Manifestation of site energy landscapes for ion transport in borate glasses.

The potential energy landscape of lithium borate glass of composition Li3B7O12 has been investigated by the charge attachment induced transport (CAIT) technique. Here, native lithium ions have been replaced by foreign alkali ions, M+ = K+, Rb+, Cs+. All experiments exhibit a pronounced decrease of native ion diffusion coefficients over more than 4 orders of magnitude with decreasing local population of Li+. The energy landscape is modelled by a site energy distribution (SED) with a concentration dependent Fermi energy of the native Li+ ions. The width of the populated part of the SED is found to be 250 meV (FWHM). The conclusion is made possible by a combination of a macroscopic ion replacement experiment with a Nernst-Planck-Poisson modelling of concentration depth profiles measured by secondary ion mass spectrometry (SIMS). Possible generalizations of macroscopic transport theory to match an Onsager ansatz are discussed.

Ion molecule reactions in the HBr+ + CH4 system: a combined experimental and theoretical study.

Reactions in the system HBr+ + CH4 have been investigated inside a guided ion-beam apparatus under single-collision conditions. The HBr+ is vibrational and rotational state selected in the electronic X2Π1/2 state created by (2+1)-REMPI. Due to the exitation scheme employed different rotational states of the HBr+ are accessible. Four reaction channels have been observed. The cross section, σ, for the exothermic proton transfer channel (PT) decreases with increasing collision energy, steeper than predicted by the Langevin model. The cross section also decreases with increasing rotational energy in the HBr+, with the effect of the rotational energy being stronger than that of translational energy. The cross section for the endothermic charge transfer (CT) increased with increasing collision energy. The energy dependence is well reproduced by a simple line of center (loc) model. Although the bromine transfer (BT) is exothermic the observed cross section increased with increasing collision energy due to an activation barrier on the potential energy surface (PES). Analysis by a modified loc model suggest the relevance of an angle dependence of σ. The cross section for the endothermic hydrogen atom abstraction (HA) exhibits a maximum at 2 eV Ecm. The measured cross sections are rationalized by means of reaction dynamics simulations which show good agreement with the experimental cross sections. The dynamics simulations are carried out with a machine learning potential that is developed and benchmarked with ab initio molecular dynamics simulation. The absolute cross sections predicted by reaction dynamics simulations are well within the same order of magnitude while reproducing the trends over three different collision energies for all four reaction channels. Furthermore, the simulations demonstrate various reaction mechanisms for these reaction channels, including a very interesting HBr+ orientation selectivity for the BT reaction channel.

Acute-to-chronic subdural hematoma: radiographic and clinical progression from acute subdural hematoma.

INTRODUCTION: The pathogenesis of chronic subdural hematoma (CSDH) has not been completely understood. However, different mechanisms can result in space-occupying subdural fluid collections, one pathway can be the transformation of an original trauma-induced acute subdural hematoma (ASDH) into a CSDH. MATERIALS AND METHODS: All patients with unilateral CSDH, requiring burr hole trephination between 2018 and 2023 were included. The population was distributed into an acute-to-chronic group (group A, n = 41) and into a conventional group (group B, n = 282). Clinical and radiographic parameters were analyzed. In analysis A, changes of parameters after trauma within group A are compared. In analysis B, parameters between the two groups before surgery were correlated. RESULTS: In group A, volume and midline shift increased significantly during the progression from acute-to-chronic (p < 0.001, resp.). Clinical performance (modified Rankin scale, Glasgow Coma Scale) dropped significantly (p = 0.035, p < 0.001, resp.). Median time between trauma with ASDH and surgery for CSDH was 12 days. Patients treated up to the 12th day presented with larger volume of ASDH (p = 0.012). Before burr hole trephination, patients in group A presented with disturbance of consciousness (DOC) more often (p = 0.002), however less commonly with a new motor deficit (p = 0.014). Despite similar midline shift between the groups (p = 0.8), the maximal hematoma width was greater in group B (p < 0.001). CONCLUSION: If ASDH transforms to CSDH, treatment may become mandatory early due to increase in volume and midline shift. Close monitoring of these patients is crucial since DOC and rapid deterioration is common in this type of SDH.

Pitfalls of predicting age-related traits by polygenic risk scores.

Polygenic risk scores (PRS) are a method increasingly used to capture the combined effect of genome-wide significant variants and those which individually do not show genome-wide significant association but are likely to contribute to the risk of developing diseases. However, their practical use incurs complications and inconsistencies that so far limit their clinical applicability. The aims of the present review are to discuss the PRS for age-related diseases and to highlight pitfalls and limitations of PRS prediction accuracy due to ageing and mortality effects. We argue that the PRS is widely used but the individual's PRS values differ substantially depending on the number of genetic variants included, the discovery GWAS and the method employed to generate them. Moreover, for neurodegenerative disorders, although an individual's genetics do not change with age, the actual score depends on the age of the sample used in the discovery GWAS and is likely to reflect the individual's disease risk at this particular age. Improvement of PRS prediction accuracy for neurodegenerative disorders will come from two sides, both the precision of clinical diagnoses, and a careful attention to the age distribution in the underlying samples and validation of the prediction in longitudinal studies.

Ion-molecule reactions in the HBr+ + HCl (DCl) system: a combined experimental and theoretical study.

Reactions in the system HBr+ + HCl (DCl) were investigated inside a guided ion-beam apparatus under single-collision conditions. In the HBr+ + HCl system, the proton transfer (PTHCl) and charge transfer (CT) are observable. In the HBr+ + DCl system, proton transfer (PTDCl) and deuterium abstraction (DA) are accessible. The cross sections for all reaction channels were measured as a function of the collision energy Ecm and of the rotational energy Erot of the ion. The rotationally state-selective formation of the ionic species was realized by resonance-enhanced multiphoton ionization (REMPI). As expected, the PT-channels are exothermic, and the cross section decreases with increasing collision energy for both PTHCl and PTDCl. The cross section for DA also decreases with an increasing Ec.m.. In the case of a considerably endothermic CT-channel, the reaction efficiency increases with increasing collision energy but has an overall much smaller cross sections compared to PT and DA reactions. Both PT-reactions are hindered by ion rotation, whereas DA is independent of Erot. The CT-channel shows a rotational enhancement near the thermochemical threshold. The experiment is complemented by theory, using ab initio molecular dynamics (AIMD, also known as direct dynamics) simulations and taking the rotational enhancement of HBr+ into account. The simulations show good agreement with the experimental results. The cross section of PTHCl decreases with an increase of the rotational energy. Furthermore, the absolute cross sections are in the same order of magnitude. The CT channel shows no reactions in the simulation.

The contribution of Compton ionization to ultrafast x-ray scattering.

We investigate the role of Compton ionization in ultrafast non-resonant x-ray scattering using a molecular model system, which includes the ionization continuum via an orthonormalized plane wave ansatz. Elastic and inelastic components of the scattering signal, as well as coherent-mixed scattering that arises from electron dynamics, are calculated. By virtue of a near-quantitative distinction between scattering related to electronic transitions into bound and continuum states, we demonstrate how Compton ionization contributes to the coherent-mixed component. Analogous to inelastic scattering, the contribution to the coherent-mixed signal is significant and particularly manifests at intermediate and high-momentum transfers. Strikingly, for molecules with inversion symmetry, the exclusion of bound or continuum transitions may lead to the prediction of spurious coherent-mixed signals. We conclude that qualitative and quantitative accuracies of predicted scattering signals on detectors without energy resolution require that elements of the two-electron density operator are used. This approach inherently accounts for all accessible electronic transitions, including ionization.

Self-management interventions for children and young people with sickle cell disease: A systematic review.

BACKGROUND: Increasing numbers of interventions are being developed to support self-management for children and young people (CYP) with sickle cell disease (SCD), but no systematic review has systematically synthesized this evidence regarding their characteristics, effectiveness, acceptability and feasibility for all published intervention types. METHODS: The Joanna Briggs Institute guidelines for mixed-method reviews were followed. A systematic search of eight databases and key journals was conducted from their inception to November 2021. Primary research of self-management interventions targeting CYP with SCD aged 8-24 years and reporting any health/social outcome and acceptability data were included. Design-specific standardized critical appraisal instruments were used. Two independent reviewers screened and appraised the articles. A third reviewer resolved disagreements. RESULTS: Of 1654 articles identified, 38 studies were included. Methodological quality was moderate. Most studies evaluated SCD education, psycho-behavioural, psychosocial and skills training and/or social support interventions. They appear to demonstrate short-term improvements in knowledge, social functioning and medical adherence outcomes. Interventions that were multifaceted in content, combined technological platforms and in-person group-based formats and involved peers, family and care providers were more acceptable and effective. The long-term impact of interventions was limited, including CYP's involvement in the intervention development and implementation. CONCLUSIONS: There is inconclusive evidence for any self-management programme. Nonetheless, support from family, peers and care providers appears to be important for self-management interventions' effectiveness and acceptability. Future research needs to prioritize CYP involvement in both intervention design and delivery, their wider social context and include CYP with SCD from non-Black backgrounds. PATIENT AND PUBLIC CONTRIBUTION: Three young people with SCD recruited acted as the review advisors. They were formally trained in the review process and involved in every aspect of the review: the design, conduct and interpretation of the findings. CYP involvement in the interventions' development and implementation was analysed as part of the review. This systematic review was conducted as part of a wider research project titled: Understanding fatigue experiences of CYP with SCD to guide the co-development of a fatigue self-management intervention. Two of the young advisors involved in the review were also involved in the development of the project funding application.

The use of the sodium fluorescein and YELLOW 560 nm filter for the resection of pediatric posterior fossa lesions.

PURPOSE: This study aimed to verify the feasibility, safety, and benefit of using fluorescein sodium (FL) and a YELLOW 560 nm filter in posterior fossa tumors in children. METHODS: All cases of pediatric posterior fossa tumors that have undergone surgery using fluorescein (2018-2022) have been included and were examined retrospectively. In those cases where resection of the tumor was planned, a blinded neuroradiologist distinguished gross total resection and subtotal resection according to the postoperative MRI findings. The surgical report and medical files were reviewed regarding the intraoperative staining grade and adverse events. The grade of fluorescent staining of the targeted lesion was assessed as described in the surgical reports. The screening was conducted for any reference to the degree of fluorescent staining: "intense," "medium," "slight," and "no staining." RESULTS: 19 cases have been included. In 14 cases, a complete resection was initially intended. In 11 of these cases, a gross total resection could be achieved (78.6%). Staining was described as intense in most cases (58.8%). Except for yellow-colored urine, no side effects obviously related to FL were found throughout the observation period. CONCLUSION: In combination with a specific filter, FL is a reliable, safe, and feasible tool in posterior fossa surgery in children.

Brain metastasis resection: the impact of fluorescence guidance (MetResect study).

OBJECTIVE: Maximal resection of brain metastases (BMs) improves both progression-free survival and overall survival (OS). Fluorescein sodium (FL) in combination with the YELLOW 560-nm filter is a safe and feasible method for visualizing residual tumor tissue during BM resection. The authors of this study aimed to show that use of FL would positively influence the volumetric extent of resection (EOR) and thus the survival outcome in patients undergoing BM resection. METHODS: Analyzing their institution's prospective brain tumor registry, the authors identified 539 consecutive patients with BMs (247 women, mean age 62.8 years) by using preoperative high-quality MR images for volumetric analysis. BMs were resected under white light (WL) in 293 patients (54.4%; WL group) and under FL guidance in 246 patients (45.6%; FL group). Sex, age, presurgical Karnofsky Performance Status (KPS), recursive partitioning analysis class, and adjuvant treatment modalities were well balanced between the two groups. Volumetric analysis was performed in a blinded fashion by quantifying pre- and postoperative tumor volume based on gadolinium-enhanced T1-weighted sequences. RESULTS: In the FL group, the postoperative tumor volume was significantly smaller (p = 0.01), and hence the quantitative EOR was significantly larger (p = 0.024) and OS was significantly longer (p = 0.0001) (log-rank testing). Multivariate Cox regression modeling showed that age, presurgical KPS, metastasis status, and FL-guided resection are independent prognostic factors for survival. CONCLUSIONS: Compared with WL resection, FL-guided BM resection increased resection quality, significantly improved EOR, and prolonged OS.

Deep demersal fish communities respond rapidly to warming in a frontal region between Arctic and Atlantic waters.

The assessment of climate impact on marine communities dwelling deeper than the well-studied shelf seas has been hampered by the lack of long-term data. For a long time, the prevailing expectation has been that thermal stability in deep ocean layers will delay ecosystem responses to warming. Few observational studies have challenged this view and indicated that deep organisms can respond exceptionally fast to physical change at the sea surface. To address the depth-specific impact of climate change, we investigated spatio-temporal changes in fish community structure along a bathymetry gradient of 150-1500 m between 1998 and 2016 in East Greenland. Here, the Arctic East Greenland Current and the Atlantic Irminger Current meet and mix, representing a sub-Arctic transition zone. We found the strongest signals of community reorganizations at depths between 350 and 1000 m and only weak responses in the shallowest and deepest regions. Changes were in synchrony with atmospheric warming, loss in sea ice and variability in physical sea surface conditions both within our study region and North of the Denmark Strait. These results suggest that interannual variability and long-term climate trends of the larger ecoregion can rapidly affect fish communities down to 1000-m depth through atmospheric ocean coupling and food web interactions.

Reclassification of Clostridium aurantibutyricum Hellinger 1944 and Clostridium roseum (ex McCoy and McClung 1935) Cato et al. 1988.

Clostridium aurantibutyricum, Clostridium felsineum and Clostridium roseum share a very high similarity based on multi-locus sequence analysis. In this study, their correct taxonomic status was determined using genomic and phenotypic investigations. Average nucleotide identity based on MUMmer alignment of the genomes and in silico DNA-DNA hybridization resulted in values of 98.55-100 and 78.7-100 %, respectively, strongly indicating that all strains are members of the same species. In addition, morphological investigations, fatty acid analyses and substrate utilization tests revealed no striking differences between the strains. Therefore, we propose the reclassification of C. aurantibutyricum and C. roseum as later heterotypic synonyms of C. felsineum. The type strain is lodged in several culture collections (ATCC 17788T=DSM 794T=NCIMB 10690T).

Coincident measurement of photo-ion circular dichroism and photo-electron circular dichroism in 1-phenylethylamine.

Here, we report the coincident measurement of PICD and PECD effects in 1-phenylethylamine upon multiphoton ionization. Both photo-ion circular dichroism (PICD) and photo-electron circular dichroism (PECD) are methods to distinguish enantiomers. In PICD, a difference in total ion yields upon multiphoton ionization with circular polarized light is measured, whereas, in PECD, circular dichroism is observed in the angular distribution of the photoelectrons. Here, we report on our continuous effort to measure the PICD and PECD effects in coincidence, i.e. simultaneously under the same measurement conditions using a home-built photoion-photoelectron coincidence spectrometer. Pure samples of R-(+)-1-phenylethylamine and S-(-)-1-phenylethylamine have been photo-ionized using a femtosecond laser operated at 394 nm.

The Potential Energy Profile of the HBr+ + HCl Bimolecular Collision.

Recently, the HBr+ + HCl bimolecular reaction has been exploited by guided ion beam studies to probe the effect of rotational excitations and collision energies on the dynamics of the ion-molecule reactions. The current manuscript employs high-level ab initio calculations and reports the potential energy of pathways leading to various products, including HBr + HCl+, H2Cl+ + Br, H2Br+ + Cl, and H2 + BrCl+. The study shows that the intermediates involved in this reaction are connected by low-lying transition states, thus frequent isomerizations and diverse products are expected. Further, this manuscript screens the performance of 192 different combinations of computationally efficient methods and basis sets in order to identify the optimal quantum chemical method for further dynamics simulations.

Challenges of Adjusting Single-Nucleotide Polymorphism Effect Sizes for Linkage Disequilibrium.

BACKGROUND: Genome-wide association studies (GWAS) were successful in identifying SNPs showing association with disease, but their individual effect sizes are small and require large sample sizes to achieve statistical significance. Methods of post-GWAS analysis, including gene-based, gene-set and polygenic risk scores, combine the SNP effect sizes in an attempt to boost the power of the analyses. To avoid giving undue weight to SNPs in linkage disequilibrium (LD), the LD needs to be taken into account in these analyses. OBJECTIVES: We review methods that attempt to adjust the effect sizes (ß-coefficients) of summary statistics, instead of simple LD pruning. METHODS: We subject LD adjustment approaches to a mathematical analysis, recognising Tikhonov regularisation as a framework for comparison. RESULTS: Observing the similarity of the processes involved with the more straightforward Tikhonov-regularised ordinary least squares estimate for multivariate regression coefficients, we note that current methods based on a Bayesian model for the effect sizes effectively provide an implicit choice of the regularisation parameter, which is convenient, but at the price of reduced transparency and, especially in smaller LD blocks, a risk of incomplete LD correction. CONCLUSIONS: There is no simple answer to the question which method is best, but where interpretability of the LD adjustment is essential, as in research aiming at identifying the genomic aetiology of disorders, our study suggests that a more direct choice of mild regularisation in the correction of effect sizes may be preferable.

A third hand to the surgeon: the use of an endoscope holding arm in endonasal sinus surgery and well beyond.

BACKGROUND: Extended endoscopic endonasal operations of the sinuses and the frontal skull base require a bimanual action of the surgeon in many cases. Thus, typically an assistant guides the endoscope and centers the field of view. In this study, we investigate in which cases an endoscope holding arm can be used alternatively. MATERIALS AND METHODS: The electromagnetic system ENDOFIXexo was used in different surgical interventions of the paranasal sinuses and beyond questioning ergonomics and geometrical limitations. The realized degrees of freedom were documented, and a topography of possible applications compiled. RESULTS: The presented system is limited by the anatomy of the anterior ethmoid and dynamic working conditions in the sagittal direction. Especially in extended interventions in the posterior ethmoid, in which parts of the nasal septum have been resected and a static position of the endoscope is desired the surgeon can greatly benefit from the robotic arm. Moreover, through the high flexibility of the endoscopic arm surgeries of the pharynx and larynx were performed, questioning the current gold standard of microscope-assisted surgical procedures. CONCLUSION: Under the impression of an urging staff shortage and due to its unlimited patience, the ENDOFIXexo arm seems promising. Taking into account the complex anatomy and the limited access, we especially see a favorable field of application in the surgery of the pituitary gland and skull base tumors.

Effect of rosuvastatin on spatial learning, memory, and anxiety-like behaviour in ovariectomized rats.

The effect of rosuvastatin (Ros) on cognitive function and anxiety-like behaviour in ovariectomized rats were evaluated. Eighteen female Wistar rats (218-310 g, 6-8 months old) were allocated into sham (n = 6), ovariectomy (Ovx, n = 6) or Ovx + Ros (up to eighth week n = 6, then n = 4) groups. Ros was administered at 20 mg/kg/day by oral gavage for 12 weeks. Behavioural tests were performed at 4, 8 and 12 weeks following Ovx. At 12 weeks, Ovx group had significantly longer escape latency than the sham group at the first day of the four-day training period of the Morris Water Maze test (p < .01). In the Elevated Plus Maze test, Ovx group spent significantly more time in the closed arms than the sham group (p < .01), and this anxiety-like behavioural effect of Ovx was prevented by 12-weeks Ros treatment (p < .05). In conclusion, Ros prevents memory deficit and anxiety-like behaviour in the ovariectomized rats, a model for human surgical menopause. Impact StatementWhat is already known on this subject? Reduced levels of oestrogen in surgical postmenopausal period has been linked to an increased risk of cognitive dysfunction. Although statins have been shown to improve cognitive function in experimental and clinical studies, there are limited studies evaluating the effect of statins on the cognitive decline and anxiety-like behaviour associated with surgical menopause.What do the results of this study add? Rosuvastatin, a long-acting statin, prevents learning and memory deficit and anxiety-like behaviour in the ovariectomized rat model.What are the implications of these findings for future clinical practice and/or future clinical research? These findings will form the basis for further experimental and clinical research on the effects of statins on cognitive functions and anxiety-like behaviour in the surgical menopause.

Endogenous calcitonin gene-related peptide in cerebrospinal fluid and early quality of life and mental health after good-grade spontaneous subarachnoid hemorrhage-a feasibility series.

The vasodilatory calcitonin gene-related peptide (CGRP) is excessively released after spontaneous subarachnoid hemorrhage (sSAH) and modulates psycho-behavioral function. In this pilot study, we prospectively analyzed the treatment-specific differences in the secretion of endogenous CGRP into cerebrospinal fluid (CSF) during the acute stage after good-grade sSAH and its impact on self-reported health-related quality of life (hrQoL). Twenty-six consecutive patients (f:m = 13:8; mean age 50.6 years) with good-grade sSAH were enrolled (drop out 19% (n = 5)): 35% (n = 9) underwent endovascular aneurysm occlusion, 23% (n = 6) microsurgery, and 23% (n = 6) of the patients with perimesencephalic SAH received standardized intensive medical care. An external ventricular drain was inserted within 72 h after the onset of bleeding. CSF was drawn daily from day 1-10. CGRP levels were determined via competitive enzyme immunoassay and calculated as "area under the curve" (AUC). All patients underwent a hrQoL self-report assessment (36-Item Short Form Health Survey (SF-36), ICD-10-Symptom-Rating questionnaire (ISR)) after the onset of sSAH (t1: day 11-35) and at the 6-month follow-up (t2). AUC CGRP (total mean ± SD, 5.7 ± 1.8 ng/ml/24 h) was excessively released into CSF after sSAH. AUC CGRP levels did not differ significantly when dichotomizing the aSAH (5.63 ± 1.77) and pSAH group (5.68 ± 2.08). aSAH patients revealed a higher symptom burden in the ISR supplementary item score (p = 0.021). Multiple logistic regression analyses corroborated increased mean levels of AUC CGRP in CSF at t1 as an independent prognostic factor for a significantly higher symptom burden in most ISR scores (compulsive-obsessive syndrome (OR 5.741, p = 0.018), anxiety (OR 7.748, p = 0.021), depression (OR 2.740, p = 0.005), the supplementary items (OR 2.392, p = 0.004)) and for a poorer performance in the SF-36 physical component summary score (OR 0.177, p = 0.001). In contrast, at t2, CSF AUC CGRP concentrations no longer correlated with hrQoL. To the best of our knowledge, this study is the first to correlate the levels of endogenous CSF CGRP with hrQoL outcome in good-grade sSAH patients. Excessive CGRP release into CSF may have a negative short-term impact on hrQoL and emotional health like anxiety and depression. While subacutely after sSAH, higher CSF levels of the vasodilator CGRP are supposed to be protective against vasospasm-associated cerebral ischemia, from a psychopathological point of view, our results suggest an involvement of CSF CGRP in the dysregulation of higher integrated behavior.

Intraoperative imaging of brain tumors with fluorescein: confocal laser endomicroscopy in neurosurgery. Clinical and user experience.

OBJECTIVE: Confocal laser endomicroscopy (CLE) is an established tool in basic research for tissue imaging at the level of microstructures. Miniaturization and refinement of the technology have made this modality available for operative imaging with a handheld device. Sufficient image contrast is provided by the preoperative application of fluorescein sodium. The authors report their first experiences in a clinical case series using the new confocal laser endomicroscope. METHODS: Handling, operative workflow, and visualization of the CLE were critically evaluated in 12 cases of different CNS tumors. Three different imaging positions in relation to the tumor were chosen: the tumor border (I), tumor center (II), and perilesional zone (III). Respective diagnostic sampling with H & E staining and matching intraoperative neuronavigation and microscope images are provided. RESULTS: CLE was found to be beneficial in terms of high-quality visualization of fine structures and for displaying hidden anatomical details. The handling of the device was good, and the workflow was easy. CONCLUSIONS: Handling ergonomics and image acquisition are intuitive. The endomicroscope allows excellent additional visualization of microstructures in the surgical field with a minimally invasive technique and could improve safety and clinical outcomes. The new confocal laser endomicroscope is an advanced tool with the potential to change intracranial tumor surgery. Imaging of these microstructures is novel, and research with comparative validation with traditional neuropathological assessments is needed.

Brain multimodality monitoring in patients suffering from acute aneurysmal subarachnoid hemorrhage: clinical value and complications.

Brain multimodality monitoring measuring brain tissue oxygen pressure, cerebral blood flow, and cerebral near-infrared spectroscopy may help optimize the neurocritical care of patients with aneurysmal subarachnoid hemorrhage and delayed cerebral ischemia. We retrospectively looked for complications associated with the placement of the probes and checked the reliability of the different tools used for multimodality monitoring. In addition, we screened for therapeutic measures derived in cases of pathological values in multimodality monitoring in 26 patients with acute aneurysmal subarachnoid hemorrhage. Computed tomography scans showed minor hemorrhage along with the probes in 12 patients (46.2%). Missing transmission of values was observed in 34.1% of the intended time of measurement for cerebral blood flow probes and 15.5% and 16.2%, respectively, for the two kinds of probes measuring brain tissue oxygen pressure. We identified 744 cumulative alarming values transmitted from multimodality monitoring. The most frequent intervention was modifying minute ventilation (29%). Less frequent interventions were escalating the norepinephrine dosage (19.9%), elevating cerebral perfusion pressure (14.9%) or inspiratory fraction of inspired oxygen (7.5%), transfusing red blood cell concentrates (1.2%), initiating further diagnostics (2.3%) and neurosurgical interventions (1.9%). As well, 355 cases of pathological values had no therapeutic consequence. The reliability of the measuring tools for multimodality monitoring regarding a continuous transmission of values must be improved, particularly for cerebral blood flow monitoring. The overall high rate of missing therapeutic responses to pathological values derived from multimodality monitoring in patients with aneurysmal subarachnoid hemorrhage underlines the need for structured tiered algorithms. In addition, such algorithms are the basic requirement for prospective multicenter studies, which are urgently needed to evaluate the role of multimodality monitoring in treating these patients.

Photoelectron Circular Dichroism in the Photodetachment of Amino Acid Anions.

The chirality of chemical compounds is of undisputed importance in science and technology. In particular with respect to pharmacological application most molecules of interest cannot be accessed by the powerful techniques developed in recent years for gas phase analytes. Here, we demonstrate that the combination of electrospray ionization (ESI) with the detection of photoelectron circular dichroism (PECD) provides access to chirality information applicable to molecular materials with negligible vapor pressure, for example, amino acids. To this end, glutamic acid and 3,4-dihydroxyphenylalanine (DOPA) have been electrosprayed into the source of a chirality spectrometer, where photodetachment is enforced and the PECD is detected. The technique can be expected to be conceptually applicable to all chemical systems with chirality based on molecular properties.