Parent Ion Research Articles

Semiclassical study of nonsequential triple ionization of Ar in strong laser fields

We study nonsequential triple ionization of Ar in strong laser fields using a classical trajectory Monte Carlo simulation. By tracing electrons' trajectories, we reveal the mechanisms of triple ionization, including multiple recollision and sequential ionization. One electron tunnels out and rescatters with its parent ion, either kicking off two electrons together or kicking off one of them and exciting another one, which will be freed by the laser field. Besides the above-dominated channels, the cascade rescattering for triple ionization is explored, in which the first tunneling electron rescatters with the parent ion ${\mathrm{Ar}}^{+}$ and kicks off the second electron and then the second electron gains energy in the laser field and rescatters with ${\mathrm{Ar}}^{2+}$, kicking off the third electron or boosting it to excited states to be freed later. Such a cascade channel connects three electrons step by step, and ${\mathrm{Ar}}^{3+}$ may have larger ultimate momenta compared to the triple ionization mediated by only one rescattering. Our simulation shows it is possible to control the cascade channel and extract it through the ion momentum distribution.

UVPD Spectroscopy of Differential Mobility-Selected Prototropic Isomers of Rivaroxaban.

Two ion populations of protonated Rivaroxaban, [C19H18ClN3O5S + H]+, are separated under pure N2 conditions using differential mobility spectrometry prior to characterization in a hybrid triple quadrupole linear ion trap mass spectrometer. These populations are attributed to bare protonated Rivaroxaban and to a proton-bound Rivaroxaban-ammonia complex, which dissociates prior to mass-selecting the parent ion. Ultraviolet photodissociation (UVPD) and collision-induced dissociation (CID) studies indicate that both protonated Rivaroxaban ion populations are comprised of the computed global minimum prototropic isomer. Two ion populations are also observed when the collision environment is modified with 1.5% (v/v) acetonitrile. In this case, the protonated Rivaroxaban ion populations are produced by the dissociation of the ammonium complex and by the dissociation of a proton-bound Rivaroxaban-acetonitrile complex prior to mass selection. Again, both populations exhibit a similar CID behavior; however, UVPD spectra indicate that the two ion populations are associated with different prototropic isomers. The experimentally acquired spectra are compared with computed spectra and are assigned to two prototropic isomers that exhibit proton sharing between distal oxygen centers.

S1-State Decay Dynamics of Benzenediols (Catechol, Resorcinol, and Hydroquinone) and Their 1:1 Water Clusters.

The S1-state decaying rates of the three different benzenediols, catechol, resorcinol, and hydroquinone, and their 1:1 water clusters have been state-specifically measured using the picosecond time-resolved parent ion transients obtained by the pump (excitation) and probe (ionization) scheme. The S1 lifetime of catechol is found to be short, giving τ ∼ 5.9 ps at the zero-point level. This is ascribed to the H-atom detachment from the free OH moiety of the molecule. Consistent with a previous report (J. Phys. Chem. Lett. 2013, 4, 3819-3823), the S1 lifetime gets lengthened with low-frequency vibrational mode excitations, giving τ ∼ 9.0 ps for the 116 cm-1 band. The S1 lifetimes at the additional vibronic modes of catechol are newly measured, showing the nonnegligible mode-dependent fluctuations of the tunneling rate. When catechol is complexed with water, the S1 lifetime is enormously increased to τ ∼ 1.80 ns at the zero-point level while it shows an unusual dip at the intermolecular stretching mode excitation (τ ∼ 1.03 ns at 146 cm-1). Otherwise, it is shortened monotonically with increasing the internal energy, giving τ ∼ 0.67 ns for the 856 cm-1 band. Two different asymmetric or symmetric conformers of resorcinol give the respective S1 lifetimes of 4.5 or 6.3 ns at their zero-point levels according to the estimation from our transients taken within the temporal window of 0-2.7 ns. When resorcinol is 1:1 complexed with H2O, the S1 decaying rate is slightly accelerated for both conformers. The S1 lifetimes of trans and cis forms of hydroquinone are measured to be more or less same, giving τ ∼ 2.8 ns at the zero-point level. When H2O is complexed with hydroquinone, the S1 decaying process is facilitated for both conformers, slightly more efficiently for the cis conformer.

Photodissociation of aliphatic PAH derivatives under relevant astrophysical conditions

Context. The interaction of polycyclic aromatic hydrocarbons (PAHs) with vacuum ultraviolet (VUV) photons triggers the emission of the well-known aromatic infrared bands (AIBs), but other mechanisms, such as fragmentation, can be involved in this interaction. Fragmentation leads to selection effects that favor specific sizes and structures. Aims. Our aim is to investigate the impact of aliphatic bonds on the VUV photostability of PAH cations in a cryogenic and collisionless environment with conditions applicable for photodissociation regions (PDRs). Methods. The studied species are derived from pyrene (C16H10) and coronene (C24H12) and contain aliphatic bonds either in the form of methyl or ethyl sidegroups or of superhydrogenation. Their cations are produced by laser desorption ionization and isolated in the cryogenic ion cell of the PIRENEA setup, where they are submitted to VUV photons of 10.5 eV energy over long timescales (~1000 s). The parent and fragment ions are mass-analyzed and their relative intensities are recorded as a function of the irradiation time. The fragmentation cascades are analyzed with a simple kinetics model from which we identify fragmentation pathways and derive fragmentation rates and branching ratios for both the parents and their main fragments. Results. Aliphatic PAH derivatives are found to have a higher fragmentation rate and a higher carbon to hydrogen loss compared to regular PAHs. On the other hand, the fragmentation of PAHs with alkylated sidegroups forms species with peripheral pentagonal cycles, which can be as stable as, or even more stable than, the bare PAH cations. This stability is quantified for the main ions involved in the fragmentation cascades by the comparison of the fragmentation rates with the photoabsorption rates derived from theoretical photoabsorption cross sections. The most stable species for which there is an effective competition of fragmentation with isomerization and radiative cooling are identified, providing clues on the structures favored in PDRs. Conclusions. This work supports a scenario in which the evaporation of nanograins with a mixed aliphatic and aromatic composition followed by VUV photoprocessing results in both the production of the carriers of the 3.4 μm AIB by methyl sidegroups and in an abundant source of small hydrocarbons at the border of PDRs. An additional side effect is the efficient formation of stable PAHs that contain some peripheral pentagonal rings. Our experiments also support the role of isomerization processes in PAH photofragmentation, including the H-migration process, which could lead to an additional contribution to the 3.4 μm AIB.

Two-Dimensional Partial Covariance Mass Spectrometry for the Top-Down Analysis of Intact Proteins.

Two-dimensional partial covariance mass spectrometry (2D-PC-MS) exploits the inherent fluctuations of fragment ion abundances across a series of tandem mass spectra, to identify correlated pairs of fragment ions produced along the same fragmentation pathway of the same parent (e.g., peptide) ion. Here, we apply 2D-PC-MS to the analysis of intact protein ions in a standard linear ion trap mass analyzer, using the fact that the fragment-fragment correlation signals are much more specific to the biomolecular sequence than one-dimensional (1D) tandem mass spectrometry (MS/MS) signals at the same mass accuracy and resolution. We show that from the distribution of signals on a 2D-PC-MS map it is possible to extract the charge state of both parent and fragment ions without resolving the isotopic envelope. Furthermore, the 2D map of fragment-fragment correlations naturally separates the products of the primary decomposition pathways of the molecular ions from those of the secondary ones. We access this spectral information using an adapted version of the Hough transform. We demonstrate the successful identification of highly charged, intact protein molecules bypassing the need for high mass resolution. Using this technique, we also perform the in silico deconvolution of the overlapping fragment ion signals from two co-isolated and co-fragmented intact proteins, demonstrating a viable new method for the concurrent mass spectrometric identification of a mixture of intact protein ions from the same fragment ion spectrum.

Classical backpropagation for probing the backward rescattering time of a tunnel-ionized electron in an intense laser field

We present a method to estimate the backward rescattering time of a tunnel-ionized electron in an intense laser pulse. The idea of the classical backpropagation method is applied to determine the backward rescattering time and its dependence on various parameters such as the ionization potential of the parent ion, its spatial profile and the peak intensity and wavelength of the driving laser field. The accurate estimation of the rescattering time would provide critical information in analyzing ultrafast rescattering dynamics in applications such as high-order harmonic generation, above-threshold ionization, and laser-induced electron diffraction experiments. We find that the backward rescattering time is significantly affected by the peak intensity of the laser pulse. The rescattering time changes by a few hundred attoseconds when the peak intensity varies from $1\ifmmode\times\else\texttimes\fi{}{10}^{14}$ to $5\ifmmode\times\else\texttimes\fi{}{10}^{14}\phantom{\rule{4pt}{0ex}}\mathrm{W}/\mathrm{c}{\mathrm{m}}^{2}$.

Thermal Decomposition of Anionic, Zwitterionic, and Cationic Polyfluoroalkyl Substances in Aqueous Film-Forming Foams.

In this study, we investigated thermal decomposition mechanisms of cationic, zwitterionic, and anionic polyfluoroalkyl substances, including those present in aqueous film-forming foam (AFFF) samples. We present novel evidence that polyfluoroalkyl substances gave quantitative yields of perfluoroalkyl substances of different chain lengths during thermal treatment. The results support a radical-mediated transformation mechanism involving random-chain scission and end-chain scission, leading to the formation of perfluoroalkyl carboxylic acids such as perfluorooctanoic acid (PFOA) from certain polyfluoroalkyl amides and sulfonamides. Our results also support a direct thermal decomposition mechanism (chain stripping) on the nonfluorinated moiety of polyfluoroalkyl sulfonamides, resulting in the formation of perfluorooctanesulfonic acid (PFOS) and other structurally related polyfluoroalkyl compounds. Thermal decomposition of 8:2 fluorotelomer sulfonate occurred through end-chain scission and recombination reactions, successively yielding PFOS. All of the studied polyfluoroalkyl substances began to degrade at 200-300 °C, exhibiting near-complete decomposition at ≥400 °C. Using a high-resolution parent ion search method, we demonstrated for the first time that low-temperature thermal treatments of AFFF samples led to the generation of anionic fluoroalkyl substances, including perfluoroheptanesulfonamide, 8:2 fluorotelomer sulfonic acid, N-methyl perfluorooctane sulfonamide, and a previously unreported compound N-2-propenyl-perfluorohexylsulfonamide. This study provides key insights into the fate of polyfluoroalkyl substances in thermal processes.

Chimera Spectrum Diagnostics for Peptides Using Two-Dimensional Partial Covariance Mass Spectrometry.

The rate of successful identification of peptide sequences by tandem mass spectrometry (MS/MS) is adversely affected by the common occurrence of co-isolation and co-fragmentation of two or more isobaric or isomeric parent ions. This results in so-called `chimera spectra’, which feature peaks of the fragment ions from more than a single precursor ion. The totality of the fragment ion peaks in chimera spectra cannot be assigned to a single peptide sequence, which contradicts a fundamental assumption of the standard automated MS/MS spectra analysis tools, such as protein database search engines. This calls for a diagnostic method able to identify chimera spectra to single out the cases where this assumption is not valid. Here, we demonstrate that, within the recently developed two-dimensional partial covariance mass spectrometry (2D-PC-MS), it is possible to reliably identify chimera spectra directly from the two-dimensional fragment ion spectrum, irrespective of whether the co-isolated peptide ions are isobaric up to a finite mass accuracy or isomeric. We introduce ‘3-57 chimera tag’ technique for chimera spectrum diagnostics based on 2D-PC-MS and perform numerical simulations to examine its efficiency. We experimentally demonstrate the detection of a mixture of two isomeric parent ions, even under conditions when one isomeric peptide is at one five-hundredth of the molar concentration of the second isomer.

Ultrafast Photo-ion Probing of the Ring-Opening Process in Trans-Stilbene Oxide.

The ultrafast photo‐induced ring opening of the oxirane derivative trans‐stilbene oxide has been studied through the use of ultrafast UV/UV pump‐probe spectroscopy by using photo‐ion detection. Single‐ and multiphoton probe paths and final states were identified through comparisons between UV power studies and synchrotron‐based vacuum ultraviolet (VUV) single‐photon ionization studies. Three major time‐dependent features of the parent ion (sub‐450 fs decay, (1.5±0.2) ps, and >100 ps) were observed. These decays are discussed in conjunction with the primary ring‐opening mechanism of stilbene oxide, which occurs through C−C dissociation in the oxirane ring. The appearance of fragments relating to the masses of dehydrogenated diphenylmethane (167 amu) and dehydrogenated methylbenzene (90 amu) were also investigated. The appearance of the 167 amu fragment could suggest an alternative ultrafast ring‐opening pathway via the dissociation of one of the C−O bonds within the oxirane ring.

Determining Collision Cross Sections from Differential Ion Mobility Spectrometry.

The experimental determination of ion-neutral collision cross sections (CCSs) is generally confined to ion mobility spectrometry (IMS) technologies that operate under the so-called low-field limit or those that enable empirical calibration strategies (e.g., traveling wave IMS; TWIMS). Correlation of ion trajectories to CCS in other non-linear IMS techniques that employ dynamic electric fields, such as differential mobility spectrometry (DMS), has remained a challenge since its inception. Here, we describe how an ion's CCS can be measured from DMS experiments using a machine learning (ML)-based calibration. The differential mobility of 409 molecular cations (m/z: 86-683 Da and CCS 110-236 Å2) was measured in a N2 environment to train the ML framework. Several open-source ML routines were tested and trained using DMS-MS data in the form of the parent ion's m/z and the compensation voltage required for elution at specific separation voltages between 1500 and 4000 V. The best performing ML model, random forest regression, predicted CCSs with a mean absolute percent error of 2.6 ± 0.4% for analytes excluded from the training set (i.e., out-of-the-bag external validation). This accuracy approaches the inherent statistical error of ∼2.2% for the MobCal-MPI CCS calculations employed for training purposes and the <2% threshold for matching literature CCSs with those obtained on a TWIMS platform.

Determination of Abundant Metabolite Matrix Adducts Illuminates the Dark Metabolome of MALDI-Mass Spectrometry Imaging Datasets.

Spatial metabolomics using mass spectrometry imaging (MSI) is a powerful tool to map hundreds to thousands of metabolites in biological systems. One major challenge in MSI is the annotation of m/z values, which is substantially complicated by background ions introduced throughout the chemicals and equipment used during experimental procedures. Among many factors, the formation of adducts with sodium or potassium ions, or in case of matrix-assisted laser desorption ionization (MALDI)-MSI, the presence of abundant matrix clusters strongly increases total m/z peak counts. Currently, there is a limitation to identify the chemistry of the many unknown peaks to interpret their biological function. We took advantage of the co-localization of adducts with their parent ions and the accuracy of high mass resolution to estimate adduct abundance in 20 datasets from different vendors of mass spectrometers. Metabolites ranging from lipids to amines and amino acids form matrix adducts with the commonly used 2,5-dihydroxybenzoic acid (DHB) matrix like [M + (DHB-H2O) + H]+ and [M + DHB + Na]+. Current data analyses neglect those matrix adducts and overestimate total metabolite numbers, thereby expanding the number of unidentified peaks. Our study demonstrates that MALDI-MSI data are strongly influenced by adduct formation across different sample types and vendor platforms and reveals a major influence of so far unrecognized metabolite–matrix adducts on total peak counts (up to one third). We developed a software package, mass2adduct, for the community for an automated putative assignment and quantification of metabolite–matrix adducts enabling users to ultimately focus on the biologically relevant portion of the MSI data.

Confirmation of unknown additives in enrofloxacin powder

应用非靶向分析技术,筛查、分析和确证恩诺沙星粉(水产用)中的非法添加物。分别制备甲酸酸化、碳酸钠碱化的恩诺沙星粉供试品溶液,经超高效液相色谱-二极管阵列检测器(UPLC-PDA)检测初筛,获取未知物色谱图。应用超高效液相色谱-飞行时间高分辨质谱(UPLC-TOF-HRMS),在正、负离子模式下对酸化、碱化样液进一步检测,获得未知物母离子和二级特征碎片的精确质荷比、同位素信息,并应用SCIEX OS软件进行分析推导。最后取疑似化合物对照品进行确证研究。UPLC-PDA初筛结果显示:酸化样液在1.870 min、5.122 min,碱化样液在5.122 min,均发现高响应未知色谱峰。对吸收波长和峰面积进行分析,推测含2个未知物,且未知物1(1.870 min)与未知物2(5.122 min)在酸性/碱性条件下可能发生转换。SCIEX OS软件分析推导结果显示:未知物2,母离子分子式拟合为C11H8O2,二级碎片结构解析含1个苯环、2个羰基和1个通过成环连接的丙烯结构,推测为甲萘醌;未知物1的分子离子峰为C11H9O5S-,二级碎片仅采集到HSO3-,丢失部分与未知物2一致,结合甲萘醌常见衍生物类型,推测为亚硫酸氢钠甲萘醌。取甲萘醌、亚硫酸氢钠甲萘醌对照品进行对比研究,UPLC-PDA检测结果显示:未知物1与亚硫酸氢钠甲萘醌、未知物2与甲萘醌,保留时间和紫外光谱一致;向供试溶液中添加对照品溶液后检测,未知物为单一峰。UPLC-TOF-HRMS检测发现:未知物1与亚硫酸氢钠甲萘醌保留时间一致,一级质谱质量偏差为1.0×10-6,二级谱库匹配度为100%;未知物2与甲萘醌保留时间一致,一级质谱质量偏差为0.6×10-6,二级谱库匹配度为99.7%。未知物1和2的结构得以确证。亚硫酸氢钠甲萘醌可止血,与恩诺沙星治疗败血症的适应证相应,佐证试验结果。随着对兽药非法添加行为的严格监管和严厉打击,非法添加物和添加手段愈发隐蔽,常规靶向分析难以满足监控需求。该文详述的使用UPLC-PDA结合UPLC-TOF-HRMS对未知物进行非靶向分析的技术,可为药品、食品、保健品、化妆品及农药等产品中非法添加物的筛查和确证提供思路和技术参考。

The Total Amount and Composition Determination of Crocetin and Its Derivatives from Gardenia Yellow by HPLC-MS-MS

Consisting of crocetin derivatives as major color materials, gardenia yellow is a water-soluble food colorant extracted from the fruits of Gardenia jasminoides Ellis. However, as color materials, the total crocetin and its derivative amount and composition cannot be determined because the structures of some crocetin derivatives are currently unknown and the commercially-available reference sample is still short. This study aims to develop a method for the total amount and composition determinations of crocetin and its derivatives from gardenia yellow. In practice, the absorption coefficient of each crocetin derivative is calculated from that of crocetin and the negative correlation of absorbance with molecular mass of each derivative, while the molecular mass of each crocetin derivative is substituted by the m/z value of its parent ion on MS. The relative standard deviation (RSD) of reproducibility was 3.17%. The recovery of added external reference sample was ≥97±1.61%. The minimum detection limit was 7.44μg/mL.

Metabolism and Tissue Distribution of Chelerythrine and Effects of Macleaya Cordata Extracts on Liver NAD(P)H Quinone Oxidoreductase

Background: Macleaya cordata (Willd.) (Papaveraceae) is listed as a feed additive in animal production by the European Food Authority.Methods: The metabolites of chelerythrine in rats were measured in vitro and in vivo by rapid and accurate high-performance liquid chromatography/quadrupole-time-of-flight mass spectrometry (HPLC/QqTOF-MS). The structures of CHE metabolites were elucidated by comparing their changes in accurate molecular masses and fragment ions with those of parent ion or metabolite. The metabolic enzymes that were involved in chelerythrine reduction were investigated using an inhibition method. The tissue distribution of chelerythrine and the effects on NQO1 following intragastric administration with M. cordata extracts in rats were examined.Results: A total of twelve metabolites of chelerythrine were characterized by this approach in rat liver S9 and in vivo. The reduction of the iminium bond of chelerythrine and subsequent O-demethylation was the main metabolic pathway of chelerythrine in rat liver S9 while the reduction of the iminium bond of chelerythrine was the main metabolic pathway of chelerythrine in rats in vivo. After the rats were given intragastric administration, the low concentration residues of sanguinarine and chelerythrine in different rat tissues were found at 48 h after the last dose, suggesting that both compounds could be widely distributed in tissues. The results also indicated that XO, NQO1, NQO2, and carbonyl reductase are involved in chelerythrine reduction. Macleaya cordata extracts treated female and male rats, respectively, showed different responses, inhibiting NQO1 activity in males, but inducing NQO1 activity in females. Chelerythrine had a weak impact on NQO1 activity, but sanguinarine inhibited NQO1 activityConclusion: Through studying the effects of cytosolic reductase inhibitors on chelerythrine reduction and the impact of chelerythrine and sanguinarine on the activity of NQO1 in vitro and in vivo, we clarified the potential drug interaction of Macleaya cordata extract in clinical application, so as to provide theoretical guidance for clinically safe medication. In addition, it provided a reference basis for the metabolic mechanism of chelerythrinein rats.

Two-dimensional electron returning trajectory in nonsequential double ionization by strong-field circularly polarized laser pulses

We investigate the features of electron returning trajectories in recollision-induced nonsequential double ionization by intense circularly polarized laser pulses within a classical ensemble model. We find typical two-dimensional returning trajectories of the first ionized electron that can be decomposed into local circular motion driven by the laser field and overall elliptical motion due to the Coulombic attraction of the parent ion. Such trajectories burst within a narrow time window of less than two laser cycles and end periodically with kinetic energies around the instantaneous ponderomotive energy after many laser cycles, which is very different from the well-known simple one-dimensional returning trajectories in the case of linear laser polarization.

A New Application of MALDI Biotyper for a Potential Use in Therapeutic Drug Monitoring of Voriconazole.

We present a proof-of-concept study on the use of MALDI Biotyper to detect and monitor the levels of voriconazole in human serum. A simple extraction-concentration method and a MALDI Biotyper protocol were developed, and a parent ion of voriconazole (1 H+) could be detected and quantified with good reproducibility. Our results point to a new application of MALDI Biotyper for therapeutic drug monitoring.

Ionization in intense laser fields beyond the electric dipole approximation: concepts, methods, achievements and future directions

The electric dipole approximation is widely used in atomic, molecular and optical physics and is typically related to a regime for which the wavelength is much larger than the atomic structure. However, studies have shown that in strong laser fields another regime exists where the dipole approximation breaks down. During the ionization process in intense laser fields and at long wavelengths the photoelectrons can reach higher velocities such that the magnetic field component of the laser field becomes significant. The ionization dynamics and the final momentum of the electron is therefore modified by the entire Lorentz force. In contrast the magnetic field interaction is neglected in the dipole approximation. Rapid developments in laser technology and advancements in the accuracy of the measurements techniques have enabled the observation of the influence of such non-dipole effects on the final angular photoelectron momentum distributions. More recently the number of studies on ionization beyond the dipole approximation has increased significantly, providing more important insight into fundamental properties of ionization processes. For example we have shown that the final three dimensional photoelectron momentum spectra is significantly affected by the non-dipole drift with the parent–ion interaction, the linear multiphoton momentum transfer on a sub-cycle time scale and the sharing of the transferred linear photon momenta between the electron and the ion. In this article we present an overview of the underlying mechanisms and we review the experimental techniques and the achievements in this field. We focus on ionization in strong laser fields in the regime where the dipole approximation is not valid but a fully relativistic description is not required.

Double and Triple Differential Cross Sections for Single Ionization of Benzene by Electron Impact.

Experimental results for the electron impact ionization of benzene, providing double (DDCS) and triple differential cross sections (TDCS) at the incident energy of 90 eV, measured with a multi-particle momentum spectrometer, are reported in this paper. The most intense ionization channel is assigned to the parent ion (C6H6+) formation. The DDCS values are presented for three different transferred energies, namely 30, 40 and 50 eV. The present TDCS are given for two fixed values of the ejected electron energy (E2), at 5 and 10 eV, and an electron scattering angle (θ1) of 10°. Different features related to the molecular orbitals of benzene from where the electron is extracted are observed. In addition, a semi-empirical formula to be used as the inelastic angular distribution function in electron transport simulations has been derived from the present DDCS result and compared with other expressions available in the literature.

Venus' Mass Spectra Show Signs of Disequilibria in the Middle Clouds.

We present a re‐examination of mass spectral data obtained from the Pioneer Venus Large Probe Neutral Mass Spectrometer. Our interpretations of differing trace chemical species are suggestive of redox disequilibria in Venus' middle clouds. Assignments to the data (at 51.3 km) include phosphine, hydrogen sulfide, nitrous acid, nitric acid, carbon monoxide, hydrochloric acid, hydrogen cyanide, ethane, and potentially ammonia, chlorous acid, and several tentative PxOy species. All parent ions were predicated upon assignment of corresponding fragmentation products, isotopologues, and atomic species. The data reveal parent ions at varying oxidation states, implying the presence of reducing power in the clouds, and illuminating the potential for chemistries yet to be discovered. When considering the hypothetical habitability of Venus' clouds, the assignments reveal a potential signature of anaerobic phosphorus metabolism (phosphine), an electron donor for anoxygenic photosynthesis (nitrite), and major constituents of the nitrogen cycle (nitrate, nitrite, ammonia, and N2).

Pseudotetrahedral high-spin manganese(II)-complexes with (S or R)-N-1-(Ar)ethyl-salicylaldimine: Chiroptical property, chirality induction at-metal, paramagnetism, redox-potential, PXRD structures and DFT/TDDFT

Pseudotetrahedral high-spin bis[(S or R)-N-1-(Ar)ethyl-salicylaldiminato-κ2N,O]-Λ/Δ-Mn(II) {Ar = C6H5 (MnSL1 or MnRL1), p-MeOC6H4 (MnSL2 or MnRL2) and p-BrC6H4 (MnSL3 or MnRL3)} are synthesized from reactions between enantiopure Schiff base ligands (S or R)-N-1-(Ar)ethyl-salicylaldimine and manganese(II) chloride with induction of Λ/Δ-chirality-at-metal. ESI mass spectra show the parent ion peak for the mononuclear species at m/z 504 (MnRL1 or MnSL1) and 662 (MnSL3 or MnRL3). The molar conductance values imply mononuclear and non-electrolyte nature of the complexes with metal-to-ligand 1:2 stoichiometry in dimethylformamide (DMF). Electronic circular dichroism (ECD) spectra exhibit mirror-image relationships, and hence confirm enantiopurity or enantiomeric excess of the R- or S-ligated complexes in solution. It suggests the diastereomer or diastereomeric excess of Δ-MnRL or Λ-MnSL in solution combined with the analyses on experimental and simulated ECD spectra by Density Functional Theory/Time-dependant Density Functional Theory (DFT/TDDFT), resulting from diastereoselectively induced Δ- or Λ-chiralityat-metal. In the contrast, DFT optimized structures in gas-phase disclose Λ-MnRL or Δ-MnSL diastereomer slightly more stable than Δ-MnRL or Λ-MnSL by 2–4 kcal/mol. Variable temperature magnetic moment values (μeff. = 5.25−5.55 μB at 263−321 K) correspond to the high-spin state of Mn(II)-complexes in methanol. Cyclic voltammograms demonstrate two one electron charge transfer processes for MnIII/II and MnII/I couples in acetonitrile, respectively. Powder XRD patterns reveal a well-defined crystalline nature and allow structure determination for the MnRL3, using the Expo-2014 program followed by Rietveld refinement. PXRD structure suggests the formation of four-coordinated mononuclear manganese(II)-complex by the two phenolate-oxygen and two imine-nitrogen atoms from two molecules of Schiff base ligands in a pseudotetrahedral geometry.