Application of Nontarget High-Resolution Mass Spectrometry Fingerprints for Qualitative and Quantitative Source Apportionment: A Real Case Study.

High-resolution mass spectrometry (HRMS) provides extensive chemical data, facilitating the differentiation and quantification of contaminants of emerging concerns (CECs) in aquatic environments. This study utilizes liquid chromatography-HRMS for source apportionment in Chebei Stream, an urban water stream in Guangzhou, South China. Initially, 254 features were identified as potential CECs by the nontarget screening (NTS) method. We then established 1689, 1317, and 15,759 source-specific HRMS fingerprints for three distinct sources, the mainstream (C3), the tributary (T2), and the rain runoff (R1), qualitatively assessing the contribution from each source downstream. Subsequently, 32, 55, and 3142 quantitative fingerprints were isolated for sites C3, T2, and R1, respectively, employing dilution curve screening for source attribution. The final contribution estimates downstream from sites C3, T2, and R1 span 32-96, 12-23, and 8-23%, respectively. Cumulative contributions from these sources accurately mirrored actual conditions, fluctuating between 103 and 114% across C6 to C8 sites. Yet, with further tributary integration, the overall source contribution dipped to 52%. The findings from this research present a pioneering instance of applying HRMS fingerprints for qualitative and quantitative source tracking in real-world scenarios, which empowers the development of more effective strategies for environmental protection.

Chemical characterization and source attribution of organic pollutants in industrial wastewaters from a Chinese chemical industrial park.

Accelerated urbanization and industrialization have led to an alarming increase in the generation of wastewater with complex chemical contents. Industrial wastewaters are often a primary source of water contamination. The chemical characterization of different industrial wastewater types is an essential task to interpret the chemical fingerprints of wastewater to identify pollution sources and develop efficient water treatment strategies. In this study, we conduct a non-target chemical analysis for the source characterization of different industrial wastewater samples collected from a chemical industrial park (CIP) located in southeast China. The chemical screening identified volatile and semi-volatile organic compounds that included dibutyl phthalate at a maximum concentration of 13.4 µg/L and phthalic anhydride at 35.9 µg/L. Persistent, mobile, and toxic (PMT) substances among the detected organic compounds were identified and prioritized as high-concern contaminants given their impact on drinking water resources. Moreover, a source analysis of the wastewater collected from the wastewater outlet station indicated that the dye production industry contributed the largest quantities of toxic contaminates (62.6%), and this result was consistent with the ordinary least squares and heatmap results. Thus, our study utilized a combined approach of a non-target chemical analysis, a pollution source identification method, and a PMT assessment of different industrial wastewater samples collected from the CIP. The results of the chemical fingerprints of different industrial wastewater types as well as the results of the PMT assessment benefit risk-based wastewater management and source reduction strategies.

Estimation of chemical oxygen demand in different water systems by near-infrared spectroscopy.

To monitor environmental water pollution effectively and meet human water needs, it is crucial to develop a fast, simple, and accurate method for monitoring chemical oxygen demand (COD) in various water systems. In this study, COD prediction models for different water systems were developed by combining near-infrared (NIR) spectroscopy with partial least squares regression (PLSR). Samples of wastewater, surface water, and seawater were collected from Guangzhou, Guangdong Province, China. Three pretreatment methods were used to preprocess the spectra in order to improve the accuracy and minimalism of the model. We investigate the performance of two variable selection algorithms, namely, binary gray wolf optimization (BGWO) and competitive adaptive reweighting sampling (CARS). The results show that both BGWO and CARS improved the performance of the model in terms of higher accuracy and less wavelength input; both of the combined model performances were better than that of PLSR alone, and CARS-PLSR achieved the best results. Using CARS-PLSR, surface water, wastewater, and seawater model inputs were reduced by 96 %, 96 %, and 82 % as compared to the PLSR results, respectively, and the testing sets R2 reached 0.860, 0.815, and 0.692, respectively. The spectral variable selection algorithm could identify the important spectral variables between COD content and NIR spectra in three water systems, thereby improving the accuracy and simplicity of the PLSR model for COD prediction. Our results have important practical value for predicting COD content in different water systems by NIR spectroscopy.

Potential toxic effects of perfluorobutanesulfonyl fluoride analysis based on multiple-spectroscopy techniques and molecular modelling analysis.

Perfluorobutanesulfonyl fluoride (PBSF) has been used in the manufacture of fluorochemicals. Since PBSF is not biodegradable, the predicted environmental levels of PBSF are also expected to rise over time. In recent years, there has been a rise in the levels of PBSF in humans. In order to clarify the impact of PBSF on the accumulation of substances in the human body, we examined the interaction mechanism between PBSF and bovine serum albumin (BSA). To investigate the interaction mechanism between PBSF and BSA, we utilized a range of methods including UV-visible spectrophotometry, fluorescence spectroscopy, circular dichroism, molecular docking simulation, and molecular dynamics (MD) simulation. The inherent fluorescence of BSA was effectively suppressed by PBSF through fluorescence quenching analysis, using a static mechanism. The Ka value of 1.34 × 105 mol-1 L indicated a strong binding between PBSF and BSA. Further analysis of the interaction between PBSF and BSA involved examining thermodynamic parameters, fluorescence resonance energy transfer, and conducting other theoretical calculations. These investigations produced results that were in strong accordance with the experimental observations. The participation of hydrophobic interactions between BSA and PBSF was uncovered through molecular docking and MD simulation investigations. Furthermore, this investigation explored the impact of copper ions (Cu2+) and calcium ions (Ca2+) on the interaction between PBSF and BSA, establishing a vital basis for comprehending the mechanism by which PBSF affects proteins in the human surroundings.

Conductive imprinted polymeric interfacially modified electrochemical sensors based on covalently bonded layer-by-layer assembly of Gr/Au with flower-like morphology for sensitive detection of 2,4,6-TCP.

Polymeric membrane sensors based on molecular imprinted polymers (MIPs) have been attractive analytical tools for detecting organic species. However, the MIPs in electrochemical sensors developed so far are usually prepared by in situ polymerization of pre-polymers and non-covalent adsorption on the surface of the working electrode. Meanwhile, the MIPs in the electrochemical sensors developed are typically made of a non-conductive polymer film. This results in a relatively low current due to the lack of electron transfer. Additionally, the smoothness of the traditional electrochemical substrate results in a low specific surface area, which reduces the sensitivity of the electrochemical sensor. Here, we describe a novel electrochemical sensor with a conductive interface and MIPs modification. The electrochemical sensor was modified by covalent coupled layer by layer self-assembly with the imprinted polymer film. The incorporation of these two conductive functional materials improves the conductivity of the electrodes and provides interface support materials to obtain high specific surface area. By using 2,4,6-trichlorophenol as the model, the sensitivity of the developed conductive sensor was greatly improved compared to that of the traditional MIPs sensor. We believe that the proposed MIPs-based sensing strategy provides a general and convenient method for making sensitive and selective electrochemical sensors.

Enhancing compound confidence in suspect and non-target screening through machine learning-based retention time prediction.

The retention time (RT) of contaminants of emerging concern (CECs) in liquid chromatography-high-resolution mass spectrometry (LC-HRMS) is crucial for database matching in non-targeted screening (NTS) analysis. In this study, we developed a machine learning (ML) model to predict RTs of CECs in NTS analysis. Using 1051 CEC standards, we evaluated Random Forest (RF), XGBoost, Support Vector Regression (SVR), and Artificial Neural Network (ANN) with molecular fingerprints and chemical descriptors to establish an optimal model. The SVR model utilizing chemical descriptors resulted in good predictive capacity with R2ext = 0.850 and r2 = 0.925. The model was further validated through laboratory NTS compound characterization. When applied to examine CEC occurrence in a large wastewater treatment plant, we identified 40 level S1 CECs (confirmed structure by reference standard) and 234 level S2 compounds (probable structure by library spectrum match). The model predicted RTs for level S2 compounds, leading to the classification of 153 level S2 compounds with high confidence (ΔRT <2 min). The model served as a robust filtering mechanism within the analytical framework. This study emphasizes the importance of predicted RTs in NTS analysis and highlights the potential of prediction models. Our research introduces a workflow that enhances NTS analysis by utilizing RT prediction models to determine compound confidence levels.

Reproducibility in nontarget screening (NTS) of environmental emerging contaminants: Assessing different HLB SPE cartridges and instruments.

Non-targeted screening (NTS) methods are integral in environmental research for detecting emerging contaminants. However, their efficacy can be influenced by variations in hydrophilic-lipophilic balance (HLB) solid phase extraction (SPE) cartridges and high-resolution mass spectrometry (HRMS) instruments across different laboratories. In this study, we scrutinized the influence of five HLB SPE cartridges (Nano, Weiqi, CNW, Waters, and J&K) and four LC-HRMS platforms (Agilent, Waters, Thermo, and AB SCIEX) on the identification of emerging environmental contaminants. Our results demonstrate that 87.6 % of the target compounds and over 59.6 % of the non-target features were consistently detected across all tested HLB cartridges, with an overall 71.2 % universally identified across the four LC-HRMS systems. Discrepancies in detection rates were primarily attributable to variations in retention time stability, mass stability of precursors and fragments, system cleanliness affecting fold change and p-values, and fragment response. These findings confirm the necessity of refining parameter criteria for NTS. Moreover, our study confirms the efficacy of the PyHRMS tool in analyzing and processing data from multiple instrumental platforms, reinforcing its utility for multi-platform NTS. Overall, our findings underscore the reliability and robustness of NTS methods in identifying potential water contaminants, while also highlighting factors that may influence these outcomes.

Anthropogenic-induced ecological risks on marine ecosystems indicated by characterizing emerging pollutants in Pearl River Estuary, China.

Anthropogenic Contaminants of Emerging Concern (CECs) in marine environments have raised significant concerns. Yet, analyses detailing their origins, fate, and environmental effects are limited. This study employs an integrated non-target screening methodology to elucidate CECs existence across 46 sampling sites in the Pearl River Estuary (PRE) of the South China Sea. Assisted by advanced liquid chromatography-high resolution mass spectrometry, we discovered 208 chemicals in six usage categories, with pesticides (33 %) and pharmaceuticals (29 %) predominating. Several CECs drew attention for their consistent detections, profound abundance, and significant ecotoxicities. The wide detection of them at offshore sites further implies that anthropogenic activities may contribute to large-scale contamination. Meanwhile, distinct distribution patterns of CECs across PRE are evident in semi-quantitative results, indicating regional anthropogenic influences. Identified transformation products may establish a novel and non-negligible negative contribution to ecology through elevated environmental toxicities, exemplified by HMMM and atrazine. Based on the ecological risks, we compiled a prioritized list of 21 CECs warranting intensified scrutiny. Our findings indicate the introduction of various CECs into the South China Sea via PRE, emphasizing the urgent necessity for ongoing surveillance of discharged CECs at estuary areas and assessment of their marine ecological consequences.

Ultrasensitive electrogenerated chemiluminescence peptide-based method for the determination of cardiac troponin I incorporating amplification of signal reagent-encapsulated liposomes.

An ultrasensitive electrogenerated chemiluminescence peptide-based (ECL-PB) method for the determination of cardiac troponin I (TnI) incorporating amplification of signal reagent-encapsulated liposome was reported for the first time. A synthesized short linear specific binding peptide (FYSHSFHENWPSK) was employed as a molecular recognition element for TnI, which was a reliable biomarker for detecting cardiac injury. Liposomes assembled using a standard sonication procedure were designed as the carrier of ECL signal reagents [bis(2,2'-bipyridine)-4,4'-dicarboxybipyridine ruthenium-di(N-succinimidyl ester) bis(hexafluorophosphate)] for signal amplification. The magnetic capture peptides for the enrichment of the target protein and magnetic separation were synthesized by covalently attaching the peptides to the surface of magnetic beads via an acylation reaction, and the liposome peptides were synthesized by covalently attaching the peptides to the signal reagent-encapsulated liposomes. In the presence of TnI, sandwich-type conjugates were generated in incubation of the magnetic capture peptides and the liposome peptides. After a magnetic separation, the sandwich-type conjugates were treated with ethanol and, thus, a great number of the ECL reagents were released and measured by the ECL method at a bare glassy carbon electrode with a potential pulse of +1.15 V versus Ag/AgCl in the presence of tri-n-propylamine. The increased ECL intensity has good linearity with the logarithm of the TnI concentration in the range from 10 pg/mL to 5.0 ng/mL, with an extremely low detection limit of 4.5 pg/mL. The proposed ECL-PB method was successfully applied to the detection of TnI in human serum samples. This work demonstrated that the employment of the magnetic capture peptides for the enrichment of the target proteins and magnetic separation and the liposome peptides for the signal amplification and polyvalent binding motifs may open a new door to ultrasensitive detection of proteins in clinical analyses.

Utility of a non-target screening method to explore the chlorination of similar sulfonamide antibiotics: Pathways and NCl intermediates.

Sulfonamides (SAs) are ubiquitous antibiotics that are increasingly detected in aquatic environments and can react with free available chlorine to produce transformation products (TPs) during disinfection. However, the TPs generated during chlorination remains poorly understood. Here, a non-target screening method based on the PyHRMS program was used to assess the transformation pathways of five SAs, particularly the transient NCl intermediates, during a simulated chlorination process. We observed 210 TPs during SA chlorination using a non-target screening method based on high-resolution mass spectrometry, and the reaction mechanisms mainly included chlorine substitution, desulfonation, and hydroxylation. Among the TPs, 87 were tentatively proposed to be NCl intermediates as they instantly disappeared after quenching with Na2S2O3. The MS2 spectra of 13 of these potential NCl intermediates were obtained, and all displayed an [M-Cl]+ fragment. A diagnostic fragment ion (DFI) strategy was applied to explore the structural relationship between parent compounds and TPs. Based on the result, five SAs and 101 TPs (if their MS2 spectra were available) could be connected through the same fragments, and this method was also proved effective in a real wastewater treatment plant effluent sample. We believe this novel method can help explore the TPs of organic compounds during chlorination in drinking water plants.

Tracing the attenuation of fipronil and its transformation products from a rice paddy field to receiving rivers using polar organic chemical integrative samplers.

Irrational use of fipronil for rice pest control often occurred, resulting in high concentrations of fipronil and its transformation products (TPs) (collectively termed fiproles) in aquatic sediment, calling for a better understanding of the migration and transformation of fipronil in surface water as well as efficient methods for source identification. Herein, the fate and transport of fiproles from a paddy field to receiving rivers were assessed in Poyang Lake basin, Jiangxi, China using polar organic chemical integrative samplers with mixed-mode adsorbents (POCIS-MMA). Average concentrations of fiproles in water were 6.16 ± 6.32 ng/L, with median, minimum, and maximum values being 2.99 ± 0.67, 0.40 ± 0.08, and 18.6 ± 3.1 ng/L, respectively. In all samples, over half of fiproles (55.9 %-90.8 %) presented in the form of TPs and fipronil desulfinyl was the dominant TP. Two approaches were applied for source identification, including the change of molar concentration ratios of fipronil to its TPs and the relative attenuation values of fiproles normalized to a reference compound (acetamiprid) that was stable in aquatic environment. While the paddy field upstream was the main source of waterborne fiproles, additional input sources in the downstream region were identified. The present study indicated that the combination of attenuation of molar concentration ratios of micro-pollutants to their respective TPs and relative attenuation values of micro-pollutants' concentrations normalized to a reference compound measured by POCIS is an effective means to study the migration and transformation of micro-pollutants in field.

[Identification of Impacts from Meteorology and Local and Transported Photochemical Generation on Ozone Trends in Changsha from 2018 to 2020].

Ozone (O3) pollution in Hunan province has become the most important factor among the six common conventional pollutants (i.e., NO2, SO2, CO, O3, PM10, and PM2.5) in the atmospheric environment. Further investigation has indicated that the relevant studies of O3 are insufficient. Therefore, it is essential to clarify the key driving factors of O3 variations for government regulators. In this study, a combined method consisting of a generalized additive model (GAM), empirical orthogonal function (EOF), and absolute principal component scores (APCs) model was employed to identify and quantify the impacts of meteorology and local photochemical generation (local) and that transported from outside (nonlocal) on O3 variations from 2018-2020. Simultaneously, the driving factors of O3 annual values from 2018 to 2019 and from 2019 to 2020 in Changsha were analyzed. The results showed that O3 episodes were commonly caused by meteorology when the relative contribution from precursors was high, on the short-term time scale. Overall, on the temporal scale, meteorology and local were the driving factors for the increasing annual O3 from 2018 to 2019. Additionally, the contribution from meteorology, local, and nonlocal decreased from 2019 to 2020, leading to a lower level of O3 concentration in 2020. Geographically, the east, north, and south of Changsha were mainly affected by meteorology, local, and nonlocal, respectively. Throughout the three years, nonlocal exhibited a sustained decreasing trend, whereas the tendencies from meteorology and local varied by year and geography. Local contribution in the north of Changsha increased from 2018 to 2019, which was likely attributed to the increasing biogenic volatile organic compound emission (BVOCs), and it became lower in the south owing to the strengthened consumption by NOx. Impacts from meteorology on O3 in all sites were enhanced from 2018 to 2019. By contrast, local contribution decreased in the north and increased in the south with the decline in BVOC and NOx emissions from 2019 to 2020, when the meteorological impacts on O3 in the whole area became weak.

Evaluation the binding of chlorogenic acid with bovine serum albumin: Spectroscopic methods, electrochemical and molecular docking.

Chlorogenic acid(CGA) is the common active phenolic acid in Chinese medicinal materials such as honeysuckle and eucommia. It is a class of small molecules with multiple activities such as antioxidant, inhibiting cancer cells, lowering blood sugar and lowering blood pressure. In this paper, UV-vis spectroscopy, fluorescence spectroscopy, circular dichroism, molecular dynamics simulation and cyclic voltammetry (CV) electrochemical analysis were used to investigate the mechanism about interaction between CGA and BSA. Based on fluorescence quenching analysis, CGA quenched the inherent fluorescence of BSA remarkably through a static mechanism. The obtained value of binding constant (Kb = 5.75 × 105 L·mol-1) revealed a high binding affinity between CGA and BSA. The simulated molecular docking showed that hydrophobic force were also involved in the interaction between BSA and CGA. This paper also investigate the effect of temperature and metal ions on the binding of CGA and BSA. When the temperature increased, the binding of BSA and CGA was destroyed. Metal ions affect both the structure of BSA and the combination of BSA and CGA. By studying the mechanism of CGA interaction with BSA, we elucidated the storage and transport mechanism of CGA in vivo under simulated human environment and temperature conditions.

Integrating data dependent and data independent non-target screening methods for monitoring emerging contaminants in the Pearl River of Guangdong Province, China.

The occurrence of Contaminants of Emerging Concern (CECs) in the Pearl River of Guandong province, China, was characterized using a nontarget screening (NTS) strategy combining both data dependent and data independent acquisition techniques. Our analysis identified 620 unique compounds, including pharmaceuticals (137), pesticides (124), industrial materials (68), personal care products (32), veterinary drugs (27), plasticizers or flame retardants (11), etc. Out of these compounds, 40 CECs were found with a detection frequency of over 60 %, including diazepam, a well-known drug to treat anxiety, insomnia, convulsion, etc., which had the highest detection rate at 98 %. Risk quotients (RQs) were calculated for CECs identified with high confidence (Level 1, confirmed with authentic standards), and it was found that 12 CECs had RQs > 1, with notable concern for pretilachlor (detection frequency: 48 %; 0.8-19.0 ng/L), bensulfuron-methyl (86 %, 3.1-56.2 ng/L), imidacloprid (80 %, 5.3-62.8 ng/L) and thiamethoxam (86 %, 9.1-99.9 ng/L), which exhibited RQs exceeding the threshold of concern (RQ > 1) at 46-80 % of sampling sites. Additionally, tentative identification of potential structurally related compounds provided valuable insight into the parent-product relationships in complex samples. This study highlights the importance and urgency of using NTS for CECs in the environment and presents a novel data sharing approach, which facilitates other scientists to assess, investigate further, and perform retrospective analyses.

[Pollution Characteristics and Risk Assessment of Nitrated Polycyclic Aromatic Hydrocarbons in the Atmosphere of Guangdong-Hong Kong-Macao Greater Bay Area].

To investigate the pollution characteristics and sources of nitrated polycyclic aromatic hydrocarbons (NPAHs) in Guangdong-Hong Kong-Macao Greater Bay Area (GBA), 44 ambient air samples were collected using the active sampling method, which were then determined via gas chromatography-triple quadrupole tandem mass spectrometry. The main results showed that filters, polyurethane foam, and XAD-2 resin were the essential materials for sampling NPAHs in ambient air in order to characterize the pollution status accurately. The levels of ρ(Σ18NPAHs) in ambient air at GBA ranged from 162 pg·m-3 to 2094 pg·m-3, and the average levels of ρ(Σ18NPAHs) were (675±430) pg·m-3 in summer and (637±349) pg·m-3 in winter. NPAHs were widely found in the ambient air of GBA and were dominated by 1-nitronaphthalene (220 pg·m-3), 2-nitronaphthalene (146 pg·m-3), 9-nitroanthracene (105 pg·m-3), and 2-nitrofluoranthene (72 pg·m-3). The congener profile characteristics of NPAHs in summer and winter were similar. The gas/particle partitioning characteristics of NPAHs revealed that dicyclic and tricyclic NPAHs tend to occur in the gas phase, and tetracyclic NPAHs tend to be adsorbed in the particle phase. The fraction of NPAHs concentrations in the particulate fraction of their total atmospheric concentrations increased with the increase in their molecular weight. In winter, NPAHs tend to be adsorbed in the particle phase, whereas in summer, NPAHs tend to exist in the gas phase. Based on the ratios of characteristic pollutants, in both the summer and winter season, photochemical reactions were the main source of NPAHs in the atmosphere of GBA and were primarily generated by the reaction of the hydroxyl radical in the daytime. The carcinogenic risk value calculation showed that the current carcinogenic risk of NPAHs in the ambient air of GBA was controllable.

[Emission Characteristics and Emission Factors of Volatile Organic Compounds from E-waste Dismantling and Recycling Processes].

A large number of volatile organic compounds (VOCs) are emitted from the high temperature treatment process in the dismantling and recycling procedure of e-wastes, which has a significant impact on the surrounding environment and human health. In this study, an e-waste dismantling and recycling yard was selected to measure the VOCs concentrations and compositions in the exhaust of treatment facilities of heating baking board, plastic granulation, wet extraction, and pyrometallurgical workshops, and the emission characteristics of VOCs and emission factors for total VOCs from different production processes were investigated. The results showed that there were significant differences in total VOCs emission concentrations among different production processes. The concentrations of total VOCs produced in different workshops followed the descending order of the heating baking board (heating rotary plate furnace) process[(2096.1±732.4) µg·m-3] > plastic granulation process[(1639.1±538.5) µg·m-3] > heating baking board (electric heater) process[(625.3±535.5) µg·m-3] > pyrometallurgical process[(436.8±305.2) µg·m-3] > wet extraction process[(271.3±73.1) µg·m-3]. The compositions of VOCs emitted from different production processes were also clearly different; however, the major components of VOCs were generally oxygenated compounds and aromatic hydrocarbons. The specific component characteristics were as follows:the dominant groups of VOCs emitted from the heating baking board process (including heating rotary plate furnaces and electric heaters) were oxygenated compounds and aromatic hydrocarbons, accounting for 74.1%-79.7% of the total. The main components of VOCs emitted from the pelletizing process were aromatic hydrocarbons and oxygenated compounds, accounting for 71.8% of the total. Oxygenated compounds and aromatic hydrocarbons, which contributed equally, were also the main groups of VOCs discharged by the wet extraction process, and the sum proportion of the two groups was 84.2%. Halogenated hydrocarbon was the dominant group of VOCs from the pyrometallurgical process, accounting for 92.1% of the sum of VOCs. There was a substantial divergence in the total VOCs emission factors of different production processes. The ranking of the mean values of emission factors of total VOCs was as follows:the heating baking board (electric heater) process (297.0 g·t-1) > plastic granulation process (29.5 g·t-1) > wet extraction process (25.4 g·t-1) > heating baking board (heating rotary plate furnace) process (25.2 g·t-1) > pyrometallurgical process (1.9 g·t-1). Therefore, the main VOCs emission processes of the e-waste centralized dismantling and recycling industry were the heating baking board process and plastic granulation process.

Unintentional formation of mixed chloro-bromo diphenyl ethers (PBCDEs), dibenzo-p-dioxins and dibenzofurans (PBCDD/Fs) from pyrolysis of polybrominated diphenyl ethers (PBDEs).

This study presents the comprehensive investigation for formation pathways of chloro-bromo-mixed products from the pyrolysis of polybrominated diphenyl ethers (PBDEs). In the study, a total of 23 PBDEs with bromination levels from mono-to deca-were selected. Each PBDE standard was sealed in the glass vial and then heated under 450 °C in the muffle furnace to simulate the pyrolysis process. The results demonstrated that PBDEs in the glass vials can unintentionally transform into chloro-bromo diphenyl ethers (PBCDEs) and dibenzo-p-dioxin and dibenzofurans (PBCDD/Fs) during the pyrolysis process. Atmosphere pressure gas chromatography (APGC) coupled with high-resolution mass spectrometry (HRMS) was used to identify these pyrolysis products, which demonstrated that all investigated nPBDEs (n represents the number of bromine substituents) can unintentionally transform into Cl1-(n-1)BDEs, Cl2-(n-2)BDEs, Cl1-(n-1)BDFs, and Cl1-(n-3)BDDs, while some nPBDEs can transform into Cl1-(n-2)PBDD/Fs during pyrolysis. Experimental phenomena assisted with density functional theory (DFT) calculations reveal that Cl atom can substitute at C-Br rather than C-H, and Cl1-(n-1)BDEs can be easily generated by Cl atom attacking at C-Br sites with low energy barriers (3.66-11.9 kcal/mol). In addition, nPBDEs with lower bromination levels are more favorable to generate Cl1-(n-1)BDEs than those with higher bromination levels. Further DFT calculations suggest that PBDEs are preferentially first transformed into Cl1-(n-1)BDEs, then subsequentially transform into PBCDD/Fs. We believe the results of this study can greatly improve our understanding of the transformation mechanism from PBDEs to cholo-bromo-mixed products in thermal treatment processes and provide new insight into controlling the emission of toxic cholo-bromo-mixed products.

Knockdown of Peroxiredoxin V increased the cytotoxicity of non-thermal plasma-treated culture medium to A549 cells.

Administration of non-thermal plasma therapy via the use of plasma-activated medium (PAM) might be a novel strategy for cancer treatment, as it induces apoptosis by increasing reactive oxygen species (ROS) levels. Peroxiredoxin V (PRDX5) scavenges ROS and reactive nitrogen species and is known to regulate several physiological and pathological reactions. However, its role in lung cancer cells exposed to PAM is unknown. Here, we investigated the effect of PRDX5 in PAM-treated A549 lung cancer cells and determined the mechanism underlying its cytotoxicity. Cell culture medium was treated with low temperature plasma at 16.4 kV for 0, 60, 120, or 180 s to develop PAM. PRDX5 was knocked down in A549 cells via transfection with short hairpin RNA targeting PRDX5. Colony formation and wound healing assays, flow cytometry, fluorescence microscopy, and western blotting were performed to detect the effect of PRDX5 knockdown on PAM-treated A549 cells. PAM showed higher cytotoxicity in lung cancer cells than in control cells, downregulated the mitogen-activated protein kinase signaling pathway, and induced apoptosis. PRDX5 knockdown significantly inhibited cell colony formation and migration, increased ROS accumulation, and reduced mitochondrial membrane potential in lung cancer cells. Hence, PRDX5 knockdown combined with PAM treatment represents an effective option for lung cancer treatment.

Amplification of fluorescence polarization signal based on specific recognition of aptamers combined with quantum quenching effect for ultrasensitive and simple detection of PCB-77.

Here, we report a novel aptasensor based on decahedral silver nanoparticles (Ag10NPs) enhanced fluorescence polarization (FP) for detecting PCB-77. Using aptamer modified Ag10NPs hybridized with DNA sequence labeled fluorescent group as an analytical probe, polychlorinated biphenyls (PCB-77) could be detected with high sensitivity and selectivity. The linear range of determination was 0.02 ng/L to 390 ng/L and the limit of detection was 5 pg/L. In addition, through the optimization of the experiment condition and signal probe DNA (pDNA), we found that the maximum FP signal could be generated when the distance between fluorescein and the surface of Ag10NPs was 3 nm. When the aptamer was immobilized on the surface of Ag10NPs could be strengthened the anti-interference performance of aptamer nanoprobe and further improved the detection ability. At the same time, we also compared the detection performance of the traditional FP signal enhancer streptavidin (SA) analysis system. The fluorescence polarization aptasensor could detect PCB-77 samples efficiently in complex environmental water, which shows a good application prospect.

Ethyl ß-Carboline-3-Carboxylate Increases Cervical Cancer Cell Apoptosis Through ROS-p38 MAPK Signaling Pathway.

BACKGROUND/AIM: Ethyl ß-carboline-3-carboxylate (ß-CCE) is one of the effective ingredients of Picrasma quassioides (P. quassioides). As a ß-carboline alkaloid, it can antagonize the pharmacological effects of benzodiazepines by regulating neurotransmitter secretion through receptors, thus affecting anxiety and physiology. However, its efficacy in cancer treatment is still unclear. MATERIALS AND METHODS: We explored the effect of b-CCE on SiHa cells using MTT assay, western blot, flow cytometry, LDH release, T-AOC, SOD, and MDA assays. RESULTS: We investigated the cytotoxicity of ß-CCE in SiHa cells and verified that ß-CCE could induce cell apoptosis in a time- and concentration-dependent manner. In this process, treatment with ß-CCE significantly increased the levels of cytoplasmic and mitochondrial reactive oxygen species (ROS), which disturb the oxidation homeostasis by regulating the total antioxidant capacity (T-AOC), superoxide dismutase (SOD) activity, and malondialdehyde (MDA) production. Notably, the addition of N-acetylcysteine (NAC) (ROS scavenger) effectively alleviated ß-CCE-induced apoptosis in SiHa cells. In addition, ß-CCE might activate the p38/MAPK signaling pathway, as the pre-treatment with SB203580 (p38 inhibitor) significantly reduced ß-CCE-induced apoptosis in SiHa cells. CONCLUSION: ß-CCE has an anti-tumor activity. It activates the p38/MAPK signaling pathway by increasing intracellular ROS levels, which subsequently induce SiHa cell apoptosis. Our results provide a novel therapeutic target for treatment of cervical cancer.