Triangle Singularity as the Origin of the a_{1}(1420).

The COMPASS Collaboration experiment recently discovered a new isovector resonancelike signal with axial-vector quantum numbers, the a_{1}(1420), decaying to f_{0}(980)π. With a mass too close to and a width smaller than the axial-vector ground state a_{1}(1260), it was immediately interpreted as a new light exotic meson, similar to the X, Y, Z states in the hidden-charm sector. We show that a resonancelike signal fully matching the experimental data is produced by the decay of the a_{1}(1260) resonance into K^{*}(→Kπ)K[over ¯] and subsequent rescattering through a triangle singularity into the coupled f_{0}(980)π channel. The amplitude for this process is calculated using a new approach based on dispersion relations. The triangle-singularity model is fitted to the partial-wave data of the COMPASS experiment. Despite having fewer parameters, this fit shows a slightly better quality than the one using a resonance hypothesis and thus eliminates the need for an additional resonance in order to describe the data. We thereby demonstrate for the first time in the light-meson sector that a resonancelike structure in the experimental data can be described by rescattering through a triangle singularity, providing evidence for a genuine three-body effect.

Evaluation of the MP Rapid 2019-NCOV IgM/IgG combo POCT test vs. an established platform-based method.

BACKGROUND: Accurate and rapid testing for SARS-COV-2 antibodies could improve the diagnosis and management of COVID-19. In this study, we aim to evaluate the diagnostic accuracy of a commercially available point-of-care lateral flow kit independently and in comparison to an established platform-based system. METHOD: Samples from 144 PCR-confirmed COVID-19 cases and 130 pre-pandemic negative controls were tested in parallel by MP Rapid 2019-NCOV IgM/IgG Combo test and Roche Elecsys. Comparison of results based on serum and capillary blood testing was undertaken. RESULTS: Sensitivity at day 15 onwards was 100% for both methods. Between days 1 and 7 post admission, the IgM/IgG Combo test and Roche Elecsys shown sensitivity of 74% (95%CI: 62%-85%) vs. 67% (95% CI: 55%-79%, P = 0.3947). Combo test specificities were 100% for IgG, 98.5% for IgM vs. Roche Elecsys specificity of 100%. Concordance analysis showed 98.5% agreement to the Roche Elecsys method (Cohen's Kappa 0.96 95% CI [0.92-0.99]). Capillary blood results showed complete agreement with serum samples using the Combo test. CONCLUSION: In comparison to Roche Elecsys, our data show that the MP Rapid 2019-NCOV IgM/IgG Combo test provides a high-confidence assay system for the detection of previous exposure to SARS-COV-2 infection with advantage of affording near-patient testing.

Temporal offset between precipitation and water uptake of Mediterranean pine trees varies with elevation and season.

For climate models that use paleo-environment data to predict future climate change, tree-ring isotope variations are one important archive for the reconstruction of paleo-hydrological conditions. Due to the rather complicated pathway of water, starting from precipitation until its uptake by trees and the final incorporation of its components into tree-ring cellulose, a closer inspection of seasonal variations of tree water uptake is important. In this study, branch and needle samples of two pine species (Pinus pinaster and Pinus nigra subsp. laricio) and several water compartments (precipitation, creek, soil) were sampled over a two-year period and analyzed for the temporal variations of their oxygen and hydrogen stable isotope ratios (δ18O and δ2H) at five sites over an elevation gradient from sea level to around 1600 m a.s.l. on the Mediterranean island of Corsica (France). A new model was established to disentangle temporal relationships of source water uptake of trees. It uses a calculation method that incorporates the two processes mostly expected to affect source water composition: mixing of waters and evaporation. The model results showed that the temporal offset from precipitation to water uptake is not constant and varies with elevation and season. Overall, seasonal source water origin was shown to be dominated by precipitation from autumn and spring. While autumn precipitation was a more important water source for trees growing at mid- (~800-1000 m a.s.l) and high-elevation (~1600 m a.s.l.) sites, trees at coastal sites mostly took up water from late winter and spring. These findings show that predicted decreases in precipitation amounts during the wet season in the Mediterranean can have strong impacts on water availability for pine trees, especially at higher elevations.

Stabilisation of tri-valent ions with a vacant coordination site at a corrole-metal interface.

By exploiting an established on-surface metallation strategy, we address the ability of the corrolic macrocycle to stabilise transition metal ions in high-valent (III) oxidation states in metal-supported molecular layers. This approach offers a route to engineer adsorbed metal complexes that cannot be easily fabricated by organic synthesis methods and bear a vacant axial coordination site for catalytic conversions.

Albumin and calcium reference interval using healthy individuals and a data-mining approach.

BACKGROUND: Harmonization of reference intervals for analytes that have a sound calibration and metrological traceability is a widely recommended practice. The UK Pathology Harmony has recently harmonized reference intervals for calcium and albumin. In this study, we have determined the reference intervals for calcium and albumin on the UK's most commonly used analytical platforms. METHOD: A prospective reference population of healthy individuals was recruited according to the IFCC CRIDL criteria. A second indirect population was collected from 14 primary care setting and measured in laboratories using various analytical platforms and methods (Roche, Abbott, Beckman and Siemens analytical platforms). RESULTS: In total, 299 subjects were recruited; the central 95th centile values for calcium for three out of four analytical platforms were in a close agreement with UK Pathology Harmony reference intervals of 2.2-2.6 mmol/L. Reference intervals of BCG methods from both cohorts and irrespective of analytical platforms were higher for both lower and upper reference limits than those for BCP. In comparison, the indirect study showed an age-related variation. The younger population reference intervals varied by up to 5.7% at the lower reference limit and up to 12% at the upper reference limit compared with Pathology Harmony reference intervals, and the older population showed a variation of up to 14% at both limits. CONCLUSION: While calcium reference intervals can be a subject for harmonization, albumin reference intervals studied showed large variation which is unsupportive of embracing a common reference interval for albumin.

The impact of the analytical performance specifications of calcium and albumin on adjusted calcium.

AIM: The generation of accurate, comparable results from traceable measurement procedures is a primary goal in harmonization efforts. In this study, the analytical performance of routine methods for calcium and albumin measurement is assessed to define the impact of the analytical bias of calcium and albumin on adjusted calcium equation performance and on reference intervals. METHOD: In collaboration with the Wales External Quality Assurance Scheme, six months' worth of anonymized data that cover a concentration range of clinical interest were collected. The data were grouped by analytical platforms/methods. RESULTS: Albumin BCG methods are positively biased (8%) to BCP methods. The overall bias for BCP methods ranges from 5.1 to -4.3% and the overall bias for BCG methods is from 2 to -6.7%. Bias for both methods is higher than the allowable minimal bias for albumin. Calcium concentrations for Roche Cobas CPC and NM-BAPTA, Beckman Arsenazo III, Abbott Architect Arsenazo III were within bias of 1.5 to -1%. However, Siemens calcium methods CPC and Arsenazo III appear to suffer from concentration-dependent bias ranging from +3 to -6%, which exceeds even the minimal allowable limits for calcium (1.3%). Adjusted calcium shows significant bias of 11%. Even with the exclusion of Siemens Advia, the scatter of adjusted calcium results exceeds that for total calcium. CONCLUSION: This study shows wider than acceptable analytical variation for albumin and calcium. This variation may contribute to overall adjusted calcium equations variation and invalidate the application of a harmonized reference interval for calcium and albumin.

The effect of different analytical platforms and methods on the performance of population-specific adjusted calcium equation.

BACKGROUND: A recent attempt to improve the diagnostic value of adjusted calcium addressed a primary care-specific adjusted calcium equation, but validated the new equation for Roche Cobas, BCG and NM-BAPTA methods only. In this study, we aim to validate a population-specific equation for other methods and platforms. METHOD: We collected retrospective patient data-sets from 15 hospital laboratories using a range of commercially available analytical platforms and methods for calcium and albumin measurements. Raw data-sets were collected and filtered according to Payne's criteria, and separate adjusted calcium equations were derived for hospitalized and primary care patients. RESULTS: Mean albumin and calcium results were significantly higher in primary care populations (P < 0.0001). The prevalence of hypocalcaemia using adjusted calcium ranged between 6% and 44% for inpatient data-sets and was higher in users of BCG methods. The application of community-specific adjustment equation to primary care data-sets reduced the prevalence of hypocalcaemia (mean 1.7%, range 0.8-3.7%). CONCLUSION: We demonstrated that the use of a community-specific calcium adjustment equation to a primary care population reduces both the percentage and the variation of hypocalcaemia between different laboratories.

Prospective study comparing the outcome of a population-specific adjusted calcium equation to ionized calcium.

BACKGROUND: Calcium circulates bound to albumin and changes in albumin concentration will therefore affect total calcium measurements. In order to mitigate this, correction factors are frequently used. The most widely used correction equation was described by Payne and colleagues in 1973. This equation was derived from well-defined hospitalized patients' data. Current clinical practice is consistent with the general application of the adjusted calcium equation irrespective of clinical setting. This study aims to assess the validity of this approach by the derivation of a community care-specific adjusted calcium equation ('community equation') and the comparison of its performance to a hospitalized patient equation and ionized calcium. METHOD: Retrospective data were collected according to Payne's criteria from an inpatient and community care setting. Data were used to derive the two equations: the in-patient equation and community equation. The outcome of these equations was compared with ionized calcium obtained from 123 healthy participants. RESULTS: The community equation correctly identified the calcium status of 92% of the 123 healthy participants, while the inpatient equation identified 46% only. Regression analysis against ionized calcium showed a higher R2 for the community equation than for the inpatient equation. Furthermore, we have shown that mean albumin and calcium concentrations are significantly different between these two populations. CONCLUSION: In this study, we found that the diagnostic accuracy of the adjusted calcium equation in ambulant patients was improved by the derivation of a population-specific equation for the community care setting.

Validation of the inverted adsorption structure for free-base tetraphenyl porphyrin on Cu(111).

Utilising normal incidence X-ray standing waves we rigourously scrutinise the "inverted model" as the adsorption structure of free-base tetraphenyl porphyrin on Cu(111). We demonstrate that the iminic N atoms are anchored at near-bridge adsorption sites on the surface displaced laterally by 1.1 ± 0.2 Å in excellent agreement with previously published calculations.

Groundwater recharge sites and pollution sources in the wine-producing Guadalupe Valley (Mexico): Restrictions and mixing prior to transfer of reclaimed water from the US-México border.

Rapid depletion of aquifers in semiarid and arid regions threatens water security. This holds true especially in emerging countries where insufficient knowledge about aquifer systems precludes the implementation of advanced management measures, such as managed aquifer recharge. This study deals with the generation of baseline knowledge for the assessment of aquifers in arid and semiarid regions where artificial recharge with reclaimed water gains increasing impetus. The Guadalupe aquifer in Baja California provides water to 57% of the Mexican wine industry. Recent plans foresee a partial replenishment of its depleted groundwater reserves by transferring treated waste water from the Mexico-USA border for irrigation. The aquifer demonstrated to have a rapid response by rising the water table of about +20 m in relation to natural recharge under an intense rainfall period of 236 mm. Two predominant recharge sources were identified based on a geochemical multi-tracer approach: (a) water of modern age (<5 yr, >1.8 TU) and mixed water of recent-submodern age (3H 0.8-1.8 TU), and (b) sub-modern waters that were recharged before 1952 (3H < 0.5 TU). Water of the first type originate in the main Guadalupe stream, which has a more depleted average δ18O isotope value (-7.8‰) than average local rainwater (-2.0‰). The stream water initially has a Na-HCO3 composition and recharges the entire Calafia zone and most groundwater along the riverbed across the valley. Water of the second type is mostly derived from hill-slope groundwater that has a stable isotope composition of mixed local rainwater and a NaCl composition. High total dissolved solids >2 g l-1 together with enriched NO3- and Se concentrations characterize groundwater in the downstream the Porvenir zone. The geochemical age of this older, hill-slope groundwater suggests that its replenishment takes at least several decades when it becomes exhausted.

Chorioamniotic membrane separation following fetal myelomeningocele repair: incidence, risk factors and impact on perinatal outcome.

OBJECTIVES: Prenatal myelomeningocele (MMC) repair has been shown to provide significant benefits to the infant, decreasing the postnatal need for ventriculoperitoneal shunt and improving motor outcome. Chorioamniotic membrane separation (CAS) is a potential complication following prenatal MMC repair and may increase the risk of preterm prelabor rupture of membranes (PPROM) and preterm birth. The objectives of this study were: (1) to evaluate the incidence of CAS after prenatal MMC repair; (2) to determine risk factors associated with its occurrence; and (3) to assess its association with adverse perinatal outcomes. METHODS: This was a retrospective cohort study of patients who underwent fetal MMC repair between November 2011 and December 2018. Surgery was performed using either a fetoscopic (laparotomy or exteriorized uterus) approach or an open-hysterotomy approach. Eligibility criteria were those reported in the Management of Myelomeningocele Study. If CAS was detected on ultrasound (US), its severity was graded as 'mild' if amnion detachment involved < 25% of the uterine cavity, 'moderate' if it involved 25-50% and 'severe' if it involved > 50%. Evolution of CAS was classified as stable, increasing or decreasing based on the difference in severity grading between the time at first diagnosis and the last US scan before delivery. Logistic regression analysis was performed to identify pre- or perisurgical factors associated with the development of CAS and to determine the risk of adverse perinatal outcome associated with CAS. RESULTS: In total, 91 cases were included. Fetoscopic or open-hysterotomy repair of MMC was performed in 52/91 (57.1%) and 39/91 (42.9%) cases, at a median gestational age (GA) of 25.0 weeks (range, 22.9-26.0 weeks) and 25.0 weeks (range, 21.3-25.9 weeks), respectively. CAS was diagnosed in 31/91 (34.1%) patients, at a median GA of 28.1 weeks (range, 24.4-37.6 weeks). Anterior placenta was identified as a risk factor for the postoperative development of CAS (odds ratio (OR), 3.72 (95% CI, 1.46-9.5); P < 0.01). This risk was dependent on the repair technique. An anterior placenta significantly increased the risk of CAS after fetoscopic repair (OR, 3.94 (95% CI, 1.14-13.6); P = 0.03) but not after open repair (OR, 2.8 (95% CI, 0.6-12.5); P = 0.16). There was no significant difference in the rate of CAS after fetoscopic repair (21/52 (40.4%)) vs open-hysterotomy repair (10/39 (25.6%)) (P = 0.14), nor were there any differences in GA at diagnosis of CAS, interval between surgery and diagnosis, distribution of CAS severity or progression of CAS between the two groups. CAS increased the risk of PPROM (50% in those with vs 12% in those without CAS) (OR, 7.6 (95% CI, 2.5-21.9); P < 0.01) and preterm delivery (70% vs 38%) (OR, 3.2 (95% CI, 1.3-8.1); P < 0.01). Fetoscopically repaired cases with CAS had a higher rate of PPROM (12/20 (60.0%) vs 2/31 (6.5%); P < 0.01) and preterm delivery (13/20 (65.0%) vs 5/31 (16.1%); P < 0.01) than those that did not develop CAS, while the differences were not significant in cases with open-hysterotomy repair. Early detection of CAS (before 30 weeks' gestation) was a risk factor for preterm delivery (90% before 30 weeks vs 36% at or after 30 weeks) (OR, 15.7 (95% CI, 2.3-106.3); P < 0.01). There was no association between PPROM or preterm delivery and the severity or progression of CAS. CONCLUSIONS: The presence of an anterior placenta was the only factor that increased the risk for CAS after fetoscopic MMC repair. Detection of CAS after fetoscopic MMC repair significantly increases the risk for PPROM and preterm delivery. Copyright © 2019 ISUOG. Published by John Wiley & Sons Ltd.

Local adsorption structure and bonding of porphine on Cu(111) before and after self-metalation.

We have experimentally determined the lateral registry and geometric structure of free-base porphine (2H-P) and copper-metalated porphine (Cu-P) adsorbed on Cu(111), by means of energy-scanned photoelectron diffraction (PhD), and compared the experimental results to density functional theory (DFT) calculations that included van der Waals corrections within the Tkatchenko-Scheffler approach. Both 2H-P and Cu-P adsorb with their center above a surface bridge site. Consistency is obtained between the experimental and DFT-predicted structural models, with a characteristic change in the corrugation of the four N atoms of the molecule's macrocycle following metalation. Interestingly, comparison with previously published data for cobalt porphine adsorbed on the same surface evidences a distinct increase in the average height of the N atoms above the surface through the series 2H-P, Cu-P, and cobalt porphine. Such an increase strikingly anti-correlates the DFT-predicted adsorption strength, with 2H-P having the smallest adsorption height despite the weakest calculated adsorption energy. In addition, our findings suggest that for these macrocyclic compounds, substrate-to-molecule charge transfer and adsorption strength may not be univocally correlated.

Riverine carbon dioxide evasion along a high-relief watercourse derived from seasonal dynamics of the water-atmosphere gas exchange.

The high-relief catchment of the Tavignanu River (Corsica Island, France) with an elevation range from sea level to 2622 m above sea level was investigated for its riverine carbon budget and stable carbon isotopes. Major riverine dissolved inorganic carbon (DIC or TCO2) sources depended on seasons and sub-catchment lithology. In winter δ13CDIC values of -2 to -7‰ (VPDB) indicated influences of atmospheric CO2. δ13CDIC values decreased gradually to values between -9 and -12‰ in July, which indicates elevated soil CO2 contribution. An observed downstream increase in the total amount of carbon species correlated with inputs from carbonate bearing tributaries and evaporation effects in summer. Main channel partial pressure of CO2 (pCO2) was seasonally highly variable in the upper silicate catchment and the lower coastal plain, where summer values exceed up to six times atmospheric levels. During winter, the central section of the Tavignanu River was found to be undersaturated with respect to atmospheric CO2 levels. The median values for main channel pCO2 were below atmospheric levels in winter and spring and above in summer and autumn. The annual carbon flux across the air-water boundary (FCO2) along the Tavignanu River was calculated with (0.77 ±â€¯0.24) Gg C yr-1, which is about seven times higher than the riverine TCO2 transport to the sea of about 0.11 Gg C yr-1. While large sections of the river experienced year-round atmospheric CO2 uptake or equilibrium, the river as a whole was a small but continuous net source of carbon to the atmosphere. This underlines the important, but so far not well-constrained, contributions of smaller streams and rivers to the terrestrial carbon flux and the need of incorporating them into future global carbon cycle models.

Absolute timing of the photoelectric effect.

Photoemission spectroscopy is central to understanding the inner workings of condensed matter, from simple metals and semiconductors to complex materials such as Mott insulators and superconductors1. Most state-of-the-art knowledge about such solids stems from spectroscopic investigations, and use of subfemtosecond light pulses can provide a time-domain perspective. For example, attosecond (10-18 seconds) metrology allows electron wave packet creation, transport and scattering to be followed on atomic length scales and on attosecond timescales2-7. However, previous studies could not disclose the duration of these processes, because the arrival time of the photons was not known with attosecond precision. Here we show that this main source of ambiguity can be overcome by introducing the atomic chronoscope method, which references all measured timings to the moment of light-pulse arrival and therefore provides absolute timing of the processes under scrutiny. Our proof-of-principle experiment reveals that photoemission from the tungsten conduction band can proceed faster than previously anticipated. By contrast, the duration of electron emanation from core states is correctly described by semiclassical modelling. These findings highlight the necessity of treating the origin, initial excitation and transport of electrons in advanced modelling of the attosecond response of solids, and our absolute data provide a benchmark. Starting from a robustly characterized surface, we then extend attosecond spectroscopy towards isolating the emission properties of atomic adsorbates on surfaces and demonstrate that these act as photoemitters with instantaneous response. We also find that the tungsten core-electron timing remains unchanged by the adsorption of less than one monolayer of dielectric atoms, providing a starting point for the exploration of excitation and charge migration in technologically and biologically relevant adsorbate systems.

Hyperventilation reduces the decrease of power output in a repeated sprint training in cyclists / La hiperventilación reduce la disminución de potencia en un entrenamiento de sprints repetidos en ciclistas / Hiperventilação reduz o decréscimo de potência em treinamento de sprints repetidos em ciclistas

Objective: To evaluate the effect of hyperventilation during a repeated sprint training on a cycle ergometer. Method: Seven cyclists performed two training sessions (10 maximal sprints of 10 s, with 60 s of rest), one with free ventilatory frequency and another one with hyperventilation (the participants breathed 60 cycles per minute during the last 30 s of recovery). Power, fatigue index and blood lactate concentration were analyzed. Results: The lactate concentrations pre- and post-training did not differ between trainings. Regarding to the maximum absolute and relative power, no differences were found between sprints in the hyperventilation condition, however, the values obtained in the first four sprints were higher than the latter two (p < 0.05) in the normal condition. In relation to the mean absolute and relative power, differences were found between sprints in both conditions. In the hyperventilation condition the value of the first sprint was higher than the penultimate (p < 0.05), while in the normal condition, the value of the first sprint was greater than the last four (p < 0.05) and the value of the second sprint exceeded the last two ones (p < 0.05). For the fatigue index, both protocols showed differences from the first to the eighth sprint (p < 0.05). Conclusion: Despite the absence of differences in lactate concentration between normal condition and hyperventilation condition, hyperventilation between efforts during a repeated sprint training could reduce the decrease in power output on a cycle ergometer

Objetivo: Evaluar el efecto de la hiperventilación durante una sesión de entrenamiento con esfuerzos repetidos en cicloergómetro. Método: Siete ciclistas realizaron dos entrenamientos (10 sprints máximos de 10 s con 60 s de recuperación), uno con frecuencia de respiración normal y otro con hiperventilación (los participantes respiraron a 60 ciclos por minuto durante los últimos 30 s de recuperación). Se analizaron la potencia, el índice de fatiga y la concentración sanguínea de lactato. Resultados: La concentración de lactato pre y postentrenamiento no difirió entre los entrenamientos. En relación con los valores de potencia máxima absoluta y relativa, no se encontraron diferencias entre los sprints en la condición de hiperventilación; sin embargo, en la condición normal, los valores obtenidos en los cuatro primeros sprints fueron superiores a los dos últimos (p < 0.05). En relación con los valores de potencia media absoluta y relativa, se encontraron diferencias entre los sprints en las dos condiciones (p < 0.001). En la condición de hiperventilación, el valor del primer sprint fue superior al penúltimo (p < 0.05), mientras que en la condición normal el valor del primer sprint fue superior a los últimos cuatro (p < 0.05) y el valor del segundo fue mayor que los dos últimos (p < 0.05). Para el índice de fatiga, ambos protocolos presentaron diferencias desde el primer hasta el octavo sprint (p < 0.05). Conclusión: Hiperventilación entre esfuerzos máximos repetidos puede reducir la disminución de potencia en cicloergómetro

Objetivo: Avaliar o efeito da hiperventilação durante um treinamento de sprints repetidos em um cicloergômetro. Método: Sete ciclistas executaram duas sessões de treinamento (10 sprints máximos de 10s, com 60s de descanso), sendo um com frequência ventilatória livre e outro com hiperventilação (o participante respirava 60 ciclos por minuto, durante os 30s de recuperação). Potência, índice de fadiga e as concentrações séricas de lactato foram analisadas. Resultados: As concentrações de lactato pré- e pós-treinamento não diferiram entre os treinamentos. Em relação à potência máxima e relativa, não foram encontradas diferenças entre os sprints na condição de hiperventilação, entretanto, os valores obtidos nos quatro primeiros sprints foram maiores que os dois últimos (p < 0.05) executados em condições normais. Quanto à média da potência absoluta e relativa, foram encontradas diferenças entre ambas as condições. Na condição de hiperventilação, o valor do primeiro sprint foi maior que o penúltimo (p < 0.05), enquanto que em condição normal, o valor do primeiro sprint foi maior que os quatro últimos (p < 0.05) e o valor do segundo sprint excedeu os dois últimos (p < 0.05). O índice de fadiga demonstrou diferenças do primeiro ao oitavo sprint (p < 0.05) em ambos os protocolos. Conclusão: Apesar da ausência de diferenças nas concentrações de lactato entre as condições estudadas, a execução da hiperventilação entre os sprints pode reduzir o decréscimo da potência em um treinamento de sprints repetidos em cicloergômetro

Identifying On-Surface Site-Selective Chemical Conversions by Theory-Aided NEXAFS Spectroscopy: The Case of Free-Base Corroles on Ag(111).

We demonstrate here that theory-assisted near-edge X-ray absorption fine-structure (NEXAFS) spectroscopy enables the site-sensitive monitoring of on-surface chemical reactions, thus, providing information not accessible by other techniques. As a prototype example, we have used free-base 5,10,15-tris(pentafluorophenyl)corroles (3H-TpFPC) adsorbed on Ag(111) and present a detailed investigation of the angle-dependent NEXAFS of this molecular species as well as of their thermally induced derivatives. For this, we have recorded experimental C and N K-edge NEXAFS spectra and interpret them based on XAS cross-section calculations by using a continuous fraction approach and core-hole including multiprojector PAW pseudopotentials within DFT. We have characterized the as-deposited low temperature (200 K) phase and unraveled the subsequent changes induced by dehydrogenation (at 330 K) and ring-closure reactions (at 430 K). By exemplarily obtaining profound insight into the on-surface chemistry of free-base corrolic species adsorbed on a noble metal this work highlights how angle-dependent XAS combined with accurate theoretical modeling can serve for the investigation of on-surface reactions, whereby even highly similar molecular structures, such as tautomers and isomers, can be distinguished.

Device-Compatible Chiroptical Surfaces through Self-Assembly of Enantiopure Allenes.

Chiroptical methods have been proven to be superior compared to their achiral counterparts for the structural elucidation of many compounds. To expand the use of chiroptical systems to everyday applications, the development of functional materials exhibiting intense chiroptical responses is essential. Particularly, tailored and robust interfaces compatible with standard device operation conditions are required. Herein, we present the design and synthesis of chiral allenes and their use for the functionalization of gold surfaces. The self-assembly results in a monolayer-thin room-temperature-stable upstanding chiral architecture as ascertained by ellipsometry, X-ray photoelectron spectroscopy, and near-edge X-ray absorption fine structure. Moreover, these nanostructures anchored to device-compatible substrates feature intense chiroptical second harmonic generation. Both straightforward preparation of the device-compatible interfaces along with their chiroptical nature provide major prospects for everyday applications.

Outcomes of capsulolabral reconstruction for posterior shoulder instability.

BACKGROUND: Surgical treatment of isolated posterior shoulder instability-a rare and often misdiagnosed condition-is controversial because of poor outcomes. Failure of physical therapy in symptomatic young athletes requires capsulolabral reconstruction or bone block procedures. The goal of this study was to report the outcomes of patients who have undergone surgical capsulolabral reconstruction and to look for risk factors that contribute to failure of this procedure. MATERIAL AND METHOD: We analyzed the outcomes of 101 patients who underwent capsulolabral reconstruction: 83 included retrospectively, 18 included prospectively. The procedures were performed alone or in combination with capsular shift, labral repair, closure of the rotator interval and notch remplissage. The primary endpoint was failure of the procedure, defined as recurrence of the instability and/or pain. We also determined the outcomes based on specific (Walch-Duplay, modified Rowe) and non-specific (Constant, resumption of activities) scores of shoulder instability. RESULTS: The results were satisfactory despite a high failure rate: 35% in the retrospective cohort with 4.8±2.6 years' follow-up and 22% in the prospective cohort with 1.1±0.3 years' follow-up. The various outcome scores improved significantly. Ninety-two percent of patients returned to work and 80% of athletes returned to their pre-injury level of sports. Eighty-five percent of patients were satisfied or very satisfied after the surgery. No risk factors for failure were identified; however, failures were more common in older patients, those who underwent an isolated procedure and those who had unclassified clinical forms. CONCLUSION: Treatment of posterior shoulder instability by capsulolabral reconstruction leads to good clinical outcomes; however, the recurrence rate is high. LEVEL OF EVIDENCE: 4 - retrospective study.

First Measurement of Transverse-Spin-Dependent Azimuthal Asymmetries in the Drell-Yan Process.

The first measurement of transverse-spin-dependent azimuthal asymmetries in the pion-induced Drell-Yan (DY) process is reported. We use the CERN SPS 190 GeV/c π^{-} beam and a transversely polarized ammonia target. Three azimuthal asymmetries giving access to different transverse-momentum-dependent (TMD) parton distribution functions (PDFs) are extracted using dimuon events with invariant mass between 4.3 GeV/c^{2} and 8.5 GeV/c^{2}. Within the experimental uncertainties, the observed sign of the Sivers asymmetry is found to be consistent with the fundamental prediction of quantum chromodynamics (QCD) that the Sivers TMD PDFs extracted from DY have a sign opposite to the one extracted from semi-inclusive deep-inelastic scattering (SIDIS) data. We present two other asymmetries originating from the pion Boer-Mulders TMD PDFs convoluted with either the nucleon transversity or pretzelosity TMD PDFs. A recent COMPASS SIDIS measurement was obtained at a hard scale comparable to that of these DY results. This opens the way for possible tests of fundamental QCD universality predictions.