Estimate of the C-Cl photoionization cross section and absolute photoionization cross sections of chlorinated organic compounds.

Chlorinated organic compounds are prominently used for industrial production, but their vapors and emission byproducts can cause detrimental effects to human health and the environment. To accurately quantify organochlorine compounds, the absolute photoionization cross section of tetrachloroethylene, chlorobenzene, 1,2-dichlorobenzene, and chloroacetone are measured using multiplexed synchrotron photoionization mass spectrometry at the Advanced Light Source at Lawrence Berkeley National Laboratory. These measurements allow for the estimation of the C-Cl photoionization cross section, increasing quantification accuracy of chlorinated emissions for kinetic modeling and pollutant mitigation. CBS-QB3 calculations of adiabatic ionization energies and thermochemical appearance energies are also presented and agree well with the experimental results.

Absolute Photoionization Cross Section and Dissociative Ionization Pathways of Alpha-Pinene.

The absolute photoionization cross section of the monoterpenoid, alpha-pinene (AP), is presented together with the relative photoionization cross sections of its dissociative fragments for the first time. Experiments are performed via multiplexed vacuum ultraviolet (VUV) synchrotron photoionization (PI) mass spectrometry in the 8.0-11.0 eV energy range. Experimental work is conducted at the Advanced Light Source of the Lawrence Berkeley National Laboratory. Dissociative fragments were identified at m/z 121, 94, 93, 92, and 80. The photoionization cross section for the parent mass at 11.0 eV was determined to be 17±4 Mb with a total ionization cross section of 92±23 Mb at the same photon energy. Experimental appearance energies of dissociative ionization fragments and potential dissociative ionization pathways calculated at the G4 level of theory are presented as well.

Sciatic nerve fascicle differentiation on high-resolution ultrasound with histological verification: An ex vivo study.

INTRODUCTION/AIMS: The development of high-resolution ultrasound (HRUS) has enabled the depiction of peripheral nerve microanatomy in vivo. This study compared HRUS fascicle differentiation to the structural depiction in histological cross-sections (HCS). METHODS: A human cadaveric sciatic nerve was marked with 10 surgical sutures, and HRUS image acquisition was performed with a 22-MHz probe. The nerve was excised and cut into five segments for HCS preparation. Selected HCS were cross-referenced to HRUS, with sutures to improve orientation. Sciatic nerve and fascicle contouring were performed to assess nerve and fascicular cross-sectional area (CSA), fascicle count, and interfascicular distances. Three groups were defined based on HRUS fascicle differentiation in comparison to HCS, namely single fascicle (SF), fascicular cluster (FC), and no depiction (ND) group. RESULTS: On cross-referenced HRUS to HCS images, 58% of fascicles were differentiated. On HRUS, significantly larger fascicle CSA and smaller fascicle count were observed compared with HCS. Group analysis showed that 41% of fascicles were defined as SF, 47% as FC, and 12% as ND. The mean fascicle CSA in the ND group was 0.05 mm2. Compared with the SF, the FC had significantly larger fascicle CSA (1.2 ± 0.7 vs. 0.6 ± 0.4 mm2; p < .001) and shorter interfascicular distances (0.1 ± 0.04 vs. 0.5 ± 0.3 µm; p < .001). DISCUSSION: While HRUS can depict fascicular anatomy, only half of the fascicles visualized on HRUS directly correspond to single fascicles observed on HCS. The amount of interfascicular epineurium appears to influence the ability of HRUS to differentiate individual fascicles.

Head of Zebu cattle (Bos Taurus indicus): sectional anatomy and 3D computed tomography.

The research was designed to use computed tomography (CT) with 3D-CT reconstruction imaging techniques and the various anatomical sections-plana transversalia, frontalis, and dorsalia-to describe the anatomical architecture of the Zebu cattle head. Our study used nine mature heads. The CT bone window created detailed images of cranial bones, mandibles, teeth, and hyoid bones. All of the head cavities were evaluated, including the cranial, orbital, oral, auricular, and nasal cavities with their paranasal and conchal sinuses. The septum nasi, attached to the vomer and maxillary bones, did not reach the nasal cavity floor caudally at the level of the second premolar teeth, resulting in a single median channel from the choanae to the nasopharynx. The positions, boundaries, and connections of the paranasal sinuses were clearly identified. There were four nasal conchal sinuses (that were named the dorsal, middle, ethmoidal, and ventral) and five paranasal sinuses that were described as the following: sinus frontalis, maxillaris, palatinorum, and lacrimalis, as defined in the different anatomical sections and computed tomographic images. The complicated sinus frontalis caused the pneumatization of all bones that surrounded the cranial cavity, with the exception of the ethmoidal and body of basisphenoid bones. The sinus maxillaris was connected to the sinus lacrimalis and palatinorum through the maxillolacrimal and palatomaxillary openings, and to the middle nasal meatus through the nasomaxillary opening. Our findings provide a detailed anatomical knowledge for disease diagnosis to internal medicine veterinarians and surgeons by offering a comprehensive atlas of the Zebu cattle anatomy.

Ionization Detail Parameters for DNA Damage Evaluation in Charged Particle Radiotherapy: Simulation Study Based on Cell Survival Database.

Details of excitation and ionization acts hide a description of the biological effects of charged particle traversal through living tissue. Nanodosimetry enables the introduction of novel quantities that characterize and quantify the particle track structure while also serving as a foundation for assessing biological effects based on this quantification. This presents an opportunity to enhance the planning of charged particle radiotherapy by taking into account the ionization detail. This work uses Monte Carlo simulations with Geant4-DNA code for a wide variety of charged particles and their radiation qualities to analyze the distribution of ionization cluster sizes within nanometer-scale volumes, similar to DNA diameter. By correlating these results with biological parameters extracted from the PIDE database for the V79 cell line, a novel parameter R2 based on ionization details is proposed for the evaluation of radiation quality in terms of biological consequences, i.e., radiobiological cross section for inactivation. By incorporating the probability p of sub-lethal damage caused by a single ionization, we address limitations associated with the usually proposed nanodosimetric parameter Fk for characterizing the biological effects of radiation. We show that the new parameter R2 correlates well with radiobiological data and can be used to predict biological outcomes.

Ionization Cross Sections of Hydrogen Molecule by Electron and Positron Impact.

We present ionization cross sections of hydrogen molecules by electron and positron impact for impact energies between 20 and 1000 eV. A three-body Classical Trajectory Monte Carlo approximation is applied to mimic the collision system. In this approach, the H2 molecule is modeled by a hydrogen-type atom with one active electron bound to a central core of effective charge with an effective binding energy. Although this model is crude for describing a hydrogen molecule, we found that the total cross sections for positron impact agree reasonably well with the experimental data. For the electron impact, our calculated cross sections are in good agreement with the experimental data in impact energies between 80 eV and 400 eV but are smaller at higher impact energies and larger at lower impact energies. Our calculated cross sections are compared with the scaled cross sections obtained experimentally for an atomic hydrogen target. We also present single differential cross sections as a function of the energy and angle of the ejected electron and scattered projectiles for a 250 eV impact. These are shown to agree well with available data. Impact parameter distributions are also compared for several impact energies.

Which are the most effective methods of teaching sectional anatomy? A scoping review.

PURPOSE: Sectional anatomy knowledge is essential for a wide spectrum of health professionals and is extensively applied to their everyday practice. We performed a scoping review to find which are the most effective methods of teaching sectional anatomy. METHODS: We searched PubMed, Scopus, and Cochrane Library to detect articles which investigated the effectiveness of sectional anatomy education methods, based on test scores. From each included paper, we extracted: author(s), number of participants, the anatomical region or regions, the method or methods of sectional anatomy education and the outcomes concerning only the acquisition of sectional anatomy knowledge. RESULTS: Seven studies were included. There were four articles, which involved combined teaching approaches, and three articles, which did not comprise such approaches. In all studies which evaluated the effectiveness of a combination of teaching methods (comprising three-dimensional digital or physical tools) compared to cross-sections only, the anatomy test scores were significantly higher in the first case. The students' interaction with the educational material significantly enhanced the effectiveness of the implemented methods. CONCLUSIONS: The multimodal teaching of sectional anatomy, especially involving three-dimensional methods, both digital and physical, was more effective than teaching based only on cross-sections. The students' interaction with the educational material improved the effectiveness of the teaching, which they received. These outcomes may stimulate anatomy teachers to enhance sectional anatomy education and encourage researchers to shed more light on the investigation of the optimal teaching strategies.

Calculation of Ionization, Excitation and Electron Capture Cross Sections for Be4+ +H(2s, 2p) Collisions.

A computational study of Be4+ +H(2s, 2p) collisions has been carried out employing the Classical Trajectory Monte Carlo (CTMC) method for the impact energy range from 20 keV/u to 1000 keV/u. The integral n partial cross sections for H(n) excitation and Be3+ (n) electron capture and, the total ionization and electron capture cross sections are calculated and compared to recent semiclassical results. A general good agreement is observed for the n partial and total electron capture and ionization cross sections. The comparative study of the three inelastic processes show no significant differences between both excited targets.

Rapid identification of pyoverdines of fluorescent Pseudomonas spp. by UHPLC-IM-MS.

Siderophores are iron-chelating molecules produced by bacteria and other microbes. They are involved with virulence in infections and play key roles in bacterial community assembly and as plant protectants due to their pathogen control properties. Although assays exist to screen whether newly isolated bacteria can produce siderophores, the chemical structures of many of these bio-active molecules remain unidentified due to the lack of rapid analytical procedures. An important group of siderophores are pyoverdines. They consist of a structurally diverse group of chromopeptides, whose amino acid sequence is characteristic for the fluorescent Pseudomonas species that secrets them. Although over 60 pyoverdine structures have been described so far, their characterization is cumbersome and several methods (isoelectrofocusing, iron uptake measurement, mass determination) are typically combined as ambiguous results are often achieved by a single method. Those additional experiments consume valuable time and resources and prevent high-throughput analysis. In this work, we present a new pyoverdine characterisation option by recording their collision cross sections (CCS) using trapped ion mobility spectrometry. This can be done simultaneously in combination with UHPLC and high-resolution MS resulting in a rapid identification of pyoverdines. The high specificity of CCS values is presented for 17 pyoverdines secreted by different Pseudomonas strains. The pyoverdine mass determination by full scan MS was supported by fragments obtained from broadband collision induced dissociation (bbCID). As iron contaminations in laboratories are not uncommon, CCS values of ferripyoverdines were also evaluated. Thereby, unusual and highly characteristic ion mobility patterns were obtained that are suitable as an alternative identification marker.

Reactivity oscillation in the heavy-light-heavy Cl + CH4 reaction.

It has long been predicted that oscillatory behavior exists in reactivity as a function of collision energy for heavy-light-heavy (HLH) chemical reactions in which a light atom is transferred between two heavy atoms or groups of atoms, but direct observation of such a behavior in bimolecular reactions remains a challenge. Here we report a joint theoretical and crossed-molecular-beam study on the Cl + CH4 → HCl + CH3 reaction. A distinctive peak at a collision energy of 0.15 eV for the CH3(v = 0) product was experimentally detected in the backward scattering direction. Detailed quantum-dynamics calculations on a highly accurate potential energy surface revealed that this feature originates from the reactivity oscillation in this HLH polyatomic reaction. We anticipate that such reactivity oscillations exist in many HLH reactions involving polyatomic reagents.

Elucidating the spatial distribution of organic contaminants and their biotransformation products in amphipod tissue by MALDI- and DESI-MS-imaging.

The application of mass spectrometry imaging (MSI) is a promising tool to analyze the spatial distribution of organic contaminants in organisms and thereby improve the understanding of toxicokinetic and toxicodynamic processes. MSI is a common method in medical research but has been rarely applied in environmental science. In the present study, the suitability of MSI to assess the spatial distribution of organic contaminants and their biotransformation products (BTPs) in the aquatic invertebrate key species Gammarus pulex was studied. Gammarids were exposed to a mixture of common organic contaminants (carbamazepine, citalopram, cyprodinil, efavirenz, fluopyram and terbutryn). The distribution of the parent compounds and their BTPs in the organisms was analyzed by two MSI methods (MALDI- and DESI-HRMSI) after cryo-sectioning, and by LC-HRMS/MS after dissection into different organ compartments. The spatial distribution of contaminats in gammarid tissue could be successfully analyzed by the different analytical methods. The intestinal system was identified as the main site of biotransformation, possibly due to the presence of biotransforming enzymes. LC-HRMS/MS was more sensitive and provided higher confidence in BTP identification due to chromatographic separation and MS/MS. DESI was found to be the more sensitive MSI method for the analyzed contaminants, whereas additional biomarkers were found using MALDI. The results demonstrate the suitability of MSI for investigations on the spatial distribution of accumulated organic contaminants. However, both MSI methods required high exposure concentrations. Further improvements of ionization methods would be needed to address environmentally relevant concentrations.

Examining Responsible Gambling Program Awareness and Engagement Trends and Relationships with Gambling Beliefs and Behaviors: A Three-Wave Study of Customers from a Major Gambling Operator.

A considerable body of literature has examined elements of responsible gambling (RG) programs in land-based gambling venues. The present pre-registered study examines GameSense RG program awareness and engagement trends and relationships with gambling beliefs and behaviors, at MGM's U.S.-based casino properties using three samples of MGM's loyalty program members. We used a repeated cross-sectional approach including observational data collected from one sample (N = 3748) shortly before the rollout of GameSense in 2017-2018, and from two samples collected 1 year (N = 4795) and 2 years (N = 3927) after the program's implementation. We found that awareness of the GameSense program increased between pre- and 1-year post-implementation, yet did not increase further at 2-years post-implementation. Bivariate analyses showed that respondents who were aware of more GameSense components had a better understanding of gambling concepts and used more RG strategies, whereas respondents who engaged with GameSense used more RG strategies than those who did not, but did not display a better understanding of gambling concepts. The relationship between GameSense awareness and self-reported use of RG strategies remained significant in multivariate analyses with covariates. Moderation analyses indicated that a positive effect of overall GameSense engagement on gambling literacy was only found for respondents who had attended a regional property, as compared to respondents who attended Las Vegas or metropolitan properties. All effect sizes were weak, which suggests that practical impacts of the program currently are limited. Our findings have implications for research on land-based RG programs and we provide recommendations for enhancing such programs.

Electron Scattering from 1-Methyl-5-Nitroimidazole: Cross-Sections for Modeling Electron Transport through Potential Radiosensitizers.

In this study, we present a complete set of electron scattering cross-sections from 1-Methyl-5-Nitroimidazole (1M5NI) molecules for impact energies ranging from 0.1 to 1000 eV. This information is relevant to evaluate the potential role of 1M5NI as a molecular radiosensitizers. The total electron scattering cross-sections (TCS) that we previously measured with a magnetically confined electron transmission apparatus were considered as the reference values for the present analysis. Elastic scattering cross-sections were calculated by means of two different schemes: The Schwinger multichannel (SMC) method for the lower energies (below 15 eV) and the independent atom model-based screening-corrected additivity rule with interferences (IAM-SCARI) for higher energies (above 15 eV). The latter was also applied to calculate the total ionization cross-sections, which were complemented with experimental values of the induced cationic fragmentation by electron impact. Double differential ionization cross-sections were measured with a reaction microscope multi-particle coincidence spectrometer. Using a momentum imaging spectrometer, direct measurements of the anion fragment yields and kinetic energies by the dissociative electron attachment are also presented. Cross-sections for the other inelastic channels were derived with a self-consistent procedure by sampling their values at a given energy to ensure that the sum of the cross-sections of all the scattering processes available at that energy coincides with the corresponding TCS. This cross-section data set is ready to be used for modelling electron-induced radiation damage at the molecular level to biologically relevant media containing 1M5NI as a potential radiosensitizer. Nonetheless, a proper evaluation of its radiosensitizing effects would require further radiobiological experiments.

A copula model of extracting DEM-based cross-sections for estimating ecological flow regimes in data-limited deltaic-branched river systems.

For operational flood control and estimating ecological flow regimes in deltaic branched-river systems with limited surveyed cross-sections, accurate river stage and discharge estimation using public domain Digital Elevation Model (DEM)-extracted cross-sections are challenging. To estimate the spatiotemporal variability of streamflow and river stage in a deltaic river system using a hydrodynamic model, this study demonstrates a novel copula-based framework to obtain reliable river cross-sections from SRTM (Shuttle Radar Topographic Mission) and ASTER (Advanced Spaceborne Thermal Emission and Reflection) DEMs. Firstly, the accuracy of the CSRTM and CASTER models was assessed against the surveyed river cross-sections. Thereafter, the sensitivity of the copula-based river cross-sections was evaluated by simulating river stage and discharge using MIKE11-HD in a complex deltaic branched-river system (7000 km2) of Eastern India having a network of 19 distributaries. For this, three MIKE11-HD models were developed based on surveyed cross-sections and synthetic cross-sections (CSRTM and CASTER models). The results indicated that the developed Copula-SRTM (CSRTM) and Copula-ASTER (CASTER) models significantly reduce biases (NSE>0.8; IOA>0.9) in the DEM-derived cross-sections and hence, are capable of satisfactorily reproducing observed streamflow regimes and water levels using MIKE11-HD. The performance evaluation metrics and uncertainty analysis indicated that the MIKE11-HD model based on the surveyed cross-sections simulates with higher accuracies (streamflow regimes: NSE>0.81; water levels: NSE>0.70). The MIKE11-HD model based on the CSRTM and CASTER cross-sections, reasonably simulates streamflow regimes (CSRTM: NSE>0.74; CASTER: NSE>0.61) and water levels (CSRTM: NSE>0.54; CASTER: NSE>0.51). Conclusively, the proposed framework is a useful tool for the hydrologic community to derive synthetic river cross-sections from public domain DEMs, and simulate streamflow regimes and water levels under data-scarce conditions. This modelling framework can be easily replicated in other river systems of the world under varying topographic and hydro-climatic conditions.

Isotopic production cross sections in proton-16O and proton-12C interactions for energies from 10 MeV/u to 100 GeV/u.

Proton interactions with 16O or 12C nuclei are frequent nuclear interaction leading to secondary radiation in tissues for space radiation and cancer therapy with protons or ion beams. The fragmentation of these ions by protons produces a large number of heavy ion (A>4) target or projectile fragments often with high ionization density. Here we develop an analytical model of energy dependent proton-16O and proton-12C cross sections for isotopic nuclei production. Using experimental data and a 2nd order optical model an accurate formula for the absorption cross section from <10 MeV/u to >10 GeV/u is obtained. The energy dependence of the elemental and isotopic cross sections is modeled as multiplicities scaled to absorption cross section with average isotopic fractions estimated from experimental data. We show that this approach results in accurate analytic formulae for isotopic fragmentation cross sections over the full energy range in hadron therapy and space radiation protection studies.

Dextran as internal calibrant for N-glycan analysis by liquid chromatography coupled to ion mobility-mass spectrometry.

LC-MS is one of the most important tools for the comprehensive characterization of N-glycans. Despite many efforts to speed up glycan analysis via optimized sample preparation (e.g., faster enzyme digestion in combination with instant or rapid labeling dyes), a major bottleneck remains the rather long measurement times of HILIC chromatography. Further complication arises from the necessity to concomitantly calibrate with an external standard to allow for accurate retention times and the conversion into more robust GU values. Here we demonstrate the use of an internal calibration strategy for HILIC chromatography to speed up glycan analysis. By reducing the number of utilized dextran oligosaccharides, the calibrant can be spiked directly into the sample such that external calibration runs are no longer required. The minimized dextran ladder shows accurate GU calibration with a minor deviation of well below 1% and can be applied without modifications in sample preparation or data processing. We further demonstrate the simultaneous use of the minimized dextran ladder as calibrant for the estimation of CCS values in traveling wave ion mobility spectrometry. In both cases, the minimized dextran ladder enables the measurement of calibrant and sample in a single HPLC run without losing information or accuracy.

Total Electron Detachment and Induced Cationic Fragmentation Cross Sections for Superoxide Anion (O2-) Collisions with Benzene (C6H6) Molecules.

In this study, novel experimental total electron detachment cross sections for O2- collisions with benzene molecules are reported for the impact energy range (10-1000 eV), as measured with a transmission beam apparatus. By analysing the positively charged species produced during the collision events, relative total ionisation cross sections were derived in the incident energy range of 160-900 eV. Relative partial ionisation cross sections for fragments with m/z ≤ 78 u were also given in this energy range. We also confirmed that heavier compounds (m/z > 78 u) formed for impact energies between 550 and 800 eV. In order to further our knowledge about the collision dynamics governing the fragmentation of such heavier molecular compounds, we performed molecular dynamics calculations within the framework of the Density Functional Theory (DFT). These results demonstrated that the fragmentation of these heavier compounds strongly supports the experimental evidence of m/z = 39-42, 50, 60 (u) cations formation, which contributed to the broad local maximum in the total ionisation observed from 550 to 800 eV. This work reveals the reactivity induced by molecular anions colliding with hydrocarbons at high energies, processes that can take place in the interstellar medium under various local conditions.

The Strong Enhancement of Electron-Impact Ionization Processes in Dense Plasma by Transient Spatial Localization.

Recent experiments have observed much higher electron-ion collisional ionization cross sections and rates in dense plasmas than predicted by the current standard atomic collision theory, including the plasma screening effect. We suggest that the use of (distorted) plane waves for incident and scattered electrons is not adequate to describe the dissipation that occurs during the ionization event. Random collisions with free electrons and ions in plasma cause electron matter waves to lose their phase, which results in the partial decoherence of incident and scattered electrons. Such a plasma-induced transient spatial localization of the continuum electron states significantly modifies the wave functions of continuum electrons, resulting in a strong enhancement of the electron-ion collisional ionization of ions in plasma compared to isolated ions. Here, we develop a theoretical formulation to calculate the differential and integral cross sections by incorporating the effects of plasma screening and transient spatial localization. The approach is then used to investigate the electron-impact ionization of ions in solid-density magnesium plasma, yielding results that are consistent with experiments. In dense plasma, the correlation of continuum electron energies is modified, and the integral cross sections and rates increase considerably. For the ionization of Mg9+e+1s22s2S→1s21S+2e, the ionization cross sections increase several-fold, and the rates increase by one order of magnitude. Our findings provide new insight into collisional ionization and three-body recombination and may aid investigations of the transport properties and nonequilibrium evolution of dense plasma.

Energy Deposition around Swift Carbon-Ion Tracks in Liquid Water.

Energetic carbon ions are promising projectiles used for cancer radiotherapy. A thorough knowledge of how the energy of these ions is deposited in biological media (mainly composed of liquid water) is required. This can be attained by means of detailed computer simulations, both macroscopically (relevant for appropriately delivering the dose) and at the nanoscale (important for determining the inflicted radiobiological damage). The energy lost per unit path length (i.e., the so-called stopping power) of carbon ions is here theoretically calculated within the dielectric formalism from the excitation spectrum of liquid water obtained from two complementary approaches (one relying on an optical-data model and the other exclusively on ab initio calculations). In addition, the energy carried at the nanometre scale by the generated secondary electrons around the ion's path is simulated by means of a detailed Monte Carlo code. For this purpose, we use the ion and electron cross sections calculated by means of state-of-the art approaches suited to take into account the condensed-phase nature of the liquid water target. As a result of these simulations, the radial dose around the ion's path is obtained, as well as the distributions of clustered events in nanometric volumes similar to the dimensions of DNA convolutions, contributing to the biological damage for carbon ions in a wide energy range, covering from the plateau to the maximum of the Bragg peak.

Near-Threshold and Resonance Effects in Rotationally Inelastic Scattering of D2O with Normal-H2.

We present a combined experimental and theoretical study on the rotationally inelastic scattering of heavy water, D2O, with normal-H2. Crossed-molecular beam measurements are performed in the collision energy range between 10 and 100 cm-1, corresponding to the near-threshold regime in which scattering resonances are most pronounced. State-to-state excitation cross-sections are obtained by probing three low-lying rotational levels of D2O using the REMPI technique. These measurements are complemented by quantum close-coupling scattering calculations based on a high-accuracy D2O-H2 interaction potential. The agreement between experiment and theory is within the experimental error bars at 95% confidence intervals, leading to a relative difference of less than 7%: the near-threshold rise and the overall shape of the cross-sections, including small undulations due to resonances, are nicely reproduced by the calculations. Isotopic effects (D2O versus H2O) are also discussed by comparing the shape and magnitude of the respective cross-sections.