Negative Ion Research Articles

Electron-driven processes in enantiomeric forms of glutamic acid initiated by low-energy resonance electron attachment.

Low-energy (0-14eV) resonance electron interaction and fragment species produced by dissociative electron attachment (DEA) for enantiomeric forms of glutamic acid (Glu) are studied under gas-phase conditions by means of DEA spectroscopy and density functional theory calculations. Contrary to a series of amino acids studied earlier employing the DEA technique, the most abundant species are not associated with the elimination of a hydrogen atom from the parent molecular negative ion. Besides this less intense closed-shell [Glu - H]- fragment, only two mass-selected negative ions, [Glu - 19]- and [Glu - 76]-, are detected within the same electron energy region, with the yield maximum observed at around 0.9eV. This value matches well the energy of vertical electron attachment into the lowest normally empty π* COOH molecular orbital of Glu located at 0.88eV according to the present B3LYP/6-31G(d) calculations. Although the detection of asymmetric DEA properties a priori is not accessible under the present experimental conditions, "chirality non-conservation" can be associated with some decay channels. Evidently, the measured spectra for the L- and D-forms are found to be identical, the results, nevertheless, being of interest for the forthcoming experiments utilizing spin-polarized electron beam as a chiral factor in the framework of conventional DEA technique.

Critical evaluation of high-resolution and low-resolution mass spectrometry for biomonitoring of human environmental exposure to pesticides

Despite increasing debates about their potential side effects on human health, data concerning the risks and the impacts associated with pesticides remains scarce. Analytical tools allowing the measurement of most pesticides and/or their metabolites to which the population can be exposed are also of need. In the present study, the limits of detection (LODs) of 3 different screening procedures based on either Low-Resolution and High-Resolution Mass Spectrometry (LR-MS and HR-MS) for the determination of pesticides in serum (among which carbamates, dithiocarbamates, neonicotinoids, organochlorines, organophosphates and pyrethroids) were explored. For HR-MS, a quadrupole time-of-flight was used in positive and negative electrospray ionization modes and data were obtained from either a targeted scheduled MSMS acquisition (HR-MSMS) or a data-independent acquisition (HR-DIA). For LR-MS, a triple quadrupole was used and data were acquired with a classical multiple-reaction monitoring (MRM) mode. Depending on the approach, the LOD values varied from 0.05 to 10 ng/mL. For the lowest concentrations, the proportion of molecules detected was systematically greater for the LR-MS approach, while those of HR-MSMS were better than those of HR-DIA. These differences in the LOD values were confirmed in a sample of 174 serums in which LR-MRM detected 89 compounds while HR-MSMS and HR-DIA detected 79 and 75 compounds, respectively. Nevertheless, for environmental and occupational purposes, HRMS approach could probably be efficient to detect most of pesticides and their metabolites in human serum and could be suitable for human biomonitoring studies or fundamental research exploring the impact of exposure to pesticides on human health.

Doping Control Analysis of Perfluorocarbons in Equine Plasma by Headspace Gas Chromatography-Tandem Mass Spectrometry.

In order to control the potential misuse of perfluorocarbons as an oxygen carrier in equine sports, a simple and sensitive method for detecting perfluorocarbons in equine plasma by gas chromatography/tandem mass spectrometry using negative chemical ionization with methane as reagent gas has been developed and fully validated. The method covers seven perfluorocarbons, which are the active components in blood substitute products, and shows good sensitivity and robustness. Limits of detection as low as 0.01 ng/mL could be achieved by the method. To the best of our knowledge, this is the first report of a detection method for the screening of perfluorocarbons in equine biological samples.

The Combined Effects of the Thermal Environment and Air Quality at Recreation Places on the Physiology and Psychology of People in Urban Parks

Urban forests, crucial to urban ecosystems, are increasingly threatened by the challenges of urbanization, such as deteriorating thermal environments and declining air quality. Despite their recognized benefits to city dwellers’ quality of life, a systematic understanding of the impact of these environmental factors on public psychophysiological well-being in recreational sites is a notable gap in the literature. The objective of this research was to bridge this gap by examining the effects of the thermal environment and air quality in urban forests on the public’s perception, offering scientific evidence to inform environmental optimization and health management strategies for urban parks, essential for sustainable urban development and public health. Three urban parks in Fuzhou, Fujian Province, namely Fuzhou National Forest Park, Xihu Park, and Jinniushan Sports Park, were selected as research sites. Environmental monitoring and questionnaire surveys were conducted at 24 recreation places from October to December 2020, collecting temperature, humidity, and wind speed; the atmospheric composition includes PM2.5, PM10, negative oxygen ion, and psychophysiological data from the public. Multivariate statistical methods were employed to assess the environmental characteristics of different recreation places types and their impact on public health. The findings reveal that environmental factors explained 1.9% to 11.8% of the variation in physiological and psychological responses, mainly influenced by temperature, wind speed, and negative oxygen ions. Forests and waterfront recreation places significantly outperform canopy and open recreation places in promoting mental invigoration, stress relief, emotional tranquility, and attention restoration. Environmental monitoring results indicate that favorable meteorological conditions and good air quality are crucial for enhancing the service functions of recreation places. Notably, the positive correlation between a negative air ion concentration and psychological well-being provides a novel perspective on understanding the health benefits of urban forests. The thermal environment and air quality of urban recreation places exert a significant influence on the psychophysiological status of the public. Increasing green coverage, improving water body environments, and rationally planning recreation places layout are of great theoretical and practical significance for enhancing the environmental quality and service functions of urban forests.

Theoretical Study of Transition Metal Chemistry in Alkali Metal Complexes [K2M(COT)2]− (M=K, Rb, Cs)

AbstractThe transition metal properties of heavy alkaline earth metals have been extensively studied, and their neighbouring heavy alkali metals have been limited to the interactions with CO‐σ ligands. Based on this, the complexes [K2M(COT)2]− (M=K, Rb, Cs) interacting with heavy alkali metals and COT‐π ligands are theoretically designed in this paper. The electronic structure analysis showed that the three complexes had 10 occupied molecular orbitals (MOs), in which 8 of them were related to the atomic orbitals (AOs) of central alkali metals, including 4 d orbitals (dxy, dx2−y2, dxz, dyz), so they also exhibited the typical behaviors of transition metals. NBO analysis indicated that the central metals in these complexes are common valence of +1, the ligands are negative, so the electrostatic coulomb interaction between positive and negative ions makes them more stable. This can be reflected by the high binding energies of −585.8 to −594.0 kcal/mol, which are much higher than those of −6.5 to −63.3 kcal/mol for the trace amount of complexes combined by neutral metals and ligands. It would be a feasible strategy for the design of the macrosynthesis of related complexes by combining the positive ions and negative ligands, which can stabilize the complexes through the favorable Coulomb attractions.

Simultaneous determination of 13 biogenic amines and their metabolites in liquid fermented food by HPLC-QTRAP-MS without derivatization

Biogenic amines and their metabolites (BAs) are among the most frequently detected compounds in liquid fermented foods, raising significant concerns about the potential risks they pose. To rapidly and selectively determine BAs, this study proposed and validated a method for the simultaneous determination of 13 BAs in liquid fermented foods using high performance liquid chromatography-triple quadrupole/linear ion trap mass spectrometry (HPLC-QTRAP-MS) without derivatization. The simultaneous separation and determination of histamine (HIS), tyramine (TYR), putrescine (PUT), octopamine (OCT), 2-phenylethylamine (2-PHE), dopamine (DOP), spermidine (SPD), epinephrine (EPI), agmatine (AGM), 5-hydroxytryptamine (5-HYD), tryptamine (TRY), L-noradrenaline (L-NOR), cadaverine (CAD) were achieved using a Waters Atlantis Premier BEH Z-HILIC (1.7 μm particle size, 100 mm × 2.1 mm id) column with a mobile phase consisting of water (containing 0.025 % formic acid) and acetonitrile (containing 0.1 % formic acid). The analysis of target compounds was performed with electrospray ionization (ESI) in positive ion mode, multiple reaction monitoring (MRM), information dependent acquisition (IDA), enhanced product ion (EPI), and multi-step mode analysis combined with EPI library searching. To enhance the extraction efficiency of BAs, factors such as extraction solvent, filter membranes, extraction methods, pH, oscillation speed, time and temperature were systematically investigated. The results demonstrated that the method exhibited low limits of detection (LOD) and quantification (LOQ), ranging from 0.05 to 2.00 µg/L and 0.16 to 6.60 µg/L, respectively. The method also showed satisfactory reproducibility, with intra-day and inter-day relative standard deviations ranging from 0.90 % to 3.80 % and 2.65 % to 8.27 %, respectively. Additionally, it had a broad linear range from 0.05 to 200.00 µg/L with excellent linearity (R>0.99) and an average recovery rate between 65.68 % and 115.14 %. Overall, the results demonstrated that the established method was convenient to operate, offered a short analysis time, and achieved high accuracy and sensitivity. It met the qualitative and quantitative requirements for detecting 13 BAs in liquid fermented food, thus providing strong technical support for BAs detection.

Reactive Gas Cluster Ion Beams for Enhanced Drug Analysis by Secondary Ion Mass Spectrometry.

In this study, we investigate the formation and composition of Gas Cluster Ion Beams (GCIBs) and their application in Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) analysis. We focus on altering the carrier gas composition, leading to the formation of (Ar/CO2)n or (H2O)n GCIBs. Our results demonstrate that the addition of a reactive species (CO2) to water GCIBs significantly enhances the secondary ion yield of small pharmaceutical compounds in the positive ion mode. In negative ion mode, the addition of CO2 resulted in either a positive enhancement or no effect, depending on the sample. However, an excess of CO2 in the carrier gas leads to the formation of carbon dioxide clusters, resulting in reduced yields compared to that of water cluster beams. Cluster size also plays a crucial role in overall yields. In a simple two-drug system, CO2-doped water clusters prove effective in mitigating matrix effects in positive ion mode compared to pure water cluster, while in negative ion mode, this effect is limited. These clusters are also applied to the analysis of drugs in a biological matrix, leading to more quantitative measurements as shown by a better fitting calibration curve. Overall, the doping of water clusters with small amounts of a reactive gas demonstrates promising benefits for higher sensitivity, higher resolution molecular analysis, and imaging using ToF-SIMS. The effectiveness of these reactive cluster beams varies depending on the experimental parameters and sample type.

A simple ultraperformance liquid chromatography mass spectrometry method for the determination of cortisol level in sea bass plasma

A simple, precise, and rapid ultra-performance liquid chromatography method for cortisol quantification in sea bass plasma, based on LC-ESI-UHR-QqTOF-MS, was optimised using tolperisone as internal standard. Sea bass plasma samples containing cortisol were spiked with tolperisone as internal standard and extracted with acetonitrile. Samples were vortexed and centrifuged at 15,000g for 10 min at 4 °C. The final extract, diluted in ammonium formate (1:1), was injected in the LC-ESI-UHR-QqTOF-MS system for analysis. Mass spectrometry acquisition parameters were set using positive ionisation mode over a m/z range from 150 to 2200. Cortisol and tolperisone were detected and quantified at m/z 363.21 and 246.18, respectively, in an Auto MS (MS/MS) mode. The detection and quantification limits of cortisol in sea bass plasma were 0.01 and 0.02 μg/mL, respectively. The mean extraction recovery of cortisol was of 99.1 ± 4.0 %. The within- and between-day precision presents a relative standard deviation (RSD) below 2.9 % and 5.3, respectively. Furthermore, the effect of four different diets (fish feed 1–4) in the basal and stress-induced plasma cortisol levels of sea bass was also assessed.

A new attempt to further reduce the work function of the cesiated surface: The strongest electronegative element fluorine co-adsorption with cesium on Mo (001) surface

The efficiency of hydrogen negative ion production in negative ion sources depends on the work function of the molybdenum surface. Deposition of cesium (Cs) atoms on the Mo surface reduces the work function from over 4.0 eV to about 1.50–1.80 eV. However, the Fermi level remains below the affinity level (−0.75 eV) of hydrogen negative ions. To explore further reduction methods, the work function of Cs co-adsorbed with fluorine on the Mo (001) surface was studied using DFT calculations. The results show that at 4/16 θ Cs coverage, adding fluorine can reduce the work function, achieving the lowest value of 1.40 eV at 8/16 θ F coverage. Analysis reveals a significant vacuum-inward dipole moment with fluorine-Cs co-adsorption, favorably reducing the work function. However, fluorine’s strong electronegativity also creates a surface-directed dipole moment, increasing the work function. Introducing fluorine is beneficial only at 4/16 θ Cs coverage, indicating that precise control of Cs coverage is necessary to achieve lower work functions.

Simulation on the hollow cathode discharge in hydrogen

A rectangular hollow cathode discharge (HCD) in hydrogen with a pressure of 2 Torr is simulated using a 2-D fluid model. The potential, electric field, particle density, and average electron temperature are calculated. The discharge space consists of the cathode sheath region near the cathode electrode and the negative glow (NG) region in the central region of the discharge cell. A high electric field of thousands of V/cm and a low electric field of tens of V/cm appear in the cathode sheath region and NG region, respectively. The average electron temperature in the cathode sheath region is tens of eV, which is significantly higher than that in the NG region. Electrons and H3 + are the main negative particles and positive ions, whose peaks appear in the NG region, and the peak magnitude is on the order of 1010 cm−3. H atom is the highest-density neutral particle other than H2 with a peak density of 1013 cm−3. The reaction kinetics of the generation and consumption of different particles are explored. The results show that each reaction generates certain particles while consuming other particles, ultimately achieving a dynamic equilibrium in the density of various particles. The electrons mainly originate from the ground state ionization between electron and H2 (e+H2 → e+H2 ++e) and are consumed by the dissociative attachment (e+H2 → H−+H). The charge transfer collision reaction (H2 ++H2 → H3 ++H) is the only reaction that produces H3 + ions. Different reactions to the consumption of H3 + ions do not differ significantly. The generation and consumption of H mainly originate from the electron collision dissociation reaction (e+H2 → e+H+H) and the ionization reaction (e+H→H++2e).

Development and validation of an LC-MS/MS method for simultaneous quantification of eight drugs in plasma and brain: Application in a pharmacokinetic study in mice

A selective and sensitive liquid chromatography coupled with tandem mass spectrometry (LC–MS/MS) method was developed and validated for simultaneous quantitation of a cassette of 8 drugs, including docetaxel, erlotinib, loperamide, riluzole, vemurafenib, verapamil, elacridar and tariquidar. Stable isotopically labeled compounds were available for use as internal standards for all compounds, except for tariquidar for which we used elacridar-d4. Sample pre-treatment involved liquid–liquid extraction using tert-butyl-methyl ether as this resulted in good recovery and low ion suppression. Chromatographic separation was achieved using a Zorbax Extend C18 analytical column and a linear gradient from 20 % to 95 % methanol in 0.1 % (v/v) formic acid in water. MS/MS detection using multiple reaction monitoring was done in positive ionization mode. We validated this assay for human and mouse plasma and mouse brain homogenates. The calibration curves were linear over a range 1–200 nM for each drug in the mix, except for tariquidar probably due to the lack of a stable isotope labeled analog. The intra-day and inter-day accuracies were within the 85–115 % range for all compounds at low, medium and high concentrations in the three different matrices. Similarly, the precision for all compounds at three different concentration levels ranged below 15 %, with the exception of tariquidar in mouse plasma and brain homogenate and riluzole in brain homogenate. Pilot studies have confirmed that the method is suitable for the analysis of mouse plasma samples and brain homogenates following cassette dosing of this mixture in mice.

PM1.0 removal enhancement in cooperated electric-ionic field by negative air ions carbon fiber electrode

The study focuses on improving the removal efficiency of submicron particles using negative air ions (NAIs), which are challenging to remove. To enhance this efficiency, cascaded carbon fiber tubular (CFT) chargers were designed to boost particle charging. Through experiments and numerical simulations, the chargers’ enhancement mechanisms, cooperation effects, and overall performance were evaluated. The optimal configuration for the CFT charger was identified as a gap distance (d = 2.0 r0) and grounded electrode length (L0 = 4πr03) that ensures high collection efficiency (96.7 % for 0.5 μm particles at 4 m/s) and ultra-low ozone generation (7.25 ppb). The study found that while the average electric field strength (E¯) and ion density significantly influence charging, an unusual improvement in collection efficiency was observed the charger with d = 2.0 r0 at u = 3 m/s, likely due to the potential predominance of the maximum electric field strength (Emax) at relative higher velocity. Besides, the CFT charger demonstrated balanced performance compared to other reported works, although higher relative humidity (80 ± 5 % RH) inhibits removal efficiency, which can be mitigated by reducing gas velocity.

Pharmaceutical metabolite identification in lettuce (Lactuca sativa) and earthworms (Eisenia fetida) using liquid chromatography coupled to high-resolution mass spectrometry and in silico spectral library.

Pharmaceuticals released into the aquatic and soil environments can be absorbed by plants and soil organisms, potentially leading to the formation of unknown metabolites that may negatively affect these organisms or contaminate the food chain. The aim of this study was to identify pharmaceutical metabolites through a triplet approach for metabolite structure prediction (software-based predictions, literature review, and known common metabolic pathways), followed by generating in silico mass spectral libraries and applying various mass spectrometry modes for untargeted LC-qTOF analysis. Therefore, Eisenia fetida and Lactuca sativa were exposed to a pharmaceutical mixture (atenolol, enrofloxacin, erythromycin, ketoprofen, sulfametoxazole, tetracycline) under hydroponic and soil conditions at environmentally relevant concentrations. Samples collected at different time points were extracted using QuEChERS and analyzed with LC-qTOF in data-dependent (DDA) and data-independent (DIA) acquisition modes, applying both positive and negative electrospray ionization. The triplet approach for metabolite structure prediction yielded a total of 3762 pharmaceutical metabolites, and anin silico mass spectral library was created based on these predicted metabolites. This approach resulted in the identification of 26 statistically significant metabolites (p < 0.05), with DDA + and DDA - outperforming DIA modes by successfully detecting 56/67 sample type:metabolite combinations. Lettuce roots had the highest metabolite count (26), followed by leaves (6) and earthworms (2). Despite the lower metabolite count, earthworms showed the highest peak intensities, closely followed by roots, with leaves displaying the lowest intensities. Common metabolic reactions observed included hydroxylation, decarboxylation, acetylation, and glucosidation, with ketoprofen-related metabolites being the most prevalent, totaling 12 distinct metabolites. In conclusion, we developed a high-throughput workflow combining open-source software with LC-HRMS for identifying unknown metabolites across various sample types.

SIL-IS LC-ESI-MS/MS method for simultaneous quick detection of amoxicillin and clavulanic acid in human plasma: Development, validation and its application to a pharmacokinetics study.

A liquid chromatography electrospray ionization tandem mass spectrometry method with amoxicillin-d4 as the stable isotope-labeled internal standard for simultaneous quick detection of amoxicillin and clavulanic acid in human plasma was developed and validated. Chromatographic separations were performed on a Hedera ODS-2 column (2.1 × 150 mm, 5μm). The mobile phases for gradient elution were aqueous solution containing 0.2% acetic acid (AA) (mobile phase A) together with organic phase solution (acetonitrile and methanol mixed solution, mobile phase B). Mass spectrometry was performed using negative electrospray ionization in multiple reaction monitoring mode. The target fragment ion pairs of amoxicillin, clavulanic acid and amoxicillin-d4 were m/z 364.1 → 223.1, 198.1 → 135.9 and 368.1 → 227.1, respectively. The linear ranges of this method were 40-5,000 ng/ml for amoxicillin and 30-2,500 ng/ml for clavulanic acid, with coefficient of determination > 0.9900. This method validation included selectivity, standard curve, lower limit of quantitation, accuracy, precision, recovery, matrix effect (hemolytic matrix and hyperlipidemic matrix), carryover, stability, dilution reliability and incurred sample reanalysis study. A successful application of this method was realized in a pharmacokinetic study after administration of amoxicillin-clavulanic acid potassium granules.

A multifunctional natural treasure based on a “one stone, many birds” strategy for designing health-promoting applications: Tordyliumapulum

Wild plants provide important bioactive compounds, and their analysis relies heavily on selecting the right extraction techniques and solvents. This study was conducted to determine the phenolic content and biopharmaceutical potential of four different extracts (ethyl acetate, ethanol, 70% ethanol, and water) from the aerial parts of wild plant Tordylium apulum L. The biochemical profile of the extract was screened using high performance liquid chromatography -mass spectrometry (HPLC-MS) analysis. The total phenolic and flavonoid content was examined using the Folin-Ciocalteu assay and the aluminium trichloride assay, respectively. The antioxidant activity was evaluated through several tests, including 2,2-Diphenyl-1-picrylhydrazyl (DPPH), 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS), cupric reducing antioxidant capacity (CUPRAC), ferric reducing antioxidant power (FRAP), phosphomolybdenum (PBD), and metal chelating activity (MCA). Five types of enzyme inhibition activity were tested against acetylcholinesterase (AChE), butrylcholinesterase (BChE), tyrosinase, α-amylase, and α-glucosidase. Additionally, For the first time, the inhibitory activity of T. apulum extract against human carbonic anhydrase isoenzymes I and II (hCA-I and hCA-II) was evaluated. Fifty-five compounds for negative ionization mode, and twenty-eight compounds for positive ionization mode were recorded in HPLC-MS analysis and they were polyphenolic, flavonoids, carbohydrates, sugar alcohol and amino acids. These results indicate that different solvents extract varying levels of antioxidants from T. apulum, with ethanol and water extracts generally exhibiting superior antioxidant activities. The ethanol extract of T. apulum exhibited the maximum contents of total phenolics measuring 33.71 mg gallic acid equivalent (GAE)/g. The ethanol extract exhibited the highest inhibition of AChE with 2.28 mg galanthamine equivalent (GALAE)/g. The ethyl acetate and ethanol extracts also showed the highest hCA-I and hCA-II inhibition potential, respectively. The ethanol-water and water extracts acted on the biofilm of E. coli (49.93% and 45.22%, respectively), and the biofilm of P. aeruginosa (50.68% and 44.46%, respectively). The extracts were tested on different cell lines for cytotoxic potentials and in particular the water extract induced the apoptotic pathways in cervical cancer (HELA) cell lines. In conclusion, T. apulum exhibit multidirectional biological properties and it could be considered as a versatile agent for the development of health-promoting applications.

A study on the determination of the metabolites of 2,4,6-Trinitrotoluene using a dual-drift tube ion mobility spectrometer

2,4,6-Trinitrotoluene (TNT) and its four metabolites, namely 2-ADNT, 4-ADNT, 2,4-DANT, and 2,6-DANT, are highly toxic substances. These metabolites also serve as biomarkers for assessing the health of individuals exposed to TNT. In this study, a homemade DDT-IMS apparatus was utilized to detect these metabolites. Under negative detection mode, the drift times of 2-ADNT and 4-ADNT showed subtle shifts within a drift tube temperature range of 100 °C–120 °C, aiding in their differentiation. In positive detection mode for 2,4-DANT and 2,6-DANT, significant variations were observed in both the number and drift time of their positive product ions across a drift tube temperature range of 80 °C–120 °C. Consequently, optimal analytical performance for these metabolites was achieved at approximately 100 °C. Evaluation of the instrumental response during the measurement of the four metabolites in both positive and negative modes revealed that negative detection mode offered greater advantages of detecting these compounds. The working ranges for measuring the four metabolites spanned two orders of magnitude, with detection limits for each metabolite nearly below 1 ng. Notably, clear identification of the signals for these metabolites was achieved even when samples were mixed in urine, highlighting the ability of the DDT-IMS in detecting TNT metabolites. The developed DDT-IMS detection method has significant potential for enhancing environmental risk assessment and biological hazard evaluation, particularly in relation to human exposure to TNT.

Development and Validation of Methodologies for the Identification of Specialized Pro-Resolving Lipid Mediators and Classic Eicosanoids in Biological Matrices.

Lipid mediators, which include specialized pro-resolving mediators and classic eicosanoids, are pivotal in both initiating and resolving inflammation. The regulation of these molecules determines whether inflammation resolves naturally or persists. However, our understanding of how these mediators are regulated over time in various inflammatory contexts is limited. This gap hinders our grasp of the mechanisms underlying the disease onset and progression. Due to their localized action and low endogenous levels in many tissues, developing robust and highly sensitive methodologies is imperative for assessing their endogenous regulation in diverse inflammatory settings. These methodologies will help us gain insight into their physiological roles. Here, we establish methodologies for extracting, identifying, and quantifying these mediators. Using our methods, we identified a total of 37 lipid mediators. Additionally, by employing a reverse-phase HPLC method, we successfully separated both double-bond and chiral isomers of select lipid mediators, including Lipoxin (LX) A4, 15-epi-LXA4, Protectin (PD) D1, PDX, and 17R-PD1. Validation of the method was performed in both solvent and surrogate matrix for linearity of the standard curves, lower limits of quantitation (LLOQ), accuracy, and precision. Results from these studies demonstrated that linearity was good with r2 values > 0.98, and LLOQ for the mediators ranged from 0.01 to 0.9 pg in phase and from 0.1 to 8.5 pg in surrogate matrix. The relative standard deviation (RSD) for inter- and intraday precision in solvent ranged from 5% to 12% at low, intermediate, and high concentrations, whereas the RSD for the inter- and intraday variability in the accuracy ranged from 95% to 87% at low to high concentrations. The recovery in biological matrices (plasma and serum) for the internal standards used ranged from 60% to 118%. We observed a marked ion suppression for molecules evaluated in negative ionization mode, while there was an ion enhancement effect by the matrix for molecules evaluated in positive ionization mode. Comparison of the integration algorithms, namely, AutoPeak and MQ4, and approaches for calculating signal-to-noise ratios (i.e., US Pharmacopeia, relative noise, peak to peak, and standard deviation) demonstrated that different integration algorithms tested had little influence on signal-to-noise ratio calculations. In contrast, the method used to calculate the signal-to-noise ratio had a more significant effect on the results, with the relative noise approach proving to be the most robust. The methods described herein provide a platform to study the SPM and classic eicosanoids in biological tissues that will help further our understanding of disease mechanisms.

Identifying the genesis of hydrothermal activities in the Xiangcheng fault belt, southwestern China: Evidence from hydrochemistry and stable isotopes

Regional faults are beneficial structures for the formation of hydrothermal activities and have thus become target areas for geothermal resource utilization. Numerous hydrothermal activities have been reported along the Xiangcheng fault belt, particularly concentrating in the Batang, Xiangcheng and Shangri-La areas. In this study, hydrochemistry and stable isotopes were used to identify the genesis of hydrothermal activities in the Xiangcheng fault belt. The pH values of the geothermal water in these regions gradually decreases in this order, while the total dissolved solids gradually increase. The δD and δ18O values indicate the geothermal waters are mainly originated from snowmelt water and meteoric water. The recharge elevation of geothermal waters in Batang, Xiangcheng, and Shangri-La was 4415–4904 m, 4585–5038 m, and 3673–3969 m, respectively. Most geothermal waters belong to the hydrochemical type HCO3-Na, however some Batang geothermal water is of the SO4·HCO3-Na type, influenced by deep geothermal gas, and some Shangri-La geothermal water is of HCO3-Ca·Na type, influenced by shallow cold water and dissolution of carbonate rocks. Correlations of major ions suggest that HCO3-Na type geothermal waters are determined by the dissolution of paragonite, K-feldspar and albite as well as positive ion exchange. According to Na-K-Mg triangle diagram and mineral saturation indices, the geothermal waters do not reach full equilibrium and are mixed with shallow cold. Geothermometers, including cationic and SiO2, and geochemical thermodynamic calculations indicate that the deep and shallow reservoir temperatures are 200–240 °C and 169–193 °C for the Batang area, 194–201 °C and 119–131 °C for the Xiangcheng area, and 156–178 °C and 100–109 °C for the Shangri-La area. Conceptual models of the genesis of hydrothermal activities in the Batang, Xiangcheng, and Shangri-La areas were constructed, respectively. CaCO3 scaling is dominated in the study area. The hydrothermal activities of Batang and Xiangcheng areas with enriched deep materials and high reservoir temperatures are beneficial for rare-alkali metal (e.g., Li). The findings of this study provide a scientific basis for the development and utilization of geothermal resources in the high-temperature hydrothermal activity areas of western Sichuan.

The Preliminary Analysis of Flavonoids in the Petals of Rhododendron delavayi, Rhododendron agastum and Rhododendron irroratum Infected with Neopestalotiopsis clavispora.

The petal blight disease of alpine Rhododendron severely impacts the ornamental and economic values of Rhododendron. Plant secondary metabolites play a crucial role in resisting pathogenic fungi, yet research on metabolites in alpine Rhododendron petals that confer resistance to pathogenic fungi is limited. In the present study, the secondary metabolites in Rhododendron delavayi, R. agastum, and R. irroratum petals with anti-pathogenic activity were screened through disease index analysis, metabolomic detection, the mycelial growth rate, and metabolite spraying experiments. Disease index analysis revealed that R. delavayi petals exhibited the strongest disease resistance, while R. agastum showed the weakest, both under natural and experimental conditions. UHPLC-QTOF-MS/MS analysis identified 355 and 274 putative metabolites in positive and negative ion modes, respectively. The further antifungal analysis of differentially accumulated baicalein, diosmetin, and naringenin showed their half-inhibitory concentrations (IC50) against Neopestalotiopsis clavispora to be 5000 mg/L, 5000 mg/L, and 1000 mg/L, respectively. Spraying exogenous baicalein, diosmetin, and naringenin significantly alleviated petal blight disease caused by N. clavispora infection in alpine Rhododendron petals, with the inhibition rates exceeding 64%. This study suggests that the screened baicalein, diosmetin, and naringenin, particularly naringenin, can be recommended as inhibitory agents for preventing and controlling petal blight disease in alpine Rhododendron.

Experimental study on plasma characteristics in the extraction region of a high-power RF negative ion source based on electrostatic probe

Abstract The plasma characteristics of the extraction region in high-power RF negative ion source have a significant impact on the production and extraction of negative hydrogen ions. This study utilized electrostatic probe to investigate the effect of RF power, source pressure, magnetic filter field and bias voltage on the plasma parameters of the extraction region (without cesium), and also studied the variation of plasma parameters with position and time. The results indicate that as RF power increases, the plasma density in the extraction region significantly rises, but it also leads to an increase in the electron temperature ( T e ) of the extraction region (which increases the loss of negative hydrogen ions); increasing the source pressure can effectively increase the electron density ( N e ) in the extraction region and reduce T e as expected; increasing the magnetic filter field can effectively reduce the T e in the extraction region, but after the plasma grid current exceeds 1900 A, the change in T e is not significant; although increasement of the bias voltage can effectively suppress the N e in the extraction region, it causes T e to rise; moreover, the distribution of plasma parameters in the extraction region is relatively uniform; in addition, the variation of plasma parameters with time is not obvious. These findings not only deepen the understanding of the physical mechanisms of plasma behavior in the extraction region of negative ion sources, but also provide important theoretical and experimental bases for the optimization of high-power RF negative ion sources.