Ferrate(VI) assists in reducing cytotoxicity and genotoxicity to mammalian cells and organic bromine formation in ozonated wastewater.

Ozonation of wastewater containing bromide (Br-) forms highly toxic organic bromine. The effectiveness of ozonation in mitigating wastewater toxicity is minimal. Simultaneous application of ozone (O3) (5 mg/L) and ferrate(VI) (Fe(VI)) (10 mg-Fe/L) reduced cytotoxicity and genotoxicity towards mammalian cells by 39.8% and 71.1% (pH 7.0), respectively, when the wastewater has low levels of Br-. This enhanced reduction in toxicity can be attributed to increased production of reactive iron species Fe(IV)/Fe(V) and reactive oxygen species (•OH) that possess higher oxidizing ability. When wastewater contains 2 mg/L Br-, ozonation increased cytotoxicity and genotoxicity by 168%-180% and 150%-155%, respectively, primarily due to the formation of organic bromine. However, O3/Fe(VI) significantly (p < 0.05) suppressed both total organic bromine (TOBr), BrO3-, as well as their associated toxicity. Electron donating capacity (EDC) measurement and precursor inference using Orbitrap ultra-high resolution mass spectrometry found that Fe(IV)/Fe(V) and •OH enhanced EDC removal from precursors present in wastewater, inhibiting electrophilic substitution and electrophilic addition reactions that lead to organic bromine formation. Additionally, HOBr quenched by self-decomposition-produced H2O2 from Fe(VI) also inhibits TOBr formation along with its associated toxicity. The adsorption of Fe(III) flocs resulting from Fe(VI) decomposition contributes only minimally to reducing toxicity. Compared to ozonation alone, integration of Fe(VI) with O3 offers improved safety for treating wastewater with varying concentrations of Br-.

Comparative molecular transformations of dissolved organic matter induced by chlorination and ammonia/chlorine oxidation process.

The ammonia/chlorine oxidation process can greatly degrade PPCPs in water. However, its effect on molecular transformations of natural organic matter (NOM) and effluent organic matter (EfOM) are still poorly understood. In this study, molecular transformations of NOM and EfOM occurring during ammonia/chlorine were explored and compared with those occurred during chlorination, using spectroscopy and mass spectrometry. Phenolic and highly unsaturated aliphatic compounds together with aliphatic compounds were found to be predominant in both NOM and EfOM samples, all of which were significantly degraded after two processes. The ammonia/chlorine process led to greater decreases in the molecular weights of such components but lower reductions in aromaticity. Compared with chlorination, ammonia/chlorine was found to be more likely to degrade compounds while remaining fluorophores or chromophores. The CH(N)O(S) precursors were found to be similar for both processes but their products were quite different. The CH(N)O(S) precursors that only found in ammonia/chlorine had higher molecular weights and greater degrees of oxidation but lower degrees of saturation. In contrast, the unique CH(N)O(S) products that only found in ammonia/chlorine exhibited lower molecular weights and lower degrees of oxidation degrees together with higher degrees of saturation. Lower total abundance of chlorinated byproducts was found by ammonia/chlorine compared with chlorination, although the former process provided a richer diversity. In all water samples, chlorinated byproducts were mainly generated by substitution reactions during ammonia/chlorine and chlorination. Overall, the findings of this study could provide new insights into the transformations of NOM and EfOM induced by ammonia/chlorine and chlorination.

Effects of dysregulated glucose metabolism on the occurrence and ART outcome of endometriosis.

BACKGROUND: Endometriosis is associated with systemic metabolic indicators, including body mass index (BMI), glucose metabolism and lipid metabolism, while the association between metabolic indexes and the occurrence and assisted reproductive technology (ART) outcome of endometriosis is unclear. We aimed to evaluate the characteristics of systemic metabolic indexes of endometriosis patients with infertility and their effects on pregnancy outcome after ART treatment. METHODS: A retrospective cohort study involve 412 endometriosis patients and 1551 controls was conducted. Primary outcome was metabolic indexes, and secondary measures consisted of the influence of metabolic indexes on the number of retrieved oocytes and ART outcomes. RESULTS: Endometriosis patients had higher insulin (INS) [6.90(5.10-9.50) vs 6.50(4.80-8.90) µU/mL, P = 0.005]. A prediction model for endometriosis combining the number of previous pregnancies, CA125, fasting blood glucose (Glu) and INS, had a sensitivity of 73.9%, specificity of 67.8% and area under curve (AUC) of 0.77. There were no significant differences in ART outcomes and complications during pregnancy. The serum levels of Glu before pregnancy were associated with GDM both in endometriosis group (aOR 12.95, 95% CI 1.69-99.42, P = 0.014) and in control group (aOR 4.15, 95% CI 1.50-11.53, P = 0.006). CONCLUSIONS: We found serum Glu is related to the number of retrieved oocytes in control group, serum INS is related to the number of retrieved oocytes in endometriosis group, while serum Glu and INS before pregnancy are related to the occurrence of GDM in two groups. A prediction model based on metabolic indexes was established, representing a promising non-invasive method to predict endometriosis patients with known pregnancy history.

Seven diterpenoids from the resin of Pinus yunnanensis Franch and their anti-inflammatory activity.

Phytochemical investigation of the 95% ethanol extract from Pinus yunnanensis Franch resin induced the isolation of six previously unreported diterpenoids pinuyunnanacids K - N, P - Q, a nor-diterpenoid with a novel skeleton pinuyunnanacid O and six known analogues. Their structures were elucidated by spectroscopic analysis and computational methods, including nuclear magnetic resonance (NMR) spectroscopy, mass spectrometry, calculated NMR chemical shifts method and electronic circular dichroic (ECD) spectra. All the compounds were analyzed for anti-inflammatory activity through western blotting and cell viability, compounds 2, 10 and 12 significantly downregulated the protein expression of iNOS at the concentration of 40 µM. At the same time, compounds 10 and 12 decreased the expression of COX-2 in LPS-treated RAW264.7 (leukemia cells in mouse macrophage) cells at the concentration of 40 µM.

Diverse undescribed compounds from the rhizome of Zingiber officinale Rosc. And their anti-inflammatory activity.

Seven undescribed compounds, including a sesquiterpenoid derivative, a γ-lactone, four gingerols, and a dihydroferulic acid lactate were isolated from the rhizome of Zingiber officinale, and named gingerterpenoid G, gingerlactone A, zingibergingerols A-D and L-dihydroferulic acid lactate, respectively. Zingibergingerols (±)-B and (±)-C were two pairs of enantiomers. The structures of all compounds were determined by 1D-NMR, 2D-NMR and mass spectrometry. The absolute configurations were determined by comparison of the experimental and theoretically calculated ECD curves or X-ray single-crystal diffraction. Bioassay showed that gingerterpenoid G, gingerlactone A, and zingibergingerols A and B exhibited significant anti-inflammatory activity in the model of LPS-induced RAW 264.7 cells.

Benign but fatal: management of endotracheal Rosai-Dorfman disease with acute onset.

Rosai-Dorfman disease (RDD) is a non-malignant condition mainly manifesting as a proliferation of histiocytes in lymph nodes. Endotracheal RDD (ERDD) with an acute onset presentation is extremely rare. There are few case reports of ERDD mainly concerning its pathology, diagnostics and bronchoscopic treatment, without providing sufficient clinical information from a comprehensive perspective. As a novel and challenging technique, tracheal resection and reconstruction (TRR) with spontaneous-ventilation video-assisted thoracoscopic surgery (SV-VATS) has been reported as feasible and safe in highly selected patients, but few centres have shared their experience with this approach. This case-based discussion includes not only practical issues in the management of a life-threatening ERDD patient, but also specialists' views on the management of acute obstructive airway, and the surgeons' reflection on TRR with SV-VATS.

Five new compounds from Zingiberis Rhizoma Recens and their anti-apoptotic activity.

Five new compounds, named gingerol A (1a and 1b), gingerol B (2), diphenylheptane glycoside A (3) and diphenylheptane glycoside B (4), were isolated from the acetone extract of Zingiberis Rhizoma Recens. The structures of new compounds were elucidated on the basis of spectroscopic methods including UV, IR, 1D NMR, 2D NMR and HR-ESI-MS. Compounds 2-4 could significantly decrease the apoptosis rate and increase the survival rate of human normal lung epithelial cells (BEAS-2B) at the concentration of 10 µM.

Diterpenes from Pinus kesiya var. langbianensis (A.Chev.) Gaussen ex Bui (Pinaceae) and their protective effects in LPS-treated BEAS-2B cells.

Eight previously undescribed diterpenoids, rosins A-H, and nine known diterpenoids were isolated from the resin from Pinus kesiya var. langbianensis (A.Chev.) Gaussen ex Bui (Pinaceae) extracted with 95% ethanol. Their structures were determined by nuclear magnetic resonance spectroscopy, mass spectrometry, J-based configuration analysis (JBCA), NOESY spectra, calculated NMR chemical shifts and electronic circular dichroic (ECD) spectra. All compounds were evaluated for their protective effects in LPS-treated human normal lung epithelial cells (BEAS-2B), and the cell viability was significantly increased after treatment with compounds 5, 10, 12, or 15 at a concentration of 10 µM.

Effects of chlorine dose on the composition and characteristics of chlorinated disinfection byproducts in reclaimed water.

During chlorination of reclaimed water, the dose of chlorine used can influence the formation of chlorinated disinfection by-products (Cl-DBPs). We used non-targeted screening by Orbitrap mass spectrometry to identify Cl-DBPs in samples of chlorinated reclaimed water, and found that chlorination was likely to form slightly oxidized unsaturated aliphatic compounds and polycyclic aromatic compounds. Increasing the chlorine dose increased the proportion of polycyclic aromatic Cl-DBPs containing one chlorine atom (Cl1-DBPs) and highly oxidized unsaturated aliphatic Cl-DBPs containing two chlorine atoms (Cl2-DBPs). In addition, increasing the chlorine dose first decreased and then increased the proportion of Cl1-DBPs with aromatic index values >0.5 and increased the proportion of Cl2-DBPs with aromatic index values <0.5. Increasing the chlorine dose increased double bond equivalent minus oxygen values of Cl1-DBPs and decreased the double bond equivalent minus oxygen values of Cl2-DBPs, while the nominal oxidant state of carbon decreased for Cl1-DBPs and increased for Cl2-DBPs. In considering the possible precursors of Cl-DBPs and their reaction pathways, substitution reactions occurred more readily with aliphatic compounds and addition reactions occurred more readily with aromatic precursors. When the chlorine dose is increased, more Cl2-DBPs may be formed by substitution. Overall, the chlorine dose influences Cl-DBP formation and composition and should be taken into account during water treatment.

Novel chlorinated disinfection byproducts from tannic acid: nontargeted identification, formation pathways, and computationally predicted toxicity.

Tannic acid is ubiquitously present in various simulated and real water sources and in wastewater. Various chlorinated disinfection byproducts (Cl-DBPs) are generated via reactions with tannic acid during disinfection with chlorine. We used high-resolution mass spectrometry in combination with our self-developed halogen extraction code to selectively identify Cl-DBPs. Our strategy enabled successful detection of 35 Cl-DBP formulas formed by chlorination of tannic acid, and we identified 26 of these structures. The structures of 17 novel Cl-DBPs are firstly reported here. The reaction pathways of these Cl-DBPs were tentatively proposed. These Cl-DBPs are likely to be generated during chlorination at various chlorine doses, from 0.0 to 10.0 mg-Cl2/L, and 14 of the 26 Cl-DBPs were detected in simulated drinking water, which implies a relatively high probability of incidence. Quantitative structure-activity relationship toxicity analyses predicted that most of these Cl-DBPs would exhibit much higher acute toxicity than the common DBPs trichloromethane and monochloroacetic acid and that some of these compounds would induce developmental toxicity and be mutagenic, which further emphasizes that these Cl-DBPs should raise concerns. This study broadens our understanding of the Cl-DBPs formed from tannic acid and should prompt wider application of our analytical strategy in environmental matrices.

Diarylheptanoid glycosides from Zingiber officinale peel and their anti-apoptotic activity.

Four new diarylheptanoid glycosides (1-4), (1S,3R,5S)-2-(4-hydroxy-3- methoxyphenyl)-6-[2-(4-hydroxyphenyl)ethyl]-tetrahydropyran-4-ol-4'-O-ß-D-glucopyranoside (1), (1S,3R,5S)-2-(4,5-dihydroxy-3-methoxyphenyl)-6-[2-(4-hydroxyphenyl) ethyl]-tetrahydropyran-4-ol-4'-O-ß-D-glucopyranoside (2), (1S,3R,5S)-2-(4-hydroxy- 3,5-dimethoxyphenyl)-6-[2-(4-hydroxy-3-methoxyphenyl)ethyl]-tetrahydropyran-4-ol-4'-O-ß-D-glucopyranoside (3), and (1R,3R,5R)-2-(4-hydroxy-3,5-dimethoxyphenyl)- 6-[2-(4-hydroxy-3-methoxyphenyl)ethyl]-tetrahydropyran-4-ol-3-O-ß-D-glucopyranoside (4) were isolated from the 50% ethanol extract of Zingiber officinale peel. The structures of the isolated compounds were determined by HR-ESI-MS and extensive spectroscopic techniques (UV, IR, 1D-NMR, and 2D-NMR). Compounds 1-4 significantly increased the survival rate of human normal lung bronchial epithelial cells (BEAS-2B) induced by lipopolysaccharide (LPS) at the concentration of 10 µM.

[A new monoterpene ester from Zingiberis Rhizoma Recens].

Five monoterpenoid compounds(1-5) were isolated and purified from the acetone fraction of the aqueous extract of Zingiberis Rhizoma Recens by MCI, Sephadex LH-20, silica gel, semi-preparative HPLC, and TLC. Their structures were identified with multiple spectroscopical methods including 1 D-NMR, 2 D-NMR, and MS. The five compounds were identified as(2E,6Z)-8-hydroxy-2,6-dimethylocta-2,6-dien-1-yl-(E)-3-(4-hydroxy-3-methoxyphenyl) acrylate(1),(2E,6E)-8-hydroxy-3,7-dimethylocta-2,6-die-noic acid(2),(E)-1,8-dihydroxy-3,7-dimethyl-2-octenoic acid(3), linalyl-ß-D-glucopyranoside(4), and ß-D-glucopyranoside-(2E)-3,7-dimethyl-2,6-octadien-1-yl(5), respectively.Compound 1 was a new monoterpene ester, and compounds 4-5 were isolated from this plant for the first time.

Nontargeted identification of chlorinated disinfection byproducts formed from natural organic matter using Orbitrap mass spectrometry and a halogen extraction code.

Natural organic matter is a major source of precursors of hazardous chlorinated disinfection byproducts (Cl-DBPs) formed during water treatment, but the majority of Cl-DBPs are still unidentified. In this study, we used a self-written halogen extraction code to identify halogen isotopic patterns in combination with the R package MFAssignR, to identify Cl-DBPs from Orbitrap mass spectra. One hundred and eighty-nine Cl-DBPs were detected during chlorination of a Suwannee River natural organic matter solution, and the structures of 20 of these compounds are reported for the first time. Kendrick mass defect analysis and structural identification confirmed that chlorinated carboxylic acids are common and likely to form during chlorination. A toxicity prediction using quantitative structure-activity relationship models indicated that most of the chlorinated carboxylic acids may be highly toxic. Our analytical strategy can identify Cl-DBPs accurately from complex mixtures and may also be applicable to the identification of other halogenated disinfection byproducts formed during water treatment.

Toxicity of Ozonated Wastewater to HepG2 Cells: Taking Full Account of Nonvolatile, Volatile, and Inorganic Byproducts.

Wastewater ozonation forms various toxic byproducts, such as aldehydes, bromate, and organic bromine. However, there is currently no clear understanding of the overall toxicity changes in ozonated wastewater because pretreatment with solid phase extraction cannot retain inorganic bromate and volatile aldehydes, yet contributions of known ozonation byproducts to toxicity are unknown. Moreover, compared with bromate, organic bromine did not receive widespread attention. This study evaluated the toxicity of ozonated wastewater by taking aldehydes, bromate, and organic bromine into consideration. In the absence of bromide, formaldehyde contributed 96-97% cytotoxicity and 92-95% genotoxicity to HepG2 cells among the detected known byproducts, while acetaldehyde, propionaldehyde, and glyoxal had little toxicity. Both formaldehyde and dibromoacetonitrile drove toxicity among the known byproducts when bromide was present. Toxicity assays in HepG2 cells showed that when secondary effluents contained no bromide, the cytotoxicity of the nonvolatile organic fraction (NVOF) was reduced by 56-70%, and genotoxicity was completely removed after ozonation. However, the formed aldehydes (volatile organic fraction, VOF) led to increased overall toxicity. In the presence of bromide, compared with the secondary effluent, ozonation increased the cytotoxicity of the NVOFBr from 3.4-4.0 mg phenol/L to 10.3-13.9 mg phenol/L, possibly due to the formation of organic bromine. In addition, considering the toxicity of VOFBr (VOF in the presence of bromide, including aldehydes, tribromomethane, etc.), the overall cytotoxicity and genotoxicity became much higher than those of the secondary effluent. Although bromate had a limited impact on cytotoxicity and genotoxicity, it caused an increase in oxidative stress in HepG2 cells. Therefore, when taking full account of nonvolatile, volatile, and inorganic fractions, ozonation generally increases the toxicity of wastewater.

Combining high resolution mass spectrometry with a halogen extraction code to characterize and identify brominated disinfection byproducts formed during ozonation.

Ozonation is widely used during water treatment but can generate a variety of toxic disinfection byproducts, especially in the presence of bromide. In the present study, our halogen extraction code was extended and modified to identify bromine isotopic patterns and combined with the R package MFAssignR in selectively identifying brominated disinfection byproducts (Br-DBPs) from high resolution mass spectra. In total, 127 Br-DBPs formed from a Suwannee River natural organic matter (SRNOM) solution were successfully detected from tens of thousands of mass spectrometry peaks. Kendrick mass defect analysis and structural characterization identified 17 structures, 15 of which were identified as brominated carboxylic acids and firstly reported here. Computational model predictions indicated that these brominated carboxylic acids may possess high toxic potencies and raise valid concerns. The adapted halogen extraction code described in this study is a powerful tool for a wider application of analyzing Br-DBPs in complex water matrices and provides an effective technique to characterize and identify these compounds in future studies.

Tracing nitrogenous byproducts during ozonation in the presence of bromide and ammonia using stable isotope labeling and high resolution mass spectrometry.

Ammonia has been widely used to inhibit bromate formation during ozonation. However, our recent study found that during ozonation in the presence of bromide and ammonia, toxicity increased under certain conditions that might be attributed to the formation of nitrogenous byproducts. Herein, a typical structural moiety of natural organic matter (NOM), hydroquinone, was evaluated for its potential to form nitrogenous byproducts. During ozonation of the hydroquinone solution containing bromide and ammonia, toxicity of organic byproducts increased significantly. As organic bromine was hardly detected, organic nitrogen was responsible for the increased toxicity. An effective method combining ultra-performance liquid chromatography in tandem with high resolution mass spectrometry (UPLC-HRMS) with an isotope labeling strategy was used to trace nitrogenous byproducts. Four newly formed nitrogenous byproducts were detected, two of which were also detected in Suwannee River natural organic matter (SRNOM) solution treated under the same ozonation condition. Furthermore, the molecular structures and formation pathways of these nitrogenous byproducts were proposed. This study highlights that, despite the widespread use, adding ammonia to inhibit bromate formation during ozonation might increase the toxicity posed by nitrogenous byproducts. During ozonation in the presence of bromide and ammonia, particular attention should be paid to nitrogenous byproducts.

Qualitative analysis on chemical constituents from different polarity extracted fractions of the pulp and peel of ginger rhizomes by ultra-high-performance liquid chromatography coupled with electrospray ionization quadrupole time-of-flight tandem mass spectrometry.

RATIONALE: Ginger pulp is the dried rhizome scraped off the skin which originates from Zingiber officinale Rosc., a Zingiberaceae plant. Ginger peel is the dried rhizome skin of Zingiber officinale Rosc. (Zingiberaceae). The present work aims to investigate the different chemical constituents that are related to the medicinal properties of the ginger pulp and ginger peel. METHODS: A rapid ultra-high-performance liquid chromatography/electrospray ionization quadrupole time-of-flight tandem mass spectrometry (UHPLC/ESI-QTOF/MS) method was developed for qualitative analysis of the constituents in different polarity extracted fractions of the pulp and peel of ginger rhizomes. RESULTS: A total of 83 compounds were identified from the pulp and peel of ginger rhizomes, including 36 diarylheptanoids, 25 gingerols and 22 other compounds. Nine of these were new compounds. In total, 46, 27, 65 and 51 compounds were identified from the crude extract, petroleum ether, ethyl acetate, and n-butanol fractions of the ginger pulp, respectively, and 60, 30, 70 and 62 compounds were identified from the crude extract, petroleum ether, ethyl acetate, n-butanol fractions of the ginger peel, respectively. Each identified compound is marked on the corresponding chromatogram. CONCLUSIONS: The integrated method is sensitive and reliable for searching the different chemical constituents from different polarity extracted fractions of the ginger pulp and ginger peel. This work may provide a significant contribution to research into the medicinal properties of the ginger pulp and ginger peel.

Surrogates for on-line monitoring of the attenuation of trace organic contaminants during advanced oxidation processes for water reuse.

The large number of trace organic contaminants (TrOCs) in wastewater has resulted in severe concerns to human health. Ozonation and UV/H2O2 are widely used to remove TrOCs in wastewater treatment process. Owing to the trace concentrations of TrOCs in wastewater, real-time monitoring of the abatement efficiency of TrOCs through ozonation and UV/H2O2 is quite challenging. Instead of a direct measurement of all the TrOCs, the research community has begun to use different surrogates to monitor the attenuation of TrOCs during AOPs. Various surrogates have been developed over the past few decades. In this review, the different types of surrogates are summarized, including ultraviolet spectroscopy and fluorescence spectroscopy. Strong linear correlations have been found for the removal of TrOCs using AOPs, and the abatement of UV absorption spectroscopy at 254 nm or total fluorescence (TF). Moreover, a two-phase linear correlation can better describe the ozone-resistant TrOCs compared with a single linear correlation. Two different kinds of predictive models exist that use surrogates as the input for ozonation: the regression model and kinetic model. The development of the models requires a further understanding of the impacts of water quality, seasonal variations, and storm events on the kinetic parameters. For the in situ monitoring system, the light-emitting diode (LED) is one of the most promising light sources, although the sensitivity and accuracy still need to be improved.

Combination of high resolution mass spectrometry and a halogen extraction code to identify chlorinated disinfection byproducts formed from aromatic amino acids.

Chlorination can lead to the formation of hazardous chlorinated disinfection byproducts (Cl-DBPs). We identified tyrosine (Tyr) and tryptophan (Trp) as precursors of toxic Cl-DBPs and developed a halogen extraction code to complement ultra performance liquid chromatography in tandem with high resolution mass spectrometry (UPLC-HRMS) in detecting and identifying Cl-DBPs. We detected 20 and 11 Cl-DBPs formed from chlorination of Tyr and Trp, respectively, and identified the structures of 15 Cl-DBPs. Fourteen structures were previously unreported. We also proposed the tentative formation pathways of these newly identified Cl-DBPs. Their incidence in real water sources demonstrated that these Cl-DBPs are likely to form during chlorination of reclaimed water. We computationally predicted the toxicity of these Cl-DBPs, which was relatively high, indicating that these Cl-DBPs could be hazardous and were of valid concern. Combining analytical data with the halogen extraction code can identify Cl-DBPs accurately from complex compounds. This analytical method can be used to identify Cl-DBPs of water treatment procedures in further studies.

Catalytic asymmetric inverse electron demand Diels-Alder reaction of fulvenes with azoalkenes.

An unprecedented copper(i)-catalyzed asymmetric inverse electron demand Diels-Alder reaction of azoalkenes with fulvenes is reported. This methodology offers a directed entry to synthesize bicyclic tetrapyridazine derivatives in good yield with exclusive regioselectivity and excellent stereoselectivity.