A Stable and Sensitive Engineering Bacterial Sensor via Physical Biocontainment and Two-Stage Signal Amplification.

Although engineering bacterial sensors have outstanding advantages in reflecting the actual bioavailability and continuous monitoring of pollutants, the potential escape risk of engineering microorganisms and lower detection sensitivity have always been one of the biggest challenges limiting their wider application. In this study, a core-shell hydrogel bead with functionalized silica as the core and alginate-polyacrylamide as the shell have been developed not only to realize zero escape of engineered bacteria but also to maintain cell activity in harsh environments, such as extremely acidic/alkaline pH, high salt concentration, and strong pressure. Particularly, after combining the selective preconcentration toward pollutants by functionalized core and the positive feedback signal amplification of engineering bacteria, biosensors have realized two-stage signal amplification, significantly improving the detection sensitivity and reducing the detection limit. In addition, this strategy was actually applied to the detection of As(III) and As(V) coexisting in environmental samples, and the detection sensitivity was increased by 3.23 and 4.39 times compared to sensors without signal amplification strategy, respectively, and the detection limits were as low as 0.39 and 0.86 ppb, respectively.

Key role of sulfur in sulfidated zerovalent iron during persulfate activation for the dynamic equilibrium of oxidative radicals including SO4•- and •OH.

Surface sulfidation has been widely investigated to effectively enhance the utilization and selectivity of iron electrons for enhanced pollutant reduction. However, there is relatively less knowledge on whether sulfidation facilitates the catalytic oxidation process and the mechanism of enhancement. Therefore, in this study, the role of surface sulfidation in modulating the oxidant decomposition pathway and reactive oxygen species generation was investigated with the sulfidated zerovalent iron (S-ZVI) activated persulfate (PS) system. The results revealed that sulfur on the surface of S-ZVI not only facilitates PS activation to generate more SO4•-, but also acts as an essential in the dynamic equilibrium between SO4•- and •OH. Specifically, the S-ZVI surface sulfide first forms sulfur monomers during catalysis, which promotes electron transfer to accelerate Fe3+ to Fe2+ cycling, prompting the generation of more SO4•- also generates SO32-. Then, SO32- is further reacted with •OH to generate the [O--O-SO3-] intermediate of SO4•-, which leads to a dynamic equilibrium of SO4•- and •OH, mitigating the further conversion of SO4•- to •OH. These findings unveiled the dynamic variation of sulfur on the surface of S-ZVI during PS activation, elevating new insights for the sulfate radical-based efficient degradation.

Discrimination and simultaneous quantification of poly(ethylene terephthalate) and poly(butylene terephthalate) microplastics in environmental samples via gas chromatography-tandem mass spectrometry.

A method has been developed to quantify PET and PBT microplastics (MPs) based on depolymerization and detection of depolymerization products by gas chromatography-tandem mass spectrometry (GC-MS/MS) without a complex separation process from environmental samples. Under the optimal depolymerization conditions, PET and PBT were efficiently converted to ethylene glycol (78%) and 1,4-butanediol (87%), respectively. Subsequently, the linear curves were constructed between signal intensities of depolymerization products and polymer masses by GC-MS/MS, and the correlation coefficients of PET and PBT were 0.996 and 0.997, respectively. The spiking and recovery experiments of PET and PBT in the environmental samples showed that the recovery was stable in the range 89-100%, and the limit of detection was 4.95 µg and 1.39 µg of PET and PBT, respectively. The method has been proven to be capable of simultaneous identification and quantification of PBT and PET MPs in real environmental water samples without complex separation process, which provided a scheme for the determination of microplastics.

Enhancement of the Peroxidase Activity of g-C3N4 with Different Morphologies for Simultaneous Detection of Multiple Antibiotics.

The classes and forms of antibiotics directly determine their ecotoxicity and environmental chemical behavior, and developing a sensor array for simultaneous and in situ detection of antibiotics is highly anticipated. In this study, different morphologies of g-C3N4 with different fluorescence properties and peroxidase activity were prepared by regulating the degree of interlayer stacking and planar connectivity. Subsequently, in order to enhance its enzyme activity and amplify the differences in response signals to different antibiotics, three morphologies of g-C3N4/MIL-101(Fe) were prepared by in situ growth of equivalent amounts of MIL-101(Fe) on g-C3N4, respectively. The sensor array constructed based on the cross-response signals between g-C3N4/MIL-101(Fe) and antibiotics not only realized the simultaneous detection of quinolones, furans, tetracyclines, and lincomamides but also could efficiently identify their seven different forms. In the range of 0.2-0.8 ppm, the minimum detection limit for antibiotics was 12 ppb. In addition, the recovery experiments of multicomponent-mixed antibiotics in environmental samples show that the recovery rate remained at 91.42-107.59%, confirming the reliability and practicality of the sensor array. This study not only revealed the influence of crystal morphology regulation on the optical properties and enzyme activities of nanozymes, but also provided support for tracing, ecological remediation, and in situ environmental chemical behavior research of antibiotics.

Simultaneous visual detection of multiple heavy metal ions by a high-throughput fluorescent probe.

To develop simultaneous and in-situ detection techniques towards Cr(VI) and Mn(II), Eu/Tb@CDs with white fluorescence were prepared by a one-step hydrothermal method. With the increase of Cr(VI), all fluorescence channels of Eu/Tb@CDs exhibited obvious quenching, and the detection limit (LOD) was 0.10 µM. In the presence of Mn(II), only the fluorescence from Tb and Eu was quenched, while the fluorescence of CDs was not effected. The LOD for Mn(II) was 0.16 µM. More importantly, in the actual water samples where Cr(VI) and Mn(II) coexist, Eu/Tb@CDs can realize their rapid and simultaneous detection by simple spectral calculation. The selective and competitive experiments have also confirmed that the detection of Cr(VI) and Mn(II) was not interfered by common pollutants in groundwater. It is undeniable that the simultaneous detection of multiple targets by one probe not only greatly improves the detection efficiency, but also has important significance for the field monitoring of water quality parameters.

Simultaneous detection of As(III/V), Cr(III/VI), and Fe(II/III) by a sensor array based on the morphology regulation of CeO2 oxidase.

To develop a convenient method for simultaneous detection of As(III/V), Cr(III/VI), and Fe(II/III), three morphologies of CeO2 oxidase have been prepared. Based on the difference in oxidase activity and binding ability with substrate TMB of CeO2 of different morphologies, a 3 (Signal unit) × 6 (Target number) × 5 (Repetition) sensor array was constructed to realize simultaneous detection of six variable valence metal ions As(III/V), Cr(III/VI), and Fe(II/III). The lowest detection limit of the array for metal ions was 1.68 µg/L. The analysis of environmental samples with multiple metal ions (binary and ternary mixtures) co-existing has confirmed that the sensor array can achieve simultaneous qualitative and quantitative results for composite samples. This study not only revealed the influencing factors of crystal morphology regulation on oxidase activity, but also provided a scheme for the morphology detection of easily convertible metal ions in the field through the construction of the sensor array.

New Insight into a Fenton-like Reaction Mechanism over Sulfidated ß-FeOOH: Key Role of Sulfidation in Efficient Iron(III) Reduction and Sulfate Radical Generation.

Sulfidation can greatly improve the efficiency of utilization of reducing equivalents for contaminant removal; however, whether this method benefits Fenton-like reactions or not and the possible mechanism are not well understood. In this study, we revealed that surface sulfidation can greatly promote the heterogeneous Fenton activity of ß-FeOOH (Fe3S4@ß-FeOOH) by 40 times, in which not only the •OH formation was enhanced but also SO4•- as a new oxidation species was generated. Moreover, their contribution to metronidazole (MTZ) degradation was 52.5 and 37.1%, respectively. In comparison, almost no HO2•/O2•- was detected in the Fe3S4@ß-FeOOH/H2O2 system. These results were different from some previously reported Fenton counterparts. Based on the characterization and probe experiments, sulfur species, including S2-, S0, and Sn2-, as an electron donor and electron shuttle were responsible for efficient conversion of Fe(III) into Fe(II) other than via the Haber-Weiss mechanism, leading to excellent •OH generation via a Fenton-like mechanism. Most importantly, HSO5- can be generated from SO32- oxidized by •OH, and its scission into SO4•- was not dependent on the extra electric potential or Fe-O2-S(IV) intermediate. These findings provided new insight for utilizing sulfidation to improve the activity of iron-based Fenton catalysts.

Hydroxyl Radical-Involving p-Nitrophenol Oxidation during Its Reduction by Nanoscale Sulfidated Zerovalent Iron under Anaerobic Conditions.

Sulfidated zerovalent iron (S-ZVI) has been extensively used for reducing pollutants. In this study, the oxidation process in the reductive removal of p-nitrophenol (PNP) by S-ZVI was confirmed under anaerobic conditions. We revealed that a PNP oxidation process involving •OH resulted from the H2O2 activation by surface-bound Fe(II) in S-ZVI, in which H2O2 was generated via a surface-mediated reaction between water and FeS2. Only the PNP reduction process occurred for ZVI. Herein, efficient PNP degradation by S-ZVI resulted from two functions: reduction into p-aminophenol due to enhanced electron transfer and PNP oxidation into p-benzoquinone by •OH radicals from the interaction of surface-bound Fe(II) and in situ generated H2O2, the contributions of the oxidation and reduction processes to PNP degradation over S-ZVI were 10 and 90%, respectively. Sulfur in S-ZVI suppressed the pH increase in the reaction media and produced more surface-bound Fe(II) than ZVI for •OH generation via the heterogeneous Fenton reaction process. Since different degradation pathways could lead to different effects on the water environment, such as toxicity, our findings suggest that the oxidizing process induced by S-ZVI during groundwater decontamination should be considered.

Fe3O4@S-doped ZnO: A magnetic, recoverable, and reusable Fenton-like catalyst for efficient degradation of ofloxacin under alkaline conditions.

In this study, an efficient and reusable heterogeneous Fenton catalyst Fe3O4@S-doped ZnO magnetic composite was synthesized for the degradation of ofloxacin (OFX) under alkaline conditions without external energy input. The Fe3O4@S-doped ZnO exhibited excellent catalytic activity toward ofloxacin degradation within 120 min. Using 0.25 g/L of catalyst and 5.0 mL/L of H2O2 under optimized conditions, the catalyst was effective in pH values ranging from 5.2 to 9.0. The catalytic performance at optimal conditions was in accordance with a pseudo-first-order kinetics model. The reaction constant of Fe3O4@S-doped ZnO (0.0354 min-1) was three times than that of Fe3O4@ZnO (0.0124 min-1) under alkaline conditions (pH 8.2). The reactive oxygen species were the ·OH and O2·-, with ·OH dominating in the degradation of OFX. It is proposed that the catalyst acts as a Lewis acid, creating an acidic microenvironment on the catalyst's surface and widening the pH range of the Fenton reaction to alkaline conditions. Additionally, the catalyst was stable and reusable after six cycles of use. The Fenton-like Fe3O4@S-doped ZnO catalyst overcomes the problem of the narrow pH of the reaction system, thus providing promising environmental applications.

Portable ratiometric probe based on the use of europium(III) coordination polymers doped with carbon dots for visual fluorometric determination of oxytetracycline.

A novel ratiometric fluorescent probe for the determination of oxytetracycline (OTC) was developed. The method is based on the use of adenosine monophosphate/Eu(III) nanoscale coordination polymers doped with carbon dots (CDs) (CD@AMP/Eu NCPs). These were fabricated by self-assembly of Eu3+ and AMP on the surface of CDs containing large amounts of hydroxyl and carbonyl groups. Under the excitation at 310 nm wavelength, the doped NCPs display strong pink emission of Eu3+ at 615 nm and blue emission of the CDs at 430 nm on exposure to OTC. The ratio of fluorescence intensity (F615/F430) of such NCPs displays excellent linear relationship with OTC concentration ranging from 0.2 to 60 µM and the limit of detection (LOD) is 25 nM (3σ). The doped NCPs were evenly immobilized on common filter paper to prepare a visual ratiometric probe for the determination of OTC. Assisted by a digital camera with an APP color detector, the paper-based test strip was applied for the quantitative determination of OTC with a LOD of 0.5 µM and a wide linear scope of 1-100 µM. The method was applied to the determination of OTC in milk samples. Graphical abstractSchematic representation of the principle for oxytetracycline (OTC) determination using carbon dots (CD)@adenosine monophosphate (AMP)/Europium (Eu3+) paper-based ratiometic probe.

Surface Facet of CuFeO2 Nanocatalyst: A Key Parameter for H2O2 Activation in Fenton-Like Reaction and Organic Pollutant Degradation.

The development of efficient heterogeneous Fenton catalysts is mainly by "trial-and-error" concept and the factor determining H2O2 activation remains elusive. In this work, we demonstrate that suitable facet exposure to elongate O-O bond in H2O2 is the key parameter determining the Fenton catalyst's activity. CuFeO2 nanocubes and nanoplates with different surface facets of {110} and {012} are used to compare the effect of exposed facets on Fenton activity. The results indicate that ofloxacin (OFX) degradation rate by CuFeO2 {012} is four times faster than that of CuFeO2 {110} (0.0408 vs 0.0101 min-1). In CuFeO2 {012}-H2O2 system, OFX is completely removed at a pH range 3.2-10.1. The experimental results and theoretical simulations show that •OH is preferentially formed from the reduction of absorbed H2O2 by electron from CuFeO2 {012} due to suitable elongation of O-O (1.472 Å) bond length in H2O2. By contrast, the O-O bond length is elongated from 1.468 to 3.290 Å by CuFeO2 {110} facet, H2O2 tends to be dissociated into -OH group and passivates {110} facet. Besides, the new formed ≡Fe2+* on CuFeO2 {012} facet can accelerate the redox cycle of Cu and Fe species, leading to excellent long-term stability of CuFeO2 nanoplates.

Oxygen Vacancy Promoted Heterogeneous Fenton-like Degradation of Ofloxacin at pH 3.2-9.0 by Cu Substituted Magnetic Fe3O4@FeOOH Nanocomposite.

To develop an ultraefficient and reusable heterogeneous Fenton-like catalyst at a wide working pH range is a great challenge for its application in practical water treatment. We report an oxygen vacancy promoted heterogeneous Fenton-like reaction mechanism and an unprecedented ofloxacin (OFX) degradation efficiency of Cu doped Fe3O4@FeOOH magnetic nanocomposite. Without the aid of external energy, OFX was always completely removed within 30 min at pH 3.2-9.0. Compared with Fe3O4@FeOOH, the pseudo-first-order reaction constant was enhanced by 10 times due to Cu substitution (9.04/h vs 0.94/h). Based on the X-ray photoelectron spectroscopy (XPS), Raman analysis, and the investigation of H2O2 decomposition, •OH generation, pH effect on OFX removal and H2O2 utilization efficiency, the new formed oxygen vacancy from in situ Fe substitution by Cu rather than promoted Fe3+/Fe2+ cycle was responsible for the ultraefficiency of Cu doped Fe3O4@FeOOH at neutral and even alkaline pHs. Moreover, the catalyst had an excellent long-term stability and could be easily recovered by magnetic separation, which would not cause secondary pollution to treated water.

A ratiometric fluorescence nanosensor for highly selective and sensitive detection of selenite.

The instant and on-site detection of selenium still remains a challenge for environmental monitoring and medical prevention. We herein developed a ratiometric fluorescent nanosensor for accurate and on-site sensing of SeO3(2-) by linking the recognition molecule 3,3'-diaminobenzidine (DAB) onto the surface of carboxyl group modified CdTe@SiO2. The fluorescence of DAB on the surface of silica nanospheres could be selectively and efficiently enhanced by SeO3(2-) through a surface chelating reaction between DAB and SeO3(2-). Thus, in the presence of SeO3(2-), the nanosensor would show two characteristic fluorescence emissions of Se-DAB and CdTe QDs under a single excitation wavelength. The selectivity and the optimal conditions for the detection of SeO3(2-) were carefully investigated. The ratio of F530/F635 linearly increased with increasing SeO3(2-) concentration in the range of 0 to 2.5 µM and the detection limit reaches as low as 6.68 nM (0.53 ppb). This developed nanosensor has the capability of on-site detection in an aqueous system without any separation step. The Se concentrations in selenium-rich food were detected and the results were consistent with the values determined by ICP-AES.

Multi-targets detection via combination of multi-stimulus-response engineered bacteria and hydrogel-based separation platform.

Establishing a method similar to ICP-MS that can quantitatively analyze multiple heavy metals simultaneously, conveniently, and in situ is highly anticipated. In this study, we integrated the sensing elements of multiple targets and different fluorescence reporting elements to construct an engineered Escherichia coli. When these targets are present, the engineered bacteria can emit a fluorescent signal at the corresponding wavelength. To avoid the inability to accurately distinguish and quantify the content of each target due to the overlap of fluorescence signals when multiple targets coexist, a hydrogel-based separation platform similar to a separation column was constructed. The hydrogel platform can change the detection limit (LOD) and sensitivity by adjusting the adsorption strength towards different targets, so as to realize the differentiation and recognition of their respective detection signals. The LODs of this new detection method for Cd(II), Hg(II), As(III), and Pb(II) are 1.249, 0.380, 3.917, and 0.755 µg/L, respectively. In addition, this biosensor system was applied to detect coexisting Cd(II), Hg(II), As(III), and Pb(II) in actual samples with a recovery rate of 85.61-110.30 %, which is consistent with the classical ICP-MS detection results, confirming the accuracy and reliability of the method for detecting multiple heavy metal coexisting samples.

Self-acclimation mechanism of pyrite to sulfamethoxazole concentration in terms of degradation behavior and toxicity effects caused by reactive oxygen species.

Pyrite has been extensively tested for oxidizing contaminants via the activation of water molecule or dissolved oxygen, while the changing of oxidation species induced by contaminant's concentration has been largely underestimated. In this study, we revealed a self-acclimation mechanism of pyrite in terms of •OH conversion to 1O2 during the sulfamethoxazole (SMX) degradation process under oxic conditions. Two reaction stages of SMX degradation by pyrite were observed. The SMX concentration decreased by 70% rapidly in the first 12 h after the reaction was initiated, then, the removal rate began to decrease as the SMX concentration decreased. Importantly, •OH and O2•- were the dominant oxidizing species in stage one, while 1O2 was responsible for the further degradation of SMX in stage two. The self-acclimated mechanism of pyrite was proven to be caused by the conversion of oxidative species at the surface of pyrite. This process can overcome the shortages of •OH such as ultrashort lifetime and limited effective diffusion in the decontamination of micropollutant. Moreover, different reactive oxygen species will lead to different degradation pathways and environmental toxicity while degrading pollutants. This finding of oxidizing species' self-acclimation mechanism should be of concern when using pyrite for water treatment.

Different effects of selenium speciation on selenium absorption, selenium transformation and cadmium antagonism in garlic.

Currently, planting selenium-rich crops using inorganic selenium such as selenate and selenite is used to address human selenium deficiency problems. In this paper, besides the above two traditional inorganic selenium speciation, we chose a new organic selenium speciation of potassium selenocyanoacetate to investigate the different effects of selenium speciation on selenium absorption, selenium transformation and cadmium antagonism via foliar application. Plantingexperiments showed that the selenium content of garlic bulbs treated with organic selenium was 1.8-3.9 times higher than that of inorganic selenium. Additionally, the absorption and transformation efficiency of organic selenium in garlic was also the highest, reaching over 95 %. Importantly, it was noteworthy that the cadmium content in bulbs treated with organic selenium was significantly lower than the Chinese food safety standard (0.2 mg/kg). Hence, this study provides an efficient organic selenium speciation which is beneficial to meet human selenium requirements and ensure safe utilization of cadmium-contaminated soils.

Chalcogen Elements in Regulating the Local Electron Density of Cu2X for an Efficient Heterogeneous Fenton-like Process.

In this work, a novel strategy for Fenton activity improvement of Cu2X was reported, in which the local electron density of Cu sites was regulated via manipulation of simple chalcogen elements (O, S, and Se). Among them, Cu2Se catalysts show excellent catalytic activity to activate H2O2 for the complete removal of ofloxacin (10 mg/L) at an initial pH of 6.5 within 120 min. Radical scavenger experiments and electron spin resonance spectroscopy confirm that •OH radicals are the primary oxygen reactive species to drive ofloxacin degradation. In addition, density functional theory calculations further proved that electrons would migrate from X and accumulate on Cu active sites in the order Se > S > O. Compared with Cu2O and Cu2S, the highly concentrated electron density of Cu atoms in Cu2Se not only decreased the activation energy of the Fenton-like reaction but also boosted the Cu2+/Cu+ cycle with the generation of more •OH radicals (18-66 µm) and the maintenance of high stability of catalysts, leading to excellent catalytic activity and application potential. We believe this work will lay the foundation for designing excellent Fenton catalysts for practical applications since developing a heterogeneous Fenton system with the highest oxidation efficiency has always been the long-term goal in this field.

New method for morphological identification and simultaneous quantification of multiple tetracyclines by a white fluorescent probe.

The threat of tetracycline antibiotics to the environment and human health is attracting widespread attention. The development of morphological analysis and quantitative techniques of multiple tetracyclines is of great significance for the evaluation of biochemical toxicity, wide-spectrum antibacterial property and degradation cycle between different tetracyclines. In this study, the white fluorescent Eu/Tb@CDs was synthesized and applied successfully to the identification and detection of the most widely used tetracycline antibiotics (tetracycline (TC), oxytetracycline (OC), chlortetracycline (CC) and doxycycline (DC)) with detection limits all below 1 nM. For the actual water samples with coexistence of the above 4 tetracyclines, their simultaneous morphology identification and accurate quantitative detection can also be realized through simple spectrometric measurement. In addition, the selective and competitive experiments have been carried out on the pollutants widely present in water, and the results have also confirmed that other pollutants could not interfere with the detection of the above 4 tetracyclines. It is undeniable that this work will conveniently and visually reveal the existence information and geographical distribution characteristics of different tetracycline antibiotics in the environment and their action mechanism on organisms.

Colloidal iron species driven enhanced H2O2 decomposition into hydroxyl radicals for efficient removal of methylene blue from water.

Colloids are wide-spread in natural waters and colloid-facilitated transport via adsorption was established as the most important mechanism for the mobilization of aqueous contaminants. This study reports another possible, but reasonable, role of colloids for the contaminants driven by redox reactions. Under the same conditions (pH 6.0, 0.3 ml 30% H2O2, and 25 °C), the degradation efficiencies of methylene blue (MB) at 240 min over Fe colloid, Fe ion, Fe oxide and Fe(OH)3 were 95.38%, 42.66%, 4.42% and 9.40%. We suggested that, Fe colloid can promote the H2O2 based in-situ chemical oxidation process (ISCO) compared with other iron species such as Fe(Ⅲ) ion, Fe oxide and Fe(OH)3 in natural water. Furthermore, the MB removal via adsorption by Fe colloid was only 1.74% at 240 min. Hence, the occurrence, behavior and fate of MB in Fe colloid containing natural water system mainly depends on the reduction-oxidation rather than adsorption-desorption process. Based on the mass balance of colloidal iron species and characterization of iron configurations distribution, Fe oligomers were the active and dominant components for Fe colloid-driven enhanced H2O2 activation among three types of Fe species. The quick and steady conversion of Fe(III) to Fe(II) was proven to be reason why Fe colloid can efficiently react with H2O2 to produce hydroxyl radicals.

Boric Acid Functional Fluorescent Covalent-Organic Framework for Sensitive and Selective Visualization of CH3Hg.

Methylmercury (CH3Hg+) recognition remains a challenging and imperative task due to its high toxicity and wide existence in the ecosystem. Herein, a novel fluorescent covalent-organic framework containing a boric acid functional group (COF-BA) was prepared by a postmodification strategy for CH3Hg+ detection. COF-BA served as a sensing platform for CH3Hg+ with fluorescence static quenching accompanied by fluorescence color changing from intense blue to colorless, and the detection limit was determined as 1.68 µM in a relatively narrow concentration range. COF-BA also exhibited superior selectivity toward CH3Hg+ detection. Furthermore, the spiked and recovery test in real water samples showed its efficient detection practicality. The detection mechanism of COF-BA toward CH3Hg+ was investigated. The recognitive boric acid group in COF-BA was first replaced by CH3Hg+. Then, the quinoline structure that served to limit the rotation of the imine bond was disrupted, leading to dramatic fluorescence quenching. The boric acid functional COF fluorescent probe can be a promising sensing platform for the detection of methylmercury and also provides new ideas for the construction of new fluorescent COF materials.