Self-powered aptasensor for picomole level pollutants based on a novel enzyme-free photofuel cell.

Atrazine (ATZ) is a highly toxic chlorine-containing aromatic structural triazine endocrine disruptor. Due to its chemical stability and electrochemical inertness, it is of great challenge and significance to establish a simple, portable, and in situ electrochemical sensor for ATZ. In the present work, a self-powered aptasensor (SPA) based on a novel enzyme-free photofuel cell (PFC) is successfully developed for ATZ for the first time. The designed SPA is constructed by the Ti-Fe-O nanotubes/nickel hydroxide (Ti-Fe-O NTs/Ni(OH)2) photoanode and Au/aptamer (Au/Apt) cathode, responsible for the spontaneous generation of electrons and specific recognition of ATZ, respectively. It is worth noting that Ti-Fe-O NTs on the photoanode can exhibit good visible-light absorption property, and modified Ni(OH)2 further enhances the photo-generated carrier separation and improves the output power generation of the SPA. The recognition is set at the cathode to ensure the detection of ATZ and the anti-interference ability. Under the separation mode, the constructed SPA has a high output power (390 µW cm-2), much better than most previous reports. It can further show specific recognition of ATZ with prominent sensitivity and a limit of detection (LOD) as low as 5.4 pM. Moreover, it has been applied to the real water sample analysis with satisfactory results. A promising self-powered sensing platform based on an enzyme-free PFC has therefore been provided for picomole level pollutants with high sensitivity and outstanding selectivity.

Efficient Adsorption of Tetracycline from Aqueous Solutions by Modified Alginate Beads after the Removal of Cu(II) Ions.

This work dealt with a potential and effective method to reuse modified alginate beads after the removal of Cu(II) ions for efficient adsorption of tetracycline (TC) from aqueous solutions. The modified alginate beads were fabricated by a polyacrylamide (PAM) network interpenetrated in alginate-Ca2+ network (PAM/CA) decorated with polyethylene glycol as a pore-forming agent. The porous PAM/CA was characterized using scanning electron microscopy, Brunauer-Emmett-Teller, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy analysis. The adsorption kinetics, isotherms, adsorption stability, and reusability studies of the adsorbent toward Cu(II) ions were scrutinized. The column performance of porous PAM/CA was tested with Cu(II)-containing electroplating wastewater. After Cu(II) adsorption, the Cu(II)-adsorbed PAM/CA (PAM/CA@Cu) was applied to remove TC from aqueous solutions without any regeneration process. The effects of pH, initial TC concentration, ionic strength, and coexisting ions on the adsorption were also discussed in detail. Compared with many reported adsorbents, the PAM/CA@Cu exhibited an excellent adsorption performance toward TC with a maximum adsorption capacity of 356.57 mg/g predicted by the Langmuir model at pH 5.0 and 30 °C with the absence of coexisting ions. The possible adsorption mechanism of TC onto the PAM/CA@Cu was revealed.

In situ monitoring of the selective adsorption mechanism of small environmental pollutant molecules on aptasensor interface by attenuated total reflection surface enhanced infrared absorption spectroscopy (ATR-SEIRAS).

In situ monitoring of the interactions and properties of pollutant molecules at the aptasensor interface is being a very hot and interesting topic in environmental analysis since its charming molecule level understanding of the mechanism of environmental biosensors. Attenuated total reflection surface enhanced infrared absorption spectroscopy (ATR-SEIRAS) provides a unique and convenient technique for the in situ analysis, but is not easy for small molecules. Herein, an ATR-SEIRAS platform has been successfully developed to in situ monitor the selective adsorption mechanism of small pollutant molecule atrazine (ATZ) on the aptasensor interface by characteristic N‒H peak of ATZ for the first time. Based on the constructed ATR-SEIRAS platform, a thermodynamics model is established for the selective adsorption of ATZ on the aptasensor interface, described with Langmuir adsorption with a dissociation constant of 1.1 nM. The adsorption kinetics parameters are further obtained with a binding rate constant of 8.08×105 M-1 s-1. A promising and feasible platform has therefore successfully provided for the study of the selective sensing mechanism of small pollutant molecules on biosensors interfaces, further broadening the application of ATR-SEIRAS technology in the field of small pollutant molecules.

Immobilization-free photoelectrochemical aptasensor for environmental pollutants: Design, fabrication and mechanism.

Atrazine (ATZ) is one of the most widely used and highly toxic triazine herbicides in the world. Photoelectrochemical (PEC) method is an attractive and sensitive alternate for ATZ. However, for conventional PEC sensors, recognition elements usually need to immobilize on electrode surface, where a complex procedure is unavoidable and the reproducibility of sensors fabrication is usually poor. Therefore, we herein proposed a new and feasible strategy for developing a signal-on immobilization-free PEC aptasensor to ATZ. Aptamer for ATZ is combined with graphene to obtain APT-GN complex, serving as the recognition element in solution. TiO2 nanotubes (NTs) electrode deposited with Au nanoparticles (NPs) is used as the substrate electrode. After further self-assembled with 1-Mercaptooctane (MCT), the photo-generated carriers transfer between the resultant electrode and the electrolyte will be blocked, leading to a signal-off of the photocurrent. But when sensing ATZ, aptamers on APT-GN will be grasped by ATZ, leaving free graphene to assemble onto MCT/Au NPs/TiO2 NTs, which will largely "turn on" the photocurrent response of the substrate electrode due to the efficient carrier transport efficiency of graphene. Meanwhile, simultaneous addition of deoxyribonuclease I (DNase I) can bring about further cycling amplification of the signal enhancement. The as-designed PEC aptasensor exhibits a linear range from 50.0 fM to 0.3 nM with detection limit of 12.0 fM for ATZ. Since the reaction of recognition elements and targets ATZ occurs in homogeneous solution rather than on the photoelectrode surface, this PEC aptasensor exhibits advantages of high stability, anti-interference ability, reproducibility, and wide pH and ion strength feasibility range. A promising immobilization-free aptasensing platform has thus been provided not only for ATZ but also for other kinds of environmental pollutants.