Unveiling the relevance of the redox character of nitroaromatic and nitroheteroaromatic compounds as potential medicines

This review discusses the state of the art, challenges, and perspectives in recent applications of nitroaromatics and nitroheteroaromatics, which are redox-bio-activated drugs or leads, in Medicinal Chemistry. It deals mainly with the electrochemical approach toward the electron transfer-based molecular mechanisms of drug action, drug design, estimation and measurement of redox potentials, correlation of physicochemical and pharmacological data, and electrochemical studies of the main representatives of nitro-containing prodrugs, along with approaches to combat their toxicity issues, aiming at a better therapeutic profile. Electrochemical investigation plays essential roles, being strategic in the design and discovery of potential medicines.     

Strategic arrivals to queues offering priority service

Queueing Systems - We consider strategic arrivals to a FCFS service system that starts service at a fixed time and has to serve a fixed number of customers, for example, an airplane boarding...     

Irradiated UAmO2 transmutation discs analyses: from dissolution to isotopic analyses

Journal of Radioanalytical and Nuclear Chemistry - This paper details the different steps for the isotopic determination of UAmO2 discs from analytical irradiation. MARIOS and DIAMINO irradiations...     

Nonclassical Recrystallization

Applications in the fields of materials science and nanotechnology increasingly demand monodisperse nanoparticles in size and shape. Up to now, no general purification procedure exists to thoroughly narrow the size and shape distributions of nanoparticles. Here, we show by analytical ultracentrifugation (AUC) as an absolute and quantitative high-resolution method that multiple recrystallizations of nanocrystals to mesocrystals is a very efficient tool to generate nanocrystals with an excellent and so-far unsurpassed size-distribution (PDI_c=1.0001) and shape. Similar to the crystallization of molecular building blocks, nonclassical recrystallization removes “colloidal” impurities (i.e., nanoparticles, which are different in shape and size from the majority) by assembling them into a mesocrystal. In the case of nanocrystals, this assembly can be size- and shape-selective, since mesocrystals show both long-range packing ordering and preferable crystallographic orientation of nanocrystals. Besides the generation of highly monodisperse nanoparticles, these findings provide highly relevant insights into the crystallization of mesocrystals.     

Large‐Scale Synthesis of Enantiopure Molecular Cages: Chiroptical and Recognition Properties

A convenient and efficient gram‐scale synthesis for enantiopure hemicryptophane–tren (tren=tris(2‐aminoethyl)amine) derivatives has been developed. The four‐step synthesis is based on the optical resolution of a key intermediate, cyclotriveratrylene, for which the energy barrier for racemization has been measured to ensure that no racemization occurs during the two last steps of the synthetic pathway. The assignments of the absolute configurations have been performed by electronic circular dichroism and the enantiopurity was determined by NMR spectroscopy in the presence of enantiopure camphor sulfonic acid. To highlight the interest of such compounds, the recognition of norephedrine neurotransmitter was investigated and showed a remarkable enantioselectivity towards the C₃ symmetrical hosts. Finally, this highly modular synthetic pathway was used to provide eight enantiopure hemicryptophanes with different sizes, shapes, and functionalities. These results underline the high potential of this approach, which could lead to many applications in chiral recognition or asymmetric supramolecular catalysis.     

A PDE based and interpolation-free framework for modeling the sifting process in a continuous domain

The empirical mode decomposition (EMD) is a powerful tool in signal processing. Despite its algorithmic origin making its theoretical analysis and formulation very difficult, a few recent works has contributed to its theoretical framework. Herein, the former local mean is formulated in a more convenient way by introducing operators to calculate local upper and lower envelopes. This enables the use of differential calculus and other classical calculations on the new local mean. Based on its more accurate formulation, a partial differential equation (PDE) consistency result is provided to approximate the sifting process iterations, without any envelope interpolation. In addition, a new stopping criterion based on the introduced local mean is proposed. This new criterion is a local measure and resolves the null integral conservative property of the previous derived PDE, which made any signal having a null integral be a PDE-based mode. Moreover, the δ inner model parameter is now linked to the signal intrinsic properties, providing to the latter a physical meaning and making the proposed model keep the auto-adaptive property of the EMD. New decomposition modes are now analytically and fully characterized, and also interpolation free. Finally, properties of the interpolation free PDE model are presented. Results obtained with our proposed approach by explicit computations thanks to the eigendecomposition of the Laplacian operator, and also by numerical resolution of the derived PDE, show noticeable improvements for both stationary and non stationary signals, in comparison to the former EMD algorithm.     

Wie empfindlich sind Gehaltsbestimmungen durch Röntgenanregung mittels radioaktiver Röntgenquellen?

Mit Berücksichtigung eines die horizontale Probeausdehnung umfassenden Geometriefaktors werden unter praktisch brauchbaren Bedingungen absolute Fluoreszens- und Streustrahlungsausbeuten für sättigungsdicke und für dünne Proben berechnet. Die aus ihnen herleitbaren Meβempfindlichkeiten zeigen, daβ sich geringe Konzentrationen von relativ leichten bis mittelschweren Elementen besonders gut messen lassen, wenn man entweder dicht oberhalb der Absorptionskanten liegenda Energien anwendel oder bei relativ hoher Anregungsenergie die Streustahlung abtrennt. Bei groβen Konzentrationen solcher Elemente kann auch ohne Streustrahlungsabtrennung mit relativ hohen Anregungsenergien gemessen werden, wobei sogar unter gewissen Bedingungen mit Zunahme der Anregungsenergie eine leichte Empfindlichkeitsverbesserung eintritt. Bei schweren Elementen ist der Gesichtspunkt der Probendicke vielfach wichtiger als die Wahl der Anregungsenergie. Für dūnne Proben lassen sich relativ recht hohe Empfindlichkeiten erzielen, was jedoch zu einem Problem der absoluten Intensitāten angesichts des Detektor-Strahlungsuntergrundes fūhren kann.     

Simulation of a mixed-conducting membrane-based gas turbine power plant for CO<Subscript>2</Subscript> capture: system level analysis of operation stability and individual process unit degradation

A gas turbine power plant for CO₂ capture, based on oxygen-permeable membranes with mixed ionic-electronic conductivity, was analysed with respect to long-term stability by means of numerical simulation. Due to the attractive transport and physicochemical properties of mixed-conducting La₂NiO_4+δ, this nickelate was selected as a prototype membrane material for this application. Experiments showed very slow degradation of La₂NiO_4+δ membranes at oxygen chemical potentials close to atmospheric conditions, which are associated with kinetic demixing and other microstructure-related factors. Interaction with CO₂ in the intermediate temperature range also leads to lower oxygen permeation, whilst increasing oxygen pressure may cause partial phase decomposition and microstructural changes, thus again limiting the range of possible operation conditions. The relevant operational constraints were included in a detailed membrane-based gas turbine power plant model. The membrane performance degradation with time was approximated by a linear function with average rate of 3.3% per 1,000 operation hours. Furthermore, performance deterioration of the gas turbine compressor and turbine were also considered. Simulations revealed that the power plant is substantially affected by degradation of the ceramic membranes and turbomachinery components. The already rather small operating window was further narrowed when compared with a conventional gas turbine power plant. Two different designs of the membrane-based power plant were analysed: (1) with and (2) without additional combustors (afterburners) between the membrane reactor and the gas turbine. Afterburners increase thermal efficiency as well as power output, but also lead to non-negligible CO₂ emissions. In order to have a frame of comparison, results for a conventional gas turbine power plant with degradation of turbomachinery components are also presented. Simulations representing changes in ambient temperature and fuel composition as well as failure incidents were executed to analyse the susceptibility of the gas turbine power plant to external and internal changes.