Low-lying Negative Ion States Probed in Potassium - Ethanol Collisions.

Dissociative electron transfer in collisions between neutral potassium atoms and neutral ethanol molecules yields mainly OH-, followed by C2H5O-, O-, CH3 - and CH2 -. The dynamics of negative ions have been investigated by recording time-of-flight mass spectra in a wide range of collision energies from 17.5 to 350 eV in the lab frame, where the branching ratios show a relevant energy dependence for low/intermediate collision energies. The dominant fragmentation channel in the whole energy range investigated has been assigned to the hydroxyl anion in contrast to oxygen anion from dissociative electron attachment (DEA) experiments. This result shows the relevant role of the electron donor in the vicinity of the temporary negative ion formed allowing access to reactions which are not thermodynamically attained in DEA experiments. The electronic state spectroscopy of such negative ions, was obtained from potassium cation energy loss spectra in the forward scattering direction at 205 eV impact energy, showing a prevalent Feshbach resonance at 9.36±0.10 eV with σ O H * / σ C H * ${{\sigma }_{OH}^{^{\ast}}/{\sigma }_{CH}^{^{\ast}}}$ character, while a less pronounced σ O H * ${{\sigma }_{OH}^{^{\ast}}}$ contribution assigned to a shape resonance has been obtained at 3.16±0.10 eV. Quantum chemical calculations for the lowest-lying unoccupied molecular orbitals in the presence of a potassium atom have been performed to support the experimental findings.

Probing the electronic structure and ground state symmetry of gas phase C60+ via VUV photoionization and comparison with theory.

Recently, some of us reviewed and studied the photoionization dynamics of C60 that are of great interest to the astrochemical community as four of the diffuse interstellar bands (DIBs) have been assigned to electronic transitions in the C60+ cation. Our previous analysis of the threshold photoelectron spectrum (TPES) of C60 [Hrodmarsson et al., Phys. Chem. Chem. Phys. 22, 13880-13892 (2020)] appeared to give indication of D3d ground state symmetry, in contrast to theoretical predictions of D5d symmetry. Here, we revisit our original measurements taking account of a previous theoretical spectrum presented in the work of Manini et al., Phys. Rev. Lett. 91(19), 196402 (2003), obtained within a vibronic model parametrized on density functional theory/local-density approximation electronic structure involving all hg Jahn-Teller active modes, which couple to the 2Hu components of the ground state of the C60+ cation. By reanalyzing our measured TPES of the ground state of the C60 Buckminsterfullerene, we find a striking resemblance to the theoretical spectrum calculated in the work of Manini et al., Phys. Rev. Lett. 91(19), 196402 (2003), and we provide assignments for many of the hg modes. In order to obtain deeper insights into the temperature effects and possible anharmonicity effects, we provide complementary modeling of the photoelectron spectrum via classical molecular dynamics (MD) involving density functional based tight binding (DFTB) computations of the electronic structure for both C60 and C60+. The validity of the DFTB modeling is first checked vs the IR spectra of both species which are well established from IR spectroscopic studies. To aid the interpretation of our measured TPES and the comparisons to the ab initio spectrum we showcase the complementarity of utilizing MD calculations to predict the PES evolution at high temperatures expected in our experiment. The comparison with the theoretical spectrum presented in the work of Manini et al., Phys. Rev. Lett. 91(19), 196402 (2003), furthermore, provides further evidence for a D5d symmetric ground state of the C60+ cation in the gas phase, in complement to IR spectroscopy in frozen noble gas matrices. This not only allows us to assign the first adiabatic ionization transition and thus determine the ionization energy of C60 with greater accuracy than has been achieved at 7.598 ± 0.005 eV, but we also assign the two lowest excited states (2E1u and 2E2u) which are visible in our TPES. Finally, we discuss the energetics of additional DIBs that could be assigned to C60+ in the future.

Photoionization and Dissociative Photoionization of Acetaldehyde in the 10.0-13.7†eV Range by Synchrotron Photoelectron Photoion Coincidence Spectroscopy.

Photoionization and dissociative photoionization of acetaldehyde (CH3CHO) in the 10.0-13.7 eV energy range are studied by using synchrotron radiation double imaging photoelectron photoion coincidence spectroscopy (i2PEPICO). The X2A' and A2A" electronic states of CH3CHO+ as well as the Franck-Condon gap region between these two states have been populated with several vibrational sequences and assigned in the high-resolution slow photoelectron spectrum (SPES). The adiabatic ionization energies (AIEs) of the X2A' and A2A" states are measured at 10.228±0.006 and 12.52±0.05 eV, respectively. The present results show that the X2A' state is a stable state while the A2A" state is fully dissociative to produce CH3CO+, CHO+ and CH4 + fragment ions. The 0 K appearance energies (AE0K) of CH3CO+ and CHO+ fragment ions are determined through the modeling of the breakdown diagram, i. e., AE0K(CH3CO+)=10.89±0.01 eV (including a reverse barrier of ~0.19 eV) and AE0K(CHO+)=11.54±0.05 eV. In addition, the dissociation mechanisms of CH3CHO+ including statistical dissociation, direct bond breaking and isomerization are discussed with the support of the calculated dissociation limits and transition state energies.

Validation of a 3D Local-Scale Adaptive Solar Radiation Model by Using Pyranometer Measurements and a High-Resolution Digital Elevation Model.

The result of the multidisciplinary collaboration of researchers from different areas of knowledge to validate a solar radiation model is presented. The MAPsol is a 3D local-scale adaptive solar radiation model that allows us to estimate direct, diffuse, and reflected irradiance for clear sky conditions. The model includes the adaptation of the mesh to complex orography and albedo, and considers the shadows cast by the terrain and buildings. The surface mesh generation is based on surface refinement, smoothing and parameterization techniques and allows the generation of high-quality adapted meshes with a reasonable number of elements. Another key aspect of the paper is the generation of a high-resolution digital elevation model (DEM). This high-resolution DEM is constructed from LiDAR data, and its resolution is two times more accurate than the publicly available DEMs. The validation process uses direct and global solar irradiance data obtained from pyranometers at the University of Salamanca located in an urban area affected by systematic shading from nearby buildings. This work provides an efficient protocol for studying solar resources, with particular emphasis on areas of complex orography and dense buildings where shadows can potentially make solar energy production facilities less efficient.

Conformer-Selective Photoelectron Circular Dichroism.

Conformational flexibility and chirality both play a key role in molecular recognition. It is therefore very useful to develop spectroscopic methods that simultaneously probe both properties. It has been theoretically predicted that photoelectron circular dichroism (PECD) should be very sensitive to conformational isomerism. However, experimental proof has been less forthcoming and only exists for a very few favorable cases. Here, we present a new PECD scheme based on resonance-enhanced two-photon ionization (RE2PI) using UV/Vis nanosecond laser excitations. The spectral resolution obtained thereby guarantees conformer-selectivity by inducing resonant conformer-specific ππ* S1←S0 transitions. We apply this experimental scheme to the study of chiral 1-indanol, which exists in two conformers linked by a ring inversion and defined by the position of the hydroxyl group, namely axial and equatorial. We show that the PECD of the equatorial and axial forms considerably differ in sign, magnitude and shape. We also discuss the influence of the total ionization energy, vibronic excitation of intermediate and final states, and relative polarization of the excitation and ionization lasers. Conformer-specificity adds a new dimension to the applications of PECD in analytical chemistry addressing now the general case of floppy systems.

Rare Case of Complete Androgen Insensitivity Syndrome.

Androgen insensitivity syndrome is a rare X-linked recessive condition in which patients present a female phenotype. After complete androgen insensitivity syndrome (CAIS) diagnosis, the timing of gonadectomy should be evaluated, considering the risks and benefits of this procedure. This paper reports an uncommon case of complete androgen insensitivity syndrome diagnosed belatedly in an adult patient. Surgical treatment was deemed necessary due to the elevated risk of gonadal malignancy.

Evidencing an elusive conical intersection in the dissociative photoionization of methyl iodide.

The valence-shell dissociative photoionization of methyl iodide (CH3I) is studied using double imaging photoelectron photoion coincidence (i2 PEPICO) spectroscopy in combination with highly-tunable synchrotron radiation from synchrotron SOLEIL. The experimental results are complemented by new high-level ab initio calculations of the potential energy curves of the relevant electronic states of the methyl iodide cation (CH3I+). An elusive conical intersection is found to mediate internal conversion from the initially populated first excited state, CH3I+(Ã2A1), into the ground cationic state, leading to the formation of methyl ions (CH3+). The reported threshold photoelectron spectrum for CH3+ reveals that the ν5 scissors vibrational mode promotes the access to this conical intersection and hence, the transfer of population. An intramolecular charge transfer takes place simultaneously, prior to dissociation. Upon photoionization into the second excited cationic state, CH3I+(B̃2E), a predissociative mechanism is shown to lead to the formation of atomic I+.

External standard calibration method for high-repetition-rate shock tube kinetic studies with synchrotron-based time-of-flight mass spectrometry.

The signal levels observed from mass spectrometers coupled by molecular beam sampling to shock tubes are impacted by dynamic pressures in the spectrometer due to rapid pressure changes in the shock tube. Accounting for the impact of the pressure changes is essential if absolute concentrations of species are to be measured. Obtaining such a correction for spectrometers operated with vacuum ultra violet photoionization has been challenging. We present here a new external calibration method which uses VUV-photoionization of CO2 to develop time-dependent corrections to species concentration/time profiles from which kinetic data can be extracted. The experiments were performed with the ICARE-HRRST (high repetition rate shock tube) at the DESIRS beamline of synchrotron SOLEIL. The calibration experiments were performed at temperatures and pressures behind reflected shock waves of 1376 ± 12 K and 6.6 ± 0.1 bar, respectively. Pyrolytic experiments with two aromatic species, toluene (T5 = 1362 ± 22 K, P5 = 6.6 ± 0.2 bar) and ethylbenzene (T5 = 1327 ± 18 K, P5 = 6.7 ± 0.2 bar), are analyzed to test the method. Time dependent concentrations for molecular and radical species were corrected with the new method. The resulting signals were compared with chemical kinetic simulations using a recent mechanism for pyrolytic formation of polycyclic aromatic hydrocarbons. Excellent agreement was obtained between the experimental data and simulations, without adjustment of the model, demonstrating the validity of the external calibration method.

Integral Electron Scattering Cross Sections from N2O for Impact Energies Ranging from 1 to 1000 eV.

Accurate total cross sections (TCS), within 5%, for electron scattering by N2O molecules have been measured with a magnetically confined electron transmission apparatus for impact energies ranging from 1 to 200 eV. For higher energies, these measurements have been complemented with our independent atom-based screening corrected additivity rule, including interference (IAM-SCAR + I) method to determine a complete reference TCS data set in the energy range (1-1000 eV). After a critical discussion that includes our calculated integral elastic and ionization cross sections and the theoretical and experimental data available in the literature, a complete set of integral elastic and inelastic (rotational, vibrational, and electronic excitation, ionization and electron attachment) cross sections, consistent with the reference TCS data, have been derived. This update on the N2O collisional database may help to improve the accuracy of radiation-induced transport models.

Investigating theoretical and experimental cross sections for elastic electron scattering from isoflurane.

We present a comprehensive analysis of elastic electron scattering from isoflurane in the intermediate energy range of 50-300 eV. This research is motivated by the significant impact of this molecule on global warming effects. We conducted this investigation through experimental measurements using a crossed-beam apparatus and covering a wide angular range from 25 to 125 degrees. Relative differential cross sections (DCSs) were obtained and subsequently normalized on an absolute scale by using the relative flow technique, with argon as the reference gas. These DCS values were then extrapolated and integrated to determine the experimental integral cross sections (ICSs). Additionally, we employed the independent atom model and the screening corrected additivity rule with incorporated Interference effects (IAM-SCAR+I) to calculate the theoretical differential and integral cross-sections. Remarkably, the calculated cross sections align closely with the experimental measurements across the entire energy and angular range. Furthermore, this study involved a comparison of the DCSs for isoflurane with previously published DCS values for two other volatile anesthetics, sevoflurane and halothane.

Elastic and electronically inelastic scattering of electrons by the pyrazine molecule.

We report on elastic and electronically inelastic integral and differential cross sections as well as ionization and total cross sections for electron collisions with the pyrazine molecule. The Schwinger multichannel method is applied in calculations carried out according to the minimal orbital basis for single configuration interactions strategy from the 1-channel up to 139-channels close-coupling level of approximation. With these calculations we have obtained integral and differential cross sections as well as excitation functions for elastic electron scattering and, also, integral and differential cross sections for electronic excitation from the ground state to the 3B1u, 3B2u, 3B3u, 1B1u, 1B2u and 1B3u excited states of pyrazine by electron impact. By summing the total ionization cross section obtained by means of the binary-encounter-Bethe model to these elastic and electronically inelastic contributions, we provided an estimate for the total cross section describing the electron-pyrazine interaction process. The independent atom model with the screening-corrected additivity rule plus interference terms method was also used in the present study to determine elastic integral and differential as well as ionization and total cross sections for electron collisions from pyrazine. The present results were, whenever possible, critically compared to the experimental and theoretical data available in the literature. In general, the overall agreement between the present results and the experiment is quite encouraging.

Rare Presentation of Postpericardiotomy Syndrome After Left Atrial Myxoma Removal.

Postpericardiotomy syndrome (PPS) is a known complication of cardiac valve surgery, but it has not been commonly reported as a postoperative complication of cardiac myxoma removal. A 78-year-old female with hypertension and atrial fibrillation presenting with angina was found to have a large left atrial myxoma (7.5 cm × 4.4 cm). The myxoma was resected; however, 1-week postoperation hemoglobin and blood pressure decreased with elevated erythrocyte sedimentation rate (ESR) and C-reactive protein (CRP). Limited transthoracic echocardiogram (TTE) showed moderate pericardial effusion, confirming the diagnosis of PPS. This case highlights the importance of monitoring patients postremoval of myxoma for symptoms of PPS.

Analysis of the volatile monoterpene composition of citrus essential oils by photoelectron spectroscopy employing continuously monitored dynamic headspace sampling.

A new photoelectron spectroscopic method permitting a quantitative analysis of the volatile headspace of several essential oils is presented and discussed. In particular, we focus on the monoterpene compounds, which are known to be the dominant volatile components in many such oils. The photoelectron spectra of the monoterpene constituents may be effectively isolated by accepting for analysis only those electrons that accompany the production of m/z = 136 ions, and by using low photon energies that restrict cation fragmentation. The monoterpene isomers are then identified and quantified by regression modelling using a library of terpene standard spectra. An advantage of this approach is that pre-concentration of the volatile vapour is not required, and all steps are performed at ambient temperature, avoiding the possible deleterious effects (such as isomerisation/decomposition) that may sometimes arise in gas chromatographic (GC) procedures. As a proof-of-principle demonstration, three citrus oils (lemon, lime, bergamot) are analysed with this approach and the results are compared with reported GC composition profiles obtained for these oils. Potential advantages of the methodology that include multiplex detection and real-time, in situ analysis are identified and discussed. Alternative and faster experimental implementations concerning laboratory-based ionization and detection schemes are proposed and considered, as is the possibility of a straightforward extension towards simultaneous determination of enantiomeric excesses.

Refining the thermochemical properties of CF, SiF, and their cations by combining photoelectron spectroscopy, quantum chemical calculations, and the Active Thermochemical Tables approach.

Fluorinated species have a pivotal role in semiconductor material chemistry and some of them have been detected beyond the Earth's atmosphere. Achieving good energy accuracy on fluorinated species using quantum chemical calculations has long been a challenge. In addition, obtaining direct experimental thermochemical quantities has also proved difficult. Here, we report the threshold photoelectron and photoion yield spectra of SiF and CF radicals generated with a fluorine reactor. The spectra were analysed with the support of ab initio calculations, resulting in new experimental values for the adiabatic ionisation energies of both CF (9.128 ± 0.006 eV) and SiF (7.379 ± 0.009 eV). Using these values, the underlying thermochemical network of Active Thermochemical Tables was updated, providing further refined enthalpies of formation and dissociation energies of CF, SiF, and their cationic counterparts.

The Apolipoprotein E neutralizing antibody inhibits SARS-CoV-2 infection by blocking cellular entry of lipoviral particles.

Severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) is the causal agent for coronavirus disease 2019 (COVID-19). Although vaccines have helped to prevent uncontrolled viral spreading, our understanding of the fundamental biology of SARS-CoV-2 infection remains insufficient, which hinders effective therapeutic development. Here, we found that Apolipoprotein E (ApoE), a lipid binding protein, is hijacked by SARS-CoV-2 for infection. Preincubation of SARS-CoV-2 with a neutralizing antibody specific to ApoE led to inhibition of SARS-CoV-2 infection. The ApoE neutralizing antibody efficiently blocked SARS-CoV-2 infection of human iPSC-derived astrocytes and air-liquid interface organoid models in addition to human ACE2-expressing HEK293T cells and Calu-3 lung cells. ApoE mediates SARS-CoV-2 entry through binding to its cellular receptors such as the low density lipoprotein receptor (LDLR). LDLR knockout or ApoE mutations at the receptor binding domain or an ApoE mimetic peptide reduced SARS-CoV-2 infection. Furthermore, we detected strong membrane LDLR expression on SARS-CoV-2 Spike-positive cells in human lung tissues, whereas no or low ACE2 expression was detected. This study provides a new paradigm for SARS-CoV-2 cellular entry through binding of ApoE on the lipoviral particles to host cell receptor(s). Moreover, this study suggests that ApoE neutralizing antibodies are promising antiviral therapies for COVID-19 by blocking entry of both parental virus and variants of concern.

Differential Susceptibility of Ex Vivo Primary Glioblastoma Tumors to Oncolytic Effect of Modified Zika Virus.

Glioblastoma (GBM), the most common primary malignant brain tumor, is a highly lethal form of cancer with a very limited set of treatment options. High heterogeneity in the tumor cell population and the invasive nature of these cells decrease the likely efficacy of traditional cancer treatments, thus requiring research into novel treatment options. The use of oncolytic viruses as potential therapeutics has been researched for some time. Zika virus (ZIKV) has demonstrated oncotropism and oncolytic effects on GBM stem cells (GSCs). To address the need for safe and effective GBM treatments, we designed an attenuated ZIKV strain (ZOL-1) that does not cause paralytic or neurological diseases in mouse models compared with unmodified ZIKV. Importantly, we found that patient-derived GBM tumors exhibited susceptibility (responders) and non-susceptibility (non-responders) to ZOL-1-mediated tumor cell killing, as evidenced by differential apoptotic cell death and cell viability upon ZOL-1 treatment. The oncolytic effect observed in responder cells was seen both in vitro in neurosphere models and in vivo upon xenograft. Finally, we observed that the use of ZOL-1 as combination therapy with multiple PI3K-AKT inhibitors in non-responder GBM resulted in enhanced chemotherapeutic efficacy. Altogether, this study establishes ZOL-1 as a safe and effective treatment against GBM and provides a foundation to conduct further studies evaluating its potential as an effective adjuvant with other chemotherapies and kinase inhibitors.

Induced photoelectron circular dichroism onto an achiral chromophore.

An achiral chromophore can acquire a chiral spectroscopic signature when interacting with a chiral environment. This so-called induced chirality is documented in electronic or vibrational circular dichroism, which arises from the coupling between electric and magnetic transition dipoles. Here, we demonstrate that a chiroptical response is also induced within the electric dipole approximation by observing the asymmetric scattering of a photoelectron ejected from an achiral chromophore in interaction with a chiral host. In a phenol-methyloxirane complex, removing an electron from an achiral aromatic π orbital localised on the phenol moiety results in an intense and opposite photoelectron circular dichroism (PECD) for the two enantiomeric complexes with (R) and (S) methyloxirane, evidencing the long-range effect (~5 Å) of the scattering chiral potential. This induced chirality has important structural and analytical implications, discussed here in the context of growing interest in laser-based PECD, for in situ, real time enantiomer determination.