N-Aminierung von Isochinolinbasen

N-Amination of Isoquinoline Bases 3, 3-Pentamethylene oxaziridine 1 forms an N N-bond with secondary isoquinoline bases 2a – f to give the cyclohexylidene hydrazines 3a – f . In some cases nitrogen elimination yielding indane derivatives 13b, 13e competes with hydrazone formation. The cyclic Schiff'base 14 and the β-carboline derivative 16 can also be aminated.     

Quantenchemische Untersuchungen zur Molekül- und Elektronenstruktur einfacher Azomethinimine und verwandter Verbindungen

Quantum Chemical Investigations of the Molecular and Electronic Structure of Simple Azomethine Imines and Related Compounds The molecular and electronic structure of simple azomethinimines are investigated by means of MINDO/3 and CNDO/2 calculations. The calculated molecular geometry is compared with X-ray results obtained for these compounds. Except for the NN-bond lengths MINDO/3 satisfactorily describes the molecular structure of azomethinimine and related π-electronic systems. The charges at the atoms along the conjugated chain are alternating as in polymethines. The terminal carbon atom carries a negative charge. This charge brings about an appreciable shielding of this carbon atom such as found in the ¹³C-n.m.r. spectrum. This result does not contradict a stabilization of azomethinimines in the crystal via = CH…︁OC interactions.     

Feature sampling in detection: Implications for the measurement of perceptual independence.

The article presents the feature sampling signal detection (FS-SDT) model, an extension of the multivariate signal detection (SDT) model. The FS-SDT model assumes that, because of attentional shifts, different subsets of features are sampled for different presentations of the same multidimensional stimulus. Contrary to the SDT model, the FS-SDT model enables the estimation of pure perceptual effects that are uncontaminated by strategic attention shifts. The consideration of feature sampling in detection and identification opens a new perspective on the problem of measuring, respectively, the separability and integrality of stimulus dimensions. Disregarding feature sampling as a component process in detection and identification usually results in biased estimations of perceptual independence concepts relevant for judgments of whether stimulus dimensions are processed independently. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Spinmarkierte Oligopeptide als substratanaloge Inhibitoren der Leucinaminopeptidase

Spin Labeled Oligopeptides as Substrate Analogous Inhibitors of Leucine Aminopeptidase The synthesis of L-Thr(Bu^t)-(L-Phe)_n-SL peptides C-terminal labeled with the nitroxide spin label 2,2,5,5-tetramethyl-3-amino-pyrrolidin-1-oxyl, is described and e.s.r. parameters of the labeled compounds are presented. As shown by e.s.r. spectroscopy studies Thr(Bu^t)-Phe-SL is a competitive inhibitor of the leucine aminopeptidase and is bound by the enzyme with high affinity.     

RECURSIVE GENERALIZED M ESTIMATES FOR AUTOREGRESSIVE MOVING-AVERAGE MODELS

Abstract. Outliers in time series seriously affect conventional parameter estimates. In this paper a robust recursive estimation procedure for the parameters of auto-regressve moving-average models with additive outliers is proposed. Using 'cleaned' residuals from an initial robust fit of an autoregression of high order as input, bounded influence regression is applied recursively. The proposal follows certain ideas of Hannan and Rissanen, who suggested a three-stage procedure for order and parameter estimation in a conventional setting.
A Monte Carlo study is performed to investigate the robustness properties of the proposed class of estimates and to compare them with various other suggestions, including least squares, M estimates, residual autocovariance and truncated residual autocovariance estimates. The results show that the recursive generalized M estimates compare favourably with them. Finally, possible modifications to master even vigourous situations are suggested.     

Influence of Zn2+ doping on the morphotropic phase boundary in lead-free piezoelectric (1 – x)Na1/2Bi1/2TiO3-xBaTiO3

A series of morphotropic phase boundary (MPB) compositions of (1–x)Na_1/2Bi_1/2TiO₃-xBaTiO₃ (x = 0.05, 0.055, 0.06, 0.065, 0.07), with and without 0.5 mol% Zn-doping was synthesized using the solid-state route. The samples were characterized using X-ray diffraction, dielectric analysis, and electromechanical measurements (piezoelectric d₃₃ coefficient, coupling factor k_p, mechanical quality factor Q_m, and internal bias field E_bias). The increase in the ferroelectric-relaxor transition temperature upon Zn-doping was accompanied by a shift of the MPB toward the Na_1/2Bi_1/2TiO₃-rich side of the phase diagram. Higher tetragonal phase fraction and increased tetragonal distortion were noted for Zn-doped (1 – x)Na_1/2Bi_1/2TiO₃-xBaTiO₃. In addition, ferroelectric hardening and the presence of an internal bias field (E_bias) were observed for all doped compositions. The piezoelectric constant d₃₃ and the coupling coefficient k_p decreased by up to ∼30%, while a 4- to 6-fold increase in Q_m was observed for the doped compositions. Apart from establishing a structure–property correlation, these results highlight the chemically induced shift of the phase diagram upon doping, which is a crucial factor in material selection for optimal performance and commercialization.     

Structure-Activity Studies Reveal Scope for Optimisation of Ebselen-Type Inhibition of SARS-CoV-2 Main Protease

The reactive organoselenium compound ebselen is being investigated for treatment of coronavirus disease 2019 (COVID-19) and other diseases. We report structure-activity studies on sulfur analogues of ebselen with the Severe Acute Respiratory Syndrome coronavirus 2 (SARS-CoV-2) main protease (M^pro), employing turnover and protein-observed mass spectrometry-based assays. The results reveal scope for optimisation of ebselen/ebselen derivative- mediated inhibition of M^pro, particularly with respect to improved selectivity.     

Untersuchungen zur heterogenen Kondensation von Wasserdampf in Membrankontaktoren

Heterogeneous condensation can contribute to improve the separation efficiency of airborne particles. Submicron particles can be separated due to inertial impaction when particle mass is previously enlarged sufficiently by water vapor condensation. This paper presents a novel, membrane‐based process for creating the requisite supersaturation for condensation. The increase of the particle size based on vapor condensation is detected by a new inline measuring technique.