Glucose oxidase-like Co-MOF nanozyme-catalyzed self-powered sensor for sensitive detection of trace atrazine in complex environments.

The self-powered sensor (SPS) is a sensor method that does not require the external power source and has the potential for portable detection of environmental contaminants. In this work, for the first time, a biomolecule-free SPS for detection of ultra-trace triazine endocrine disruptor atrazine (ATZ) with high sensitivity and selectivity is constructed using a glucose oxidase (GOD)-like cobalt metal-organic framework (Co-MOF) nanozyme-modified high-performance anode and a molecularly imprinted cathode. By modulating the size and morphology of the prepared materials, Co-MOF nanozyme with superior GOD-like property (Michaelis constant Km = 15.8 mM) has been obtained and modified at the anode to catalyze glucose oxidation with high efficiency and provide energy continuously and stably for the SPS. The separation mode of anodic energy supply-cathodic recognition ensures the recognition effect without affecting the catalytic characteristic of Co-MOF and the output signal of the SPS. The designed SPS has a wide linear range of 1 pM-100 nM and a detection limit as low as 0.65 pM, as well as superior selectivity and good stability. The present work provides a promising approach for the design of self-powered sensors which can be extended to detection of a wider range of environmental pollutants.

Immobilization-Free Photoelectrochemical Aptasensor for Atrazine Based on Bifunctional Graphene Signal Amplification and a Controllable Sulfhydryl-Assembled BiOBr/Ag NP Microinterface.

Immobilization-free sensors (IFSs), with no requirement of fixing the recognition element to the electrode surface, have received increasing attention due to their unique advantages of reusable electrodes, not being limited by the load of the recognition element, and not being easily changed to the structure of the probe. In the present work, an effective visible light-driven immobilization-free photoelectric aptasensor for ultrasensitive detection of atrazine (ATZ) was proposed based on a reusable BiOBr/Ag NP substrate electrode with ultrafast charge transfer. Controllable thiols were used as conditioning agents for the photoelectric signal. The ingeniously designed bifunctional graphene can act as not only a molecular "bridge" for the ATZ aptamer through a strong π-π stacking effect, obtaining a graphene-aptamer complex, serving as a homogeneous recognition element, but also a switch for signal modulation for quantitative detection of target substances. Benefiting from the synergistic effect of the above-mentioned factors, the proposed sensor is capable of ultrasensitive and highly selective detection of ATZ in real water samples with a low detection limit of 1.2 pM and a wide linear range from 5.0 pM to 10.0 nM. Furthermore, it shows high stability, good selectivity, and strong anti-interference ability. Thus, this work has provided a fresh perspective for designing advanced immobilization-free photoelectric sensors and convenient detection of environmental pollutants.

A highly sensitive and selective photoelectrochemical aptasensor for atrazine based on Au NPs/3DOM TiO2 photonic crystal electrode.

A photoelectrochemical (PEC) sensing platform with high sensitivity and selectivity has been fabricated based on Au nanoparticles (Au NPs) modified three dimensionally ordered macroporous (3DOM) TiO2 nanostructure frame for trace detection of an endocrine disrupting pesticide, atrazine (ATZ). The resultant photoanode (Au NPs/3DOM TiO2) shows enhanced PEC performance under visible light due to multi signal amplification of the unique structure of 3DOM TiO2 and surface plasmon resonance (SPR) of Au NPs. ATZ aptamers are used as recognition elements and immobilized on Au NPs/3DOM TiO2 by Au-S bond in large packing density and dominant spatial orientation. The specific recognition and high binding affinity between aptamer and ATZ provides the PEC aptasensor with excellent sensitivity. The detection limit is 0.167 ng/L. Besides, this PEC aptasensor exhibits outstanding anti-interference ability in 100-fold concentration of other endocrine disrupting compounds and has been applied successfully to analyze ATZ in real water samples. A simple but efficient PEC aptasensing platform has therefore been successfully developed with high sensitivity, selectivity and repeatability for pollutant monitoring and potential risk evaluation in the environment with great application prospect.

Effects of carbendazim on catalase activity and related mechanism.

The different techniques like spectroscopy and fluorescence quenching were used to study the interactive effect of carbendazim (CARB) and catalase (CAT) at the molecular level. The results showed that conditions were beneficial to the quenching mechanism at 25.0 °C, pH 7.0, while the binding constant k was 1.92 × 105 L mol-1 and the number of binding site was 1.0385. The thermodynamic parameters indicated that CARB could interact spontaneously with CAT to form a complex mainly by van der Waals' interactions and hydrogen bonds. The interaction mechanism between CARB and CAT was that the effects of CARB on CAT in soil were activated and then restore stability. However, the effects of CARB on simple CAT were activated and then inhibited.

Heavy metals contamination and accumulation in submerged macrophytes in an urban river in China.

Deteriorating urban water quality has attracted considerable attention in China. We investigated the contamination levels and distribution of heavy metals (As, Cd, Cu, Ni, Pb, and Zn) in Yuxi River water and sediments, and assessed the heavy metal accumulation capability of five species of submerged macrophytes: Vallisneria natans (Lour.) Hara, Potamogeton pectinatus L., Hydrilla verticillata (L. f.) Royle, Myriophyllum spicatum L., and Potamogeton crispus L. Samples were collected from upstream and downstream locations in different season. The results showed that the levels of heavy metals in the downstream areas were higher than in the upstream areas. Heavy metal concentrations in the river water during the dry seasons were higher than those during the rainy seasons, and the opposite results appeared in sediments and submerged macrophytes. In general, the river was slightly contaminated by heavy metals, and the concentrations of Pb and Ni in this river should serve as a warning, while Cd and Zn pollution in the sediments desperately needs to be removed. Furthermore, Potamogeton pectinatus L. showed a higher accumulation capacity for these metals among the five native submerged macrophytes and could be defined as a hyperaccumulator for Cd. Therefore, the potential use of native aquatic plants in contaminated rivers is worth further exploration.

Structure and function of the bacterial communities during rhizoremediation of hexachlorobenzene in constructed wetlands.

Vertical flow constructed wetlands (VF CWs) are considered to be effective for treating organic pollutants. The rhizosphere of macrophytes such as Phragmites sp., Typha sp. serves as an active and dynamic zone for the microbial degradation of organic pollutants. However, it is still not clear how soil bacterial communities respond to macrophytes and pollutants during the process. For this purpose, the seedlings of Phragmites australis and Typha angustifolia were planted respectively in the VF CWs added with HCB at a dose of 2 mg/kg. During 96 days of cultivation, we monitored hexachlorobenzene (HCB) removal efficiency by GC/MS and the structure of the rhizosphere bacterial communities in the different VF CWs by denaturing gradient gel electrophoresis (DGGE), and constructed bacterial clone library based on PCR-amplified 16S rRNA gene. As expected, the rhizosphere bacterial communities also remained insensitive to HCB exposure in the wetland soil. The diversity of these microbes presented two stages, from the varied up and down to equilibrium in the entire experimental period. Molecular analysis revealed that the phylum Firmicutes dominated over the bacterial communities. The genera that increased under HCB stress included the well-known HCB-degrading bacteria (Pseudomonas sp. and Alcaligenes sp.) and other common bacteria found in contaminated soil but with lesser known practical functions (Burkholderia sp., Lysinibacillus fusiformis, and Bacillus cereus). Furthermore, there was a certain variance in the relative abundances of the bacterial phyla and HCB removal efficiency among different VF CW treatments. The degradation of HCB in T. angustifolia microcosms was faster than that in P. australis and unvegetated wetlands, and the highest bacterial diversity and richness was found in the VF CWs comprising T. angustifolia.

An approach to biodegradation of chlorobenzenes: combination of Typha angustifolia and bacterial effects on hexachlorobenzene degradation in water.

Although rhizoremediation is an effective approach to remove organic pollutants from the environment, little is known about the mechanism of hexachlorobenzene (HCB) biodegradation in water. In this study, we used Typha angustifolia (T. angustifolia) grown in sterile Hoagland nutrient solution to determine the rhizosphere effects on the ability of bacteria in water to reduce HCB levels. The results revealed that T. angustifolia could facilitate HCB degradation and that the initial HCB concentration was the major factor responsible for HCB degradation in nutrient solution. Furthermore, HCB biodegradation in low-HCB nutrient solution with T. angustifolia fitted the first-order kinetics, owing to the high concentration of total organic carbon, low HCB toxicity, and unique bacterial community in the T. angustifolia rhizosphere. Denaturing gradient gel electrophoresis indicated that the rhizosphere effects and different dosages of HCB have significant effects on the bacterial communities by repressing and favoring certain populations. The most successful bacteria to adapt to HCB contamination was Bacillus sp., while the dominant bacterial phyla in HCB-polluted water were Proteobacteria and Firmicutes.