Stereospecific and chemoselective copper-catalyzed deaminative silylation of benzylic ammonium triflates

A method for the synthesis of benzylsilanes starting from the corresponding ammonium triflates is reported. Silyl boronic esters are employed as silicon pronucleophiles, and the reaction is catalyzed by copper(I) salts. Enantioenriched benzylic ammonium salts react stereospecifically through an SN2‐type displacement of the ammonium group to afford α‐chiral silanes with inversion of the configuration. A cyclopropyl‐substituted substrate does not undergo ring opening, thus suggesting an ionic reaction mechanism with no benzyl radical intermediate.DFG, 388910461, Ionische und radikalische Kreuzkupplungen zur Kohlenstoff‒Silicium-BindungsknüpfungTU Berlin, Open-Access-Mittel - 201

The seed of goal-related doubts : a longitudinal investigation of the roles of failure and expectation of success among police trainee applicants

Various theories on personal goal striving rely on the assumption that failure raises doubts about the goal. Yet, empirical evidence for an association between objective failure experiences and doubts about personal long-term goals is still missing. In a longitudinal field study, applicants for a job as a police trainee (n = 172, Mage = 25.15; 55 females and 117 males) were accompanied across three measurement times over a period of five months. We investigated the effects of failure and initial expectation of success (in the standardized selection process) on doubts regarding the superordinate goal of becoming a police officer. As hypothesized, both failure and low initial expectation of success as well as their interaction led to increased goal-related doubts over time. The findings provide first empirical evidence for the role of failure in the emergence of goal-related doubts in personal long-term goals and, therefore, the disengagement process as it is hypothesized in various theories on goal striving and life-span development

Formal controls, neighborhood disadvantage, and violent crime in U.S. cities: Examining (un)intended consequences

Purpose This study examines the intended and unintended effects of formal social controls on violent crime within and across U.S. cities. Methods Using data from the National Neighborhood Crime Study, we assess whether greater police arrest activity and jail incarceration risk are associated with lower violent crime rates across cities. We also investigate whether greater use of these formal social controls exacerbates the relationship between extreme neighborhood disadvantage and violent crime. Results Results from multilevel analyses show that some formal controls (jail incarceration risk) reduce violent crime across cities, but other formal controls (police arrest activity) amplify the relationship between extreme neighborhood disadvantage and violent crime within cities. Conclusions Two main conclusions can be drawn from our analyses. First, we found evidence that some formal controls do reduce violent crime, while others do not. Second, our results support scholars\u27 arguments that formal controls have unintended consequences (e.g., Clear, 2007, 2008; Rose & Clear, 1998), specifically, by amplifying the effect of extreme neighborhood disadvantage on violent crime

Positive noise cross-correlations in superconducting hybrids: Roles of interfaces and interactions

Shot noise cross-correlations in normal metal-superconductor-normal metal structures are discussed at arbitrary interface transparencies using both the scattering approach of Blonder, Tinkham and Klapwik and a microscopic Green's function approach. Surprisingly, negative crossed conductance in such set-ups [R. Melin and D. Feinberg, Phys. Rev. B 70, 174509 (2004)] does not preclude the possibility of positive noise cross-correlations for almost transparent contacts. We conclude with a phenomenological discussion of interactions in the one dimensional leads connected to the superconductor, which induce sign changes in the noise cross-correlations.Comment: 15 pages, 9 figure

Association of PET-measured myocardial flow reserve with echocardiography-estimated pulmonary artery systolic pressure in patients with hypertrophic cardiomyopathy

BackgroundPulmonary hypertension (PH) is a known complication of HCM and is a strong predictor of mortality. We aim to investigate the relationship between microvascular dysfunction measured by quantitative PET and PH in HCM patients.MethodsEighty-nine symptomatic HCM patients were included in the study. Each patient underwent two 20-min 13N-NH3 dynamic PET scans for rest and stress conditions, respectively. A 2-tissue irreversible compartmental model was used to fit the segments time activity curves for estimating segmental and global myocardial blood flow (MBF) and myocardial flow reserve (MFR). Echocardiographic derived PASP was utilized to estimate PH.ResultsPatients were categorized into two groups across PASP: PH (PASP > 36 mmHg) and no-PH (PASP ≤ 36 mmHg). patients with PH had larger left atrium, ratio of higher inflow early diastole (E) and atrial contraction (A) waves, E/A, and ratio of inflow and peak early diastolic waves, E/e', significantly reduced global stress MBF (1.85 ± 0.52 vs. 2.13 ± 0.56 ml/min/g; p = 0.024) and MFR (2.21 ± 0.57 vs. 2.62 ± 0.75; p = 0.005), while the MBFs at rest between the two groups were similar. There were significant negative correlations between global stress MBF/MFR and PASP (stress MBF: r = -0.23, p = 0.03; MFR: r = -0.32, p = 0.002); for regional MBF and MFR measurements, the highest linear correlation coefficients were observed in the septal wall (stress MBF: r = -0.27, p = 0.01; MFR: r = -0.31, p = 0.003). Global MFR was identified to be independent predictor for PH in multivariate regression analysis.ConclusionEchocardiography-derived PASP is negatively correlated with global MFR measured by 13N-NH3 dynamic PET. Global MFR is suggested to be an index of PH in HCM patients.</div

Improvements on coronal hole detection in SDO/AIA images using supervised classification

We demonstrate the use of machine learning algorithms in combination with segmentation techniques in order to distinguish coronal holes and filaments in SDO/AIA EUV images of the Sun. Based on two coronal hole detection techniques (intensity-based thresholding, SPoCA), we prepared data sets of manually labeled coronal hole and filament channel regions present on the Sun during the time range 2011 - 2013. By mapping the extracted regions from EUV observations onto HMI line-of-sight magnetograms we also include their magnetic characteristics. We computed shape measures from the segmented binary maps as well as first order and second order texture statistics from the segmented regions in the EUV images and magnetograms. These attributes were used for data mining investigations to identify the most performant rule to differentiate between coronal holes and filament channels. We applied several classifiers, namely Support Vector Machine, Linear Support Vector Machine, Decision Tree, and Random Forest and found that all classification rules achieve good results in general, with linear SVM providing the best performances (with a true skill statistic of ~0.90). Additional information from magnetic field data systematically improves the performance across all four classifiers for the SPoCA detection. Since the calculation is inexpensive in computing time, this approach is well suited for applications on real-time data. This study demonstrates how a machine learning approach may help improve upon an unsupervised feature extraction method.Comment: in press for SWS

Effects of sex chromosome dosage on corpus callosum morphology in supernumerary sex chromosome aneuploidies.

BackgroundSupernumerary sex chromosome aneuploidies (sSCA) are characterized by the presence of one or more additional sex chromosomes in an individual's karyotype; they affect around 1 in 400 individuals. Although there is high variability, each sSCA subtype has a characteristic set of cognitive and physical phenotypes. Here, we investigated the differences in the morphometry of the human corpus callosum (CC) between sex-matched controls 46,XY (N =99), 46,XX (N =93), and six unique sSCA karyotypes: 47,XYY (N =29), 47,XXY (N =58), 48,XXYY (N =20), 47,XXX (N =30), 48,XXXY (N =5), and 49,XXXXY (N =6).MethodsWe investigated CC morphometry using local and global area, local curvature of the CC boundary, and between-landmark distance analysis (BLDA). We hypothesized that CC morphometry would vary differentially along a proposed spectrum of Y:X chromosome ratio with supernumerary Y karyotypes having the largest CC areas and supernumerary X karyotypes having significantly smaller CC areas. To investigate this, we defined an sSCA spectrum based on a descending Y:X karyotype ratio: 47,XYY, 46,XY, 48,XXYY, 47,XXY, 48,XXXY, 49,XXXXY, 46,XX, 47,XXX. We similarly explored the effects of both X and Y chromosome numbers within sex. Results of shape-based metrics were analyzed using permutation tests consisting of 5,000 iterations.ResultsSeveral subregional areas, local curvature, and BLDs differed between groups. Moderate associations were found between area and curvature in relation to the spectrum and X and Y chromosome counts. BLD was strongly associated with X chromosome count in both male and female groups.ConclusionsOur results suggest that X- and Y-linked genes have differential effects on CC morphometry. To our knowledge, this is the first study to compare CC morphometry across these extremely rare groups

Discovery of an old nova remnant in the Galactic globular cluster M 22

A nova is a cataclysmic event on the surface of a white dwarf in a binary system that increases the overall brightness by several orders of magnitude. Although binary systems with a white dwarf are expected to be overabundant in globular clusters (GCs) compared to the Galaxy, only two novae from Galactic globular clusters have been observed. We present the discovery of an emission nebula in the Galactic globular cluster M 22 (NGC 6656) in observations made with the integral-field spectrograph MUSE. We extract the spectrum of the nebula and use the radial velocity determined from the emission lines to confirm that the nebula is part of NGC 6656. Emission-line ratios are used to determine the electron temperature and density. It is estimated to have a mass of 1 to $17 \times 10^{-5}$ solar masses. This mass and the emission-line ratios indicate that the nebula is a nova remnant. Its position coincides with the reported location of a 'guest star', an ancient Chinese term for transients, observed in May 48 BCE. With this discovery, this nova may be one of the oldest confirmed extrasolar events recorded in human history.Comment: 7 pages, 3 figures; accepted for publication in Astronomy & Astrophysic

Scanning-gate microscopy of semiconductor nanostructures: an overview

This paper presents an overview of scanning-gate microscopy applied to the imaging of electron transport through buried semiconductor nanostructures. After a brief description of the technique and of its possible artifacts, we give a summary of some of its most instructive achievements found in the literature and we present an updated review of our own research. It focuses on the imaging of GaInAs-based quantum rings both in the low magnetic field Aharonov-Bohm regime and in the high-field quantum Hall regime. In all of the given examples, we emphasize how a local-probe approach is able to shed new, or complementary, light on transport phenomena which are usually studied by means of macroscopic conductance measurements.Comment: Invited talk by SH at 39th "Jaszowiec" International School and Conference on the Physics of Semiconductors, Krynica-Zdroj, Poland, June 201