Asymmetric C(sp3)–H functionalization of unactivated alkylarenes such as toluene enabled by chiral Brønsted base catalysts

Benzylic functionalisation of unactivated alkylarenes remains as a significant challenge in asymmetric catalysis due to their less reactive nature. Here, we show development of catalytic asymmetric C(sp3)–H functionalization of unactivated alkylarenes such as toluene with imines. The reactions proceeded smoothly under proton-transfer conditions using a chiral, strong Brønsted base catalyst system. A chiral Brønsted base prepared from an alkylpotassium and a chiral amine ligand was found to effectively form a promising asymmetric environment around a benzyl anion. Optimization of the reaction conditions revealed that the use of the alkaline metal amide, potassium hexamethyldisilazide (KHMDS), as an additive was most effective, and enantioselective and atom economical carbon–carbon bond-forming reactions at the benzylic positions of unactivated alkylarenes was achieved without using any transition-metal catalyst.

Deep Learning-Based Localization for UWB Systems

Localization has been extensively studied owing to its huge potential in various areas, such as Internet of Things, 5G, and unmanned aerial vehicle services. Its wide applications include home automation, advanced production automation, and unmanned vehicle control. In this study, we propose a novel localization method that utilizes convolutional neural network (CNN) and ultra-wideband (UWB) signals. A localization problem is converted to a regression problem with the proposed CNN, in which the ranging and positioning phases are integrated. By integrating the ranging and positioning phases, the proposed CNN estimates the location of UWB transmitter directly without any additional step. To integrate both phases of localization, a simple-yet efficient input image generation method is proposed. In the proposed input image generation method, three oversampled two-dimensional input images are generated from the three received UWB signals and they are provided to the designed CNN through the three channels, which are represented by red-, green-, and blue-color channels, respectively. The proposed CNN-based localization system then estimates the location of the UWB transmitter directly using the three-channel image as an input of the CNN. Simulation results verify that the proposed CNN-based localization method outperforms the traditional threshold-based and existing CNN-based methods. Also, it is observed that the proposed method performs well under an asymmetric environment, unlike the existing method.

Bacterial Cellulose: A Versatile Chiral Host for Circularly Polarized Luminescence

Materials capable of circularly polarized luminescence (CPL) have attracted considerable attention for their promising potential applications. Bacterial cellulose (BC) was characterized as having a stable right-handed twist, which makes it a potential chiral host to endow luminophores with CPL. Then, the CPL-active BC composite film was constructed by simply impregnating bacterial cellulose pellicles with dilute aqueous solutions of luminophores (rhodamine B, carbon dots, polymer dots) and drying under ambient conditions. Simple encapsulation of luminophores renders BC with circularly polarized luminescence with a dissymmetry factor of up to 0.03. The multiple chiral centers of bacterial cellulose provide a primary asymmetric environment that can be further modulated by supramolecular chemistry, which is responsible for its circular polarization ability. We further demonstrate that commercial grade paper may endow luminophores with CPL activity, which reifies the universality of the method.

The population of TeV pulsar wind nebulae in the H.E.S.S. Galactic Plane Survey

The nine-year H.E.S.S. Galactic Plane Survey (HGPS) has yielded the most uniform observation scan of the inner Milky Way in the TeV gamma-ray band to date. The sky maps and source catalogue of the HGPS allow for a systematic study of the population of TeV pulsar wind nebulae found throughout the last decade. To investigate the nature and evolution of pulsar wind nebulae, for the first time we also present several upper limits for regions around pulsars without a detected TeV wind nebula. Our data exhibit a correlation of TeV surface brightness with pulsar spin-down power Ė. This seems to be caused both by an increase of extension with decreasing Ė, and hence with time, compatible with a power law RPWN(Ė) ~Ė−0.65±0.20, and by a mild decrease of TeV gamma-ray luminosity with decreasing Ė, compatible with L1−10 TeV ~Ė0.59±0.21. We also find that the offsets of pulsars with respect to the wind nebula centre with ages around 10 kyr are frequently larger than can be plausibly explained by pulsar proper motion and could be due to an asymmetric environment. In the present data, it seems that a large pulsar offset is correlated with a high apparent TeV efficiency L1−10 TeV∕Ė. In addition to 14 HGPS sources considered firmly identified pulsar wind nebulae and 5 additional pulsar wind nebulae taken from literature, we find 10 HGPS sources that are likely TeV pulsar wind nebula candidates. Using a model that subsumes the present common understanding of the very high-energy radiative evolution of pulsar wind nebulae, we find that the trends and variations of the TeV observables and limits can be reproduced to a good level, drawing a consistent picture of present-day TeV data and theory.