Efficient Discrimination of Hazardous Organophosphate Flame Retardants via Cataluminescence-Based Multidimensional Ratiometric Sensing.

Emerging contaminants have recently evolved into a severe worldwide environmental issue. Organophosphate flame retardants (OPFRs) with neurotoxicity, genotoxicity, and reproductive and developmental toxicity are a class of notorious emerging contaminants that cause great concern. The development of high-efficiency and portable sensors for rapid online monitoring of OPFRs has become the primary demand for the exploration of the environmental migration and transformation of OPFRs. In this work, interestingly, the cataluminescence (CTL) phenomenon of OPFRs is first observed, and an ingenious multidimensional ratiometric CTL sensing strategy is developed for the recognition of multiple OPFRs. Three characteristic ratios are extracted from the multipeak CTL spectral curves based on energy transfer of single Tb/Eu-modified MgO sensing material, and thus a novel three-dimensional (3D) code recognition could be mapped out. This obtained 3D coordinate is found to be a unique characteristic for a given OPFR, just like an exclusive person's ID number, which can successfully discriminate and detect 10 kinds of OPFR vapors, including homologous series and isomers. More importantly, CTL mechanism investigations for OPFRs demonstrate that OPFRs undergo a series of chemical reaction processes, e.g., oxidative pyrolysis and hydroxylation, and different high-energy excited intermediates are generated, which trigger discrepant energy-transfer efficiency toward rare earth ions, leading to multipeak spectral profiles. Briefly, this proposed CTL analytical platform for OPFRs recognition initiates a new sensing principle for the efficient identification of emerging contaminants and shows significant prospects on rapid on-site detection.

Tailoring the Coordination Environment of Fe/Zn-BDC to Boost Peroxidase-like Activity for Highly Selective Detection of PFOS.

Perfluorooctanesulfonic acid potassium salt (PFOS) residues in ecosystems over long periods are of increasing concern and require a selective and stable optical probe for monitoring. Herein, two functional groups (-F and -NH2) with opposite electronic modulation ability were introduced into Fe/Zn-BDC (denoted as Fe/Zn-BDC-F4 and Fe/Zn-BDC-NH2, respectively) to tailor the coordination environment of the Fe metal center, further regulating the nanozyme activity efficiently. Notably, the peroxidase-like activity is related to the coordination environment of the nanozymes and obeys the following order Fe/Zn-BDC-F4 > Fe/Zn-BDC > Fe/Zn-BDC-NH2. Based on the excellent peroxidase-like activity of Fe/Zn-BDC-F4 and the characteristics of being rich in F atoms, a rapid, selective, and visible colorimetric method was developed for detecting PFOS with a detection limit of 100 nM. The detection mechanism was attributed to various interaction forces between Fe/Zn-BDC-F4 and PFOS, including electrostatic interactions, Fe-S interactions, Fe-F bonds, and halogen bonds. This work not only offers new insights into the atomic-scale rational design of highly active nanozymes but also presents a novel approach to detecting PFOS in environmental samples.

Convenient Size Analysis of Polystyrene Nanoplastics via Regulating the Radiative Transition Efficiency.

Developing a convenient method to efficiently determine the size of nanoplastics in the environment is urgent in terms of ecological or human health protection. In this work, a novel strategy for discriminating the size of polystyrene (PS)-based nanoplastics was reported via regulating the radiative transition efficiency of NH2-UIO-66 (NU) with benzoic acid (BA) as the auxiliary ligand. The elaborately doped BA capped the defect sites and triggered nonradiative transition efficiency of NU. As a result, the formed composite (denoted as BA-NU) was more sensitive to interaction among neighboring NU and nanoplastics. The interaction between particles limited the rotation and vibration of the benzene ring within the BA-NU molecule, thus increasing the BA-NU fluorescence. The sensitivity of BA-NU on nanoplastics was well controlled by manipulating the doping contents of BA, leading to precisely tunable physicochemical properties for this structure. Deriving from the exquisitely designed nanostructures, the composite of BA-NU was successfully used to discriminate different size PS as an ultrasensitive turn-on probe. This work highlights the possibility of boosting the detection performance by regulating the main structure with guest molecules at the molecular level.

On-Site Ratiometric Analysis of UO22+ with High Selectivity.

Uranyl ions (UO22+) are recognized as important indicators for monitoring sudden nuclear accidents. However, the interferences coexisting in the complicated environmental matrices impart serious constraints on the reliability of current on-site monitoring methods. Herein, a novel ratiometric method for the highly sensitive and selective detection of UO22+ is reported based on a [Eu(diaminoterephthalic acid)] (Eu-DATP) metal-organic framework. Benefiting from the unique chemical structure of Eu-DATP, energy transfer from DATP to UO22+ was enabled, resulting in the up-regulated fluorescence of UO22+ and the simultaneous down-regulated fluorescence of Eu3+. The limit of detection reached as low as 2.7 nM, which was almost 2 orders of magnitude below the restricted limit in drinking water set by the United States Environmental Protection Agency (130 nM). The Eu-DATP probe showed excellent specificity to UO22+ over numerous interfering species, as the intrinsic emissions of UO22+ were triggered. This unprecedentedly high selectivity is especially beneficial for monitoring UO22+ in complicated environmental matrices with no need for tedious sample pretreatment, such as filtration and digestion. Then, by facilely equipping a Eu-DATP-based sampler on a drone, remotely controlled sampling and on-site analysis in real water samples were realized. The concentrations of UO22+ were determined to be from 16.5 to 23.5 nM in the river water of the Guangzhou downtown area, which was consistent with the results determined by the gold-standard inductively coupled plasma mass spectrometry. This study presents a reliable and convenient method for the on-site analysis of UO22+.

Efficient and Durable Oxidation Removal of Formaldehyde over Layered Double Hydroxide Catalysts at Room Temperature.

Room temperature catalytic oxidation (RTCO) using non-noble metals has emerged as a highly promising technique for removal of formaldehyde (HCHO) under ambient conditions; however, non-noble catalysts still face the challenges related to poor water resistance and low stability under harsh conditions. In this study, we synthesized a series of layered double hydroxides (LDHs) incorporating various dual metals (MgAl, ZnAl, NiAl, NiFe, and NiTi) for formaldehyde oxidation at ambient temperature. Among the synthesized catalysts, the NiTi-LDH catalyst showed an HCHO removal efficiency and CO2 yield close to 100.0%, and exceptional water resistance and chemical stability on running 1300 min. The abundant hydroxyl groups in LDHs directly bonded with HCHO, leading to the production of CO2 and H2O, thus inhibiting the formation of CO, even in the absence of O2 and H2O. The coexistence of O2 effectively reduced the reaction barrier for H2O molecule dissociation, facilitating the formation of hydroxyl groups and their subsequent backfill on the catalyst surface. The mechanisms underlying the involvement and regeneration of hydroxyl groups in room temperature oxidation of formaldehyde were elucidated with the combined in situ DRIFTS, HCHO-TPD-MS, and DFT calculations. This work not only demonstrates the potential of LDH catalysts in environmental applications but also advances the understanding of the fundamental processes involved in room temperature oxidation of formaldehyde.

Occurrence and distribution of legacy and novel brominated flame retardants in river and sediments in southwest China: A seasonal investigation.

Brominated flame retardants (BFRs) and their substitutes are prevalent in the environment, especially near industrial point sources. In non-point source pollution areas, it is crucial to investigate the seasonal pollution characteristics to identify the pollution sources. In this study, compositional profiles, seasonal variations, and ecological risks of legacy BFRs and novel BFRs (NBFRs) in the water and sediment from the Tuojiang River located in southwest China were investigated. The results indicated that ΣBFRs ranged from not detected (n.d.) to 42.0 ng/L in water and from 0.13 to 17.6 ng/g in sediment, while ΣNBFRs ranged from n.d. to 15.8 ng/L in water, and from 0.25 to 6.82 ng/g in sediment. A significant seasonal variation was observed in water and sediments with high proportions of legacy BFRs (median percentage of 68.8% and 51.3% in water and sediment) in the dry season, while NBFRs (median percentage of 53.2% and 71.6% in water and sediment) exhibited predominance in the wet season. This highlighted the importance of surface runoff and atmospheric deposition as important sources of NBFRs in aquatic environments. Moreover, there were high ratios of decabromodiphenyl ethane (DBDPE) and BDE-209 (average: 1.38 and 2.76 in dry and wet season) in sediments adjacent to the residual areas, indicating a consumption shift from legacy BFRs to NBFRs in China. It was observed that legacy BFRs showed higher ecological risks compared to NBFRs in both water and sediment environments, with BDE-209 posing low to medium risks to sediment organisms. This study provides better understanding of contamination characteristics and sources of legacy BFRs and NBFRs in non-point source pollution areas.

Surfactant encapsulating N-doped carbon dots with enhanced optical properties as a selective sensor for Cr(VI) detection.

Detecting hexavalent chromium (Cr(VI)) is important for human health and environmental protection due to its high toxicity, carcinogenicity and persistence, but developing a sensor to selectively detect Cr(VI) remains challenging. Here, we proposed a selective fluorescent sensor for Cr(VI) detection using cetyltrimethylammonium chloride (CTAC) modified N-doped carbon dots (N-CDs-CTAC) synthesized via a post-modification strategy. Specifically, the introduced CTAC molecules could self-assemble into micelles for encapsulating fluorescent N-CDs, causing the aggregation of N-CD particles and then displaying enhanced fluorescence emission owing to the aggregation-induced emission effect. Moreover, the positively charged CTAC can interact with negatively charged Cr(VI) in the form of an anion (Cr2O72-), boosting the ability of the selective recognition of Cr(VI). Thus, a N-CDs-CTAC fluorescent probe was designed to selectively monitor Cr(VI) with an ultralow detection limit down to 40 nM, and was further used for Cr(VI) detection in real environmental samples. The fluorescence quenching mechanism of N-CDs-CTAC by Cr(VI) was attributed to dynamic quenching. The proposed assay opens an avenue for the selective detection of Cr(VI) in the environmental monitoring field.

Efficient photocatalytic degradation of ciprofloxacin by graphite felt-supported MnS/Polypyrrole composite: Dominant reactive species and reaction mechanisms.

The accumulation of antibiotics in aquatic environments poses a serious threat to human health. Photocatalytic degradation is a promising method for removing antibiotics from water, but its practical implementation requires improvements in photocatalyst activity and recovery. Here, a novel graphite felt-supported MnS/Polypyrrole composite (MnS/PPy/GF) was constructed to achieve effective adsorption of antibiotics, stable loading of photocatalyst, and rapid separation of spatial charge. Systematic characterization of composition, structure and photoelectric properties indicated the efficient light absorption, charge separation and migration of the MnS/PPy/GF, which achieved 86.2% removal of antibiotic ciprofloxacin (CFX), higher than that of MnS/GF (73.7%) and PPy/GF (34.8%). The charge transfer-generated 1O2, energy transfer-generated 1O2, and photogenerated h+ were identified as the dominant reactive species, which mainly attacked the piperazine ring in the photodegradation of CFX by MnS/PPy/GF. The •OH was confirmed to participate in the defluorination of CFX via hydroxylation substitution. The MnS/PPy/GF-based photocatalytic process could ultimately achieve the mineralization of CFX. The facile recyclability, robust stability, and excellent adaptability to actual aquatic environments further confirmed MnS/PPy/GF is a promising eco-friendly photocatalyst for antibiotic pollution control.

A two-staged adsorption/thermal desorption GC/MS online system for monitoring volatile organic compounds.

Real-time online monitoring of volatile organic compounds (VOCs) in ambient air is crucial for timely and effective human health protection. Here, we developed an innovative, automated two-staged adsorption/thermal desorption gas chromatography/mass spectrometry (GC/MS) system for real-time online monitoring of 117 regulated volatile organic compounds (VOCs). This system comprised a sampling unit, water management trap, two-staged adsorption/thermal desorption unit, thermoelectric coolers (TECs), and a commercial GC/MS system. By implementing a micro-purge-and-trap (MP & T) step and a two-staged adsorption/thermal desorption unit, the presence of interfering substances was effectively minimized. The utilization of a heart-cutting GC, combined with a single MS detector, facilitated the precise separation and detection of 117 C2-C12 VOCs, while circumventing the identification and coelution challenges commonly associated with traditional GC-FID or GC-FID/MS methods. The performance of our newly developed online system was meticulously optimized and evaluated using standard gas mixtures. Under optimal conditions, we achieved impressive results, with R2 values ≥ 0.9946 for the standard linear curves of all 117 VOCs, demonstrating a precision (RSD) ranging from 0.2% to 6.4%. When applied in the field monitoring, the concentration drifts for 10 ppbv standard gas mixtures were 0.01-5.64% within 24 h. Our study developed a system for online monitoring of 117 atmospheric VOCs with relatively high accuracy and robustness.

Phenotyping Bacteria through a Black-Box Approach: Amplifying Surface-Enhanced Raman Spectroscopy Spectral Differences among Bacteria by Inputting Appropriate Environmental Stress.

Surface-enhanced Raman spectroscopy (SERS) stands out in the field of microbial analysis due to its rich molecular information, fast analysis speed, and high sensitivity. However, achieving strain-level differentiation is still challenging because numerous bacterial species inevitably have very similar SERS profiles. Here, a method inspired by the black-box theory was proposed to boost the spectral differences, where the undifferentiated bacteria was considered as a type of black-box, external environmental stress was used as the input, and the SERS spectra of bacteria exposed to the same stress was output. For proof of the concept, three types of environmental stress were explored, i.e., ethanol, ultraviolet light (UV), and ultrasound. Enterococcus faecalis (E. faecalis) and three types of Escherichia coli (E. coli) were all subjected to the stimuli (stress) before SERS measurement. Then the collected spectra were processed only by simple principal component analysis (PCA) to achieve differentiation. The results showed that appropriate stress was beneficial to increase the differences in bacterial SERS spectra. When sonication at 490 W for 60 s was used as the input, the optimal differentiation of bacteria at the species (E. faecalis and E. coli) and strain-level (three E. coli) can be achieved.

Like Cures like: Detoxification Effect between Alkali Metals and Sulfur over the V2O5/TiO2 deNOx Catalyst.

The V2O5/TiO2 (VTi) catalyst has been widely employed for the NH3 selective catalytic reduction (NH3-SCR) reaction, and sulfur (S) and alkali metals (K) were usually considered as poisons during this reaction. In this work, the synergistic effect of S and K over the VTi catalyst for the NH3-SCR reaction was analyzed and discussed. It is surprisingly observed that the synergistic effects of S and K exhibited a detoxification effect on the NH3-SCR reaction. That is, although the VTi catalyst exhibited moderate resistance to S poisoning and unsatisfactory resistance to K deactivation, the SCR activity was restored to close to fresh VTi when K and S coexisted. This detoxification effect also could occur between other alkali metals (e.g., Ca and Na) and sulfur. X-ray photoelectron spectroscopy and charge density difference studies both indicate that the introduction of K could significantly affect the electronic structure of V, but this toxic effect was recovered by the further addition of S because of the strong interaction between S and K. Therefore, this detoxification effect can occur in the practical reaction atmosphere, which alleviates the alkali metal poisoning of commercial catalysts.

Assessing the effect of different pH maintenance situations on bacterial SERS spectra.

Phenotyping of bacteria with vibrational spectroscopy has caught much attention in bacteria-related research. It is known that many factors could affect this process. Among them, solution pH maintenance is crucial, yet its impact on the bacterial SERS spectra is surprisingly neglected. In this work, we focused on two situations related to pH maintenance: the effect of the same buffer on the SERS spectra of bacteria under different pH values, and the influence of different buffers on the SERS spectra of bacteria under the same pH value. Specifically, Britton-Robison (BR) buffer was used to evaluate the effect of pH value on bacteria SERS spectra thanks to its wide pH range. Four different buffers, namely BR buffer, acetate buffer, phosphate buffer, and carbonate buffer, were used to illustrate the impact of buffer types on SERS spectra of bacteria. The results showed that the intensity and number of characteristic peaks of the SERS spectra of Gram-negative (G -) bacteria changed more significantly than Gram-positive (G +) bacteria with the change of pH value. Furthermore, compared with phosphate buffer and carbonate buffer, BR buffer could bring more characteristic SERS bands with better reproducibility, but slightly inferior to acetate buffer. In conclusion, the influence of the pH and types of the buffer on the SERS spectra of bacteria are worthy of further discussion.

Quantitative detection of 6-thioguanine in body fluids based on a free-standing liquid membrane SERS substrate.

The adverse reactions caused by 6-thioguanine (6-TG) in anti-cancer treatment are closely related to the dose, leading to the urgent need for clinical monitoring of its concentration. In this work, a highly reproducible free-standing liquid membrane (FLM) surface-enhanced Raman spectroscopy (SERS) substrate was developed to detect 6-TG in human urine and serum quantitatively. Briefly, a prepared sample was adjusted to pH 2 and mixed with concentrated core-shell bimetallic nanoparticle (AgcoreAushell NP) suspension. The Au/Ag ratio of the AgcoreAushell NPs was optimized. Then the mixture was formed into an FLM using a custom mold. The relative standard deviation (RSD) of the experimental results can be stabilized below 10% (n ≥ 10). The R2 of the calibration curve in the range of 10 ~ 100 µg kg-1 was 0.988. In addition, the limit of detection (LOD) (3σ/k) of 6-TG was 5 µg kg-1. The FLM SERS platform has been successfully applied to the rapid and reliable analysis of 6-TG spiked in body fluids.

Fluorescence immunoassay rapid detection of 2019-nCoV antibody based on the fluorescence resonance energy transfer between graphene quantum dots and Ag@Au nanoparticle.

Severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2), which has dramatically changed the world, is a highly contagious virus. The timely and accurate diagnosis of SARS-CoV-2 infections is vital for disease control and prevention. Here in this work, a fluorescence immunoassay was developed to detect 2019 Novel Coronavirus antibodies (2019-nCoV mAb). Fluorescent graphene quantum dots (GQDs) and Ag@Au nanoparticles (Ag@AuNPs) were successfully synthesized and characterized. Fluorescence resonance energy transfer (FRET) enables effective quenching of GQDs fluorescence by Ag@AuNPs. With the presence of 2019-nCoV mAb, a steric hindrance was observed between the Ag@AuNPs-NCP (2019-nCoV antigen) complex and GQDs, which reduced the FRET efficiency and restored the fluorescence of GQDs. The fluorescence enhancement efficiency has a satisfactory linear relationship with the logarithm of the 2019-nCoV mAb in a concentration range of 0.1 pg mL-1-10 ng mL-1, and the limit of detection was 50 fg mL-1. The method has good selectivity. When the serum sample was spiked with 2019-nCoV mAb, the recovery rate was between 90.8% and 103.3%. The fluorescence immunosensor demonstrates the potential to complement the existing serological assays for COVID-19 diagnosis.

Boosting bacteria differentiation efficiency with multidimensional surface-enhanced Raman scattering: the example of Bacillus cereus.

Surface-enhanced Raman scattering (SERS) is a powerful tool for constructing biomolecular fingerprints, which play a vital role in differentiation of bacteria. Due to the rather subtle differences in the SERS spectra among different bacteria, artificial intelligence is usually adopted and enormous amounts of spectral data are required to improve the differentiation efficiency. However, in many cases, large volume data acquisition on bacteria is not only technical difficult but labour intensive. It is known that surface modification of SERS nanomaterials can bring additional dimensionality (difference) of the SERS fingerprints. Here in this work, we show that the concept could be used to improve the bacteria differentiation efficiency. Ag NPs were modified with 11-mercaptoundecanoic acid, 11-mercapto-1-undecanol, and 1-dodecanethiol to provide additional dimensionality. The modified NPs then were mixed with cell lysate from different strains of Bacillus cereus (B. cereus). Even by applying a simple PCA process to the resulting SERS spectra data, all the three modified Ag NPs showed superior differentiation results compared with bare Ag NPs, which could only separate Staphylococcus aureus (S. aureus) and B. cereus. It is believed that the multidimensional SERS could find great potential in bacteria differentiation.

Halogen ion-modified silver nanoparticles for ultrasensitive surface-enhanced Raman spectroscopy detection of polycyclic aromatic hydrocarbons.

Rapid ultrasensitive detection of trace polycyclic aromatic hydrocarbons (PAHs) is essential and significant for pollution control due to their hazard, persistence, and the wide distribution in the environment. Therefore, rapid detection of PAHs is critical for controlling pollution and protecting the ecology. Considering the advantages of surface-enhanced Raman spectroscopy (SERS), a simple and reliable SERS method was proposed in this work for detecting PAHs in water. Three chemicals, namely NaCl, KBr, and KI, were chosen to modify Ag nanoparticles (NPs) for phenanthrene (Phe) detection, and Ag NPs modified with KBr (Ag-Br NPs) showed the best SERS response. The mixing sequence and the concentration of KBr were optimized. The addition order of mixing KBr and Ag NPs before Phe solution was the best sequence, and the optimal concentration of KBr was 20 mM. Under optimal conditions, the limits of quantification for Phe, pyrene (Pyr), and anthracene (Ant) were 10-6  M, 10-7  M, and 10-7  M, respectively. Mixed PAHs (Phe, Pyr, and Ant) in spiked water samples were identified and quantified successfully. The proposed method has good application prospects in environmental pollution monitoring.

Determination of organophosphate flame retardant tris(2-chloroethyl)phosphine based on the luminol-H2 O2 chemiluminescence system.

Organophosphorus flame retardants (OPFRs) are new types of environmental pollutants, therefore the rapid and sensitive detection of OPFRs is a very important objective. A new experimental phenomenon was found in which tris(2-chloroethyl)phosphine (TCEP), a type of OPFR, could effectively enhance the signal of the luminol-H2 O2 chemiluminescence (CL) system. Combined with the controllability of flow injection analysis, a rapid, stable, and sensitive CL method was established. The CL intensity responded linearly to the concentration of TCEP in the range 0.5-100 µg/L (R2 = 0.999) with a low detection limit of 33 ng/L. Relative standard deviation (RSD) was 2.2% (n = 7, c = 100 µg/L). Water samples were labelled and recycled with RSDs of 1.1-5.7% and recoveries of 88.7-116.1%. Based on these results, this study established a new CL detection method for the environmental pollutant TCEP.

Recent advances of environmental pollutants detection via paper-based sensing strategy.

Paper has become one of the most promising substrates for building low-cost and powerful sensing platforms due to its self-pumping ability and compatibility with multiple patterning methods. Paper-based sensors have been greatly developed in the field of environmental monitoring. In this review, we introduced the research and application of paper-based sensors in environmental monitoring, focusing on the deposition and patterning methods of building paper-based sensors, and summarized the applications of detecting environmental pollutants, including metal ions, anions, explosives, neurotoxins, volatile organic compounds, and small molecules. In addition, the development prospects and challenges of promoting paper-based sensors are also discussed. The current review will provide references for the construction of portable paper-based sensors, and has implications for the field of on-site real-time detection of the environment.

Ratiometric fluorescent probe for tetracycline detection based on waste printing paper.

Tetracycline (TC) is a broad-spectrum antibiotic used to treat bacterial infections. In this study, a ratiometric fluorescence (FL) probe was developed to detect TC in water samples using waste printing paper extract as a FL indicator. For this ratiometric probe, the emission of printing paper extract at 436 nm gradually decreased and the emission of a mixed solution at 538 nm significantly increased with the sequential addition of TC upon excitation at 390 nm, coupled with a marked FL colour change from bright blue to faint yellow. Therefore, a ratiometric F538 /F436 FL probe was created for TC detection by simply mixing the printing paper extraction and TC. Under the optimized conditions, a linear range from 1 to 100 µM and a detection limit of 0.48 µM (S/N = 3) for TC were obtained. Importantly, the FL probe can be easily prepared with rapid response, high sensitivity, and good selectivity. The application of waste printing paper extract for detection of TC in environmental water samples was demonstrated.

Surface-enhanced Raman spectroscopy for on-site analysis: A review of recent developments.

On-site identification and quantification of chemicals is critical for promoting food safety, human health, homeland security risk assessment, and disease diagnosis. Surface-enhanced Raman spectroscopy (SERS) has been widely considered as a promising method for on-site analysis due to the advantages of nondestructive, abundant molecular information, and outstanding sensitivity. However, SERS for on-site application has been restricted not only by the cost, performance, and portability of portable Raman instruments, but also by the sampling ability and signal enhancing performance of the SERS substrates. In recent years, the performance of SERS for on-site analysis has been improved through portable Raman instruments, SERS substrates, and other combined technologies. In this review, popular commercial portable Raman spectrometers and the related technologies for on-site analysis are compared. In addition, different types of SERS substrates for on-site application are summarized. SERS combined with other technologies, such as electrochemical and microfluidics are also presented. The future perspective of SERS for on-site analysis is also discussed.