Ionization Conditions Research Articles

TLC-electrostatic field induced spray ionization-MS analysis of diverse structural skeletons and its coupling with TLC bioautography for characterization of lipase inhibitory components in American ginseng

Natural compounds with diverse structural skeletons have different ionization efficiencies and different mass spectrometry (MS) responses. Some key factors influencing the electrostatic field induced spray ionization (EFISI)-MS for a variety of natural compounds have been optimized and improved. Fifteen reference substances representing ten well-known skeletons of natural products including alkaloids, flavonoids, phenolic acids, lignans, coumarins, anthraquinones, monoterpenoids, sesquiterpenoids, diterpenoids and triterpenoids, were selected and investigated for their EFISI-MSn responses on TLC plates using a dot-blot test. The optimized ionization conditions for these compounds in the positive ion mode were achieved, together with their limits of detection. In addition, to avoid the limitation of some compounds being difficultly ionized in the positive ion mode, the negative ion mode of the TLC-EFISI-MS method was developed and optimized for the first time. By coupling with a TLC bioautographic assay, nine lipase inhibitory components in American ginseng (Panax quinquefolium roots) have been successfully identified/ tentatively identified in situ by their EFISI-MSn data and further confirmed by comparisons of their Rf values and MSn data with those of reference substances. These lipase inhibitory compounds were 24(S)-pseudo-ginsenoside F11, ginsenosides Rg1, Re, XVII, Rc, Rb2/Rb3, Rb1, Ro and malonyl-ginsenoside Rb1. This is the first report that the TLC-EFISI-MSn method is adapted to a broad-spectrum analysis of structural skeletons present in herbal medicines.

The Crystal Structure of N-(1-Arylethyl)-4-methyl- 2,2-dioxo-1H-2λ6,1-benzothiazine-3-carboxamides as the Factor Determining Biological Activity Thereof

In order to detect new structural and biological patterns in a series of hetaryl-3-carboxylic acid derivatives, the optically pure (S)- and (R)-enantiomers of N-(1-arylethyl)-4-methyl- 2,2-dioxo-1H-2λ6,1-benzothiazine-3-carboxamides, their true racemates, and mechanical racemic mixtures have been synthesized in independent ways. The particular features of the 1Н- and 13С-NMR spectra of all synthesized substances, liquid chromato-mass spectrometric behavior thereof under electrospray ionization conditions, and also the results of polarimetric and X-ray diffraction studies have been discussed. Pharmacological screening on a model of carrageenan inflammation has found a clear relationship between the spatial structure of the studied objects and biological activity thereof. Enantiomers with chiral centers having (S)-configuration showed weak inhibition of pain and inflammatory reactions, while their mirror (R)-isomers exhibited very powerful analgesic and antiphlogistic properties under the same conditions, with the level of specific activity exceeding that of Lornoxicam and Diclofenac. Taking obtained data into account, a noticeable decrease in the activity of mechanical racemic mixtures, consisting of one-half of the “wrong” (S)-enantiomers, is quite natural. The true racemate of N-(1-phenylethyl)-amide proved itself in a similar way, while 4-methoxy-substituted analog thereof stood out against this background with unexpectedly high analgesic and anti-inflammatory activities. A comparative analysis of X-ray diffraction data has found that crystalline and molecular structure of racemic N-[1-(4-methoxyphenyl)ethyl]-4-methyl-2,2-dioxo-1H-2λ6,1-benzothiazine-3-carboxamide is completely different from that of the original enantiomers and, moreover, very unusual for racemates. Obviously, it is the factor determining the unique character of the biological effects of the said substance.

Simultaneous Determination of Selegiline, Desmethylselegiline, R/S-methamphetamine, and R/S-amphetamine on Dried Urine Spots by LC/MS/MS: Application to a Pharmacokinetic Study in Urine.

Objective: Chiral analysis is a crucial method to differentiate selegiline intake from drug abuse. A dried urine spot (DUS) analytical method based on spotting urine samples (10 μL) onto dried spot collection cards, and followed by air-drying and extraction, was developed and validated for the determination of selegiline, desmethylselegiline, R/S-methamphetamine, and R/S-amphetamine.Methods: Methanol (0.5 mL) was found to be the ideal extraction solvent for target extraction from DUSs under orbital-horizontal stirring on a lateral shaker at 1,450 rpm for 30 min. Determinations were performed by direct electrospray ionization tandem mass spectrometry (ESI-MS/MS) under positive electrospray ionization conditions using multiple reaction monitoring mode. The chromatographic system consisted of a ChirobioticTM V2 column (2.1 × 250 mm, 5 μm) and a mobile phase of methanol containing 0.1% (v/v) glacial acetic acid and 0.02% (v/v) ammonium hydroxide.Results and conclusions: The calibration curves were linear from 50 to 5,000 ng/mL, with r > 0.995 for all analytes, imprecisions ≤ 15% and accuracies between −11.4 and 11.7%. Extraction recoveries ranged from 48.6 to 105.4% with coefficients of variation (CV) ≤ 13.7%, and matrix effects ranged from 45.4 to 104.1% with CV ≤ 10.3%. The lower limit of quantification was 50 ng/mL for each analyte. The present method is simple, rapid (accomplished in 12 min), sensitive, and validated by a pharmacokinetic study in human urine collected after a single oral administration of SG.

Connecting substellar and stellar formation: the role of the host star’s metallicity

Context.Most of our current understanding of the planet formation mechanism is based on the planet metallicity correlation derived mostly from solar-type stars harbouring gas-giant planets.Aims.To achieve a more extensive grasp on the substellar formation process, we aim to analyse in terms of their metallicity a diverse sample of stars (in terms of mass and spectral type) covering the whole range of possible outcomes of the planet formation process (from planetesimals to brown dwarfs and low-mass binaries).Methods.Our methodology is based on the use of high-precision stellar parameters derived by our own group in previous works from high-resolution spectra by using the iron ionisation and equilibrium conditions. All values were derived in an homogeneous way, except for the M dwarfs where a methodology based on the use of pseudo equivalent widths of spectral features was used.Results.Our results show that as the mass of the substellar companion increases the metallicity of the host star tends to lower values. The same trend is maintained when analysing stars with low-mass stellar companions and a tendency towards a wide range of host star’s metallicity is found for systems with low-mass planets. We also confirm that more massive planets tend to orbit around more massive stars.Conclusions.The core-accretion formation mechanism for planet formation achieves its maximum efficiency for planets with masses in the range 0.2–2MJup. Substellar objects with higher masses have higher probabilities of being formed as stars. Low-mass planets and planetesimals might be formed by core-accretion even around low-metallicity stars.

Potential pitfalls in LC-MS/MS quantification of colistin for therapeutic drug monitoring of patients treated with colistimethate

Starting from a warning of possible artificially high plasma colistin concentrations observed in clinical samples in our recently published LC–MS/MS method, we reviewed our analytical assay and demonstrated, for the first time, that caution must be paid to ionization conditions employed in the MS system.The artefact reported here demonstrates that additional experiments should be performed in the course of validation of LC–MS/MS methods to be used in samples containing both colistin and colistimethate.

Multi-phase outflows in Mkn 848 observed with SDSS-MaNGA integral field spectroscopy

Aims. The characterisation of galaxy-scale outflows in terms of their multi-phase and multi-scale nature, amount, and effects of flowing material is crucial to place constraints on models of galaxy formation and evolution. This study can proceed only with the detailed investigation of individual targets. Methods. We present a spatially resolved spectroscopic optical data analysis of Mkn 848, a complex system consisting of two merging galaxies at z ∼ 0.04 that are separated by a projected distance of 7.5 kpc. Motivated by the presence of a multi-phase outflow in the north-west system revealed by the SDSS integrated spectrum, we analysed the publicly available MaNGA data, which cover almost the entire merging system, to study the kinematic and physical properties of cool and warm gas in detail. Results. Galaxy-wide outflowing gas in multiple phases is revealed for the first time in the two merging galaxies. We also detect spatially resolved resonant Na ID emission associated with the outflows. The derived outflow energetics (mass rate, and kinetic and momentum power) may be consistent with a scenario in which both winds are accelerated by stellar processes and AGN activity, although we favour an AGN origin given the high outflow velocities and the ionisation conditions observed in the outflow regions. Further deeper multi-wavelength observations are required, however, to better constrain the nature of these multi-phase outflows. Outflow energetics in the North-West system are strongly different between the ionised and atomic gas components, the latter of which is associated with mass outflow rate and kinetic and momentum powers that are one or two dex higher; those associated with the south-east galaxy are instead similar. Conclusions. Strong kiloparsec-scale outflows are revealed in an ongoing merger system, suggesting that feedback can potentially impact the host galaxy even in the early merger phases. The characterisation of the neutral and ionised gas phases has proved to be crucial for a comprehensive study of the outflow phenomena.

Stochastic dynamic electrospray ionization mass spectrometric diffusion parameters and 3D structural analysis of coordination species of copper(II) ion with glycylhomopentapeptide and its dimeric associates

The kernel idea for this paper came from our more recent development of a mass spectrometric model equation, based on stochastic dynamics. It treats quantitatively the experimental intensity of analytes and their fragment ions under soft ionization conditions. The effort has resulted to exact universally applicable and empirically testable relationship, between mass spectrometric stochastic dynamic diffusion and the intensity. A linear correlation at high level of statistical significance occurs between DSD and the corresponding quantum chemical diffusions, obtained within the Arrhenius' approximation. It provides bridge between experimental MS parameters and 3D structure of analyte ions. Furthermore, we have claimed that the total intensity of the ions is proportional to their DSD parameter according to our model equation; or Itot ~ DSD. As evident from the small–scale of our contributions, so far, the simplistic theoretical concept and corresponding model equation need to be translated into a broad practical employment, because of; there is extended the capability of mass spectrometry beyond its routine application as irreplaceable method for quantitative analysis to the analytical practice. The superior features of the mass spectrometric instrumentation can offer us a new perspective of looking at the implementation of the method to exact 3D structural analysis in condense phase. As far as any such statement should be strongly quantified from the point of view of the chemometrics, this work deals with application of our stochastic dynamic concept of mass spectrometric diffusion to structural analysis of complex ions of CuII–ion with glycylhomopentapeptide and its dimeric associates. The large difference in the coordination fashion of oligopeptides, and competitive fragment paths together with the variety of the coordination modes of CuII–ion; and accounting, in parallel, for the different oxidation states of copper allows for us to demonstrate the great capability of our theoretical concept, studying so challenging research area. The experimental design is based on high resolution electrospray ionization mass spectrometric data in positive operation mode. High accuracy ab initio and methods based on theory on functional of density are used. Both static and molecular dynamic methods are employed.

Investigation of electrospray for a capillary electrophoresis-mass spectrometry interface in reverse polarity and negative ion mode.

Capillary zone electrophoresis (CZE) paired with mass spectrometry (MS) is a powerful analytical technique for examining mixtures of ionic analytes such as glycosaminoglycans. This study examines the mechanics of the electrospray process for a sheath flow CZE-MS interface under reverse polarity negative ionization conditions. Liquid flow in a sheath flow nano-electrospray CZE-MS interface is driven by two mechanisms, electroosmotic flow and electrospray nebulization. The contribution of these two processes to the overall flow of solution to the electrospray tip is influenced by the surface coatings of the sheath flow emitter tip and by the solvent composition. We have investigated the application of this interface to the reverse polarity separation of glycosaminoglycans and find that the role of electroosmotic flow is far less than has been reported previously, and the electrospray process itself is the largest contributor to the flow of the sheath liquid.

Comprehensive two-dimensional gas chromatography-mass spectrometry using milder electron ionization conditions: A preliminary evaluation

The present research is based on the use of comprehensive two-dimensional gas chromatography-quadrupole mass spectrometry (GC × GC-QMS), using “milder” electron ionization (EI) conditions. The term milder refers to the use of lower energy EI conditions (e.g., 20 eV), instead of the most common electron energy of 70 eV. The effects of using lower source temperatures were also evaluated. Within such an analytical context, GC × GC-QMS was applied to the analysis of a variety of different molecular-mass compounds with various polarities (sterols, linear alkanes, fatty acid methyl esters, vitamin E, squalene, a linear alcohol, and a group of fifteen pesticides).In general, the results attained indicate that milder EI conditions, and lower source temperatures, generate mass spectra with a higher relative abundance of ions at higher mass-over-charge (m/z) values, comprising the molecular ion, and reduced fragmentation at lower m/z values. The extent to which such a phenomenon occurred was obviously related to the chemical structure of each analyte. Spectral repeatability was also assessed, and was found to be satisfactory. Finally, with regard to analyte signal-to-noise ratios these were generally comparable in applications involving different electron ionization energies.

Isoreticular Tp*–W–Cu–S cluster-based one-dimensional coordination polymers with an uncommon [Tp*WS3Cu2] + [Cu] combination and their third-order nonlinear optical properties

Three isoreticular W/Cu/S 1D coordination polymers show good third-order NLO performance.

Peculiarities of Mass Spectra of Substituted Pyrroloquinolines

The results of the mass spectrometric studies of a series of substituted isomeric pyrrolo[2,3-g], [3,2-f], [3,2-g], and [2,3-f]quinolines are presented and analyzed. Angular pyrroloquinolines with bulk peri substituents are less stable under electron ionization conditions than the corresponding linear isomers. The differences in the magnitude of the ratio of the intensity of a molecular ion peak to the total ionic current expressed as a percentage (WM) depend on the steric requirements of peri-located groups in angular systems. The data obtained make it possible to identify the structure of the resulting isomeric tricyclic heterosystems. A mechanism for the mass spectral decomposition of methyl-, phenyl-, methoxy-, hydroxyl-, and ethoxycarbonyl-substituted pyrroloquinolines is proposed.

Combating selective ionization in the high resolution mass spectral characterization of complex mixtures.

Direct "dilute and shoot" mass spectral analysis of complex naturally-occurring mixtures has become the "standard" analysis in environmental and petrochemical science, as well as in many other areas of research. Despite recent advances in ionization methods, that approach still suffers several limitations for the comprehensive characterization of compositionally complex matrices. Foremost, the selective ionization of highly acidic (negative electrospray ionization ((-) ESI)) and/or basic (positive electrospray ionization ((+) ESI)) species limits the detection of weakly acidic/basic species, and similar issues (matrix effects) complicate atmospheric pressure photo-ionization (APPI)/atmospheric pressure chemical ionization (APCI) analyses. Furthermore, given the wide range of chemical functionalities and structural motifs in these compositionally complex mixtures, aggregation can similarly limit the observed species to a small (10-20%) mass fraction of the whole sample. Finally, irrespective of the ionization method, the mass analyzer must be capable of resolving tens-of-thousands of mass spectral peaks and provide the mass accuracy (typically 50-300 ppb mass measurement error) required for elemental composition assignment, and thus is generally limited to high-field Fourier transform ion cyclotron mass spectrometry (FT-ICR MS). Here, we describe three approaches to combat the above issues for (+) ESI, (-) ESI, and (+) APPI FT-ICR MS analysis of petroleum samples. Each approach relies on chromatographic fractionation to help reduce selective ionization discrimination and target either specific chemical functionalities (pyridinic and pyrrolic species (nitrogen) or carboxylic acids (oxygen)) or specific structural motifs (single aromatic core (island) or multi-core aromatics (archipelago)) known to be related to ionization efficiency. Each fractionation method yields a 2-10-fold increase in the compositional coverage, exposes species that are undetectable using direct "dilute and shoot" analysis, and provides coarse selectivity in chemical functionalities that can both increase the assignment confidence and optimize ionization conditions to maximize compositional coverage.

Measuring the Physical Conditions in High-redshift Star-forming Galaxies: Insights from KBSS-MOSFIRE

Abstract We use photoionization models that are designed to reconcile the joint rest-UV-optical spectra of high-z star-forming galaxies to self-consistently infer the gas chemistry and nebular ionization and excitation conditions for ∼150 galaxies from the Keck Baryonic Structure Survey (KBSS), using only observations of their rest-optical nebular spectra. We find that the majority of z ∼ 2–3 KBSS galaxies are moderately O-rich, with an interquartile range in 12 + log(O/H) = 8.29–8.56, and have significantly sub-solar Fe enrichment, with an interquartile range of [Fe/H] = [−0.79, −0.53], which contributes additional evidence in favor of super-solar O/Fe in high-z galaxies. The model-inferred ionization parameters and N/O are strongly correlated with common strong-line indices (such as O32 and N2O2), with the latter exhibiting similar behavior to local extragalactic H ii regions. In contrast, diagnostics commonly used for measuring gas-phase O/H (such as N2 and O3N2) show relatively large scatter with the overall amount of oxygen present in the gas and behave differently than observed at z ∼ 0. We provide a new calibration for using R23 to measure O/H in typical high-z galaxies, although it is most useful for relatively O-rich galaxies; combining O32 and R23 does not yield a more effective calibration. Finally, we consider the implications for the intrinsic correlations between physical conditions across the galaxy sample and find that N/O varies with O/H in high-z galaxies in a manner that is almost identical to local H ii regions. However, we do not find a strong anti-correlation between ionization parameter and metallicity (O/H or Fe/H) in high-z galaxies, which is one of the principal bases for using strong-line ratios to infer oxygen abundance.

Investigation of mycobacteria fatty acid profile using different ionization energies in GC-MS.

Gas chromatography (GC) coupled with electron ionization (EI) mass spectrometry (MS) is a well-established technique for the analysis of volatile and semi-volatile compounds. The main advantage is the highly repeatable fragmentation of the compounds into the ion source, generating intense and diagnostic fragmentation when the ionization is performed at 70 eV; this is considered the standard ionization condition and has been used for creating many established databases, which are of great support in the analyte identification process. However, such an intense fragmentation often causes the loss of the molecular ion or more diagnostic ions, which can be detrimental for the identification of homologous series or isomers, as for instance fatty acids. To obtain this information chemical or soft ionization can be used, but dedicated ion sources and conditions are required. In this work, we explored different ionization voltages in GC-EI-MS to preserve the intensity of the molecular ion using a conventional quadrupole MS. Twenty, 30, 50, and 70 eV were tested using a mixture of fatty acid methyl esters standards. Intensity and repeatability of the most informative ions were compared. Twenty and 70 eV were then used to analyze the fatty acid composition of six different strains of mycobacteria. Two approaches were used for elaborating the data: (1) a single average spectrum of the entire chromatogram was derived, which can be considered (in terms of concept) as a direct EI-MS analysis; (2) the actual chromatographic separation of the compounds was considered after automatic alignment. The results obtained are discussed herein. Graphical abstract ᅟ.

Liquid chromatography-time-of-flight high-resolution mass spectrometry study and determination of the dansylated products of estrogens and their hydroxylated metabolites in water and wastewater.

A method combining liquid chromatography with a dual-probe ultraspray electrospray ionization (ESI) source and time-of-flight high-resolution mass spectrometry (LC-ESI-TOF/MS) was developed for the simultaneous determination of four steroidal sex hormones, estrone (E1), 17β-estradiol (E2), 17α-ethinyl estradiol (EE2), and estriol (E3), as well as five of their hydroxylated metabolites, 2-hydroxyestrone (2-OHE1), 4-hydroxyestrone (4-OHE1), 16α-hydroxyestrone (16-OHE1), 2-hydroxyestradiol (2-OHE2), and 4-hydroxyestradiol (4-OHE2), in water samples in a short chromatographic run of 10 min. Derivatization of the analytes was optimized using dansyl chloride as the derivatizing agent. Under optimal positive ionization conditions, the following signals, which had not been previously reported, were observed (with theoretical values of m/z 377.1373 for 2- and 4-OHE1 and 378.1452 for 2- and 4-OHE2), corresponding to doubly derivatized catechol estrogens in the form of [M+2H]2+. These mass spectrometric signals were more abundant than those reported previously for the [M+H]+ forms of these hydroxylated metabolites. Solid-phase extraction (SPE) with an octadecyl-endcapped sorbent was used to pretreat tap water and effluent from a wastewater treatment plant (WWTP) in Santiago, Chile. The method achieved the simple, fast, and sensitive measurement of nine estrogens with quantitative recoveries (higher than 85.4%). Detection and quantification limits were between 1 and 17 ng L-1 and between 3 and 58 ng L-1, respectively, for all compounds in water. The estrogens E1 and E2 were found in WWTP effluent at concentrations of 7 ± 1 and 41 ± 1 ng L-1, respectively, and EE2 was detected at a concentration below the limit of quantitation. This study shows that the proposed method is suitable for the accurate, rapid, and selective determination of all these analytes at trace levels. Graphical abstract ᅟ.

The COS CGM Compendium. I. Survey Design and Initial Results

Abstract We present a neutral hydrogen-selected absorption-line survey of gas with H i column densities at using the Cosmic Origins Spectrograph on the Hubble Space Telescope. Our main aim is to determine the metallicity distribution of these absorbers. Our sample consists of 224 absorbers selected on the basis of their H i absorption strength. Here we discuss the properties of our survey and the immediate empirical results. We find singly and doubly ionized metal species, and H i typically have similar velocity profiles, implying they probe gas in the same or similar environments. The ionic ratios (e.g., / , / ) indicate that the gas in these absorbers is largely ionized, and the ionization conditions are quite comparable across the sampled range. The Doppler parameters of the H i imply K on average, consistent with the gas being photoionized. The Mg ii column densities span >2 orders of magnitude at any given , indicating a wide range of metallicities (from solar to <1/100 solar). In the range of , there is a gap in the distribution corresponding to gas with ∼10% solar metallicity, consistent with the gap seen in the previously identified bimodal metallicity distribution in this column density regime. Less than 3% of the absorbers in our sample show no detectable metal absorption, implying that truly pristine gas at is uncommon. We find [Fe ii/Mg ii] , and since α-enhancement can affect this ratio, dust depletion is extremely mild.

ULTRASONIC EFFECT ON ELECTRIC SPARK FORMING AND DEVELOPMENT IN ELECTROACOUSTIC SPRAYING

Introduction. The electroacoustic application of wear-resistance coatings is studied. The work objective is to obtain a mathematical model of the ultrasonic effect on the formation and development of an electric spark occurring in the process of the electroacoustic sputtering.Materials and Methods. The effect of ultrasonic vibrations on the processes occurring during the formation and development of a spark discharge is analyzed; the equations of continuity, energy motion and transfer, with the ultrasonic field contribution are considered. Factors affecting the thermal conductivity and electrical conductivity of strongly ionized gas are studied. Research Results. When obtaining the model, it was assumed that the heat removal from the channel is carried out by a “clear emitter”. Then, for the channel region, a self-similar solution is made: pressure, temperature and density are constant over the cross-section, and velocity is proportional to the radius. A mathematical model that describes the processes occurring in the spark channel with the ultrasonic field energy effect is obtained.Discussion and Conclusions. On the basis of the developed model, it is specified that under the ultrasonic radiation effect, the radius and temperature of the spark channel increase, and conditions of the double ionization under high ultrasonic energy are created.

Determination of steviol glycosides in commercial extracts of Stevia rebaudiana and sweeteners by ultra-high performance liquid chromatography Orbitrap mass spectrometry

Stevia rebaudiana extracts are used as sweeteners in several countries worldwide. Several extracts of diverse composition are available on the market, and their taste depends on the contents of the various steviol glycosides. This study presents an accurate method for the qualitative and quantitative determination of steviol glycosides in 40 Stevia extracts, 7 sweeteners and 3 Stevia-sweetened beverages by a UHPLC coupled to an Orbitrap mass spectrometer. The sub-2 μm amide column provided the separation of all the target analytes in a run time of 30 min with high resolution. The effect of different eluent compositions on the ionisation efficiency of the steviol glycosides was studied. The optimal ionisation conditions were achieved in negative mode using 0.05% formic acid. Under this condition, adducts were not found, [M-H]− were the main ions and the spontaneous loss of a glucose residue at C19 was reduced. The %RSD for intra- and inter-day precision for all eleven analytes varied from 2.1 to 4.2% and 3.0–5.1%, respectively. The recoveries from spiked Stevia extract samples were greater than 95% for all analytes. Rebaudioside A was the most abundant, ranging from 23 to 102%. Nine Stevia extracts and one drink were not compliant with the European Regulation. Isosteviol was under the LOD in all samples and steviol was found in four samples in quantities in the range 0.01–0.03%.

Collision cross section (CCS) as a complementary parameter to characterize human and veterinary drugs

In the context of human and veterinary drugs identification, ion mobility spectrometry (IMS) in combination with mass spectrometry (MS) may provide a relevant complementary piece of information to mass-to-charge ratio (m/z), the so-called collision-cross-section (CCS). Up to now, however, the application of CCS as identification parameter has not been fully investigated due to the reduced number of these drugs that have being characterized in terms of CCS. This work proposes a CCS database for 92 human and veterinary drugs, including eighteen benzimidazoles, eleven 5-nitroimidazoles, eleven aminoglycosides, nineteen quinolones, eighteen β-lactams, ten sulfonamides and five tetracyclines. Among them, 37 drugs have been characterized in terms of CCS for the first time. The CCS values of the other 55 compounds have been compared with those from a recently published database in order to evaluate inter-laboratory reproducibility, which is crucial for the implementation of the CCS as identification parameter. CCS values were measured by traveling wave ion mobility spectrometry (TWIMS) under positive ionization conditions. Nitrogen was used as drift gas in the ion mobility cell. The proposed database covers 173 ions including [M+H]+ and [M+Na]+ species. High correlation between m/z and CCS has been observed for [M+H]+ (R2 = 0.9518, n = 91) and [M+Na]+ (R2 = 0.9135, n = 82) ions. As expected, CCS values for sodium adducts are generally greater than for protonated molecules because they exhibit higher molecular weight. However, sodium adducts of aminoglycosides, β-lactams, and of several quinolones and benzimidazoles, were characterized as more compact ions than their related protonated molecule. In addition, this work describes the fragmentation pattern observed for the studied molecules. For the first time, the main fragment ions for most of the compounds have also been characterized in terms of CCS, involving a total of 238 ions. As proof of concept, for the application of this database to biological matrices, eleven veterinary drugs in bovine urine samples were characterized in terms of CCS, showing that this parameter was not influenced by the matrix.

Regaining Switching by Overcoming Single-Transistor Latch in Ge Junctionless MOSFETs

This paper reports on the suppression of single-transistor latch, an extreme condition of impact ionization (I.I.), in n-type double-gate germanium (Ge) junctionless (JL) transistors. It is shown that JL transistors can be latched to the on-state due to an increase in the I.I. generated power per unit volume with an increase in drain bias, film thickness, oxide thickness, and doping. Latch, being detrimental to switching, can be effectively suppressed by applying an appropriate negative (positive) back-gate bias for n-type (p-type) JL MOSFET. The independent gate operation with appropriate back bias allows the device to overcome latching and regain switching action with a subthreshold swing ( ${S}$ -swing) <10 mV/decade at room temperature. The work showcases the limit imposed on back bias due to an increase in off-state current due to band-to-band tunneling along with the utility of sidewall spacer to effectively suppress the same. We also show the tunability of hysteresis using back-gate bias. The work highlights a systematic methodology to eliminate single-transistor latch while preserving sub-60 mV/decade switching in Ge JL MOSFETs.