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The ovarian reserve determines the success of in vitro fertilization (IVF) and embryo transfer treatment. It predicts the ovarian response in controlled ovarian hyperstimulation cycles. Apoptosis in granulosa cells surrounding oocytes is important for ovarian function and has been closely associated with follicular atresia. PTEN (encoding phosphatase and tensin homolog) is a well-known tumor suppressor gene that functions as a mediator of apoptosis and is crucial for mammal reproduction. In the present study, we analyzed the expression level of PTEN in human granulosa cells and aimed to investigate its association with the ovarian response and clinical outcomes in IVF. Apoptosis in granulosa cells were analyzed using Annexin V-Allophycocyanin staining after PTEN short hairpin RNA lentivirus transfection. Real-time fluorescent quantitative PCR analysis showed that the PTEN transcript level was significantly higher in poor responders and significantly lower in high responders, compared with that in normal responders. However, PTEN expression in the pregnancy group decreased slightly, but not significantly, compared with that in the non-pregnancy group. The apoptosis rate of granulosa cells declined significantly after 24-h transfection of the PTEN-shRNA lentivirus. These results suggest a fundamental role of PTEN in the regulation of follicular development, and that it might be involved in the pathogenesis of follicular dysplasia and ovarian dysfunction. [ABSTRACT FROM AUTHOR]

[Display omitted] • ZIFs-based materials are efficient for ECR due to their compositional and structural merits. • Ligand adjusting and physical regulating are optimistic for enhanced ECR activity. • ZIFs-derived single-atom-site materials exhibit the most promising activity among ZIF-derivates. • Perspective of the developments and applications of ZIFs in ECR have been proposed. The electrochemical reduction of carbon dioxide (ECR) is an efficient approach to alleviate environment and energy crisis for its high technological and economic feasibility. To date, massive studies demonstrated that zeolitic imidazolate frameworks (ZIFs) are optimal for CO 2 capture, which is a pivotal precondition for the subsequent reduction steps. Additionally, ZIFs are promising candidates as catalysts, precursors, or carriers for their adjustable metal sites, ligands, and porosity, tremendous progress has been made in applying ZIFs in ECR applications in recent years. Herein, the review summarized the recent works focusing on applying ZIFs and ZIFs-derivatives for ECR. including reaction mechanism, application strategies, and catalytic performance analysis, aiming to provide a basis for future design and synthesis of highly active and selective ZIFs and ZIFs-derivatives electrocatalysts in this direction. [ABSTRACT FROM AUTHOR]

Distinct naphthenic acid (NA) species were isolated from oil sands process water (OSPW) into 20 fractions via silver-ion solid phase extraction, prior to treatment using potassium ferrate(VI). Untreated and treated fractions F1–F20 were characterized using ultra performance liquid chromatography traveling-wave ion mobility time-of-flight mass spectrometry to identify classical NAs (aliphatic O 2 –NAs mainly found in fractions F1–F4), aromatic NAs (aromatic O 2 –NAs in F6–F9), oxidized NAs (O 3 –, O 4 –, and O 5 –NAs in F14–F17), and sulfur-containing NAs (F16–F19). The Fe(VI) oxidation reactivity of individual NA species was studied with minimized confounding effects from the complicated OSPW matrix. Aliphatic and aromatic O 2 –NAs were found to have different reactivity towards Fe(VI) oxidation, with removals ranging from <50% up to 90% at 200 mg/L ferrate dose. The O 3 –NAs and O 4 –NAs from raw OSPW were recalcitrant species with slight degradation under Fe(VI) oxidation conditions. The Fe(VI) oxidation of O 2 –NAs generated new O 3 –NAs as byproducts or intermediate byproducts which finally resulted in more oxygen-rich O x –NAs as the final byproducts depending on the Fe(VI) doses. Besides the obtained knowledge on chemical reactivity, current methodology (i.e., treatment of Ag-ion fractions of OSPW versus raw OSPW) could be applied to evaluate other treatment approaches as well as toxicity of distinct NA species for environmental applications. Unlabelled Image • The Ag-ion SPE allowed a good separation of OSPW into 20 fractions. • Fe(VI) reactivity of isolated NA species was studied for the first time. • Fe(VI) oxidation removed O 2 –NAs favorably rather than other oxidized NAs. • Fe(VI) treatment could oxidize O 2 –NAs to generate O 4 –NAs directly. [ABSTRACT FROM AUTHOR]

This work reports the monitoring and assessment of naphthenic acids (NAs) in oil sands process-affected water (OSPW), Pleistocene channel aquifer groundwater (PLCA), and oil sands basal aquifer groundwater (OSBA) from an active oil sands development in Alberta, Canada, using ultra performance liquid chromatography time-of-flight mass spectrometry (UPLC-TOF-MS) analysis with internal standard (ISTD) and external standard (ESTD) calibration methods and Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) for compositional analysis. PLCA was collected at 45–51 m depth and OSBA was collected at 67–144 m depth. Results of O x −NA concentrations follow an order as OSPW > OSBA > PLCA, indicating that occurrences of NAs in OSBA were likely related to natural bitumen deposits instead of OSPW. Liquid-liquid extraction (LLE) was applied to avoid the matrix effect for the ESTD method. Reduced LLE efficiency accounted for the divergence of the ISTD and ESTD calibrated results for oxidized NAs. Principle component analysis results of O 2 and O 4 species could be employed for differentiation of water types, while classical NAs with C13−15 and Z (-4)−(-6) and aromatic O 2 −NAs with C16−18 and Z (-14)−(-16) could be measured as marker compounds to characterize water sources and potential temporal variations of samples, respectively. FTICR-MS results revealed that compositions of NA species varied greatly among OSPW, PLCA, and OSBA, because of NA transfer and transformation processes. This work contributed to the understanding of the concentration and composition of NAs in various types of water, and provided a useful combination of analytical and statistical tools for monitoring studies, in support of future safe discharge of treated OSPW. [ABSTRACT FROM AUTHOR]

There are several established methods for the determination of naphthenic acids (NAs) in waters associated with oil sands mining operations. Due to their highly complex nature, measured concentration and composition of NAs vary depending on the method used. This study compared different common sample preparation techniques, analytical instrument methods, and analytical standards to measure NAs in groundwater and process water samples collected from an active oil sands operation. In general, the high- and ultrahigh-resolution methods, namely high performance liquid chromatography time-of-flight mass spectrometry (UPLC-TOF-MS) and Orbitrap mass spectrometry (Orbitrap-MS), were within an order of magnitude of the Fourier transform infrared spectroscopy (FTIR) methods. The gas chromatography mass spectrometry (GC-MS) methods consistently had the highest NA concentrations and greatest standard error. Total NAs concentration was not statistically different between sample preparation of solid phase extraction and liquid-liquid extraction. Calibration standards influenced quantitation results. This work provided a comprehensive understanding of the inherent differences in the various techniques available to measure NAs and hence the potential differences in measured amounts of NAs in samples. Results from this study will contribute to the analytical method standardization for NA analysis in oil sands related water samples. [ABSTRACT FROM AUTHOR]

Ultra-performance liquid chromatography ion mobility time-of-flight mass spectrometry (UPLC-IM-TOFMS) was utilized for the analysis of naphthenic acids (NAs) in fractions of pH-dependent sequential liquid-liquid extractions from oil sands process-affected water. Ion-mobility separation technique allowed the differentiation of O y S−NAs (2 ≤ y ≤ 4) from O x −NAs (2 ≤ x ≤ 5) via drift time versus retention time separations. The results indicated that the addition of S atom to the O 2 −NA molecule led to a lower increase in the dissociation constant (pK a ) compared to that caused by the addition of O atom. Because additional O is present as OH while the S atom is present as the C S C structure, the latter does not involve into the deprotonation process directly. The pK a value decreased along with increasing carbon number and |Z| number for O 2 −, O 3 −, O 4 −, and O 2 S−NA species, except for O 5 −, O 3 S−, and O 4 S−NA species, each of which are comprised of chemical structures with distinct functional groups. A calculation model was developed to estimate pK a values for individual and total NA species via nonlinear regression curve fitting, utilizing the relative abundances of detected NA species. pK a values were calculated as 3.9 for total NAs, 3.3 for O 2 −NAs, 4.4 for O 3 −NAs, 7.3 for O 4 −NAs, and 4.1 for O 2 S−NAs. Knowledge of NAs pK a is crucially important for the comprehensive understanding of their potential transformation route and toxicity as well as for the development of water remediation applications. Both the ion-mobility separation technique and the new calculation model could be widely applied for the investigation of other complicated pollutants present in water and wastewater. [ABSTRACT FROM AUTHOR]

[Display omitted] • BDD/PMS/Fe(III) process is dominated by radical oxidation. • DSA/PMS/Fe(III) process is dominated by nonradical oxidation. • BDD/PMS/Fe(III) system is inclined to oxidize electron-rich contaminants. • DSA/PMS/Fe(III) system is apt to oxidize electron-deficient contaminants. • Degradation pathways of sulfamethoxazole were systematically revealed. Herein, peroxymonosulfate (PMS) activation via electro-cocatalytic system with circulated Fe(III)/Fe(II) was investigated with boron-doped diamond (BDD) anode and dimensionally stable anode (DSA) for degradation of sulfamethoxazole (SMX). Radicals of OH and SO 4 − as well as non-radicals of 1O 2 and Fe(IV) were all present in BDD/PMS/Fe(III) and DSA/PMS/Fe(III) systems, according to the results of scavenging experiment and electron paramagnetic resonance (EPR) analysis. Interestingly based on the results of chemical probe experiments, the ratio of OH, SO 4 −, and 1O 2 were 9% (7.19 μmol/L), 76% (58.39 μmol/L), and 15% (11.45 μmol/L) in BDD/PMS/Fe(III) system, and were 28% (5.81 μmol/L), 18% (3.76 μmol/L), and 54% (10.93 μmol/L) in DSA/PMS/Fe(III) system. The yield of Fe(IV) in DSA/PMS/Fe(III) process was relatively higher than that in BDD/PMS/Fe(III) process. These results indicated that BDD/PMS/Fe(III) is a radical oxidation system while DSA/PMS/Fe(III) system is mainly non-radical system. Due to the high electrochemical activity of BDD anode, the one-electron transfer reaction might occur to produce more SO 4 −. The co-existing ions including Cl−, H 2 PO 4 −, and NO 3 − showed significant effects on the degradation efficiency of BDD/PMS/Fe(III) and nonsignificant impacts on DSA/PMS/Fe(III) process, indicating that DSA/PMS/Fe(III) process could be less affected by complex water matrix. BDD/PMS/Fe(III) is inclined to oxidize electron-rich contaminants, while DSA/PMS/Fe(III) is apt to oxidize electron-deficient contaminants. The degradation routes of SMX and its toxicity evolution were systematically studied with the analysis of byproducts. Overall results compared the oxidation mechanisms and primary oxidation pathways of electro-cocatalytic systems with BDD versus DSA anodes, and revealed the merits of each system for future selection and system optimization of treatment processes regarding targeted contaminants. [ABSTRACT FROM AUTHOR]

This work investigated the oxidative transformation of the organic species in oil sands process-affected water (OSPW) using Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) and ultra-performance liquid chromatography time-of-flight mass spectrometry (UPLC-TOF-MS) in both negative and positive electrospray ionization (ESI) modes. This is the first time to apply FTICR-MS to investigate species transformation in OSPW treatments by ferrate (VI), UV/H 2 O 2 , and molecular ozone, and also this is the first preliminary study to use positive ESI to investigate organic species in addition to naphthenic acids (NAs) in these treatment processes. The oxidation processes with potassium ferrate (VI), UV/H 2 O 2 , and ozone transformed the distribution profiles of O x , O x S y , and O x N y organic fractions (i.e., species containing oxygen, sulfur, and nitrogen, with x, y specifying the oxygen number and sulfur/nitrogen number, respectively), with O x S y distribution profiles showing the most sensitive responses to the oxidation extent and can be used as a signature fraction to evaluate the oxidation effectiveness. Negative mode UPLC-TOF-MS confirmed the transformation pattern of O x species observed with FTICR-MS, but positive mode UPLC-TOF-MS results showed severe discrepancies with FTICR-MS results and should be subjected for future further investigation, regarding the relatively low mass resolution of UPLC-TOF-MS. The investigation of the transformation patterns of different organic species using two ionization modes was a preliminary study to enhance the understanding of the efficiency, selectivity, and mechanism of different oxidation processes in OSPW remediation for both NAs and non-NA species. [ABSTRACT FROM AUTHOR]

This review covers the characterization and distribution of metals and nonmetals in the Alberta oil sands region (AOSR) of Canada. The development of the oil sands industry has resulted in the release of organic, metal and nonmetal contaminants via air and water to the AOSR. For air, studies have found that atmospheric deposition of metals in the AOSR decreased exponentially with distance from the industrial emission sources. For water, toxic metal concentrations often exceeded safe levels leading to the potential for negative impacts to the receiving aquatic environments. Interestingly, although atmospheric deposition, surface waters, fish tissues, and aquatic bird eggs exhibited increasing level of metals in the AOSR, reported results from river sediments showed no increases over time. This could be attributed to physical and/or chemical dynamics of the river system to transport metals to downstream. The monitoring of the airborne emissions of relevant nonmetals (nitrogen and sulphur species) was also considered over the AOSR. These species were found to be increasing along with the oil sands developments with the resultant depositions contributing to nitrogen and sulphur accumulations resulting in ecosystem acidification and eutrophication impacts. In addition to direct monitoring of metals/nonmetals, tracing of air emissions using isotopes was also discussed. Further investigation and characterization of metals/nonmetals emissions in the AOSR are needed to determine their impacts to the ecosystem and to assess the need for further treatment measures to limit their continued output into the receiving environments. [ABSTRACT FROM AUTHOR]

Naphthenic acids (NAs) from oil sand process-affected water (OSPW) were liquid–liquid extracted using six organic solvents (n-pentane, n-hexane, cyclohexane, dichloromethane, ethyl ether, and ethyl acetate) at three pHs (2.0, 8.5, and 12.0). The NAs exist in ionic (ions) and non-ionic (molecules) forms in the water phase depending on their dissociation constants and the solution pH. Results showed the extractability of NA molecules depends on the solvent polarity and the extractability of NA ions on the water solubility in solvent. The organic solvent type and solution pH were found to not only impact the extracted amounts of each NA species, but also the NAs distribution in terms of molecule carbon number and hydrogen deficiency. Overall, it is concluded that ethyl ether can be used as an alternative to dichloromethane (DCM) given their similar extraction efficiencies and extracted NA profiles. This is important since DCM is known to have metabolic toxicity and transitioning to the safer ethyl ether would eliminate laboratory DCM exposures and risk to human health. Despite the higher extraction efficiency of NAs at pH 2.0, extraction at pH 12.0 could be useful for targeted extraction of low-concentration nonpolar organic compounds in OSPW. This knowledge may assist in the determination of the specific NAs species that are known to have chronic, sub-chronic and acute toxicity to various organisms, and the potential targeting of treatment to these NAs species. [ABSTRACT FROM AUTHOR]

The fractionation of oil sands process-affected water (OSPW) via pH-dependent extractions was performed to quantitatively investigate naphthenic acids (NAs, C n H 2 n + Z O 2 ) and oxidized NAs (O x -NAs) species (C n H 2 n + Z O 3 and C n H 2 n + Z O 4 ) using ultra-performance liquid chromatography time-of-flight mass spectrometry (UPLC-TOFMS). A mathematical model was also developed to estimate the dissociation constant p K a for NAs species, considering the liquid–liquid extraction process and the aqueous layer acid-base equilibrium. This model provides estimated dissociation constants for compounds in water samples based on fractionation extraction and relative quantification. Overall, the sum of O 2 -, O 3 -, and O 4 -NAs species accounted for 33.6% of total extracted organic matter. Accumulative extracted masses at different pHs revealed that every oxygen atom added to NAs increases the p K a (i.e., O 2 -NAs < O 3 -NAs < O 4 -NAs), indicating that the additional O atoms exist as –OH in O 3 - and O 4 -NAs. Molecule electron-withdrawing groups such as double bonds and aromatic groups, as indicated by higher carbon and − Z number, may be responsible for the lower p K a of O 2 -, O 3 -, and O 4 -NAs. The model obtained estimated p K a values of 3.5 for O 2 -NAs, 4.8 for O 3 -NAs, and 6.8 for O 4 -NAs via nonlinear regression curve fittings. These p K a values are valuable physicochemical parameters for environmental engineering applications targeting OSPW NAs treatment. [ABSTRACT FROM AUTHOR]

The nicotine metabolites, cotinine and trans-3′-hydroxycotinine (3HC) are considered as superior biomarkers for identifying tobacco exposure. More importantly, the ratio of 3HC to cotinine is a good indicator to phenotype individuals for cytochrome P450 2A6 activity and to individualize pharmacotherapy for tobacco addiction. In this paper, a simple, robust and novel method based on surface-enhanced Raman spectroscopy coupled with thin-layer chromatography (TLC) was developed to directly quantify the biomarkers in human urine samples. This is the first time surface-enhanced Raman spectroscopy (SERS) was used to detect cotinine and 3HC in urine samples. The linear dynamic range for the detection of cotinine is from 40 nM to 8 μM while that of 3HC is from 1 μM to 15 μM. The detection limits are 10 nM and 0.2 μM for cotinine and 3HC, respectively. The proposed method was further validated by quantifying the concentration of both cotinine and 3HC in smokers' urine samples. This TLC-SERS method allows the direct detection of cotinine in the urine samples of both active and passive smokers and the detection of 3HC in smokers. [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]

Abstract: Metal nanoparticles and carbon nanotubes have been shown to possess high electrocatalytic activity. Indium tin oxide (ITO) is a popular electrode material, but the electro-catalytic properties of its nano-materials have not been reported. We demonstrate here for the first time facile electrocatalytic oxidation of ascorbic acid on ITO nanoparticle-modified electrodes. Compared to the conventional ITO thin film electrode, the voltammetric peak potential for ascorbic acid oxidation was lowered by 800mV on ITO nanoparticle-modified electrodes to a potential similar to metal electrodes. The ITO nanoparticle was composed of 90% In2O3 and 10% SnO2. Since the electrocatalytic activity was also found on In2O3 nanoparticle electrodes but not on SnO2 nanoparticle electrodes, the In2O3 composition in ITO nanoparticle is mainly responsible for the high activity. In photoluminescence measurement, two intense emission peaks at 415nm and 438nm associated with surface oxygen vacancies were observed on the semiconductor electrodes. It was hypothesized that the oxygen vacancies could be the active sites for electrocatalytic reactions. A linear relationship between the oxidation current and ascorbic acid concentration was found in the range of 10μM to 5mM, with a lower detection limit of 5μM and 7.9% RSD (n =11). The high electro-catalytic activity and transmittance of In2O3 and ITO nanoparticle electrodes make them potentially very useful in opto-electronic devices and chemical/bio-sensors. [Copyright &y& Elsevier]

Abstract: Electrochemiluminescence (ECL) systems using (bpy=2,2′-bipyridyl) and tripropylamine (TPA) on metal and carbon electrodes are widely used in immunoassay and DNA hybridization detections. The large overpotential of TPA oxidation on indium tin oxide (ITO) electrodes has limited their ECL application. In this work, significant enhancement of ECL signal from the /TPA system was achieved on ITO nanoparticle-modified electrode. Due to the electrocatalytic activity of ITO nanoparticle electrodes, TPA oxidation potential was found to shift negatively by 600mV, leading to 24-fold increases in ECL peak intensity over the conventional ITO electrode, and 2-fold increases in the integrated signal over the conventional gold electrode. As a result, the detection limit for in solution was 20-fold lower than the value on the conventional ITO electrode. Because the transmittance of ITO at 610nm (the wavelength of emission maximum) was reduced only slightly after nanoparticle modification, it may offer a better alternative than metal and carbon electrodes in ECL measurements. [Copyright &y& Elsevier]

Abstract: Non-covalent binding interactions of small molecules with DNA play important roles in regulating gene expression and gene function. In this work, a highly sensitive electrochemiluminescence (ECL) displacement method has been developed to investigate such interactions, particularly for weak DNA binders. This ECL method relies on a double-stranded DNA film deposited on an indium tin oxide electrode (ITO) surface by layer-by-layer self-assembly. A DNA intercalator, [Ru(bpy)2(dppz)]2+ (bpy=2,2′-bipyridine, dppz=dipyrido[3,2-a:2′3′-c]phenazine), is employed as the ECL signal indicator. If a test compound competes with the indicator for the same binding sites in DNA, it would displace the indicator from the film and reduce ECL signal. The new method was validated by measuring five well-known DNA-binding organic molecules including quinacrine, H33258, thiazole orange, ethidium bromide and 4,6-diamidine-2-phenylindole dihydrochloride. Due to high ECL sensitivity, only 0.4μmolL−1 [Ru(bpy)2(dppz)]2+ was needed in the ECL displacement measurement, which is about 75-fold less than the concentration in the voltammetric measurement. The lowered concentration permitted direct measurement of IC50 values of eight hydroxylated polycyclic aromatic hydrocarbons in their ECL displacement curves and subsequent calculation of their binding constants with DNA. The ECL displacement method is particularly useful for investigating weak DNA binders with limited aqueous solubility. [ABSTRACT FROM AUTHOR]

Abstract: Influence of laser wavelength, laser irradiance and the buffer gas pressure were studied in high irradiance laser ablation and ionization source coupled with an orthogonal time-of-flight mass spectrometer. Collisional cooling effects of energetic plasma ions were proved to vary significantly with the elemental mass number. Effective dissociation of interferential polyatomic ions in the ion source, resulting from collision and from high laser irradiance, was verified. Investigation of relative sensitivity coefficients (RSC) of different elements performed on a steel standard GBW01396, which was ablated at 1064 nm, 532 nm, 355 nm, and 266 nm, has demonstrated that the thermal ablation mechanism could play a critical role with the first three wavelengths, while 266 nm induces non-thermal ablation principally. Experimental results also indicated that there is no evident discrepancy for most metal elements on RSCs and LODs among four wavelengths at high irradiance, except that high boiling point elements like Nb, Mo, and W have higher RSCs at higher irradiance regions of 1064 nm, 532 nm, and 355 nm due to thermal ablation. A geological standard and a garnet stone were also used in the experiment subsequently, and their RSCs and LODs for metal elements show nonsignificant dependence on wavelength at designated irradiances. All results reveal that relatively uniform sensitivity can be achieved at any wavelength for metal elements in the solids used in our experiments at an appropriate irradiance for the low pressure high irradiance laser ablation and ionization source. [Copyright &y& Elsevier]

Abstract: In the present work, a novel method for immobilization of carbon nanotubes (CNTs) on the surface of graphite electrode was proposed. We further found that superoxide ion was electrogenerated on this CNTs-modified electrode, which can react with sulfide ion combing with a weak but fast electrogenerated chemiluminescence (ECL) emission, and this weak ECL signal could be enhanced by the oxidative products of rhodamine B. In addition, the rate constant of this electrochemical reaction k 0 was investigated and confirmed that the speed of electrogenerating superoxide ion was in accordance with the subsequent fast CL reaction. Thus, the fast CL reaction of superoxide ion with target brought in the possibility of high selectivity based on time-resolved, relative to other interferences. Based on these findings, an excellently selective and highly sensitive ECL method for sulfide ion was developed. Under the optimum conditions, the enhancing ECL signals were linear with the sulfide ion concentration in the range from 6.0×10−10 to 1.0×10−8 molL−1, and a 2.0×10−10 molL−1 detection limits (3σ) was achieved. In addition, the proposed method was successfully used to detect sulfide ion in environmental water samples. [Copyright &y& Elsevier]

A Correction to this paper has been published: https://doi.org/10.1007/s43032-021-00568-5 [ABSTRACT FROM AUTHOR]

In recent years, increasing attention has been paid to DNA mediated chemiluminescence (CL) bioassays due to the merits provided by both of CL and functional DNAs. CL exhibits the advantages of low background, high sensitivity and simple equipment. Meanwhile, various functional DNAs facilitate the target recognition, signal transduction and signal amplification of the CL bioassays. However, a comprehensive summarization focused on the DNA-mediated CL bioassays is still lacking now. In this review, the CL systems for biosensing and approaches of DNA-based target recognition and signal transduction for CL bioassays were summarized. The strategies and mechanisms of signal amplification and background reducing for ultrasensitive CL assays were also discussed in detail. The applications for the detection of various analytes including nucleic acids, proteins, toxins, environmental pollutants, and metal ions were systematically reviewed as well. Finally, the further prospects and challenges were highlighted to promote the advancement of DNA-mediated CL bioassays. • The DNA-based target recognition and signal transduction for CL bioassays were summarized. • The strategies of signal amplification and background reducing for ultrasensitive CL assays were systematically reviewed. • The advantages, applicable situations and future developments of DNA-based CL bioassay were discussed in detail. [ABSTRACT FROM AUTHOR]

This work describes a novel application of atmospheric pressure gas chromatography time-of-flight mass spectrometry (APGC-TOF-MS) combined with solid-phase microextraction (SPME) for the simultaneous analysis of hydrocarbons and naphthenic acids (NAs) species in raw and ozone-treated oil sands process water (OSPW). SPME method using polydimethylsiloxane (PDMS)-coated fibers was validated using gas chromatography with flame ionization detector (GC-FID) to ensure the SPME extractions were operated appropriately. The ionization pathways of the hydrocarbon species in OSPW in the APGC source were verified by analyzing a mixture of eight polyaromatic hydrocarbons which were ionized primarily via charge transfer to produce [M+] while NAs in OSPW were found to be ionized through protonation to generate [MH+] in the wet APGC source. SPME/APGC-TOF-MS analysis demonstrated a different composition profile in OSPW #1, with 74.5% of hydrocarbon species, 23.4% of O 2 –NAs, and 2.1% of the oxidized NA species at extraction pH 2.0 compared with that obtained by UPLC-TOF-MS analysis (36.9% of O 2 –NAs, 26.8% of O 3 –NAs, 24.9% of O 4 –NAs, 9.1% of O 5 –NAs, 2.3% of O 6 –NAs). Moreover, the peak areas of the total NAs and the total peak areas of NAs + hydrocarbons measured by SPME/APGC-TOF-MS correlated excellently with the total NA concentration determined by UPLC-TOF-MS (R2 = 0.90) and the concentrations of the total acid-extractable organics determined by SPME/GC-FID (R2 = 0.98), respectively. APGC-TOF-MS integrated with the SPME techniques could extend the range of target compounds and be a promising alternative to evaluate and characterize NAs and hydrocarbon in different water types. Image 1 • SPME coupled with APGC-TOF-MS was used for analysis of hydrocarbons and NAs. • PDMS fibers preferably extracted neutral organic compounds at natural pH. • The PDMS fibers extracted hydrocarbons and some protonated NAs species at pH 2.0 • PAHs were ionized via charge transfer while NAs were ionized through protonation. • O x -NAs peak areas by SPME/APGC-TOF-MS correlated to the O x -NAs by UPLC-TOF-MS. [ABSTRACT FROM AUTHOR]

Background: Chromosome aberrations of 10p monosomy and 10q trisomy resulting from parental pericentric inversion 10 are extremely rare, and to date, very few reports have been published on the matter. Case Presentation: A 30-year-old pregnant woman with recurrent pregnancy loss is enrolled in this research. In this pregnancy, spontaneous abortion occurred in the first trimester of her pregnancy. Chromosomal microarray analysis of the abortion tissue showed a partial 10p monosomy (arr[GRCh37] 10p15.3p11.21(100,047_34,848,853) × 1) and a duplication of 10q (arr[GRCh37] 10q26.13q26.3(126,093,990_135,426,386) × 3). Further parental karyotype analysis indicated that the chromosomal abnormalities in the fetus was resulted from paternal pericenric inversion inv(10)(p11.21q26.13). This study presents the first case of a large deletion of 10p combined with 10q trisomy, resulting in pregnancy loss. Of these two manifestations, the large deletion of chromosome 10p may be the primary reason for spontaneous abortion in this subject. Conclusions: This study presents the first case of partial 10p monosomy associated with 10q trisomy in Chinese population. It provides more information on the chromosome aberration of 10p monosomy and 10q trisomy and further strengthens the application value of microarray in the molecular etiological diagnosis of recurrent spontaneous abortion. [ABSTRACT FROM AUTHOR]

This paper reported the impact of UV/H 2 O 2 , UV/chlorine, and UV/persulfate advanced oxidation processes on the molecular transformations of dissolved organic matter (DOM), removal of naphthenic acids (NAs) and acute toxicity in oil sands process water (OSPW). The UV/persulfate process exhibited the highest removal (81.2% with 2 mM dose) towards classical NAs and highest reduction in acute toxicity to Vibrio fischeri among the three processes. The fraction of DOM such as CHOS class species decreased along with the increase of the oxidant doses in all processes. The increase in O/C ratio and lack of change in the H/C and double bond equivalence indicated that H-abstraction followed by the OH-addition was the main reaction pathway for all processes. This observation aligned with previous studies using model compounds and proved that OSPW DOM reacted similarly to model compounds. Sulfur containing organic matters were the most liable compounds in OSPW NOM, while UV/chlorine was the most effective process to oxidize nitrogen containing organic matters. Overall results revealed that the UV/persulfate process could be used as a promising technique for the removal of OSPW NA and reduction of acute toxicity towards Vibrio fischeri. In addition, this DOM characterization approach could be utilized to investigate the transformation of complicated OSPW DOM and to identify the byproducts generated during different water treatment processes. Unlabelled Image • UV/persulfate had the highest O 2 -NA removal. • UV/persulfate had the highest reduction in acute toxicity to Vibrio fischeri. • H-abstraction followed by OH-addition was the main reaction pathway for all processes. • Sulfur containing organic matters were the most liable compounds in OSPW NOM. • Chlorinated byproducts were formed in both UV/chlorine and UV/persulfate. [ABSTRACT FROM AUTHOR]

The ultraviolet light-activated persulfate process (UV/Persulfate) has received much attention in recent years as a novel advanced oxidation method for the treatment of municipal and industrial wastewater. This work investigated the UV/Persulfate and UV/H 2 O 2 processes for the treatment of real oil sands process water (OSPW) at ambient pH condition using a medium pressure mercury lamp (emission between 200 and 530 nm). The degradation performances towards fluorophore organic compounds and naphthenic acids (NAs) in OSPW were evaluated using synchronous fluorescence spectrometry and ultra performance liquid chromatography time-of-flight mass spectrometry, respectively. Compared to the UV/H 2 O 2 process, the UV/Persulfate process exhibited higher efficiency to remove both NAs and fluorophore organic compounds. Under 40 min of UV exposure and incident irradiance of 3.50 mW cm−2, fluorophore organic compounds were greatly degraded by UV/Persulfate (2 mM) and two- and three-ring fused organics were completely removed. 59.4%, 83.8% and 92.2% of O 2 -NAs in OSPW were removed with persulfate dosages of 0.5, 2, and 4 mM, respectively. The removal efficiency decreased along with the number of oxygen atoms in NAs (83.8%, 49.3%, and 46.8% for O 2 -, O 3 -, and O 4 -NAs, respectively) with 2 mM of persulfate, because of the formation of oxidized NAs in the same process. The structure-reactivity of O 2 -NA compounds fitted pseudo-first order kinetics in UV/Persulfate process with the rate constants ranging from 0.0156 min−1 to 0.1511 min−1. NAs with higher carbon numbers and double bond equivalence were more reactive in the UV/Persulfate oxidation process. The acute toxicity of OSPW to Vibrio fischeri was significantly reduced after the UV/Persulfate and UV/H 2 O 2 treatments. Overall results demonstrated that the UV/Persulfate oxidation can be an effective alternative for future reclamation of OSPW. Unlabelled Image • UV/Persulfate was investigated for the treatment of real OSPW. • Higher removal efficiency towards NAs was obtained with UV/Persulfate compared to UV/H 2 O 2. • NAs with higher carbon and |Z| numbers showed high reactivity in UV/Persulfate. • UV/Persulfate and UV/H 2 O 2 reduced the acute toxicity of OSPW towards Vibrio fischeri. [ABSTRACT FROM AUTHOR]

This study investigated the application of a natural plant polyphenol, gallic acid (GA) to form complex with iron to promote the redox cycle of Fe(III)/Fe(II) under neutral initial pH conditions in the electrochemical (EC) system for activation of peroxymonosulfate (PMS) to efficiently degrade carbamazepine (CBZ). Results demonstrated that the synergistic effects of GA and EC significantly improved the removal efficiency, and the EC/GA/Fe(III)/PMS system effectively removed 100% of CBZ within a wide initial pH range of 3.0–7.0. The optimum stoichiometric ratio of GA to Fe(III) was found as 2:1. Investigations including quenching experiment, chemical probe analysis, and electron paramagnetic resonance (EPR) analysis were conducted to identify the primary reaction radicals as •OH, SO 4 •−, along with the 1O 2 and Fe(IV). In the EC/GA/Fe(III)/PMS system, the synergistic effect of GA and electrochemistry led to a remarkable enhancement in the generation of •OH. Furthermore, the complexation reduction mechanism of GA and Fe(III) was proposed based on experimental and instrumental analyses, which demonstrated that the semi-quinone products of GA were the main substances promoting the Fe(III)/Fe(II) cycle. Mass spectrometry results showed that CBZ generated 27 byproducts during degradation, with formic acid as the main product of GA. The degradation efficiency of the EC/GA/Fe(III)/PMS system remained stable and excellent, exhibiting remarkable performance in the presence of various inorganic anions, including Cl− and NO 3 −, as well as naturally occurring organic compounds such as fulvic acid (FA). Overall results indicated that the EC/GA/Fe(III)/PMS system can be applied to effectively treat practical wastewater treatment without requirement of pH adjustment. [Display omitted] • The EC/GA/Fe(III)/PMS system could efficiently remove CBZ at neutral pH condition. • Electro-synergistic GA significantly enhance the cycling of Fe(III)/Fe(III). • Electro-synergistic GA promoted the formation of •OH. • Chelation-reduction between GA and Fe(III) was examined under electric field. • The degradation pathways and byproducts of CBZ and GA were analyzed. [ABSTRACT FROM AUTHOR]

The investigation into the degradation of metronidazole (MNZ), a frequently employed antibiotic, through the electrochemical activation of peroxymonosulfate (PMS) utilizing either boron-doped diamond (BDD) or dimensional stable anode (DSA) as the anode, was conducted in a systematic manner. The enhancement of MNZ removal was observed with increasing current density, PMS dosage, and initial pH. Response surface methodology (RSM), based on a Box–Benken design, was utilized to evaluate the efficiency of MNZ elimination concerning current density (ranging from 11.1 to 33.3 mA/cm2), initial pH (ranging from 3 to 9), PMS dosage (ranging from 1 to 5 mmol·L−1), and reaction time (ranging from 25 to 45 min). The optimal operational conditions for MNZ removal were determined as follows: a current density of 13.3 mA/cm2, a pH of 3.7, a PMS dosage of 2.4 mmol·L−1, and a reaction time of 40 min. Electron paramagnetic resonance (EPR), quenching experiments, and chemical probe experiments confirmed the involvement of •OH, SO4•− and 1O2 radicals as the primary reactive species in MNZ degradation. The presence of HCO3− and H2PO4− hindered MNZ removal, whereas the presence of Cl− accelerated it. The degradation pathways of MNZ were elucidated by identifying intermediates and assessing their toxicity. Additionally, the removal efficiencies of other organic pollutants, such as sulfamethoxazole (SMX), carbamazepine (CBZ), and nitrobenzene (NB), were compared. This study contributes to a comprehensive understanding of MNZ degradation efficiency, mechanisms, and pathways through electrochemical activation of PMS employing BDD or DSA anodes, thereby offering valuable insights for the selection of wastewater treatment systems. [ABSTRACT FROM AUTHOR]

• Serum profile based on LC-MS was utilized to metabolomic analysis of breast cancer (BC). • The use of machine learning methods allowed for the identification of significant serum metabolic differences between TNBC and non-TNBC groups. • Two metabolic panels were expected to predict BC and TNBC, respectively. Breast cancer (BC), the most common form of malignant cancer affecting women worldwide, was characterized by heterogeneous metabolic disorder and lack of effective biomarkers for diagnosis. The purpose of this study is to search for reliable metabolite biomarkers of BC as well as triple-negative breast cancer (TNBC) using serum metabolomics approach. In this study, an untargeted metabolomics technique based on ultra-high performance liquid chromatography combined with mass spectrometry (UHPLC-MS) was utilized to investigate the differences in serum metabolic profile between the BC group (n = 53) and non-BC group (n = 57), as well as between TNBC patients (n = 23) and non-TNBC subjects (n = 30). The multivariate data analysis, determination of the fold change and the Mann-Whitney U test were used to screen out the differential metabolites. Additionally, machine learning methods including receiver operating curve analysis and logistic regression analysis were conducted to establish diagnostic biomarker panels. There were 36 metabolites found to be significantly different between BC and non-BC groups, and 12 metabolites discovered to be significantly different between TNBC and non-TNBC patients. Results also showed that four metabolites, including N-acetyl-D-tryptophan, 2-arachidonoylglycerol, pipecolic acid and oxoglutaric acid, were considered as vital biomarkers for the diagnosis of BC and non-BC with an area under the curve (AUC) of 0.995. Another two-metabolite panel of N-acetyl-D-tryptophan and 2-arachidonoylglycerol was discovered to discriminate TNBC from non-TNBC and produced an AUC of 0.965. This study demonstrated that serum metabolomics can be used to identify BC specifically and identified promising serum metabolic markers for TNBC diagnosis. [ABSTRACT FROM AUTHOR]

A novel fluorescence and colorimetric dual probe based upon the inner filter effect (IFE) is reported to selectively and sensitively determine alkaline phosphatase (ALP). First, up-conversion nanoparticles (UCNPs) were prepared via a facile hydrothermal method and characterized by transmission electron microscopy (TEM), X-ray diffractometry (XRD), Fourier transform infrared spectroscopy (FT-IR), and zeta potential. Under near infrared (NIR) excitation at 980 nm, the prepared nanoparticles emit green light at 541 nm. The absorption band of p-phenylenediamine (PPD) overlaps the emission of UCNPs, which effectively quenches the fluorescence of UCNPs. However, ascorbic acid (AA) generated from the reaction of ascorbic acid 2-phosphate (AAP) and ALP impedes the oxidation of PPD and the fluorescence is restored. Based on this change, a "turn-on" sensor was used to determine AA and ALP with the limits of detection of 2.49 μM and 0.018 U/L, respectively. The constructed assay was applied to determine ALP in serum and the recoveries were from 93.3% to 101.3% with a relative standard deviation from 1.1% to 3.3%. A facile and efficient approach is reported for the determination ALP and offers a theoretical basis for the related diseases. [ABSTRACT FROM AUTHOR]

[Display omitted] • The main active species in EC/PI system are •OH, IO 3 •, and 1O 2. • The carbon felt cathode shows excellent capacity for PI activation in EC/PI system. • The EC/PI system is robust with complex water background and wide pH range. • Degradation byproducts and pathways of sulfamethoxazole were revealed. Herein, this work investigated a novel strategy utilizing electrochemical activation of periodate (EC/PI) for effective degradation of sulfamethoxazole (SMX) with wide appliable pH range. The EC/PI system achieved 100% degradation efficiency of SMX under optimum conditions of 7.78 mA/cm2 current density, 1 mmol/L IO 4 − dosage, and 20 mmol/L Na 2 SO 4 as the supporting electrolyte. Strong synergistic effect between applied electric current and IO 4 − activation was observed, indicating the robustness of EC/PI system. Through a series of chemical probe experiments and electron paramagnetic resonance analysis, it was revealed that EC/PI is a composite oxidation system with multiple active species, including hydroxyl radical (•OH), iodate radical (IO 3 •), and singlet oxygen (1O 2). The production mechanisms of these active species were comprised of two routes: direct production via the electrode supplying electrons and indirect production via hydrogen peroxide (H 2 O 2) and superoxide radical (O 2 •−) as intermediates. The EC/PI process was slightly affected by the coexisting substances in the water background, and cycle experiments verified its degradation stability, indicating that this EC/PI system exhibits excellent capacity for treatment of authentic wastewater. Finally, the SMX degradation intermediates and pathways were obtained using mass spectrometry analysis and Gauss theory calculations. These results indicated the establishment of EC/PI system provides an efficient and environmental-friendly strategy for treatment of emerging organic pollutants. [ABSTRACT FROM AUTHOR]

The rise of emerging pollutants in the current environment and requirements of trace analysis in complex substrates pose challenges to modern analytical techniques. Ion chromatography coupled with mass spectrometry (IC-MS) is the preferred tool for analyzing emerging pollutants due to its excellent separation ability for polar and ionic compounds with small molecular weight and high detection sensitivity and selectivity. This paper reviews the progress of sample preparation and ion-exchange IC-MS methods in the analysis of several major categories of environmental polar and ionic pollutants including perchlorate, inorganic and organic phosphorus compounds, metalloids and heavy metals, polar pesticides, and disinfection by-products in past two decades. The comparison of various methods to reduce the influence of matrix effect and improve the accuracy and sensitivity of analysis are emphasized throughout the process from sample preparation to instrumental analysis. Furthermore, the human health risks of these pollutants in the environment with natural concentration levels in different environmental medias are also briefly discussed to raise public attention. Finally, the future challenges of IC-MS for analysis of environmental pollutants are briefly discussed. [Display omitted] • This review covers the application of IC-MS in environmental monitoring. • Pretreatment methods of different pollutants are summarized and discussed. • The pros and cons of different IC-MS methods are discussed. • The review summarizes the environmental retention levels of different pollutants. • Future perspectives of IC-MS analysis of environmental pollutants are discussed. [ABSTRACT FROM AUTHOR]

Periodate (PI) has recently been studied as an excellent oxidant in advanced oxidation processes, and its reported mechanism is mainly the formation of reactive oxygen species (ROS). This work presents an efficient approach using N-doped iron-based porous carbon (Fe@N-C) to activate periodate for the degradation of sulfisoxazole (SIZ). Characterization results indicated the catalyst has high catalytic activity, stable structure, and high electron transfer activity. In terms of degradation mechanism, it is pointed out that the non-radical pathway is the dominant mechanism. In order to prove this mechanism, we have carried out scavenging experiments, electron paramagnetic resonance (EPR) analysis, salt bridge experiments and electrochemical experiments, which demonstrate the occurrence of mediated electron transfer mechanism. Fe@N-C could mediate the electron transfer from organic contaminant molecules to PI, thus improving the efficiency of PI utilization, rather than simply inducing the activation of PI through Fe@N-C. The overall results of this study provided a new understanding into the application of Fe@N-C activated PI in wastewater treatment. [Display omitted] • The activation of PI was successfully promoted with Fe@N-C. • The reaction mechanism of Fe@N-C/PI system is electron transfer mechanism. • The degradation pathway of pollutants in Fe@N-C/PI system was proposed. • No iodate and other harmful byproducts were produced during the reaction. [ABSTRACT FROM AUTHOR]

The ethylenediamine-N,N′-disuccinic acid (EDDS) was utilized to form Fe-EDDS complex to activate peroxymonosulfate (PMS) in the electrochemical (EC) co-catalytic system for effective oxidation of naphthenic acids (NAs) under neutral pH conditions. 1-adamantanecarboxylic acid (ACA) was used as a model compound to represent NAs, which are persistent pollutants that are abundantly present in oil and gas field wastewater. The ACA degradation rate was significantly enhanced in the EC/PMS/Fe(III)-EDDS system (96.6%) compared to that of the EC/PMS/Fe(III) system (65.4%). The addition of EDDS led to the formation of a stable complex of Fe-EDDS under neutral pH conditions, which effectively promoted the redox cycle of Fe(III)-EDDS/Fe(II)-EDDS to activate PMS to generate oxidative species for ACA degradation. The results of quenching and chemical probe experiments, as well as electron paramagnetic resonance (EPR) analysis, identified significant contributions of •OH, 1O2, and SO4•− in the removal of ACA. The ACA degradation pathways were revealed based on the results of high resolution mass spectrometry analysis and calculation of the Fukui index. The presence of anions, such as NO3−, Cl−, and HCO3−, as well as humic acids, induced nonsignificant influence on the ACA degradation, indicating the robustness of the current system for applications in authentic scenarios. Overall results indicated the EC/PMS/Fe(III)-EDDS system is a promising strategy for the practical treatment of NAs in oil and gas field wastewater. [ABSTRACT FROM AUTHOR]

Ghrelin is a gastric acyl-peptide that plays an important role in cell proliferation. In the present study, we explored the role of ghrelin in A549 cell proliferation and the possible molecular mechanisms. We found that ghrelin promotes A549 cell proliferation, knockdown of the growth hormone secretagogue receptor (GHSR) attenuated A549 cell proliferation caused by ghrelin. Ghrelin induced the rapid phosphorylation of phosphatidylinositol 3-kinase (PI3K), Akt, ERK, mammalian target of rapamycin (mTOR) and P70S6K. PI3K inhibitor (LY 294002), ERK inhibitor (PD98059) and mTOR inhibitor (Rapamycin) inhibited ghrelin-induced A549 cell proliferation. Moreover, GHSR siRNA inhibited phosphorylation of PI3K, Akt, ERK, mTOR and P70S6K induced by ghrelin. Akt and mTOR/P70S6K phosphorylation was inhibited by LY 294002 but not by PD98059. These results indicate that ghrelin promotes A549 cell proliferation via GHSR-dependent PI3K/Akt/mTOR/P70S6K and ERK signaling pathways. [ABSTRACT FROM AUTHOR]

Herein, electro-catalysis (EC) as the electron donor to accelerate the continuable Fe(III)/Fe(II) cycles in different inorganic peroxides (i.e., peroxymonosulfate (PMS), peroxydisulfate (PDS) and hydrogen peroxide (HP)) activation systems were established. These electro-cocatalytic Fenton-like systems exhibited an excellent degradation efficiency of sulfamethoxazole (SMX). A series of analytical and characterization methods including quenching experiments, probe experiments, and electron paramagnetic resonance spectrometry (EPR) were implemented to systematically sort out the source and yield of reactive oxygen species (ROS). A wide kind of ROS including hydroxyl radical (•OH), singlet oxygen (1O 2), and sulfate radical (SO 4 •−), which contributed 38%, 37%, and 24% were produced in EC/Fe(III)/PMS system, respectively. •OH was the dominant ROS in both EC/Fe(III)/PDS and EC/Fe(III)/HP processes. According to the analysis of SMX degradation routes and biotoxicity, abundant degradation pathways were identified in EC/Fe(III)/PMS process and lower environmental impact was achieved in EC/Fe(III)/HP process. The diversiform ROS of EC/Fe(III)/PMS system makes it exhibit greater environmental adaptability in complex water matrixes and excellent low-energy consumption performance in many organic pollutants degradation. Continuous flow treatment experiments proved that the three systems have great sustainability and practical application prospect. This work provides a strong basis for constructing suitable systems to achieve different treatment requirements. [Display omitted] • EC/Fe(III)/oxidant processes exhibited distinguished degradation efficiency of SMX. • Oxidation mechanisms in various EC/Fe(III)/oxidant processes was lucubrated. • Different pollutant degradation routes and biotoxicity were identified. • Sustainability of processes was testified via continuous flow treatment experiments. [ABSTRACT FROM AUTHOR]

[Display omitted] • Efficient degradation of NAs was achieved by EC/PMS/Fe(III) system. • The redox cycle of Fe(III)/Fe(II) was triggered on the cathode. • The chemical structures of NA molecules affect their reactivity. • •OH, SO 4 •− and 1O 2 are the main reactive species in EC/PMS/Fe(III) system. • CHA degradation pathways and byproducts were revealed. In this study, an electrochemical/peroxymonosulfate/Fe(III) (EC/PMS/Fe(III)) system was established for efficient degradation of four naphthenic acids (NAs) compounds including cyclohexanecarboxylic (CHA), heptanoic (HPA), benzoic (BA) and 2-methylhexanoic acids (2-MHA). The introduction of electric field enhances the redox cycle of Fe(III)/Fe(II) to activate PMS for degredation of NAs. Complete degradation of NAs compounds (5 mg/L) has been achieved within 30 min in the EC/PMS/Fe(III) system. The results of electron paramagnetic resonance (EPR) analysis, scavenging experiment, and chemical probe experiments indicated hydroxyl radical (•OH), sulfate radical (SO 4 •−) and singlet oxygen (1O 2) are primary reactive oxygen species (ROS) in the EC/PMS/Fe(III) system. NAs compounds with different structures exhibit inconsistent degradation efficiency in current system (k CHA > k BA > k HPA > k 2-MHA), depending on the selectivity of the different ROS and stability of respective intermediate organic radicals. Besides, multiple degradation pathways of CHA, mainly including hydroxylation and carbonylation, were proposed by combining the results of mass spectrometry analysis with the calculated Fukui index based on density functional theory (DFT) calculation. In addition, the EC/PMS/Fe(III) system exhibited robust performance with the addition of co-existing ions. This work provides a novel strategy for efficient degradation of NAs for future remediation of petroleum wastewater. [ABSTRACT FROM AUTHOR]

Herein, an electrochemical (EC) system was applied as "co-catalyst" to enhance the activation of peroxymonosulfate (EC/Fe(III)/PMS) for efficient Sulfamethoxazole (SMX) degradation. The cathodic reduction reaction can facilitate electron transfer to Fe(III) and trigger the sustainable Fe(III)/Fe(II) redox cycle. Unexpectedly, in addition to hydroxyl radical (•OH) and sulfate radical (SO 4 •−), non-radicals mechanism including singlet oxygen (1O 2) and Fe(IV) were also found involved in EC/Fe(III)/PMS system. The degradation of SMX in EC/Fe(III)/PMS system was accomplished by the collaboration of radicals and non-radicals oxidation. The generation routes and mechanisms of involved reactive oxygen species (ROS) were explored. The relative contributions of •OH, SO 4 •−, and nonradical species for the degradation of SMX were calculated to 4.75 %, 25.31 %, and 69.94 %, respectively. Besides, multiple degradation pathways of SMX were proposed by identifying the formed byproducts. The EC/Fe(III)/PMS process could efficiently degrade SMX under the influence of co-existing ions and inactivate pathogens in the wastewater. [Display omitted] • Electrochemical system was used as a "co-catalyst" to promote the Fe(III)/Fe(II) redox cycle. • SMX is effectively degraded with a weak electrical current consumption in EC/Fe(III)/PMS system. • EC/Fe(III)/PMS system is mainly a non-radical pathway dominated by 1O 2 and Fe(IV). • EC/Fe(III)/PMS system demonstrated the ability to simultaneously eliminate contaminants and pathogens. [ABSTRACT FROM AUTHOR]

Electrochemical aptasensing systems have been developed for screening low-abundance disease-related proteins, but most of them involve multiple washings and multi-step separation during measurements, and thus are disadvantageous for routine use. In this work, an innovative and simple electrochemical aptasensing platform was designed for the voltammetric detection of prostate-specific antigen (PSA) in biological fluids without any washing and separation steps. This system mainly included a PSA-specific aptamer, a DNA walker and two hairpin DNA probes (i.e., thiolated hairpin DNA1 and ferrocene-labeled hairpin DNA2). Introduction of target PSA caused the release of the DNA walker from a partially complementary aptamer/DNA walker hybridization strand. The dissociated DNA walker opened the immobilized hairpin DNA1 on the electrode, accompanying subsequent displacement reaction with hairpin DNA2, thus resulting in the DNA walker step-by-step reaction with numerous hairpin DNA1 probes on the sensing interface. In this case, numerous ferrocene molecules were close to the electrode to amplify the voltammetric signal within the applied potentials. All reactions and electrochemical measurements including the target/aptamer reaction and hybridization chain reaction were implemented in the same detection cell. Under optimal conditions, the fabricated electrochemical aptasensor gave good voltammetric responses relative to the PSA concentrations within the range of 0.001–10 ng mL−1 at an ultralow detection limit of 0.67 pg mL−1. A good reproducibility with batch-to-batch errors was acquired for target PSA down to 11.5%. Non-target analytes did not interfere with the voltammetric signals of the electrochemical aptasensors. Meanwhile, 15 human serum specimens were measured with electrochemical aptasensors, and displayed well-matched results in comparison with the referenced human PSA enzyme-linked immunosorbant assay (ELISA) method. Significantly, this method provides a new horizon for the quantitative monitoring of low-concentration biomarkers or nucleic acids. [ABSTRACT FROM AUTHOR]

• The EC/PMS/Fe(III)-EDTA system was tested under a pH range of 3–9. • Fe(II)-EDTA complex maintains high reaction rates to degrade ACA at neutral pH. • •OH, 1O 2 , SO 4 •− and Fe(IV) are the dominant reactive species in the system. • The addition of EDTA established a new pathway for producing 1O 2 in the system. • ACA degradation pathways and byproducts were revealed based on mass spectra. In this work, ethylene diamine tetraacetic acid (EDTA) was applied as a chelating agent to stabilize Fe(III)/Fe(II) cycle to effectively activate peroxymonosulfate (PMS) in an electrochemical (EC) co-catalytic system for elimination of naphthenic acids (NAs) under neutral pH condition. 1-Adamantanecarboxylic acid (ACA) was applied as the model compound for NAs that are persistent contaminants in petroleum industrial wastewater. In the PMS/EC/Fe(III)-EDTA system, complete removal of ACA has been achieved in 20-min reaction under neutral pH condition. Degradation mechanisms were investigated via electron paramagnetic resonance (EPR) analysis, probe experiments and quenching experiments to reveal the reactive species •OH, SO 4 •− and 1O 2 for ACA removal, the production of which have been significantly facilitated by the introduction of EDTA complex. A new pathway has been found for the production of 1O 2 via several intermediates including hydrogen peroxide and superoxide radicals. Density functional theory (DFT) calculations and mass spectrometry analysis were applied to predict ACA degradation pathways and byproducts. Decarboxylation, hydroxyl substitution and carbonyl substitution byproducts of ACA were detected. The PMS/EC/Fe(III)-EDTA system suffered nonimportant influence at the presence of humic acid, H 2 PO 4 -, HCO 3 –, NO 3 – and Cl- for ACA removal. Overall results demonstrate the effectiveness and reliability of the PMS/EC/Fe(III)-EDTA system for efficient removal of NAs in petroleum wastewater in natural environment under neutral pH condition. [ABSTRACT FROM AUTHOR]

In this study, the Fe(III)/WS 2 /peroxymonosulfate (PMS) system was found to remove up to 97% of cyclohexanecarboxylic acid (CHA) within 10 min. CHA is a model compound for naphthenic acids (NAs), which are prevalent in petroleum industrial wastewater. The addition of WS 2 effectively activated the Fe(III)/PMS system, significantly enhancing its ability to produce reactive oxidative species (ROS) for the oxidation of CHA. Further experimental results and characterization analyses demonstrated that the metallic element W(IV) in WS 2 could provide electrons for the direct reduction of Fe(III) to Fe(II), thus rapidly activating PMS and initiating a chain redox process to produce ROS (SO 4 •−, •OH, and 1O 2). Repeated tests and practical exploratory experiments indicated that WS 2 exhibited excellent catalytic performance, reusability and anti-interference capacity, achieving efficient degradation of commercial NAs mixtures. Therefore, applying WS 2 to catalyze the Fe(III)/PMS system can overcome speed limitations and facilitate simple, economical engineering applications. [Display omitted] • Fe(III)/WS 2 /PMS system can achieve 97% removel rate of CHA within 10 min. • •OH, SO 4 •−, and 1O 2 are main ROS in the Fe(III)/WS 2 /PMS system. • W(IV) contained in WS 2 can promoting Fe(III)/Fe(II) cycle by providing electrons. • Fe(III)/WS 2 /PMS system can achieve efficient degradation of commercial NAs. • Fe(III)/WS 2 /PMS system exhibits excellent reusability and anti-interference. [ABSTRACT FROM AUTHOR]

[Display omitted] • The EF-TPP system was explored without extra oxidants. • Mechanistic analysis of the degradation of pollutants for EF-TPP system. • Elucidation of the slow-release mechanism of iron ions. • OH and O 2 − are the main reactive species in the system. • Determination of the structure and species of TPP-Fe complexes in EF-TPP system. This study utilized tetrapolyphosphate (TPP) as the electrolyte in the electro-Fenton (EF) system to efficiently generate reactive oxygen species (ROS) for effective degradation of diclofenac sodium (DCF) by activating dissolved molecular oxygen without aeration. The results indicated that the EF-TPP process produced a higher concentration of Fe(II) ions but a lower concentration of total iron than those concentrations in the regular EF-Na 2 SO 4 process, resulting in the higher degradation efficiency of the former system without producing iron sludge. It was found both hydroxyl (OH) and superoxide radicals (O 2 −) are primary reactive species in the EF-TPP system. The EF-TPP system produced a much higher amount of OH (3.886 μmol/L) than that of the EF-Na 2 SO 4 system (0.042 μmol/L). In addition, results of density functional theory (DFT) calculations and characterization experiments revealed the reaction pathway of dissolved molecular oxygen with Fe-TPP complexes, which are primarily present as [Fe(TPP)(H 2 O) 2 ]− and [Fe(TPP) 2 ]4− in the EF-TPP system. These results indicated that both speciation of Fe-TPP complexes can effectively activate molecular oxygen to generate ROS. DCF degradation pathways were proposed by identifying the formed byproducts. Overall results indicated the electrolyte TPP in the EF-TPP system induces the slow release of iron ions, the formation of Fe-TPP complex to stabilize the Fe(II) in the neutral pH condition, and the enhanced activation of dissolved molecular oxygen via one-electron transfer pathway. [ABSTRACT FROM AUTHOR]

Abstract: A newly developed two-dimensional mapping high irradiance laser ionization orthogonal time-of-flight mass spectrometer (LI-O-TOFMS) has been applied for the elemental mapping of polymetallic nodules. Two polymetallic nodule standards were used to demonstrate the efficacy of LI-O-TOFMS for the standardless semiquantitative analysis and the spatial distribution of elements in a deep-sea Pacific polymetallic nodule was mapped. It was found that the two groups of elements, Mn–Ni–Cu–Fe and Co–Si–Al, show clear element-dependent spatial relationships. It is hypothesized that these spatial distributions reflect the environmental and physico-chemical conditions during the nodule formation. LI-O-TOFMS is shown to be a powerful tool in elemental analysis of polymetallic nodules, with the detection limits down to 10−7 g/g and a dynamic range of 7 orders of magnitude. Based on the images acquired, the contents of elements and their relationships can be revealed visually. [Copyright &y& Elsevier]

Abstract: The imprinted gene Grb10 influences fetal growth, adult behavior and tumor formation. Investigating this gene often involves consecutive passaging of cells in vitro. We analyzed changes in Grb10 DNA methylation and histone modifications in serially passaged adult mouse tail-tip fibroblast cells with bisulfite genomic sequencing method and chromatin immunoprecipitation (ChIP) respectively. There was a significant reduction in global DNA methylation, but no changes in methylation at CpG island 1 (CGI1) of Grb10. There were no changes in methylation at histone H3K4me2, but less methylated histone H3K27me3 was detected, along with more of the acetylated histones H3Ac and H4Ac. The major-type transcript level of Grb10 in fibroblasts increased mildly after extended cultivation. These results suggest consecutive passaging may affect epigenetic modifications of Grb10 in adult fibroblast cells. [Copyright &y& Elsevier]

Although peptide amphiphiles have been explored as nanomaterialsfor different applications, nanostructures formed by hierarchicalmolecular assembly of sequence-specific peptidomimetics are much lessdeveloped. Such protein-like nanomaterials could enhance the currentapplication of peptide-based amphiphiles by enriching the diversityof nanostructures, increasing in vivostability forbiomedical applications, and facilitating the understanding of biomacromolecularself-assembly. Herein we present a biomimetic γ-AApeptide amphiphilewhich forms nanorods. Our results demonstrate the capability of γ-AApeptideamphiphiles as a potential scaffold for the preparation of biomimeticand bioinspired nanostructures. The programmability and biocompatibilityof γ-AApeptides could lead to novel nanomaterials for a widevariety of applications. [ABSTRACT FROM AUTHOR]

Abstract: The evolution of high-irradiance laser-ionization time-of-flight mass spectrometry (LI-TOF-MS) mainly progressed following significant improvements in the laser source, the TOF mass analyzer and construction geometries. We summarize the main developments in LI-TOF-MS, including the instrumentation and the applications. We also present particular instruments that our group developed recently. [Copyright &y& Elsevier]

Abstract: Laser ablation and ionization in ambient helium and argon gases were studied by multiple-stage time-of-flight mass spectrometry. Measurements made at different gas pressures indicated that there exists an optimal pressure for adequately cooling energetic ions and reducing multiply charged ions that are higher for He than for Ar. The temporal distributions of ions were compared at various laser fluences and gas pressures, and the broad distributions for He could be ascribed to elastic scattering and thermodynamic processes. The diffusion of ions in He resulted in a longer delay before the instrument registered its maximal signal. Ions with different masses were observed to have the same kinetic energies in He, which was confirmed using the SIMION software, while ion movement was hydrodynamically controlled in Ar. The velocities of singly and doubly charged ions were also studied, and doubly charged ions showed much higher kinetic energy because of their frontal location in the plasma expansion. [Copyright &y& Elsevier]

Recently, long noncoding RNAs (lncRNAs) have been reported to play important role in the pathogenesis of various cancers. However, the functions of RNF185-AS1 in hepatocellular carcinoma (HCC) remain unknown. The RNF185-AS1 expression in HCC cells and tissues was measured by quantitative real-time polymerase chain reaction (qRT-PCR). The effects of RNF185-AS1 on tumor cell proliferation, migration and invasion were assessed by Cell Counting Kit-8 (CCK8) assay, colony formation assay, transwell assay. The luciferase reporter assay, RNA-binding protein immunoprecipitation assay, qRT-PCR and Western blot were performed to explore and confirm the interaction between RNF185-AS1 and miR-221-5p and integrin β5. The role of RNF185-AS1 in tumor progression was explored through in vivo experiments. RNF185-AS1 was highly expressed in HCC tissues and cell lines. High levels of RNF185-AS1 were correlated with advanced TNM stage, distant metastasis and a poorer overall survival rate. RNF185-AS1 knockdown inhibited cell proliferation, migration and invasion. Additionally, RNF185-AS1 acted as a sponge for miR-221-5p and integrin β5 was identified as a target gene of miR-221-5p. Rescue assays showed that miR-221-5p inhibitor or integrin β5 overexpression rescued the function of RNF185-AS1 knockdown on cell proliferation, migration, and invasion. Moreover, we found that RNF185-AS1 knockdown inhibited tumor growth and metastasis. Our study demonstrates that RNF185-AS1 is a new oncogenic lncRNA in HCC and suggests that the RNF185-AS1/miR-221-5p/integrin β5 axis might be a potential therapeutic target for HCC. [ABSTRACT FROM AUTHOR]

Naphthenic acid fraction compounds (NAFCs), defined herein as the polar organic compounds extracted from the acidified oil sands process water (OSPW) samples using dichloromethane, are becoming the research hotspot due to their presence in large amount in OSPW and along with other potentially NA-contaminated water streams from the mining site. Fourier transform infrared spectroscopy (FTIR) method is commonly used to quantify NAFCs and assumes that the total NA concentration is measured as the sum of the responses for all carboxylic acid functional groups. In this study, the NAFCs in various OSPW and groundwater (GW) samples from an active oil sands mining site were analyzed using FTIR. All water samples were pretreated using either solid-phase extraction (SPE) or liquid-liquid extraction (LLE) methods before analysis. The results showed that SPE produced higher recoveries of NAFCs than LLE for most water samples under current experimental conditions. For the quantification of NAFCs, commercial Fluka NA mixture and a pre-calibrated OSPW extract were employed as the calibration standards. The NAFCs calibrated with Fluka NA mixture and OSPW extract had clear linear relationships. The concentrations of NAFCs obtained using OSPW extract standard curve were 2.5 times the NAFC concentrations obtained using the Fluka NA mixture standard curve. Additionally, good linear correlations were observed between the total NAs and O 2 -O 6 NA species determined by ultra-performance liquid chromatography coupled with time-of-flight mass spectrometry (UPLC-TOFMS) and the NAFCs measured by FTIR. According to these correlations, the NA compositions in NAFCs were developed, and the relative abundances of O 2 -O 6 NA species in NAFCs were similar for SPE and LLE pretreated samples. The findings of this study demonstrated that FTIR could be used as a promising tool to monitor total NA species and to estimate the NA profile in different environmental water samples. Unlabelled Image • We compared FTIR and UPLC-TOFMS with different extraction methods (LLE and SPE). • SPE produced higher recoveries of NAFCs than LLE for most water samples. • Higher NAFC concentrations were produced with OSPW extract than those with Fluka. • Good linear correlations were observed between UPLC-TOFMS and FTIR. • FTIR provided fast and accurate estimation of the NA species composition. [ABSTRACT FROM AUTHOR]

Chronic rhinosinusitis (CRS) is one of the most common types of respiratory disease and affects a large proportion of the population worldwide. The clinical differences between CRS with nasal polyps (CRSwNP) and CRS without nasal polyps (CRSsNP) facilitate studies on the development of polyps. In the present study, next-generation sequencing was performed to identify differentially expressed microRNAs (miRNAs/miRs) in CRSwNP vs. CRSsNP tissues and subsequently validated the expression of selected genes using reverse transcription-quantitative polymerase chain reaction analysis. In total, 6 miRNAs were identified to be downregulated in the CRSwNP samples compared with those in the CRSsNP samples. The predicted targets of these miRNAs were determined to be enriched in a number of signaling pathways, including the ErbB, Ras, cyclic adenosine monophosphate and Janus kinase (Jak)/signal transducer and activator of transcription (STAT) pathways. The expression of miR-4492 and that if its targets predicted by a bioinformatics analysis, tumor necrosis factor α (TNF-α) and interleukin (IL)-10, was validated in 96 clinical specimens. miR-4492 was downregulated and IL-10 was upregulated in CRSwNP vs. CRSsNP tissues, and an inverse correlation between miR-4492 and IL-10 was determined in CRS tissues; however no difference was identified in the expression of TNF-α between the different groups. The present results indicate that the miR-4492/IL-10 interaction in the Jak/STAT signaling pathway may be one of the key mechanisms in CRSwNP. [ABSTRACT FROM AUTHOR]

The acceleration of Fe(III)/Fe(II) conversion in Fenton systems is the critical route to achieve the long-lasting generation of reactive oxygen species towards the oxidation of refractory contaminants. Here, we found that waste leather derived porous carbon materials (LPC), as a simple and readily available metal-free biochar material, can promote the Fe(III)/H 2 O 2 system to generate hydroxyl radicals (•OH) for oxidizing a broad spectrum of contaminants. Results of characterizations, theoretical calculations, and electrochemical tests show that the surface carbonyl groups of LPC can provide electron for direct Fe(III) reduction. More importantly, the graphitic-N on surface of LPC can enhance the reactivity of Fe(III) for accelerating H 2 O 2 induced Fe(III) reduction. The presence of LPC accelerates the Fe(III)/Fe(II) redox cycle in the Fe(III)/H 2 O 2 system, sustainable Fenton chain reactions is thus initiated for long-lasting generation of hydroxyl radicals without adding Fe(II). The continuous flow mode that couples in-situ Fenton-like oxidation and LPC with excellent adsorption catalytic properties, anti-coexisting substances interference and reusability performance enables efficient, green and sustainable degradation of trace organic pollutants. Therefore, the application of metal-free carbon materials in Fenton-like system can solve its rate-limiting problem, reduce the production of iron sludge, achieve green Fenton chemistry, and facilitate the actual engineering application of economic and ecological methods to efficiently remove trace organic contaminants from actual water sources. [Display omitted] • Waste leather-derived porous carbon can effectively boost Fenton oxidation. • H 2 O 2 can act as an electron donor for green and sustainable Fenton oxidation. • Surface nitrogen of LPC can elevate the reactivity of Fe(III) species. • Sustainable removal of trace refractory organic pollutants was achieved. • Hydroxyl radical induced oxidation pathway of DEP was proposed. [ABSTRACT FROM AUTHOR]

In this work, the pulsed electrochemical (PE) system was investigated to activate peroxymonosulfate (PMS) with the addition of Fe(III) to achieve efficient degradation of sulfamethoxazole (SMX) with reduced energy consumption, in comparison with the direct current (DC) electrochemical system. The operational conditions of PE/PMS/Fe(III) system were optimized as 4 kHz pulse frequency, 50% duty cycle, and pH 3, at which 67.6% reduction of energy consumption and enhanced degradation performance were achieved compared to the DC/PMS/Fe(III) system. Results of electron paramagnetic resonance spectroscopy analysis and quenching and chemical probe experiment revealed the presence of •OH, SO 4 •−, and 1O 2 in the system, with •OH being the dominant role. The concentrations of these active species were averagely 15 ± 1% higher in the PE/PMS/Fe(III) system than those of the DC/PMS/Fe(III) system. Identification of SMX byproducts was achieved based on high resolution mass spectrometry analysis to predict the degradation pathways. The SMX byproducts could eventually be eliminated by the PE/PMS/Fe(III) system with extended treatment time. Overall, the PE/PMS/Fe(III) system was demonstrated with high energy and degradation performance, and is appear to be an robust strategy for practical treatment of wastewater. [Display omitted] ● The PE system are more energy-efficient and effective than DC system. ● PE/PMS/Fe(III) system can improve the utilization of iron ions. ● •OH is the dominant active species in PE/PMS/Fe(III) system. ● The degradation pathways and byproducts toxicity of SMX were further evaluated. [ABSTRACT FROM AUTHOR]