Ionization Conditions Research Articles

Between the Extremes: A JWST Spectroscopic Benchmark for High-redshift Galaxies Using ∼500 Confirmed Sources at z ≥ 5

The exceptional spectra of the most luminous z > 10 sources observed so far have challenged our understanding of early galaxy evolution, requiring a new observational benchmark for meaningful interpretation. As such, we construct spectroscopic templates representative of high-redshift, star-forming populations, using 482 confirmed sources at z = 5.0−12.9 with JWST/NIRSpec prism observations, and report on their average properties. We find z = 5−11 galaxies are dominated by blue UV continuum slopes (β = −2.3 to −2.7) and reduced Balmer indices, characteristic of dust-poor and young systems, with a shift towards bluer slopes and younger ages with redshift. The evolution is mirrored by ubiquitous C iii] detections across all redshifts (rest-frame equivalent widths of 5−14 Å), which increase in strength towards early times. Rest-frame optical lines reveal elevated ratios (O32 = 7–31, R23 = 5–8, and Ne3O2 = 1−2) and subsolar metallicities (log(O/H) = 7.3−7.9), typical of ionization conditions and metallicities rarely observed in z ∼ 0 populations. Within our sample, we identify 57 Lyα emitters, which we stack and compare to a matched sample of nonemitters. The former are characterized by more extreme ionizing conditions with enhanced C iii], C iv, and He ii + [O iii] line emission, younger stellar populations from Balmer jumps, and a more pristine interstellar medium seen through bluer UV slopes and elevated rest-frame optical line ratios. The novel comparison illustrates important intrinsic differences between the two populations, with implications for Lyα visibility. The spectral templates derived here represent a new observational benchmark with which to interpret high-redshift sources, lifting our constraints on their global properties to unprecedented heights and extending out to the earliest of cosmic times.

DART isotope dilution high resolution mass spectrometry and 19F-NMR detection of fluorotelomeric alcohols in hydrolyzed food contact paper

Fluorotelomer-based acrylate polymers and surfactants used to grease-proof food contact paper (FCP) are potential sources of dietary exposure to perfluoroalkyl substances (PFAS). Food contact substances (FCS) containing polyfluorinated long-chains (≥C8) were voluntarily removed by their manufacturers from the U.S. market in 2011 due to health concerns and largely replaced with FCSs containing short-chain (≤C7) PFAS. In 2020, FDA findings of potential biopersistence of 6:2 FTOH (CF3(CF2)5CH2CH2OH) similarly prompted an additional voluntarily phase-out of FCSs containing 6:2 FTOH by their manufacturers that was completed by the end of 2023. To monitor the phase-out process, a screening method was developed to detect FCPs containing ester-linked polyfluorinated pendant chains. Direct Analysis in Real Time-Isotope Dilution-High Resolution Mass Spectrometry (DART-ID-HRMS) enabled rapid semi-quantitative detection of 6:2 FTOH in FCP saponification reaction headspace without requiring sample concentration or chromatography. 19F-NMR analysis confirmed 6:2 FTOH pendant chain identity and detection dependence on saponification. The speed and specificity of this approach arise from ester saponification in the presence of stable isotopically labeled 6:2 FTOH; high FTOH differential volatility relative to nonfluorinated matrix, and the facile production of FTOH gas-phase anions (e.g., [M + O2]·−, [M-H + CO2]−) under ambient ionization conditions. The efficiency of this simple workflow makes it well-suited for monitoring the phase-out of FCS containing ester-linked polyfluorinated chains from the U.S. marketplace.

TOF-MS based characterization of polyglycerol polyricinoleate (PGPR) samples

Time-of-flight mass spectrometry (TOF-MS) was used to unravel the composition of commercial polyglycerol polyricinoleate (PGPR) samples, by identifying the various molecular species present. To cover the broad range of molecular weights for the present species, a combination of three ionisation conditions was used. Species exceeding the molecular weight of pentaglycerol hexaricinoleate were difficult to detect. Over 100 molecular species were observed and identified in the analysed samples, including free polyglycerols, ricinoleates, and PGPR-esters. Commercial PGPR samples were shown to be mainly composed of esterification products of di-, tri-, and tetraglycerol, while the esterification degree mainly varied from 1 to 5. The TOF-MS analysis was proven to be reproducible with a relative standard deviation (RSD) below 2.86% for three independent measurements on different days. The method proved to be very suitable to evaluate batch-to-batch variations and to compare the composition of different types of commercial PGPR’s. Moreover, this method can be applied to monitor the quality of PGPR products during the synthesis process. Furthermore, it can also provide fundamental knowledge for optimizing PGPR composition to improve its functionality.

Determination of persistent and mobile organic compounds in the river–groundwater interface of the Besòs river delta, Spain, using a wide extraction approach

Climate change impacts the Mediterranean region, transforming it from region with a semi-arid climate to a region with an arid climate. Under this situation, while groundwater is an essential hydric resource, its existence is in danger due to anthropogenic pressures. Persistent mobile organic compounds (PMOCs) have recently been recognised as an emerging problem; however, PMOCs in groundwater need to be better characterised. Here, we present a new analytical method to characterise the profile of PMOCs in groundwater based on two parallel solid-phase extraction (SPE), using weak anion exchange and weak cation exchange. Extracts were analysed by ultraperformance liquid chromatography (UPLC) using mix-mode chromatography for those compounds analysed under negative ionisation conditions and hydrophilic interaction liquid chromatography (HILIC) under positive conditions coupled to high-resolution mass-spectrometry (HRMS) using a Q-Exactive Orbitrap™ analyser. For the suspect screening of PMOCs in groundwater, the acquisition mode was in full scan (FS) by “independent scan of all ion fragmentation”. For the tentative identification, different online databases such as Environmental and Food Safety (EFS) HRAM Compound database, PFAS NIST database, ChemSpider for chemical structural information, MzCloud as a mass spectral database, and an in-house list with 1280 PMOC structures have been used. The performance of the method was assessed with 29 representative PMOCs which were selected based on the previous literature. The recovery rates have been between 63 and 110 % for 90 % of the target compounds and method limits of quantification (MLQ) between 0.3 and 10.5 ng/L.The optimised approach was applied to assess PMOCs in the Besòs River aquifer, NE Spain, showing 148 tentatively identified structures at confidence levels 1–3. Among them, 66 suspects were tentatively identified at level 3, 54 at level 2, and 28 confirmed at level 1. Most of these compounds were polar and highly polar compounds which are difficult to retain with other extraction approaches. Major detected compounds were pharmaceuticals and personal care products (46), followed by perfluoroalkyl and polyfluoroalkyl substances (PFAS) (32), industrial additives (27), and pesticides (23), among other groups. Some compounds, such as ultrashort chain PFAS and fluorinated betaines, were detected for the first time in groundwaters in Spain.

Evidence of Extreme Ionization Conditions and Low Metallicity in GHZ2/GLASS-Z12 from a Combined Analysis of NIRSpec and MIRI Observations

GHZ2/GLASS-z12, one of the most distant galaxies found in JWST observations, has been recently observed with both the NIRSpec and MIRI spectrographs, establishing a spectroscopic redshift z spec = 12.34 and making it the first system at z > 10 with complete spectroscopic coverage from rest-frame UV to optical wavelengths. This galaxy is identified as a strong C iv λ1549 emitter (EW = 46 Å) with many other detected emission lines, such as N iv] λ1488, He ii λ1640, O iii] λ λ1661,1666, N iii] λ1750, C iii] λ λ1907,1909, [O ii] λ λ3726,3729, [Ne iii] λ3869, [O iii] λ λ4959,5007, and Hα, including a remarkable detection of the O iii Bowen fluorescence line at rest frame λ = 3133 Å. We analyze in this paper the joint NIRSpec + MIRI spectral data set. Combining six optical strong-line diagnostics (namely R2, R3, R23, O32, Ne3O2, and Ne3O2Hd), we find extreme-ionization conditions, with log10 ([O III] λ λ4959,5007/[O II] λ λ3726,3729) = 1.39 ± 0.19 and log10 ([Ne III] λ3869/[O II] λ λ3726,3729) = 0.37 ± 0.18 in stark excess compared to typical values in the interstellar medium (ISM) at lower redshifts. These line properties are compatible either with an active galactic nucleus (AGN) or with a compact, very dense star-forming environment (ΣSFR ≃ 102–103 M ⊙ yr−1 kpc−2 and ΣM* ≃ 104–105 M ⊙ pc−2), with a high ionization parameter (log10(U) =−1.75 ± 0.16), a high ionizing photon production efficiency log(ξion)=25.7−0.1+0.3 , and a low gas-phase metallicity (also confirmed by the direct, T e method) ranging between 4% and 11% Z ⊙, indicating a rapid chemical enrichment of the ISM in the past few megayears. These properties also suggest that a substantial amount of ionizing photons (∼10%) are leaking outside of GHZ2 and starting to reionize the surrounding intergalactic medium, possibly due to strong radiation-driven winds. The general lessons learned from GHZ2 are the following: (i) the UV-to-optical combined nebular indicators are broadly in agreement with UV-only or optical-only indicators; (ii) UV+optical diagnostics fail to discriminate between an AGN and star formation in a low-metallicity, high-density, and extreme-ionization environment; and (iii) comparing the nebular line ratios with local analogs may be approaching its limits at z ≳ 10, as this approach is potentially challenged by the unique conditions of star formation experienced by galaxies at these extreme redshifts.

Mechanism of metastable krypton atom preparation via laser-induced ionization

Preparation of metastable Kr atoms in the 5s[3/2]2 level via laser-induced ionization has been achieved. The temporal evolution of the intensity of Kr atomic spectral lines at 760.15 nm, 811.29 nm, and 431.96 nm was used to elucidate the production mechanisms of metastable Kr atoms. These mechanisms primarily involve two processes: the “excitation + radiation” process, dominated by multiphoton excitation and initial plasma-induced electron impact excitation, and the “ion-electron recombination” process, governed by avalanche ionization. The decay time constants of Kr atomic spectral lines, corresponding to the “excitation + radiation” and “ion-electron recombination” processes respectively, were obtained experimentally under both strong and weak ionization conditions. The experiments revealed delay in preparations of metastable Kr atoms between these two processes. To reduce the loss of metastable Kr atoms and effectively utilize their peak concentration, we drew inspiration from metastable rare gas lasers and proposed the “cycling” idea to keep metastable Kr atoms produced by these two processes as synchronized as possible. We used 811.29 nm laser to excite metastable Kr atoms generated rapidly during the “excitation + radiation” stage to the 5p[5/2]3 level. The Kr atoms returned to the 5s[3/2]2 level through spontaneous radiation, merging with metastable Kr atoms that were slowly produced during the “ion-electron recombination” stage. We hope that the “cycling” idea can shorten the delay in preparations of metastable Kr atoms from both processes and enhance the peak concentration of metastable Kr atoms. However, the experimental results didn't meet expectations, as we observed a decrease in the 811.29 nm fluorescence after laser excitation, attributed to the accumulation of 5p[5/2]3 level Kr atoms. These atoms undergo energy pooling to populate the 4d’[3/2]1 and 5d[7/2]3 levels, followed by absorption of 811.29 nm laser energy leading to photoionization. Reducing the concentration of 5p[5/2]3 level Kr atoms helps mitigate the reionization issue.

Possibility of identifying 1H-indolylaminium trifluoroacetates with antimicrobial activity by mass spectrometry

The present study proposes a convenient approach to identify a series of novel substituted 1H-indol-5-,6-ylaminium trifluoroacetates with antimicrobial activity based on mass spectral data obtained using direct injection into an ion source at an elevated temperature when the salts decompose with the release of counterions: acids and organic bases – substituted 1H-indolylamines. By the presence of ions with m/z 69, 45, 28, 17 in the spectra, it is judged that the salts are formed by trifluoroacetic acid. Using the available literature data on the mass spectrometry of substituted indoles, aromatic amines, and carboxylic acids, substantiated schemes for the decomposition of molecular ions of organic bases, 1H-indolylamines, are compiled and discussed, in which the mechanism of formation and the structure of fragment ions arising under electron ionization conditions are given. The revealed general, as well as individual for individual representatives with a certain character and place of substitution in the indole bicycle, patterns of behavior of 1H-indolylamine radical ions under conditions of high-temperature mass spectral imaging make it possible to judge their structure and, in general, the structure of 1H-indolylamine trifluoroacetates. The approach used in this work can also be used to prove compounds of a similar group based on the analysis of their mass spectra.

Emission-line Ratios and Ionization Conditions of CEERS Star-forming Galaxies with JWST/NIRSpec

Galaxy emission-line fluxes can constrain star formation rates (SFRs) and interstellar medium (ISM) ionization. We investigate rest-frame optical emission lines of 71 star-forming galaxies (SFGs) at redshift 0.7 < z < 7 using JWST/NIRSpec measurements from the Cosmic Evolution Early Release Science survey. We use Hα to measure SFR and utilize Hubble Space Telescope CANDELS stellar mass estimates to determine specific SFR (sSFR) and compare with the SFG main sequence (MS). We create [O iii]λ5008/Hβ versus [Ne iii]λ3870/[O ii]λ3728 line ratio diagrams. The line ratios appear to correlate with sSFR, and our results suggest that sSFR is the parameter that governs ionization conditions rather than SFR or a galaxy’s distance from the MS. These measurements reveal a rich diversity of ISM conditions and physical galaxy properties throughout cosmic time.

CAVITY: Calar Alto Void Integral-field Treasury surve. I. First public data release

The Calar Alto Void Integral-field Treasury surveY (CAVITY) is a legacy project aimed at characterising the population of galaxies inhabiting voids, which are the most under-dense regions of the cosmic web, located in the Local Universe. This paper describes the first public data release (DR1) of CAVITY, comprising science-grade optical data cubes for the initial 100 out of a total of sim 300 galaxies in the Local Universe ($0.005 &lt; z &lt; 0.050$). These data were acquired using the integral-field spectrograph PMAS/PPak mounted on the 3.5m telescope at the Calar Alto observatory. The DR1 galaxy sample encompasses diverse characteristics in the color–magnitude space, morphological type, stellar mass, and gas ionisation conditions, providing a rich resource for addressing key questions in galaxy evolution through spatially resolved spectroscopy. The galaxies in this study were observed with the low-resolution V500 set-up, spanning the wavelength range 3745–7500 with a spectral resolution of 6.0 (FWHM). Here, we describe the data reduction and characteristics and data structure of the CAVITY datasets essential for their scientific utilisation, highlighting such concerns as vignetting effects, as well as the identification of bad pixels and management of spatially correlated noise. We also provide instructions for accessing the CAVITY datasets and associated ancillary data through the project's dedicated database.

Effects of geometric isomerism in electron ionization mass spectra of dialkyl 1,4-cyclohexanedicarboxylates.

1,4-Cyclohexanedicarboxylic acid and its esters are widely used as building blocks in the production of polymers and copolymers. The properties of such compounds directly depend on the ratio of cis- and trans-isomers in the starting materials. The identification of such stereoisomers by mass spectrometry can be used for the analysis of complex reactions and pyrolysis mixtures. 1,4-Cyclohexanedicarboxylic acid propyl, isopropyl, butyl, 2-butyl, pentyl, 2-pentyl, 4-methylpentyl, heptyl, octyl, and nonyl esters were synthesized and analyzed by gas chromatography-electron ionization mass spectrometry. The general fragmentation patterns of the synthesized compounds in electron ionization conditions were determined using high-resolution mass spectrometry. The relative response factors for the isomers were established on the basis of NMR and GC-MS data. Regardless of the structure of the alkyl groups, the EI mass spectra of cis- and trans-dialkyl 1,4-cyclohexanedicarboxylates differ very sharply. The stereoselectivity of fragmentation processes is due to the steric proximity of the substituents in the case of cis-isomers. Elemental composition of all ions appearing in the mass spectra of the analytes under study was confirmed by high-resolution mass spectrometry. Despite the perceptible differences in the EI mass spectra of the isomers their ionization efficiencies are close. The possibility of the unambiguous identification of stereoisomeric dialkyl cis and trans 1,4-cyclohexanedicarboxylates on the basis of their EI mass spectra was shown. The differences in mass spectra of the isomers are due to the conformational rigidity of the considered monocyclic molecules, which ensures the unique stereoselectivity of the elimination of neutral molecules owing to the 1,3-cis-diaxial proximity effect.

Effect of multi-temperature models on heat transfer and electron behavior in hypersonic flows

In hypersonic computational fluid dynamics, the two-temperature (2-T) model is widely used to simulate thermochemical nonequilibrium. The 2-T model incorporates translational-rotational and electron-electronic-vibrational energies, assuming that the integrated energies have the equivalent temperature. In this study, multi-T models are constructed to accurately predict the effects on heat flux and free electrons due to the separation of energy modes under hypersonic environments. The three-temperature (3-T) model separates the electron-electronic energy from the electron-electronic-vibrational energy of the 2-T model. The 3-T model can accurately predict the distribution and temperature of free electrons by separating the energy of free electrons, which has different characteristics from heavy particles. The four-temperature model treats rotational energy as a nonequilibrium energy mode, distinct from translational-rotational energy. While the rotational temperature reaches equilibrium rapidly at low temperatures, at high-temperature regime rotational temperature shows a relaxation time similar to that of vibrational temperature, which cannot be ignored. To develop multi-T models, electron-vibrational relaxation and translational-rotational relaxation, which are omitted in the 2-T model, are considered. Various flight test and ground facility conditions are analyzed to verify the effects of electron and heat flux under circumstances that include shock, expansion, and shock wave boundary layer interaction. The results of the multi-T models show significant differences in electron temperature and distribution caused by electron-electronic nonequilibrium. Additionally, rotational nonequilibrium increases the shock standoff distance and alters the electron distribution at high altitudes. The heat flux difference across multi-T models is found to be negligible, except in the high degree of ionization condition.

Characterization of a Monoclonal Antibody by Native and Denaturing Top-Down Mass Spectrometry.

Established in recent years as an important approach to unraveling the heterogeneity of intact monoclonal antibodies, native mass spectrometry has been rarely utilized for sequencing these complex biomolecules via tandem mass spectrometry. Typically, top-down mass spectrometry has been performed starting from highly charged precursor ions obtained via electrospray ionization under denaturing conditions (i.e., in the presence of organic solvents and acidic pH). Here we systematically benchmark four distinct ion dissociation methods─namely, higher-energy collisional dissociation, electron transfer dissociation, electron transfer dissociation/higher-energy collisional dissociation, and 213 nm ultraviolet photodissociation─in their capability to characterize a therapeutic monoclonal antibody, trastuzumab, starting from denatured and native-like precursor ions. Interestingly, native top-down mass spectrometry results in higher sequence coverage than the experiments carried out under denaturing conditions, with the exception of ultraviolet photodissociation. Globally, electron transfer dissociation followed by collision-based activation of product ions generates the largest number of backbone cleavages in disulfide protected regions, including the complementarity determining regions, regardless of electrospray ionization conditions. Overall, these findings suggest that native mass spectrometry can certainly be used for the gas-phase sequencing of whole monoclonal antibodies, although the dissociation of denatured precursor ions still returns a few backbone cleavages not identified in native experiments. Finally, a comparison of the fragmentation maps obtained under denaturing and native conditions strongly points toward disulfide bonds as the primary reason behind the largely overlapping dissociation patterns.

Evolution of the star formation rate and Sigma_SFR of galaxies at cosmic morning (4&lt;z&lt;10)

The galaxy-integrated star formation rate (SFR) surface density measurement ($ SFR $) has been proposed as a valuable diagnostic of the mass accumulation in galaxies given it is more tightly related to the physics of star formation and stellar feedback than other indicators. In this work, we assembled a statistical sample of $230$ galaxies observed with JWST in the GLASS and CEERS spectroscopic surveys to estimate Balmer line-based dust attenuations and SFRs (i.e., from Halpha , Hbeta , and Hgamma ), along with the UV rest-frame effective radii. We studied the evolution of galaxy SFR and $ SFR $ in the first $1.5$ billion years of our Universe, from a redshift of $z to $z We found that $ SFR $ is mildly increasing with redshift with a linear slope of $0.16 0.06$. We explored the dependence of SFR and $ SFR $ on stellar mass, showing that a star-forming main sequence and a $ SFR $ main sequence are present out to $z=10$. This dependence exhibits a similar slope compared to the same relations at lower redshifts, but with a higher normalization. We find that the specific SFR (sSFR) and $ SFR $ are correlated with the ratio and with indirect estimates of the escape fraction of Lyman continuum photons; hence, they are likely to play an important role in the evolution of ionization conditions at higher redshifts and in the escape of ionizing radiation. We also searched for spectral outflow signatures in the Halpha and emission lines in a subset of galaxies observed at high resolution (R$=2700$) by the GLASS survey, finding an outflow incidence of $2/11$ 32&lt;!PCT!&gt; 9&lt;!PCT!&gt; $) at $z&lt;6$, but no evidence at $z&gt;6$ ($0/6$, $&lt;26&lt;!PCT!&gt;$). Finally, we find a positive correlation between A$_V$ and $ SFR $, and a flat trend as a function of sSFR, indicating that there is no evidence of a drop in A$_V$ in extremely star-forming galaxies between $z 4$ and $ 10$. This result might be at odds with a dust-clearing outflow scenario, which may instead take place at redshifts of $z 10$, as suggested by some theoretical models.

Bio-analytical Methodology for Exploring Ripretinib’s Pharmacokinetic Profile in Rat Plasma Employing Bosutinib as an Internal Standard Utilizing LC-MS/MS

A robust, consistent, straightforward, swift, and precise liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was tailored for the bioanalytical analysis of ripretinib, with bosutinib serving as the comparative standard. This article provides a synopsis of recent developments in bioanalytical LC-MS/MS techniques utilizing a phenyl column (150x4.6 mm, 3.5 μ) and an eluting agent composed of ammonium formate at a pH of 2.5, which was altered in a 50:50 ratio with formic acid and acetonitrile. The chromatogram was utilized to analyse ripretinib, and the MS detector was equipped with electrospray ionization (ESI) method functioning in positive ionization conditions with multiple reactions monitoring (MRM). This allowed for the recording of transition m/z values of 531.4465→170.9638 for ripretinib and 511.4230 → 160.7133 for BTB. In the chromatographic analysis, ripretinib was retained for approximately 2.433 minutes, whereas BTB was retained for around 3.608 minutes. The validity of the approach extends across a linearity scale of 5 to 100 ng/mL for ripretinib, boasting a correlation index of 0.9999. In the realm of biological matrices, the extraction procedure employing the protein precipitation technique yields recovery rates of 99.6, 99.2, and 98% at the lower, middle, and higher quality control levels, respectively. The obtained results for accuracy, precision, matrix effect, and stability were determined to be within the acceptable range. To observe the investigated analyte in bodily fluids, pharmacokinetic studies yielded key parameters, including a half-life of 10 hours and a time to reach a maximum drug level of 4 hours. This thorough assessment affirms that the method satisfies rigorous criteria for system suitability and specificity well within predefined acceptance limits. Such performance positions it as an indispensable asset in the realm of bioanalysis, significantly broadening its clinical applicability.

Using ion mobility spectrometry to understand signal dilution during tandem mass spectrometry sequencing of digital polymers: Experimental evidence of intramolecular cyclization.

Optimizing the structure of digital polymers is an efficient strategy to ensure their tandem mass spectrometry (MS/MS) readability. In block-truncated poly(phosphodiester)s, homolysis of C-ON bonds in long chains permits the release of smaller blocks amenable to sequencing. Yet the dissociation behavior of diradical blocks was observed to strongly depend on their charge state. Polymers were ionized in negative mode electrospray and activated in-source so that blocks released as primary fragments can be investigated using ion mobility spectrometry (IMS) or sequenced in the post-IMS collision cell. Collision cross sections (CCS) were derived from arrival times using a calibration procedure developed for polyanions using the IMSCal software. A multistep protocol based on quantum methods and classical molecular dynamics was implemented for molecular modeling and calculation of theoretical CCS. Unlike their triply charged homologues, dissociation of diradical blocks at the 2- charge state produces additional fragments, with +1m/z shift for those holding the nitroxide α-termination and -1m/z for those containing the carbon-centered radical ω-end. These results suggest cyclization of these diradical species, followed by H• transfer on activated reopening of this cycle. This assumption was validated using IMS resolution of the cyclic/linear isomers and supported by molecular modeling. Combining IMS with molecular modeling provided new insights into how the charge state of digital blocks influences their dissociation. These results permit to define new guidelines to improve either ionization conditions or the structural design of these digital polymers for best MS/MS readability.

Study on the Mass Spectrometry Cleavage Pattern of Quinolone Antibiotics.

Quinolone antibiotics are extensively used clinically for human treatment and in agriculture. However, improper and excessive use can lead to the persistence of quinolone residues in animal tissues, potentially accumulating in the human body and posing health risks. Investigating the correlation between mass spectrometry cleavage patterns and molecular structural features enhances the analytical framework for detecting trace or unknown impurities in quinolones. To collect data, we employed triple quadrupole linear ion trap mass spectrometry in electrospray positive ion mode. Primary mass spectrometry scanning was utilized to confirm parent ions, while secondary mass spectrometry scanning enabled the observation of fragment ions. The cleavage characteristics and pathways of the compounds were inferred from accurate mass-to-charge ratios obtained from both primary and secondary mass spectrometry. Under soft ionization conditions, the compounds generally exhibited characteristic fragment ions of [M+H-H2O]+, [M+H-CO]+, and [M+H-H2O-CO]+. Additionally, subtle variations were observed in each compound due to differences in modifying groups. For instance, upon deacidification, the piperazine ring structure underwent breakage and rearrangement, yielding fragment ion peaks devoid of neutral molecules such as C2H5N, C3H7N, or C4H8N. Notably, compounds featuring a cyclopropyl substituent group at the N-1 position typically exhibited characteristic fragments resulting from the loss of the cyclopropyl radical (⋅C3H5). Moreover, substituents at the N-1 and C-8 positions, when linked to form a six-membered carbocyclic ring, were prone to cleavage, releasing the neutral C3H6 molecule. Quinolone antibiotics share structural similarities in their parent nuclei, leading to partially similar cleavage pathways. Nevertheless, distinct cleavage patterns emerge due to variations in functional groups. According to the difference of mass spectrometry cleavage patterns, it can provide an identification basis for the measured detection of antibiotics.

GA-NIFS: The core of an extremely massive protocluster at the epoch of reionisation probed with JWST/NIRSpec

The SPT0311-58 system resides in a massive dark-matter halo at z sim 6.9. It hosts two dusty galaxies (E and W) with a combined star formation rate (SFR) of sim 3500 mostly obscured and identified by the rest-frame IR emission. The surrounding field exhibits an overdensity of submillimetre sources, making it a candidate protocluster. Our main goal is to characterise the environment and the properties of the interstellar medium (ISM) within this unique system. We used spatially resolved low-resolution ($R$=100) and high-resolution ($R$=2700) spectroscopy provided by the JWST/NIRSpec Integral Field Unit to probe a field of sim 17 times 17 kpc$^2$ around this object, with a spatial resolution of sim 0.5 kpc. These observations reveal ten new galaxies at zsim 6.9 characterised by dynamical masses spanning from sim 109 to 1010 and a range in radial velocity of sim 1500 in addition to the already known E and W galaxies. The implied large number density (phi sim $) and the wide spread in velocities confirm that is at the core of a protocluster immersed in a very massive dark-matter halo of sim (5 pm 3) times 1012 and therefore represents the most massive protocluster ever found at the epoch of reionisation (EoR). We also studied the dynamical stage of its core and find that it is likely not fully virialised. The galaxies in the system exhibit a wide range of properties and evolutionary stages. The contribution of the ongoing Halpha -based unobscured SFR to the total star formation (SF) varies significantly across the galaxies in the system. Their ionisation conditions range from those typical of the field galaxies at similar redshift recently studied with JWST to those found in more evolved objects at lower redshift, with OIII varying from sim 0.25 to 1. The metallicity spans more than 0.8 dex across the FoV, reaching nearly solar values in some cases. The detailed spatially resolved spectroscopy of the E galaxy reveals that it is actively assembling its stellar mass, showing inhomogeneities in the ISM properties at subkiloparsec scales, and a metallicity gradient (sim 0.1 dex/kpc) that can be explained by accretion of low metallicity gas from the intergalactic medium. The kinematic maps also depict an unsettled disc characterised by deviations from regular rotation, elevated turbulence, and indications of a possible precollision minor merger. These JWST/NIRSpec IFS observations confirm that is at the core of an extraordinary protocluster, and reveal details of its dynamical properties. They also unveil and provide insights into the diverse properties and evolutionary stages of the galaxies residing in this unique environment.

Deep Learning Voigt Profiles. I. Single-Cloud Doublets

Voigt profile (VP) decomposition of quasar absorption lines is key to studying intergalactic gas and the baryon cycle governing the formation and evolution of galaxies. The VP velocities, column densities, and Doppler b parameters inform us of the kinematic, chemical, and ionization conditions of these astrophysical environments. A drawback of traditional VP fitting is that it can be human-time intensive. With the coming next generation of large all-sky survey telescopes with multiobject high-resolution spectrographs, the time demands will significantly outstrip our resources. Deep learning pipelines hold the promise to keep pace and deliver science-digestible data products. We explore the application of deep learning convolutional neural networks (CNNs) for predicting VP-fitted parameters directly from the normalized pixel flux values in quasar absorption line profiles. A CNN was applied to 56 single-component Mg ii λ λ2796, 2803 doublet absorption line systems observed with HIRES and UVES (R = 45,000). The CNN predictions were statistically indistinct from those of a traditional VP fitter. The advantage is that, once trained, the CNN processes systems ∼105 times faster than a human expert fitting VP profiles by hand. Our pilot study shows that CNNs hold promise to perform bulk analysis of quasar absorption line systems in the future.

Utilizing derivatizing agents for the differentiation of cannabinoid isomers in complex food, beverage and personal-care product matrices by ambient ionization mass spectrometry

Recent legalization and decriminalization of marijuana at the state level has not only contributed to a rise in the recreational use of Cannabis sativa, also known simply as Cannabis, but also to an increase in the range of matrices into which cannabinoids derived from it are infused. Traditional methods for analyzing these products, which are typically chromatography-based, are often matrix-dependent and demand time-consuming and resource-intensive sample preparation protocols that are highly nuanced and not readily applicable to multiple matrix types. Furthermore, the differentiation of cannabinoids can be troublesome without implementing lengthy run times to achieve resolution of chromatographic peaks. With complex samples such as edibles, beverages, personal-care products, and plant materials, a method that can be more universally applied to rapidly detect and differentiate between cannabinoids is highly desirable. In this study, foods and personal-care products under the categories of sweets, spreads, condiments/toppings, beverages, oils, and commercial body products were spiked with cannabinoids including Δ9-tetrahydrocannabinol (THC), cannabidiol (CBD), cannabicitran (CBT), and cannabigerol (CBG). Chemical derivatization of the samples with N-methyl-N-(trimethylsilyl)trifluoroacetamide (MSTFA) followed by direct analysis in real time – high-resolution mass spectrometry (DART-HRMS) analysis readily revealed the presence of cannabinoids in the products despite the matrix complexity (i.e., the contributions from matrix-derived peaks did not interfere with the differentiation of cannabinoids). When analyzed under ambient soft ionization conditions, CBT, THC and CBD are indistinguishable because they are isomers with a molecular formula of C21H30O2 and a protonated monoisotopic mass of 315.2324. However, due to the different number of hydroxyl (-OH) groups (zero in CBT, one in THC, and two in CBD) that engage with the derivatizing agent, the cannabinoids are differentiated based on the mass disparities of the protonated adducts formed (m/z 315.2324, 387.2719 and 459.3119 for CBT, THC, and CBD, respectively), which is readily revealed by DART-HRMS. This approach circumvents some of the challenges currently encountered by forensic laboratories in the analysis of highly complex and diverse cannabinoid-infused matrices. The results show proof-of-concept for an approach that can aid in the differentiation of cannabinoid isomers by DART-HRMS that accommodates high matrix diversity and complexity, and demonstrates the potential for the approach to be integrated into current workflows for the forensic analysis of Cannabis-related materials and evidence.

Simultaneous determination of 31 banned veterinary drugs during egg-laying period in poultry eggs by ultra performance liquid chromatography-tandem mass spectrometry

The consumption of poultry eggs has increased in recent years owing to the abundance of production and improvements in living standards. Thus, the safety requirements of poultry eggs have gradually increased. At present, few reports on analytical methods to determine banned veterinary drugs during egg-laying period in poultry eggs have been published. Therefore, establishing high-throughput and efficient screening methods to monitor banned veterinary drugs during egg-laying period is imperative. In this study, an analytical method based on ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) combined with QuEChERS-based techniques was developed for the simultaneous determination of 31 banned veterinary drugs encompassing nine drug classes (macrolides, antipyretic and analgesic drugs, sulfonamides, antibacterial synergists, anticoccidials, antinematodes, quinolones, tetracyclines, amphenicols) in different types of poultry eggs. The main factors affecting the response, recovery, and sensitivity of the method, such as the extraction solvent, purification adsorbent, LC separation conditions, and MS/MS parameters, were optimized during sample pretreatment and instrumental analysis. The 31 veterinary drug residues in 2.00 g eggs were extracted with 2 mL of 0.1 mol/L ethylene diamine tetraacetic acid disodium solution and 8 mL 3% acetic acid acetonitrile solution, and salted out with 2 g of sodium chloride. After centrifugation, 5 mL of the supernatant was cleaned-up using the QuEChERS method with 100 mg of octadecylsilane-bonded silica gel (C18), 50 mg of N-propylethylenediamine (PSA), and 50 mg of NH2-based sorbents. After nitrogen blowing and redissolution, the 31 target analytes were separated on a Waters CORTECS UPLC C18 analytical chromatographic column (150 mm×2.1 mm, 1.8 μm) at a flow rate, column temperature, and injection volume of 0.4 mL/min, 30 ℃, and 5 μL, respectively. Among these analytes, 26 analytes were acquired in dynamic multiple reaction monitoring (MRM) mode under positive electrospray ionization (ESI+) conditions using (A) 5 mmol/L ammonium acetate (pH 4.5) and (B) acetonitrile as mobile phases. The gradient elution program was as follows: 0-2.0 min, 12%B-30%B; 2.0-7.5 min, 30%B-50%B; 7.5-10.0 min, 50%B; 10.0-10.1 min, 50%B-100%B; 10.1-12.0 min, 100%B; 12.0-12.1 min, 100%B-12%B; The five other target analytes were acquired in MRM mode under negative electrospray ionization (ESI-) conditions using (A) H2O and (B) acetonitrile as mobile phases. The gradient elution program was as follows: 0-2.0 min, 12%B-40%B; 2.0-6.0 min, 40%B-80%B; 6.0-6.1 min, 80%B-100%B; 6.1-8.0 min, 100%B; 8.0-8.1 min, 100%B-12%B. Matrix-matched external standard calibration was used for quantification. The results showed that all the compounds had good linear relationships within their respective ranges, with correlation coefficients of >0.99. The limits of detection (LODs) and quantitation (LOQs) were 0.3-3.0 μg/kg and 1.0-10.0 μg/kg, respectively. The average recoveries of the 31 banned veterinary drugs spiked at three levels (LOQ, maximum residue limit (MRL), and 2MRL) in poultry eggs ranged from 61.2% to 105.7%, and the relative standard deviations (RSDs) ranged from 1.8% to 17.6%. The developed method was used to detect and analyze banned veterinary drugs in 30 commercial poultry egg samples, including 20 eggs, 5 duck eggs, and 5 goose eggs. Enrofloxacin was detected in one egg with a content of 12.3 μg/kg. The proposed method is simple, economical, practical, and capable of the simultaneous determination of multiple classes of banned veterinary drugs in poultry eggs.