Ortho C-H Bond Activations in an Atmospheric Microwave Plasma Ion Source.

C-H bond ortho-substitution reaction has always been a significant and challenging topic in organic chemistry. We proposed a synthesis method based on microwave plasma torches. High-resolution mass spectrometry was used to monitor rapid reaction products. 2-Alkylbenzimidazole can be formed through the reaction of phenylnitrenium ion and nitriles on a millisecond scale. This reaction can achieve the one-step formation of benzimidazoles from benzene ring single-substituted compounds without the addition of external oxidants or catalysts. A similar C-H bond activation reaction can be accomplished with ketones. Meanwhile, the microwave plasma reactor was modified, and the resulting 2-methylbenzimidazole was successfully collected, indicating the device has good application potential in organic reactions such as C-H bond activation reaction.

Pulsed Direct Current Arc-Induced Nanoelectrospray Ionization Mass Spectrometry.

This study explores the innovative field of pulsed direct current arc-induced nanoelectrospray ionization mass spectrometry (DCAI-nano-ESI-MS), which utilizes a low-temperature direct current (DC) arc to induce ESI during MS analyses. By employing a 15 kV output voltage, the DCAI-nano-ESI source effectively identifies various biological molecules, including angiotensin II, bradykinin, cytochrome C, and soybean lecithin, showcasing impressive analyte signals and facilitating multicharge MS in positive- and negative-ion modes. Notably, results show that the oxidation of fatty acids using a DC arc produces [M + O - H]- ions, which aid in identifying the location of C═C bonds in unsaturated fatty acids and distinguishing between isomers based on diagnostic ions observed during collision-induced dissociation tandem MS. This study presents an approach for identifying the sn-1 and sn-2 positions in phosphatidylcholine using phosphatidylcholine and nitrate adduct ions, accurately determining phosphatidylcholine molecular configurations via the Paternò-Büchi reaction. With all the advantages above, DCAI-nano-ESI holds significant promise for future analytical and bioanalytical applications.

Long term online desalting analysis of MS/LC-MS using thermal assisted recrystallization ionization.

Mass spectrometric analysis of non-volatile salts containing samples remains challenging due to salt-induced ion suppression and contamination. This challenge is even more pronounced for a liquid chromatography-mass spectrometry analysis, where the accumulation of salts in the transmission system poses an ongoing problem. In this study, a novel thermal assisted recrystallization ionization mass spectrometry (TARI-MS) device was developed to achieve efficient on-line desalting and prolonged analysis of saline samples. The core component of this device was a heated plate positioned between the electrospray unit and the MS inlet. The desalting mechanism was demonstrated as the spontaneous separation of target molecules from salts during the "crystallization" process. After optimization, the angle between the nebulizer and the heated plate was 45°; the distance between the front end of the heated plate and the MS inlet was 2 mm; the distance between the front edge of the heated plate and the center of the sample spray projected onto the heating plate was 3 mm; the distance between the emitter of nebulizer and the heated plate was 3 mm. TARI-MS realized direct analysis of eight drugs dissolved in eight commonly used non-volatile salts solutions (up to 0.5 mol/L). The high sensitivity, repeatability, linearity, accuracy, and intra- and inter-day precision of TARI-MS confirm its reliability as a robust tool for the analysis of saline samples. Furthermore, TARI-MS allowed continuous analysis of salty eluates of LC for up to nearly 1 h without maintenance and verified the feasibility of LC-MS analysis through detecting a five-drug mixture and a crude aripiprazole product. Finally, six impurities in the crude aripiprazole product were successfully detected by LC-TARI-MS. The established method holds promise for applications across academic and pharmaceutical domains.

Nonderivatized Method for the Detection of Perfluoroalkane Sulfonyl Fluorides by Liquid Chromatography-Microwave Plasma Torch Ionization Mass Spectrometry.

Per- and polyfluoroalkyl substances (PFAS) have caused widespread environmental concern in recent years. Among them, the levels of perfluoroalkane sulfonyl fluorides (PFASFs) in the environment have rarely been reported due to the lack of sensitive analytical methods. Herein, a novel liquid chromatography-microwave plasma torch ionization-mass spectrometry (LC-MPTI-MS) technique was designed for the direct analysis of PFASFs in the environment. The collaborative action of reactive oxygen species (such as hydroxyl radicals) and the elevated temperature within the ambient MPTI environment results in the replacement of the fluorine atom in sulfonyl fluoride by oxygen, leading to the detection of perfluoroalkanesulfonic acid (PFSA) ions by MS. Concurrently, LC was employed to separate other PFSAs that are present in the environment. Three PFASFs exhibited good linearity within the range of 1-500 µg/L with R2 > 0.994. The limit of detections (LODs) and the limit of quantifications (LOQs) were measured at 39.32-87.87 and 131.07-292.90 ng/L, respectively. The method was utilized for the direct detection of spiked perfluorooctane sulfonyl fluoride (PFOSF) in wastewater with recoveries of 77.16 to 124.81%. Our approach circumvents the laborious process of chemical derivatization and is anticipated to serve as a robust tool for determining the levels and behaviors of PFASFs in the environment.

Gas-Phase Alcoholysis of Benzylic Halides in the Atmospheric Pressure Ionization Source.

The present study investigates the gas-phase alcoholysis reaction of benzylic halides under atmospheric pressure chemical ionization (APCI) conditions. The APCI corona discharge is used to initiate the novel reaction, which is monitored by ion trap mass spectrometry (IT-MS). The model compound α,α,α-trifluorotoluene is applied to observe the cascade methoxylation reaction during the +APCI-MS analysis, resulting in the formation of [PhC(OCH3)2]+. Based on the results of isotopic labeling and substrate expansion experiments, an addition-elimination mechanism is proposed: initially, the reaction was initiated by the dissociation of fluorine from PhCF3 under APCI condition, leading to the formation of [PhCF2]+; subsequently, two methanol molecules nucleophilicly attack [PhCF2]+ stepwisely, accompanied by the elimination of HF, yielding the product ion [PhC(OCH3)2]+. The proposed mechanism was further corroborated by theoretical calculations. The results of substrate scope expansion experiments suggest that this in-source reaction has the potential to differentiate the positional isomers of alcohols and phenols.

Separation, identification, and structural characterization of sucrose ester isomers from tobacco.

Sucrose esters (SEs) are crucial tobacco smoke flavor precursors and play a significant role in tobacco's functionality. Due to their structural complexity, the separation and analysis of SEs in tobacco remain a major challenge, and massive structures of SEs have not yet been fully identified. In this study, the fractions enriched in SEs were obtained from oriental and flue-cured tobacco through a series of pretreatments, and two types of SEs (Types I and II) were distinguished by liquid chromatography-tandem mass spectrometry (LC-MSn ) analysis, with Type II SEs newly characterized in tobacco. Five groups of main SEs were further purified using preparative high-performance LC (HPLC) coupled to an evaporative light scattering detector, and their structures were characterized by nuclear magnetic resonance spectrometry techniques including 1 H, 13 C, correlation spectroscopy, heteronuclear single quantum correlation, and heteronuclear multiple bond correlation. By combining LC-MSn and nuclear magnetic resonance spectrometry, the structures of eight SE isomers were finally proposed, of which four were newly identified. These findings further enhance the understanding of the structural diversity of SEs in tobacco, serving as a valuable reference for future research on the elucidation, synthesis, and metabolism of SEs.

Radical-Induced Dissociation for Oligonucleotide Sequencing by TiO2/ZnAl-Layered Double Oxide-Assisted Laser Desorption/Ionization Mass Spectrometry.

De novo sequencing of oligonucleotides remains challenging, especially for oligonucleotides with post-transcriptional or synthetic modifications. Mass spectrometry (MS) sequencing can reliably detect and locate all of the modification sites in oligonucleotides via m/z variance. However, current MS-based sequencing methods exhibit complex spectra and low ion abundance and usually require coupled instrumentation. Herein, we demonstrate a method of oligonucleotide sequencing using TiO2/ZnAl-layered double oxide (LDO)-assisted laser desorption/ionization (LDI)-MS based on radical-induced dissociation (RID). ·CH2OH radicals can be produced on the surface of a TiO2/ZnAl-LDO matrix via ultraviolet light, inducing an attack on the active site of the oligonucleotide phosphate skeleton to create typical "a-, a-B-, c·-, d-, w-, and y"-type fragments. Compared with the spectra obtained via collision-based methods, such as collision-induced dissociation and higher-energy collisional dissociation, the LDI-MS spectra based on RID exhibit single-charged signals, fewer types of fragments, and a lower proportion of unknown noise peaks. We demonstrate full sequence coverage for a 6-mer 2'-O-methyl-modified oligonucleotide and a 21-mer small interfering RNA and show that RID can sequence oligonucleotides with modifications. Importantly, the mechanism responsible for the RID of the oligonucleotide phosphate skeleton was investigated through offline experiments, demonstrating consistent results with density functional theory calculations.

Ultrasensitive and Green Bubbling Extraction Strategies: An Extensible Solvent-Free Re-Enrichment Approach for Ultratrace Pollutants in Aqueous Samples.

Ultratrace organic pollutants in the environment pose severe threats to human health; hence, their accurate detection is essential. In this study, we develop a secondary solvent-free enrichment strategy based on bubbling extraction (BE). Especially, we used BE solid-phase microextraction and BE carbon nanotube paper absorption to capture aerosols from a liquid water surface, desorb analytes, and analyze the analytes using mass spectrometry. The application of a solvent-free enrichment strategy helps overcome technical challenges in implementing BE technology, including reproducibility, quantification, and sensitivity. This approach objectively demonstrates the enrichment efficiency of BE, resulting in improved mass spectrometry response and quantification. It effectively tackles the difficulties in detecting and quantifying ultratrace environmental pollutants in mass spectrometric analysis. The present study successfully conducted a quantitative analysis of 16 polycyclic aromatic hydrocarbons and 7 antibiotics in 48 environmental water samples. This strategy proved effective in detecting the presence and distribution of polar and nonpolar environmental pollutants in rivers and lakes. Moreover, this strategy has several advantages, such as ultrahigh sensitivity at the femtograms per liter level, good greenness, multiplexed quantitation, low sample consumption, and ease of operation. Overall, the utilization of the ultrasensitive and environmentally friendly BE approach presents a reliable and adaptable method for the identification of ultratrace environmental pollutants in water specimens, thereby enabling early monitoring of pollutant levels.

A PdPt nanoparticle-decorated thiol-functionalized MOF with high peroxidase-like activity for colorimetric sensing of D-glucose and chlorophenol isomers.

The peroxidase (POD)-like catalytic activity of various nanozymes was extensively applied in many significant fields. In this study, a thiol-functionalized MOF-loaded PdPt nanocomposite (UiO-66-(SH)2@PdPt) was fabricated, which possesses superior and selective POD-like activity with strong affinity towards H2O2 and 3,3',5,5'-tetramethylbenzidine under mild conditions. The POD-like property of UiO-66-(SH)2@PdPt was used to sensitively detect the concentration of D-glucose under near-neutral (pH = 6.5) conditions. The detection limit of D-glucose was as low as 2.7 µM, and the linear range of D-glucose was 5-700 µM. In addition, UiO-66-(SH)2@PdPt could accelerate the oxidative coupling chromogenic reaction of chlorophenol (CP) and 4-aminoantipyrine (4-AAP) in the presence of H2O2. Based on this phenomenon, a simple and visualized sensing array for the identification of chlorophenol contaminant isomers was further constructed to finally achieve the effective differentiation of three monochlorophenol isomers and six dichlorophenol isomers. Furthermore, a colorimetric detection method for 2-chlorophenol and 2,4-dichlorophenol was established. This work provides an effective means to improve the catalytic activity and selectivity of nanozymes by introducing an ideal carrier, which will be of significant value for the design of efficient nanozymes.

Predictive Value of Endometrial Receptivity for Pregnancy Outcomes of In-vitro Fertilization Embryo Transfer for Patients of Different Ages.

Context: In recent years, the number of women with unexplained infertility has increased, and clinicians consider poor endometrial receptivity (ER) to be one of the main reasons. ER can have great predictive value for in-vitro fertilization embryo transfer (IVF-ET)-induced pregnancy. Objective: The study intended to investigate the predictive value of ER-endometrial thickness (EMT) and type and hemodynamic parameters-using color-doppler ultrasound on the pregnancy outcome of IVF-ET for women of different ages. Design: The research team performed a prospective controlled study. Setting: The study took place at the Department of Reproductive Medicine at Hebei Reproductive Hospital in Shijiazhuang, China. Participants: Participants were 841 infertile patients undergoing IVF-ET treatment at the hospital between March 01, 2018 and December 30, 2018. The research team divided participants into two groups: (1) participants diagnosed as having a clinical pregnancy after IVF-ET became the pregnancy group, with 439 participants, and (2) participants who didn't become pregnant became the nonpregnancy group, with 402 participants. Outcome Measures: The research team: (1) measured EMT, (2) determined endometrium types, (3) classified the intimal and subintimal blood flow, and (4) determined the hemodynamic parameters of the endometrium and subendometrium. The team also measured: (1) the systolic blood flow velocity (VS), (2) diastolic blood flow velocity (VD), and (3) average blood flow velocity (VM) three times and recorded the average value. Results: Statistically significant differences existed in the pregnancy and implantation rates among the different age groups for the groups with EMTs of <8 mm and 8-13 mm (P < .05). The results were similar in the endometrial Type A and endometrial Type B groups as well as between the endometrial blood flow Type 1 and Type 2 groups (P < .05). The distribution of endometrial blood flow types was significantly different between the groups (P = .002). In addition, statistically significant differences existed in the implantation rates between the <30 years and 30-34 groups in different blood-flow-type groups (P < .05). Based on the results of the ROC curve, high-quality embryos (0.566, 95%CI: 0.527-0.605) and endometrial blood flow types (0.554, 95%CI: 0.515-0.593) could not predict clinical pregnancy. Conclusions: The pregnancy and implantation rates increased between the <30 and 30-34 age groups and them decreased between the age groups as age increased. EMT, endometrial type, and blood flow type can be valuable parameters in predicting the implantation and pregnancy rates of patients of different ages.

Determination of Perfluorooctane Sulfonyl Fluoride and Perfluorohexane Sulfonyl Fluoride in Soil by Chemical Derivatization and Liquid Chromatography-Tandem Mass Spectrometry.

Perfluorooctane sulfonyl fluoride (PFOSF) and perfluorohexane sulfonyl fluoride (PFHxSF) were listed as persistent organic pollutants by the Stockholm Convention in 2009 and 2022, respectively. To date, their concentrations in environmental samples have not been reported due to the lack of sensitive methods. Herein, a novel chemical derivatization was developed for quantitative analysis of trace PFOSF and PFHxSF in soil by derivatizing them to the corresponding perfluoroalkane sulfinic acids. The method showed good linearity in the range from 25 to 500 ng L-1 with correlation coefficients (R2) better than 0.99. The detection limit of PFOSF in soil was 0.066 ng g-1 with recoveries in the range of 96-111%. Meanwhile, the detection limit of PFHxSF was 0.072 ng g-1 with recoveries in the range of 72-89%. Simultaneously, perfluorooctane sulfonic acid (PFOS) and perfluorohexane sulfonic acid (PFHxS) were also detected accurately without being affected by the derivative reaction. By applying this method in an abandoned fluorochemical manufacturing facility, PFOSF and PFHxSF were successfully detected at concentrations ranging from 2.7 to 357 ng g-1 and 0.23 to 26 ng g-1 dry weight, respectively. It is very interesting that 2 years after factory relocation, there still exists high concentrations of PFOSF and PFHxSF, which is of concern.

Catalyst-Free Oxidation Reactions in a Microwave Plasma Torch-Based Ion/Molecular Reactor: An Approach for Predicting the Atmospheric Oxidation of Pollutants.

The atmospheric oxidation of chemicals has produced many new unpredicted pollutants. A microwave plasma torch-based ion/molecular reactor (MPTIR) interfacing an online mass spectrometer has been developed for creating and monitoring rapid oxidation reactions. Oxygen in the air is activated by the plasma into highly reactive oxygen radicals, thereby achieving oxidation of thioethers, alcohols, and various environmental pollutants on a millisecond scale without the addition of external oxidants or catalysts (6 orders of magnitude faster than bulk). The direct and real-time oxidation products of polycyclic aromatic hydrocarbons and p-phenylenediamines from the MPTIR match those of the long-term multistep environmental oxidative process. Meanwhile, two unreported environmental compounds were identified with an MPTIR and measured in the actual water samples, which demonstrates the considerable significance of the proposed device for both predicting the environmental pollutants (non-target screening) and studying the mechanism of atmospheric oxidative processes.

Heat-Assisted Dual Neutral Spray Ionization for High-Performance Online Desalting in Mass Spectrometric Analysis.

In mass spectrometry (MS), nonvolatile salts contaminate the transmission system and cause ion suppression, hampering MS analysis. When MS is combined with liquid chromatography (LC) that uses a salty mobile phase, the problems become more intractable due to long analysis time. Here, a novel heat-assisted dual neutral spray ionization (HADSI) method was developed, which projected sample solution spray and solvent spray onto a heated plate to achieve online desalting and high ionization. The experimental parameters of HADSI were optimized, which indicated that the plate temperature was crucial for ionization and desalination. Eight drug compounds dissolved in various commonly used buffers were directly analyzed using HADSI-MS, even though the concentration of PBS buffer reached 500 mmol/L. The established method showed considerable sensitivity in the positive ion mode with the limits of detection at the level of nmol/L, and good linearity (R2 > 0.99) was achieved for all the analyzed compounds. The repeatability and intra- and interday precisions of the method were evaluated, demonstrating the feasibility and reliability of the analysis of salty samples by HADSI-MS. Further, the method was demonstrated to tolerate the long-time analysis of high-salt LC eluates and the device was easy to maintain. Finally, a crude roxithromycin product was separated by LC and then analyzed by HADSI-MS, and seven unknown impurities and nine known impurities were successfully detected. Our results indicated that HADSI-MS may have potential applications in academic and industrial fields.

Toxic arsenic in marketed aquatic products from coastal cities in China: Occurrence, human dietary exposure risk, and coexposure risk with mercury and selenium.

To improve the accuracy of dietary risk assessment of arsenic (As) from aquatic products, toxic As species (As(III), As(V), monomethylarsonic acid [MMA], and dimethylarsinic acid [DMA]) and total As were analyzed in 124 marketed aquatic products from eight coastal cities in China. Distribution characteristics of Toxic As (the sum of the four toxic As species) in the samples and associated risk of human dietary exposure were emphatically investigated. The impact of cooccurrence of As and other chemical elements in the aquatic products was assessed based on our former results of mercury (Hg) and selenium (Se). Toxic As contents (maximum value 0.358 mg kg-1 wet weight) in the samples accounted for at most 14.1% of total As. DMA was the major component (mean proportion 50.8% for shellfish, 100% for fish) of Toxic As in aquatic products. Shellfish contained more Toxic As than fish did. Mean estimated daily intakes of Toxic As for the residents with aquatic product consumption rates of 46.1-235 g day-1 ranged from 0.034 to 0.290 µg kg-1 day-1. Potential health risk was indicated among those who greatly consumed aquatic products, as their target hazard quotient (THQ) and target cancer risk (TR) values exceeded safety thresholds (1 for THQ, 10-4 for TR). DMA and MMA exposure contributed to 3.42-7.72% of the THQToxic As. Positive correlations between concentrations of As and Hg (Fish: r = 0.47, p < 0.01; Shellfish: r = 0.60, p < 0.01), as well as between that of As and Se (Fish: r = 0.69, p < 0.01; Shellfish: r = 0.37, p < 0.01) were found in the samples. It requires attentions urgently that As and Hg coexposure through aquatic product consumption rose the sum THQ of Toxic As and methylmercury (MeHg) to approximately two to eight times as high as the THQToxic As.

In situ localization of tris(2,3-dibromopropyl) isocyanurate in mouse organs by MALDI-IMS with auxiliary matrix strategy.

Tris(2,3-dibromopropyl) isocyanurate (TBC) is one of the novel brominated flame retardants that has been widely used in consumer goods. Humans may be exposed to TBC daily. Studies showed that TBC can induce significant toxicity. However, there is currently no report on its in situ localization in organs. In this study, we aimed to develop a reliable and reproductive method to determine the in situ localization of TBC in mouse organs by matrix-assisted laser desorption/ionization imaging mass spectrometry (MALDI-IMS). As commercially available matrices were not able to detect TBC in tissue section, we then developed a novel MALDI-IMS method based on 1,5-diaminonaphthalene hydrochloride and silver trifluoromethanesulfonate (NDA/AgOTf) as the matrix for the in situ localization of TBC. AgOTf used as the auxiliary matrix in the negative-ion mode showed an excellent MS signal of TBC. The detection limit of [2AgOTf + Br]- was at the µg/mL level. The developed MALDI-IMS method was successfully employed to obtain the TBC spatial distribution in the mouse organs collected from mice exposed to 160 mg/kg/day of TBC for 30 days. High-pressure liquid chromatography-tandem mass spectroscopy (HPLC-MS/MS) was also used to evaluate the accumulation of TBC in liver, kidney, heart, and brain. The combination of MALDI-IMS and HPLC-MS/MS showed that TBC can accumulate in mice organs and it is mainly distributed in the renal parenchyma. In summary, an innovative method was developed for the analysis of TBC spatial distribution by MALDI-IMS using a novel NDA/AgOTf matrix, extending the application of MALDI-IMS in environmental pollutants.

Ambient electric arc ionization for versatile sample analysis using mass spectrometry.

A novel, convenient ambient electric arc ionization (AEAI) device was developed as a mass spectrometry ion source for versatile sample analysis. AEAI could be considered as a soft ionization technique in which the protonated ion ([M + H]+) is the main ion species with little or no in-source fragmentation for most analytes. Coupled with a high-resolution Orbitrap mass spectrometer, AEAI could be applied to the analysis of a variety of organic compounds having a wide range of polarities, ranging from non-polar species such as polybenzenoid aromatic hydrocarbons (PAHs) to highly polar species such as amino acids. With its versatile capabilities in the mass spectrometric analysis of small molecules, AEAI has the potential to be an alternative to traditional ionization methods such as electrospray ionization (ESI), atmospheric pressure chemical ionization (APCI), and electron impact (EI) ionization. The limitations of AEAI are also discussed.

Occurrence and spatial distribution of legacy and novel brominated flame retardants in seawater and sediment of the South China sea.

The occurrence and spatial distribution of polybrominated diphenyl ethers (PBDEs) and novel brominated flame retardants (NBFRs) in seawater and surficial sediment samples (N = 19 and 45, respectively) from the South China Sea (SCS) in 2018 were investigated, and the correlation between BFRs and site parameters (total organic carbon, depth, etc.) were assessed by principal component analysis. The concentration ranges of ΣPBDEs in seawater and sediments were 0.90-4.40 ng/L and 0.52-22.67 ng/g dry weight (dw), respectively, while those of ΣNBFRs were 0.49-37.42 ng/L and 0.78-82.29 ng/g dw, respectively. BDE-209 and decabromodiphenyl ethane were the predominant BFRs, accounting for 38.65% and 36.94% in seawater and 26.71% and 68.42% in sediments, respectively. Notably, tris(2,3-dibromopropyl)isocyanurate and 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine, seldomly detected in aquatic matrices worldwide, were detected for the first time in the study area, and their relatively high levels and detection frequencies indicate the ubiquitous application of these NBFRs in the Pearl River Delta. Zhuhai and Jiangmen are the main sources of NBFRs in the SCS. Preliminary risk assessment on NBFRs using hazard quotient indicates low to medium risks to marine organisms at some sites. The occurrence of NBFRs in the SCS highlights the prioritization of more toxicological information on these compounds.

Evaluation of the Estrogenic/Antiestrogenic Activities of Perfluoroalkyl Substances and Their Interactions with the Human Estrogen Receptor by Combining In Vitro Assays and In Silico Modeling.

The potential estrogenic activities of perfluoroalkyl substances (PFASs) are controversial. Here, we investigated the estrogenic/antiestrogenic activities of PFASs and explored the corresponding interaction mode of PFASs with the estrogen receptor (ER) by combining in vitro assays and in silico modeling. We found that three PFASs (perfluorobutanoic acid, perfluorobutane sulfonate, and perfluoropentanoic acid) exerted antiestrogenic effects by inhibiting luciferase activity, whereas perfluorohexane sulfonate (PFHxS) and perfluorooctane sulfonate (PFOS) exerted estrogenic effects by inducing luciferase activity. When coexposed to 17ß-estradiol (E2), all tested PFASs attenuated the E2-stimulated luciferase activity; unexpectedly, each PFAS could further attenuate the luciferase activity generated by the cotreatment with ICI 182,780 and E2, with a minimal effective concentration comparable to that found in human serum. PFHxS and PFOS significantly induced the gene expression of TFF1; additionally, all PFASs inhibited the E2-induced gene expression of TFF1 and EGR3. Furthermore, the results of the blind docking analyses suggested that the interaction with the coactivator-binding region on the ER surface should be included as a pathway through which PFASs exert estrogenic and antiestrogenic activities. Finally, we revealed the critical molecular property of the zero-order molecular connectivity index (MCI) (0χ) that affects the antiestrogenic activity of PFASs.

Total mercury, methylmercury, and selenium in aquatic products from coastal cities of China: Distribution characteristics and risk assessment.

This study analyzed total mercury (THg), methylmercury (MeHg) and selenium (Se) in 114 aquatic product samples (representing 39 species) from eight coastal cities of China. The THg and MeHg levels in different parts of the same sample species were in the order of muscle ≥ skin/shell > roe, whereas Se levels were much higher in roe. Concentrations of THg, MeHg, and Se in the muscles were between 2.27-154, 0.36-135, and 57.8-1.20 × 103 ng g-1 wet weight (ww), respectively. Although significant differences in analyte concentrations were not observed among cities, they existed among three species; marine fish, freshwater fish, and shellfish. Shellfish had generally lower Hg content (mean: 20.2 ng g-1 ww THg, 6.71 ng g-1 ww MeHg, and 30.9% MeHg/THg ratio); however it had higher Se content (528 ng g-1 ww) than the other types of fish (mean: 33.3 ng g-1 ww THg, 28.2 ng g-1 ww MeHg, and 79.2% MeHg/THg ratio, 257 ng g-1 ww Se). In addition to species, the individual growth and HgSe interaction influenced Hg distribution. Evident correlations were observed between several individual body features and Hg content, and between Se and THg concentrations (p < 0.05). The greater correlation coefficient between two elements for fish indicated stronger HgSe antagonism through HgSe compound formation in fish. Relatively low THg daily intakes (mean 0.013-0.080 µg kg-1 day-1) and MeHg daily intakes (0.006-0.065 µg kg-1 day-1) along with Se:Hg molar ratios >1 and positive HBVSe values suggest that aquatic products from these sites will not pose immediate health problems to consumers. Fish was the dominating contributor for MeHg intake whereas shellfish was the dominating contributor for Se intake. To safeguard against mercury exposure, residents in these areas can appropriately increase shellfish intake (especially bivalves), rather than exclusively consuming marine fish.

Estrogenic activity of benzotriazole UV stabilizers evaluated through in vitro assays and computational studies.

Benzotriazole UV stabilizers (BUVs) are used in a variety of products to prevent yellowing and degradation. However, knowledge of the estrogenic activity of BUVs is still lacking. In the present study, a strategy combining in vitro assays and computational studies was adopted to evaluate the estrogenic activity of BUVs. 2-(2-Hydroxy-5-methlphenyl) benzotriazole (UV-P), 2-(5-tert-butyl-2-hydroxyphenyl)benzotriazole (UV-PS), and 2-(3-Allyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole (UV-9) induced partial estrogenic activity while 2-(2-hydroxy-5-tert-octyl-phenyl)benzotriazole (UV-329), 2-(3-s-butyl-5-tert-butyl-2-hydroxyphenyl)benzotriazole (UV-350), and 3-(2H-benzotriazolyl)-5- (1,1-di-methylethyl)-4-hydroxy-benzene-propanoic acid octyl esters (UV-384) showed no estrogenic activity in MVLN assays. The results of in vitro assays were in accord with the results of computational studies. Moreover, ICI 182,780 suppressed the estrogenic activity of BUVs both in the absence and presence of E2, demonstrating that the estrogen responsive element (ERE) transcription activities of BUVs are generated through an estrogen receptor (ER) mediated pathway. Our findings suggest that the endocrine disruption effects of BUVs are a cause for concern.