOPS on FAM-Labeled Aptamer.

Analytical performance and efficiency are two pivotal issues for developing an on-site and real-time aptasensor for cadmium (Cd2+) determination. However, suffering from redundant preparations, fabrications, and incubation, most of them fail to well satisfy the requirements. In this work, we found that fluorescence intensity of 6-carboxyfluorescein(FAM)-labeled aptamer (FAM-aptamer) could be remarkably amplified by 3-(N-morpholino)propane sulfonic acid (MOPS), then fell proportionally as Cd2+ concentration introduced. Importantly, the fluorescence variation occurred immediately after addition of Cd2+, and would keep stable for at least 60 min. Based on the discovery, a facile and ultra-efficient aptasensor for Cd2+ determination was successfully developed. The sensing mechanism was confirmed by fluorescence pattern, circular dichroism (CD) and intermolecular interaction related to pKa. Under the optimal conditions, Cd2+ could be determined rapidly from 5 to 4000 ng mL-1. The detection limit (1.92 ng mL-1) was also lower than the concentration limit for drinking water set by WHO and EPA (3 and 5 ng mL-1, respectively). More than a widely used buffer, MOPS was firstly revealed to have fluorescence amplification effect on FAM-aptamer upon a given context. Despite being sensitive to pH, this simple, high-performance and ultra-efficient aptasensor would be practical for on-site and real-time monitoring of Cd2+.

Label-free colorimetric assay for arsenic(III) determination based on a truncated short ssDNA and gold nanoparticles.

A short ssDNA (Apt-21) rationally truncated from the parent 100 nt As(III) aptamer was used for colorimetric determination of As(III). Apt-21 serves dual functions, i.e., recognition of trace As(III) and regulation of AuNPs dispersion by surface attachment, while gold nanoparticles (AuNPs) functioned as colorimetric signal reporters. Under the optimal conditions, the ratio of the absorbance at 650 nm to 520 nm (A650/A520) of AuNPs changed proportionally with increasing concentration of As(III), which showed a linear relationship within the concentration ranges 1-30 ppb and 30-100 ppb with a detection limit of 0.18 ppb. The feasibility of this assay was demonstrated by determining As(III) in spiked water samples with mean recoveries ranging from 96.5-107.1%. Schematic representation of colorimetric detection of As(III) based on the short ssDNA (Apt-21) and gold nanoparticles (AuNPs).

An Electrochemical Aptasensor for Pb2+ Detection Based on Metal-Organic-Framework-Derived Hybrid Carbon.

A new double-shelled carbon nanocages material was synthesized and developed an aptasensor for determining Pb2+ in aqueous solution. Herein, nanoporous carbon materials derived from core-shell zeolitic imidazolate frameworks (ZIFs) demonstrated excellent electrochemical activity, stability, and high specificity surface area, consequently resulting in the strong binding with aptamers. The aptamer strands would be induced to form G-quadruplex structure when Pb2+ was introduced. Under optimal conditions, the aptasensor exhibited a good linear relationship of Pb2+ concentration ranging from 0.1 to 10 µg L-1 with the detection limits of 0.096 µg L-1. The feasibility was proved by detecting Pb2+ in spiked water samples and polluted soil digestion solution. The proposed aptasensor showed excellent selectivity and reproducibility, indicating promising applications in environmental monitoring.

Label-Free and Sensitive Determination of Cadmium Ions Using a Ti-Modified Co3O4-Based Electrochemical Aptasensor.

The current work demonstrates an electrochemical aptasensor for sensitive determination of Cd2+ based on the Ti-modified Co3O4 nanoparticles. In this unlabeled system, Ti-modified Co3O4 nanoparticles act as current signal amplifiers modified on the screen-printed carbon electrode (SPCE) surface, while the derivative aptamer of Cd2+ works as a target recognizer. In addition, the sensing is based on the increase in electrochemical probe thionine current signal due to the binding of aptamer to Cd2+ via specific recognition. In the current study, key parameters, including aptamer concentration, pH, and incubation time were optimized, respectively, to ensure sensing performance. Cyclic voltammetry was used not only to characterize each preparation and optimization step, but also to profile the bindings of aptamer to Cd2+. Under optimal conditions, Cd2+ can be determined in a linear range of 0.20 to 15 ng/mL, with a detection limit of 0.49 ng/mL, significantly below the maximum concentration limit set by the U.S. Environmental Protection Agency. Based on comparative analysis and the results of recovery test with real samples, this simple, label-free but highly selective method has considerable potential and thus can be used as an in-situ environmental monitoring platform for Cd2+ testing.

An electrochemical aptasensor based on gold@polypyrrole composites for detection of lead ions.

This work describes an electrochemical aptasensor for determination of lead ions (Pb2+). Composites prepared from gold nanoparticles and polypyrrole (Au@PPy) with good electrical conductivity were used to modify the surface of a screen printed carbon electrode for amplifying the current signal. Single strand DNA was immobilized on the electrode and binds lead(II) as confirmed by cyclic voltammetry at voltage of -0.2 V~0.6 V. Differential pulse voltammetry, measured at 0.10 V (vs.  Ag/AgCl), was used to monitor the interaction between aptamer and lead(II) using hexacyanoferrate as an electrochemical probe. In the presence of Pb2+, the aptamer forms a G-quadruplex, and the peak current is increased. By this method, Pb2+ can be detected in the range of 0.5-10 nM with a low detection limit of 0.36 nM. The aptasensor was successfully applied to the determination of Pb2+ in polluted soil and baby's nail. The method showed outstanding sensitivity and selectivity in detecting Pb2+, therefore is considered to have great potential in developing an environmental monitoring platform. Graphical abstract Schematic illustration of Pb2+ detection procedure and principle using an electrochemical aptasensor.

A mini-review on functional nucleic acids-based heavy metal ion detection.

Recent years have witnessed great progress in developing functional nucleic acids (FNAs)-based sensors for the detection of heavy metal ion. In this review, four types of the FNAs that most widely-used in heavy metal ions detection were briefly introduced and a dozen of recently published review articles which summarized those FNAs-based sensors were introduced. Particularly, according to the degree of automation and system integration, those FNAs-based sensors which belong to the lab-on-a-chip (LOC) category were reviewed in more detail by classifying them into six types such as microfluidic LOC system, microchip, lateral flow dipstick, personal glucose meter, microfluidic paper-based analytical devices (µPADs) and disc-based analytical platform. After gave a brief description of the sensing strategies, properties, advantages or disadvantages of these FNAs-based sensors, existing problems and future perspectives were also discussed.

Fluorescent detection of Hg2+ and Pb2+ using GeneFinder™ and an integrated functional nucleic acid.

This paper reports a simple fluorescent assay for the determination of Hg(2+) and Pb(2+) by using a DNA intercalator GeneFinder™ (GF) and an integrated functional nucleic acid (FNA). In the absence of Hg(2+) and Pb(2+), GF intercalated with the FNA and released moderate strong fluorescence. While in the presence of Hg(2+) or Pb(2+), the FNA would be induced to form T-Hg(2+)-T or G-quadruplex structure, interacted with which the GF would exhibit extremely strong or very weak fluorescence. By monitoring the fluorescence changes upon addition of these two ions, the Hg(2+) and Pb(2+) could be selectively detected as low as 3.23 ppb and 2.62 ppb. As the main advantage of this assay is simplicity and the feasibility was demonstrated by detecting Hg(2+) and Pb(2+) in spiked water samples, this assay holds great potential for the development of a cost effective and useful tool for environmental monitoring.

Sensitive fluorescent assay for copper (II) determination in aqueous solution using copper-specific ssDNA and Sybr Green I.

This paper reports a fluorescent turn-off assay for sensitive detection of Cu(2+) in an aqueous solution by using a copper-specific ssDNA Cu100 and Sybr Green I. By monitoring the fluorescence changes arose from different interactions of Sybr Green I with Cu100 and Cu100/Cu(2+) complex, the Cu(2+) could be linearly detected from 5.57 to 250 ppb, with a detection limit of 5.57 ppb. The feasibility of this assay was demonstrated by detecting Cu(2+) in certified reference materials and spiked water samples with satisfactory results.

A simple and label-free sensor for mercury(II) detection in aqueous solution by malachite green based on a resonance scattering spectral assay.

Mercury ions (Hg(2+)) can specifically interact with the thymine-rich Hg(2+) aptamer and malachite green (MG) to form the Hg(2+) aptamer-MG-Hg(2+) complex, inducing the increase of resonance scattering (RS) intensity at 611 nm, which enables the label-free detection of Hg(2+) in aqueous solution with high selectivity and a detection limit of 1.7 nM.

A disposable immunosensor for Shigella flexneri based on multiwalled carbon nanotube/sodium alginate composite electrode.

A novel Shigella flexneri immunosensor based on horseradish peroxidase-labeled antibodies to S. flexneri (HRP-anti-S. flexneri) immobilized by physical adsorption on the multiwalled carbon nanotube (MWCNT)/sodium alginate (SA) composite modified screen-printed electrode surface was successfully fabricated. In this strategy, MWCNT/SA biocomposite acted as the matrix to adsorb and immobilize HRP-anti-S. flexneri. The modified electrodes were characterized with an atomic force microscope and cyclic voltammetry (CV). The analytical performance of the proposed immunosensor toward S. flexneri was investigated by CV. Under optimal conditions, the linear range of S. flexneri was from 104 to 10¹¹ cfu/ml with a detection limit of 3.1×10³ cfu/ml (signal/noise=3). The specificity, reproducibility, stability, and accuracy of the proposed immunosensor were also evaluated. The proposed immunosensor showed simply fabricative, economical, efficient, and potential application for early assessment of S. flexneri.