Late-Stage Diversification of Tryptophan-Derived Biomolecules.

Gruß H, Sewald N. Late-Stage Diversification of Tryptophan-Derived Biomolecules. Chemistry - A European Journal. 2020;26(24):5328-5340.Pd-mediated reactions have emerged as a powerful tool for the site-selective and bioorthogonal late-stage diversification of amino acids, peptides and related compounds. Indole moieties of tryptophan derivatives are susceptible to C2 H-activation, whereas halogenated aromatic amino acids such as halophenylalanines or halotryptophans provide a broad spectrum of different functionalisations. The compatibility of transition-metal-catalysed cross-couplings with functional groups in peptides, other biologically active compounds and even proteins has been demonstrated. This Review primarily compiles the application of different cross-coupling reactions to modify halotryptophans, halotryptophan containing peptides or halogenated, biologically active compounds derived from tryptophan. Modern approaches use regio- and stereoselective biocatalytic strategies to generate halotryptophans and derivatives on a preparative scale. The combination of bio- and chemocatalysis in cascade reactions is given by the biocompatibility and bioorthogonality of Pd-mediated reactions. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA

Exposure-plant response of ambient ozone over the tropical Indian region

A high resolution regional chemistry-transport model has been used to study the distribution of exposure-plant response index (AOT40, Accumulated exposure Over a Threshold of 40 ppb, expressed as ppb h) over the Indian geographical region for the year 2003 as case study. The directives on ozone pollution in ambient air provided by United Nations Economic Commission for Europe (UNECE) and World Health Organization (WHO) for vegetation protection (AOT40) have been used to assess the air quality. A substantial temporal and spatial variation in AOT40 values has been observed across the Indian region. Large areas of India show ozone values above the AOT40 threshold limit (3000 ppb h for 3 months). Simulated AOT40 values are found to be substantially higher throughout the year over the most fertile Indo-Gangetic plains than the other regions of India, which can have an adverse effect on plants and vegetation in this region. The observed monthly AOT40 values reported from an Indian station, agree reasonably well with model simulated results. There is an underestimation of AOT40 in the model results during the periods of highest ozone concentration from December to March. We find that the simulated AOT40 target values for protection of vegetation is exceeded even in individual months, especially during November to April. Necessary and effective emission reduction strategies are therefore required to be developed in order to curb the surface level ozone pollution to protect the vegetation from further damage in India whose economy is highly dependent on agricultural sector and may influence the global balance

Noise current spectrum in submicrometer samples

The noise current spectral density in submicrometer samples is computed using the Monte Carlo method. The normalized spectral density is found to decrease with sample length and increase with the field. The high-field noise is like shot noise and increases with current in agreement with experimental results

Correlating contexts and NFR conflicts from event logs

In the design of autonomous systems, it is important to consider the preferences of the interested parties to improve the user experience. These preferences are often associated with the contexts in which each system is likely to operate. The operational behavior of a system must also meet various non-functional requirements (NFRs), which can present different levels of conflict depending on the operational context. This work aims to model correlations between the individual contexts and the consequent conflicts between NFRs. The proposed approach is based on analyzing the system event logs, tracing them back to the leaf elements at the specification level and providing a contextual explanation of the system’s behavior. The traced contexts and NFR conflicts are then mined to produce Context-Context and Context-NFR conflict sequential rules. The proposed Contextual Explainability (ConE) framework uses BERT-based pre-trained language models and sequential rule mining libraries for deriving the above correlations. Extensive evaluations are performed to compare the existing state-of-the-art approaches. The best-fit solutions are chosen to integrate within the ConE framework. Based on experiments, an accuracy of 80%, a precision of 90%, a recall of 97%, and an F1-score of 88% are recorded for the ConE framework on the sequential rules that were mined

Formation of antihydrogen in antiproton - positron collision

A quantum mechanical approach is proposed for the formation of antihydrogen in the ground and excited states (2s, 2p) via the mechanism of three body recombination (TBR) inside a trapped plasma of anti proton and positron or in the collision between the two beams of them. Variations of the differential (DCS) as well as the total (TCS) formation cross sections are studied as a function of the incident energies of both the active and the spectator positrons. Significantly large cross sections are found at very low incident energies in the TBR process as compared to other processes leading to antihydrogen. The present formation cross section decreases with increasing positron energy (temperature) but no simple power law could be predicted for it covering the entire energy range, corroborating the experimental findings qualitatively. The formation cross sections are found to be much higher for unequal energies of the two positrons than for equal energies, as expected physically.Comment: 14 pages, 13 figure