Dual-signal amplified electrochemical aptasensor based on Au/MrGO and DNA nanospheres for ultra-sensitive detection of BPA without directly modified working electrode.

Rapid and sensitive analysis of bisphenol A (BPA) is essential for preventing health risks to humans and animals. Hence, a signal-amplified electrochemical aptasensor without repetitive polishing and modification of working electrode was developed for BPA using Au-decorated magnetic reduced graphene oxide (Au/MrGO)-based recognition probe (RP) and DNA nanospheres (DNS)-based signal probe (SP) cooperative signal amplification. The DNS served as a signal molecule carrier and signal amplifier, while Au/MrGO acted as a signal amplifier and excellent medium for magnetic adsorption and separation. Moreover, utilizing the excellent magnetic properties of Au/MrGO eliminates the need for repetitive polishing and multi-step direct modification of the working electrode while ensuring that all detection processes take place in solution and that used Au/MrGO can be easily recycled. The proposed aptasensor exhibited not only good stability and selectivity, but also excellent sensitivity with a limit of detection (LOD) of 8.13 fg/mL (S/N = 3). The aptasensor's practicality was proven by spiking recovery tests on actual water samples and comparing the results with those detected by HPLC. The excellent sensitivity and selectivity make this aptasensor an alternative and promising avenue for rapid detection of BPA in environmental monitoring.

In vitro metabolism of triclosan and chemoprevention against its cytotoxicity.

Triclosan (TCS), a broad-spectrum antibacterial chemical, has been extensively used in personal daily care items, household commodities, and clinical medications; therefore, humans are at risk of being exposed to TCS in their daily lives. This chemical also accumulated in food chains, and potential risks were associated with its metabolism in vivo. The aim of this study was to investigate the difference in metabolic profile of TCS by hepatic P450 enzymes and extrahepatic P450s, and also identify chemical structures of its metabolites. The results showed that RLM mediated the hydroxylation and cleavage of the ether moiety of TCS, resulting in phenolic metabolites that are more polar than the parent compound, including 4-chlorocatechol, 2,4-dichlorophenol and monohydroxylated triclosan. The major metabolite of CYP1A1 and CYP1B1 mediated TCS metabolism is 4-chlorochol. We also performed molecular docking experiments to investigate possible binding modes of TCS in the active sites of human CYP1B1, CYP1A1, and CYP3A4. In addition to in vitro experiments, we further examined the cytotoxic effects of TCS on HepG2 cells expressing hepatic P450 and MCF-7/1B1 cells expressing CYP1B1. It exhibited significant cytotoxicity on HepG2, MCF-10A and MCF-7/1B1 cells, with IC50 values of 70 ± 10 µM, 20 ± 10 µM and 60 ± 20 µM, respectively. The co-incubation of TCS with glutathione (GSH) as a chemopreventive agent could reduce the cytotoxicity of TCS in vitro. The chemopreventive effects of GSH might be ascribed to the promotion of TCS efflux mediated by membrane transporter MRP1 and also its antioxidant property, which partially neutralized the oxidative stress of TCS on mammalian cells. This study contributed to our understanding of the relationship between the P450 metabolism and the toxicity of TCS. It also had implications for the use of specific chemopreventive agents against the toxicity of TCS.

An ultrasensitive electrochemical biosensor for bisphenol A based on aptamer-modified MrGO@AuNPs and ssDNA-functionalized AuNP@MBs synergistic amplification.

Bisphenol A (BPA) is a harmful endocrine disruptor, sensitive and rapid quantification of BPA is highly desirable. In this work, a novel synergistic signal-amplifying electrochemical biosensor was developed for BPA detection by using a recognition probe (RP) constructed by BPA aptamer modified gold nanoparticles-loaded magnetic reduced graphene oxide (Aptamer-MrGO@AuNPs), and a signal probe (SP) constructed by BPA aptamer-complementary single-stranded DNA (ssDNA) functionalized methylene blue (MB)-loaded gold nanoparticle (ssDNA-AuNP@MBs). The RP and SP can self-assemble to form a stable RP-SP complex through complementary base pairing. The current intensity of the biosensor correlates with the number of RP-SP complexes. In the presence of BPA, the BPA aptamer can capture BPA with high selectivity and affinity, form an RP-BPA complex and dissociate the RP-SP complex to release SP, resulting in a decrease in the current signal intensity of the biosensor. A single AuNP could be loaded with multiple BPA aptamers and MBs, which improves the recognition efficiency and enhances the signal intensity. Due to the magnetic properties of MrGO@AuNPs, the magnetic separation and adsorption of RP or RP-SP complex is very convenient, enabling all reaction processes to be carried out in solution, which not only improves the mass transfer efficiency, but also simplifies the operation. Under optimal conditions, the developed biosensor had a detection limit as low as 0.141 pg/mL and had been successfully applied to the detection of real environmental water samples. Therefore, the synergistic signal amplification strategy of RP and SP has potential value in the detection of trace pollutants in the water environment.

A highly sensitive electrochemical biosensor for Hg2+ based on entropy-driven DNA walker-based amplification.

Herein, a sensitive electrochemical biosensor based on an enzyme-free and entropy-driven DNA walker is presented for the determination of Hg2+. This biosensor uses Hg2+ as a key to induce a mismatch between thymine-rich oligonucleotides to start the DNA walker, and it utilizes the entropy change of the sensing system to continuously drive the hybridization of oligonucleotides as a driving force for its walking. As the DNA walker runs, the detection signal is amplified to improve the sensitivity of the biosensor. Square wave voltammetry (SWV) of this biosensor shows a linear response of the methylene blue (MB) oxidation signal with an increase of Hg2+ concentration in the range of 0 to 80 nM with a detection limit of 0.136 nM, which satisfactorily meets the sensitivity requirement of the U.S. Environmental Protection Agency (EPA). The biosensor also exhibits excellent selectivity over a spectrum of interfering ions and performs well in real water samples, suggesting that it is a promising candidate for Hg2+ detection.

A fluorescent DNA based probe for Hg(II) based on thymine-Hg(II)-thymine interaction and enrichment via magnetized graphene oxide.

The authors describe a fluorometric assay for the determination of Hg(II). A naphthalimide derivative is used as a label for a thymine (T) rich ssDNA, and graphene oxide magnetized with Fe3O4 nanoparticles acts as a quencher and preconcentrators. In the absence of Hg(II), the labeled ssDNA does not separate from the magnetized graphene oxide. As a result, fluorescence is fully quenched. In the presence of Hg(II), a T-Hg(II)-T link is formed dues to the highly affinity between T and Hg(II). Hence, fluorescence is restored. The assay has a linear response in the 1.0 to 10.0 nM Hg(II) concentration range, and a 0.65 nM detection limit. The method is selective and sensitive. It was applied to the analysis of spiked environmental water samples, and data agreed well with those obtained by atomic fluorescence spectrometry. Graphical abstract Strategy of a fluorescent probe for detecting Hg(II). The method has a 0.65 nM detection limit and is selective. MGO: magnetized graphene oxide, AHN: a fluorescent derivative of naphthalimide.

Magnetic separate "turn-on" fluorescent biosensor for Bisphenol A based on magnetic oxidation graphene.

Bisphenol A (BPA) is commonly considered to cause a health hazard to wildlife and humans, acting as an exogenous estrogen. Herein, a magnetic separate "turn-on" fluorescent method for the detection of BPA was proposed based on fluorescence resonance energy transfer (FRET) between fluorescein-labeled BPA aptamer and magnetic oxidation graphene (MGO). At different concentrations of BPA, the fluorescence intensity of the sensing system was varied. The detection limit of 0.071ng/mL was obtained with the linear range of 0.2-10ng/mL. The biosensor exhibited excellent anti-interference ability and selectivity in actual water samples.

A Fluorescence Sensor for Lead (II) Ions Determination Based on Label-Free Gold Nanoparticles (GNPs)-DNAzyme Using Time-Gated Mode in Aqueous Solution.

This paper describes a label-free 17E DNAzyme-based time-gated fluorescence sensor for Pb2+ detection by unmodified gold nanoparticles (GNPs) and a terbium ternary complex. The fluorophore that used in this paper is a terbium ternary complex. Its signal can be measured in a time-gated manner which could eliminate most of the unspecific fluorescent background. It is well known that unfolded single-stranded DNA (ssDNA) could be adsorbed on GNPs while double-stranded DNA could not. The cleavage of the substrate by the 17E DNAzyme in the presence of Pb2+ causes the release of ssDNA from the 17E-17S duplex to be absorbed onto GNPs, preventing the aggregation of GNPs and then leading to a fluorescence decrease of terbium ternary complex. By means of this method, the authors have successfully detected Pb2+ over a range of 10 nM to 2500 nM with a detection limit of 1.7 nM. The sensor also exhibited good selectivity. The sensor provided a simple, cost-effective, rapid and sensitive measurement tool for Pb2+ detection.