Evaluation of DNA adduct damage using G-quadruplex-based DNAzyme.

Toxicity assessment is a major problem in pharmaceutical candidates and industry chemicals development. However, due to the lack of practical analytical methods for DNA adduct analysis, the safety evaluation of drug and industry chemicals was severely limited. Here, we develop a DNAzyme-based method to detect DNA adduct damage for toxicity assessment of drugs and chemicals. Among 18 structural variants of G4 DNAzyme, EA2 DNAzyme exhibits an obvious DNA damaging effect of styrene oxide (SO) due to its unstable structure. The covalent binding of SO to DNAzyme disrupts the Hoogsteen hydrogen bonding sites of G-plane guanines and affects the formation of the G4 quadruplex. DNA damage chemicals reduce the peroxidase activity of the G4 DNAzyme to monitor the DNA adduct damage by disrupting the structural integrity of the G4 DNAzyme. Our method for genotoxic assessment of pharmaceutical candidates and industrial chemicals can elucidate the complex chemical pathways leading to toxicity, predict toxic effects of chemicals, and evaluate possible risks to human health.

Simultaneous detection of acetaminophen, catechol and hydroquinone using a graphene-assisted electrochemical sensor.

Simple, rapid and sensitive analysis of drug-derived pollutants is critically valuable for environmental monitoring. Here, taking acetaminophen, hydroquinone and catechol as a study example, a sensor based on an ITO/APTES/r-GO@Au electrode was developed for separate and simultaneous determination of phenolic pollutants. ITO electrodes that are modified with 3-aminopropyltriethoxysilane (APTES), graphene (GO) and Au nanoparticles (Au NPs) can significantly enhance the electronic transport of phenolic pollutants at the electrode surface. The redox mechanisms of phenolic pollutants include the electron transfer with the enhancement of r-GO@Au. The modified ITO electrode exhibits excellent electrical properties to phenolic pollutants and a good linear relationship between ECL intensity and the concentration of phenolic pollutants, with a limit of detection of 0.82, 1.41 and 1.95 µM, respectively. The separate and simultaneous determination of AP, CC and HQ is feasible with the ITO/APTES/r-GO@Au electrode. The sensor shows great promise as a low-lost, sensitive, and rapid method for simultaneous determination of drug-derived pollutants.

Electrochemiluminescence sensor for point-of-care detection of pyrrolizidine alkaloids.

Pyrrolizidine alkaloids (PAs) and PA N-oxides are hepatotoxic natural products, produced by over 6000 plant species worldwide. However, an unmet need remains for confirmative measurement of PAs in routine clinical tests. Here, we develop a visual, easy-to-use, and economic mesoporous silica-electrochemiluminescence (MPS-ECL) sensor for point-of-care (POC) testing of PAs, utilizing MPS's amplification effect on positive ions. The relationship between PAs' different structures and corresponding Ru(bpy)32+ ECL activity shows that reaction mechanism, stability of intermediate, molecular geometry and alternative anodic reactivity significantly affect the ECL activity. The ECL intensity varies among different PAs: monocrotaline ˃ senecionine N-oxide ˃ retrorsine ˃ senkirkine. The POC sensors possess excellent linearity (0.9993 > R2 > 0.9944), low detection limits (0.02 µM-0.07 µM), and good recoveries (90.12%-105.93%), indicating good accuracy and practicability. The portable and low-cost sensor is user-friendly, which holds promise to be applied to POC testing of PAs in drugs, food products, and clinical samples, which is promising for initial assessments of PA-induced health risk.

Simple, rapid, and visual electrochemiluminescence sensor for on-site catechol analysis.

Environmental pollution caused by aromatic compounds such as catechol (Cat) has become a major issue for human health. However, there is no simple, rapid, and low-cost method for on-site monitoring of Cat. Here, based on ECL quenching mechanism, we develop a simple, rapid and visual mesoporous silica (MSNs)-electrochemiluminescence (ECL) sensor for on-site monitoring of Cat. The mechanism of ECL quenching is due to the interaction between Cat and Ru(bpy)3 2+* and the interactions between the oxidation products of Cat and DBAE. MSNs films with ordered perpendicular mesopore channels exhibit an amplification effect of ECL intensity due to the negatively charged pore channel. There is a good linear relationship between ECL intensity and Cat concentration in the range of 10 ∼ 1000 µM with the limit of detection (LOD) of 9.518 µM (R 2 = 0.99). The on-site sensor is promising to offer new opportunities for pharmaceuticals analysis, on-site monitoring, and exposure risk assessment.

Electrogenerated chemiluminescence of a Ru(bpy)3 2+/arginine system: a specific and sensitive detection of acetaminophen.

Ru(bpy)3Cl2/TPrA is a prominent and widely used ECL system in analytical science. However, the co-reactant TPrA restricts the variety of applications because of its toxicity, volatility, and high cost. Here, we use arginine (Arg) as an alternative co-reactant for Ru(bpy)3 2+ by taking advantage of its low cost, non-toxicity, and biocompatibility. The mechanism of the Ru(bpy)3 2+/Arg system is that the deprotonated Arg can react with Ru(bpy)3 2+ to release emission. The similarity between the Ru(bpy)3 2+/Arg, Ru(bpy)3 2+/TPrA, and Ru(bpy)3 2+/DBAE systems demonstrates that Arg can be used as an alternative co-reactant for Ru(bpy)3 2+ ECL. As a proof of concept, we achieve an excellent performance for acetaminophen (Ace) detection based on the specificity of Arg and Ace, with excellent linearity, low detection limits, and good recoveries. This work is promising to expand the scope of the Ru(bpy)3 2+/Arg system and move forward their applications in bioassays.

Mesoporous silica-mediated controllable electrochemiluminescence quenching for immunosensor with simplicity, sensitivity and tunable detection range.

Straightforward and accurate measurement of medical biomarkers is of essential importance in clinical diagnostics and treatments. However, the major challenge is the diversity in dynamic range of different biomarkers ranging from pg mL-1 to µg mL-1 in various body fluids and tissues among patients. Here, we develop a mesoporous silica (MS)-mediated controllable electrochemiluminescence (ECL) quenching of immunosensor that allows accurate immunoassays with simplicity, sensitivity and tunable sensing range. MS is employed to enhance the sensitivity and tune ECL quenching to broaden the detection range just by altering luminophore (Ru(bpy)32+) and coreactant (DBAE) concentration without additional modifications. The immunoassay is followed: homogeneous sandwich immunoreaction, magnetic separation, and ECL quenching detection. As a proof-of-concept, simple and sensitive detection of IgG is achieved ranging from pg mL-1 to µg mL-1, and applications of the strategy are extended by the combination of ECL immunosensor with commercial ELISA kit. This study will not only be expected to serve as a new avenue for the assay of physiological and clinical implications of immunological biomarkers, but also benefit a wide range of applications that require a tunable detection range and ultrahigh sensitivity.

Comparison Study on the Estimation of the Spatial Distribution of Regional Soil Metal(loid)s Pollution Based on Kriging Interpolation and BP Neural Network.

Soil pollution by metal(loid)s resulting from rapid economic development is a major concern. Accurately estimating the spatial distribution of soil metal(loid) pollution has great significance in preventing and controlling soil pollution. In this study, 126 topsoil samples were collected in Kunshan City and the geo-accumulation index was selected as a pollution index. We used Kriging interpolation and BP neural network methods to estimate the spatial distribution of arsenic (As) and cadmium (Cd) pollution in the study area. Additionally, we introduced a cross-validation method to measure the errors of the estimation results by the two interpolation methods and discussed the accuracy of the information contained in the estimation results. The conclusions are as follows: data distribution characteristics, spatial variability, and mean square errors (MSE) of the different methods showed large differences. Estimation results from BP neural network models have a higher accuracy, the MSE of As and Cd are 0.0661 and 0.1743, respectively. However, the interpolation results show significant skewed distribution, and spatial autocorrelation is strong. Using Kriging interpolation, the MSE of As and Cd are 0.0804 and 0.2983, respectively. The estimation results have poorer accuracy. Combining the two methods can improve the accuracy of the Kriging interpolation and more comprehensively represent the spatial distribution characteristics of metal(loid)s in regional soil. The study may provide a scientific basis and technical support for the regulation of soil metal(loid) pollution.