Carbanionisch vermittelte „Methylen“-Insertionen mit N,N-Dimethylformamid als C1-Synthon

In der vorliegenden Dissertation wurde untersucht, ob deprotonierte Phenylessigsäureamide in SET-gestützten C-C-, C-N- oder C-O-Verknüpfungsreaktionen einsetzbar sind. Als potentieller Ein-Elektronenakzeptor fand N,N-Dimethylformamid (DMF) Verwendung. Obwohl bei den Umsetzungen der Amide mit NaH in DMF unter Argon in einem Temperaturbereich von 20-154 °C keine Produkte gewonnen werden konnten, die auf SET-gestützte Reaktionsfolgen zurückzuführen waren, entstanden zahlreiche Verbindungen, deren Bildungssequenzen auf außergewöhnlichen „Methylen“-Insertionen mit DMF als C1-Synthon basieren. So entstehen bei der Umsetzung von Phenylessigsäureamid unter Rückfluß aus jeweils zwei Edukt- und einem DMF-Molekül neben 3,5-Diphenylpyridin-2,6-diol und 3,5-Diphenylpyridin-2-ol (I) die methylenverbrückten Dimere racem- und meso-3,5-Diphenylpiperidin-2,6-dion sowie 3,5-Diphenyl-3,4-dihydropyridin-2(1H)-on (II). Der postulierte Entstehungsweg von I bzw. II schließt die direkte Reduktion einer amidischen Carbonylgruppe durch NaH ein. Dieses Reaktionsverhalten zeigt deutlich, daß sich die Reduktionskraft von NaH in DMF erheblich steigern läßt. Die beobachteten „Methylen“-Insertionen ließen sich auf Phenylessigsäure bzw. deren Esterderivate sowie auf 3-Phenylpropionsäureamid ausdehnen. Im Anschluß an diese Versuchsreihen konnte gezeigt werden, daß in Anwesenheit von Luftsauerstoff intramolekular verlaufende, SET-vermittelte C=C- bzw. C=N- Doppelbindungsbildungen realisierbar sind. So entsteht bei der Umsetzung von Biphenyl-2,2'-diacetamid mit NaH in DMF bei 70 °C Phenanthren-9,10-dicarboxyimid. Benzol-1,2-diacetamid reagiert mit NaH in DMF bei Raumtemperatur unter Bildung von 3-Hydroxyisochinolin-1-carboxamid. Dabei findet die unter synthetischen Gesichtspunkten sehr reizvolle Verknüpfung einer CH-aciden Methylengruppe mit einer amidischen NH2-Gruppe statt. Wird N-(Phenylacetyl)phenylessigsäureamid mit NaH in DMF bei Raumtemperatur umgesetzt, entsteht Diphenylmaleinsäureimid

Divergence-free reconstruction operators for pressure-robust Stokes discretizations with continuous pressure finite elements

Classical inf-sup stable mixed finite elements for the incompressible (Navier--)Stokes equations are not pressure-robust, i.e., their velocity errors depend on the continuous pressure. How-ever, a modification only in the right hand side of a Stokes discretization is able to reestablish pressure-robustness, as shown recently for several inf-sup stable Stokes elements with discontinuous discrete pressures. In this contribution, this idea is extended to low and high order Taylor--Hood and mini elements, which have continuous discrete pressures. For the modification of the right hand side a velocity reconstruction operator is constructed that maps discretely divergence-free test functions to exactly divergence-free ones. The reconstruction is based on local H(div)-conforming flux equilibration on vertex patches, and fulfills certain orthogonality properties to provide consistency and optimal a-priori error estimates. Numerical examples for the incompressible Stokes and Navier--Stokes equations confirm that the new pressure-robust Taylor--Hood and mini elements converge with optimal order and outperform signi--cantly the classical versions of those elements when the continuous pressure is comparably large

Three-Dimensional Light Bullets in Arrays of Waveguides

We report the first experimental observation of 3D-LBs, excited by femtosecond pulses in a system featuring quasi-instantaneous cubic nonlinearity and a periodic, transversally-modulated refractive index. Stringent evidence of the excitation of LBs is based on time-gated images and spectra which perfectly match our numerical simulations. Furthermore, we reveal a novel evolution mechanism forcing the LBs to follow varying dispersion/diffraction conditions, until they leave their existence range and decay.Comment: 4 pages, 5 figures - Published by the American Physical Societ

Revealing Hidden Potentials of the q-Space Signal in Breast Cancer

Mammography screening for early detection of breast lesions currently suffers from high amounts of false positive findings, which result in unnecessary invasive biopsies. Diffusion-weighted MR images (DWI) can help to reduce many of these false-positive findings prior to biopsy. Current approaches estimate tissue properties by means of quantitative parameters taken from generative, biophysical models fit to the q-space encoded signal under certain assumptions regarding noise and spatial homogeneity. This process is prone to fitting instability and partial information loss due to model simplicity. We reveal unexplored potentials of the signal by integrating all data processing components into a convolutional neural network (CNN) architecture that is designed to propagate clinical target information down to the raw input images. This approach enables simultaneous and target-specific optimization of image normalization, signal exploitation, global representation learning and classification. Using a multicentric data set of 222 patients, we demonstrate that our approach significantly improves clinical decision making with respect to the current state of the art.Comment: Accepted conference paper at MICCAI 201

Ein optimierter Versorgungsprozess bei Patienten mit schlafbezogenen Atmungsstörungen – Pilotstudie

Background: To date, patients have been instructed in diagnostic polygraphy (PG) by a trained specialist. This process is time- and cost-intensive. In a pilot study, we tested an innovative procedure in sleep-disordered breathing (SDB) to achieve faster diagnoses and more effective referral for treatment. For this purpose, study participants had a PG device delivered at home directly from the provider. Methods: Patients self-administered the PGs independently using a manual, and, if necessary, received telephone support. After the night of recording, the device was sent back to the supplier. Diagnosis by a physician was done online via an encrypted portal. In addition, subjective satisfaction with the process was assessed using a questionnaire and PG results were compared with polysomnography (PSG) within a narrow timescale. Results: Fifty patients middle-aged (50.5 ± 13.7 years), male = 30/female = 20, with suspected SDB were included in the study. The study participants had a similar mean Apnea-Hypopnea Index (AHI; PSG) of M = 20.8 (SD 23.2) and a mean AHI measured using PG of M = 20.2 (SD 18.9) under both measurement methods. At AHI values between ≥15–30/h showed sensitivity of 88% and specificity of 91%. Conclusion: In assessing whether clinically relevant sleep apnea occurred, we found a weak to moderate match between the individual diagnostic categories of the measuring process, with the most frequent matches occurring in the highest and lowest diagnosis groups. However, these results do not allow for a prediction of feasibility in a general or multimorbid patient population because of the selective sample.Hintergrund: Die Einweisung der Patienten in die diagnostische Polygraphie wird bisher von einer medizinisch ausgebildeten Fachkraft durchgeführt. Dieser Prozess ist zeit- und ressourcenintensiv. In dieser Pilotstudie wurde ein innovativer Versorgungsweg bei schlafbezogenen Atmungsstörungen (SBAS) untersucht, um eine beschleunigte Diagnostik und effektivere Therapiezuweisung zu erreichen. Hierfür wurde den Studienteilnehmern ein Polygrafie (PG)-Gerät direkt von der versorgenden Firma nach Hause geliefert. Methodik: Der Patient legte die PG selbstständig nach einer Bedienungsanleitung an und erhielt bei Bedarf telefonische Unterstützung. Nach der Untersuchungsnacht wurde das Gerät zurückgesendet. Die ärztliche Befundung erfolgte online über ein verschlüsseltes Portal. Zusätzlich erfolgte eine Befragung zur subjektiven Zufriedenheit mit dem Ablaufprozess sowie ein Vergleich der PG-Ergebnisse mit einer zeitnahen Polysomnografie (PSG). Ergebnisse: Es wurden 50 Patienten (m = 30/w = 20) mit Verdacht auf SBAS im mittleren Alter von 50,5 ± 13,7 Jahren eingeschlossen. Die Probanden wiesen unter beiden Messverfahren einen ähnlichen mittleren Apnoe-Hypopnoe-Index (AHI) (PSG) von M = 20,8 (SD 23,2) und AHI (PG) von M = 20,2 (SD 18,9) auf. Bei AHI-Werten zwischen ≥15–30/h lag die Sensitivität bei 88 % und die Spezifität bei 91 %. Diskussion: In der Beurteilung, ob eine klinisch relevante Schlafapnoe vorliegt, zeigte sich eine eher schwache, moderate Übereinstimmung zwischen den einzelnen Diagnosekategorien der Messverfahren, wobei sich die häufigsten Übereinstimmungen in den höchsten und niedrigsten Diagnosegruppen zeigten. Die Ergebnisse lassen jedoch aufgrund der selektiven Stichprobe keine Prognosen hinsichtlich der Durchführbarkeit in einer allgemeinen oder multimorbiden Patientengruppe zu

Reduction of CPR artifacts in the ventricular fibrillation ECG by coherent line removal

<p>Abstract</p> <p>Background</p> <p>Interruption of cardiopulmonary resuscitation (CPR) impairs the perfusion of the fibrillating heart, worsening the chance for successful defibrillation. Therefore ECG-analysis <it>during ongoing chest compression </it>could provide a considerable progress in comparison with standard analysis techniques working only during "hands-off" intervals.</p> <p>Methods</p> <p>For the reduction of CPR-related artifacts in ventricular fibrillation ECG we use a localized version of the <it>coherent line removal </it>algorithm developed by Sintes and Schutz. This method can be used for removal of periodic signals with sufficiently coupled harmonics, and can be adapted to specific situations by optimal choice of its parameters (e.g., the number of harmonics considered for analysis and reconstruction). Our testing was done with 14 different human ventricular fibrillation (VF) ECGs, whose fibrillation band lies in a frequency range of [1 Hz, 5 Hz]. The VF-ECGs were mixed with 12 different ECG-CPR-artifacts recorded in an animal experiment during asystole. The length of each of the ECG-data was chosen to be 20 sec, and testing was done for all 168 = 14 × 12 pairs of data. VF-to-CPR ratio was chosen as -20 dB, -15 dB, -10 dB, -5 dB, 0 dB, 5 dB and 10 dB. Here -20 dB corresponds to the highest level of CPR-artifacts.</p> <p>Results</p> <p>For non-optimized <it>coherent line removal </it>based on signals with a VF-to-CPR ratio of -20 dB, -15 dB, -10 dB, -5 dB and 0 dB, the signal-to-noise gains (SNR-gains) were 9.3 ± 2.4 dB, 9.4 ± 2.4 dB, 9.5 ± 2.5 dB, 9.3 ± 2.5 dB and 8.0 ± 2.7 (mean ± std, <it>n </it>= 168), respectively. Characteristically, an original VF-to-CPR ratio of -10 dB, corresponds to a variance ratio <it>var</it>(VF):<it>var</it>(CPR) = 1:10. An improvement by 9.5 dB results in a restored VF-to-CPR ratio of -0.5 dB, corresponding to a variance ratio <it>var</it>(VF):<it>var</it>(CPR) = 1:1.1, the variance of the CPR in the signal being reduced by a factor of 8.9.</p> <p>Discussion</p> <p>The <it>localized coherent line removal </it>algorithm uses the information of a single ECG channel. In contrast to multi-channel algorithms, no additional information such as thorax impedance, blood pressure, or pressure exerted on the sternum during CPR is required. Predictors of defibrillation success such as mean and median frequency of VF-ECGs containing CPR-artifacts are prone to being governed by the harmonics of the artifacts. Reduction of CPR-artifacts is therefore necessary for determining reliable values for estimators of defibrillation success.</p> <p>Conclusions</p> <p>The <it>localized coherent line removal </it>algorithm reduces CPR-artifacts in VF-ECG, but does not eliminate them. Our SNR-improvements are in the same range as offered by multichannel methods of Rheinberger et al., Husoy et al. and Aase et al. The latter two authors dealt with different ventricular rhythms (VF and VT), whereas here we dealt with VF, only. Additional developments are necessary before the algorithm can be tested in real CPR situations.</p

Discrete multivortex solitons

We introduce discrete multivortex solitons in a ring of nonlinear oscillators coupled to a central site. Regular clusters of discrete vortices appear as a result of mode collisions and we show that their stability is determined by global symmetries rather than the stability of constituent vortices. Stable multivortex solitons support complex vortex dynamics including charge flipping and spiraling.Comment: 3 pages, 3 figure

Gas phase mean opacities for varying [M/H], N/O, and C/O

We present a set of gas-phase Planck mean and Rosseland mean opacity tables applicable for simulations of star and planet formation, stellar evolution, disk modelling at various metallicities in hydrogen-rich environments. The tables are calculated for gas temperatures between 1000K and 10000K and total hydrogen number densities between 10^2 cm^-3 and 10^17 cm^-3. The carbon-to-oxygen ratio is varied from 0.43 to well above 2.0, the nitrogen-to-oxygen ration between 0.14 and 100.0. The tables are calculated for a range of metallicities down to [M/H]'= log N_M/N_H=-7.0. We demonstrate how the mean opacities and the abundances of the opacity species vary with C/O, N/O, and [M/H]'. We use the element abundances from Grevesse, Asplund & Sauval (2007), and we provide additional tables for the oxygen-abundance value from Caffau et al.(2008). All tables will be available online under http://star-www.st-and.ac.uk/$\sim$ch80/datasources.htmlComment: 10 pages, accepted for publication in MNRA