Search results for "ATAL"
showing 10 items of 10591 documents
Sub-milliarcsecond imaging of a bright flare and ejection event in the extragalactic jet 3C 111
2020
Context. Flares in radio-loud active galactic nuclei are thought to be associated with the injection of fresh plasma into the compact jet base. Such flares are usually strongest and appear earlier at shorter radio wavelengths. Hence, very long baseline interferometry (VLBI) at millimeter(mm)-wavelengths is the best-suited technique for studying the earliest structural changes of compact jets associated with emission flares. Aims. We study the morphological changes of the parsec-scale jet in the nearby (z = 0.049) γ-ray bright radio galaxy 3C 111 following a flare that developed into a major radio outburst in 2007. Methods. We analyse three successive observations of 3C 111 at 86 GHz with th…
Alternative Military Keynesianism as a Tool of Civil-Military Cooperation in the Framework of the EU Defence Policy
2015
During the last year the security threats to the European Union have increased dramatically under the influence of military crisis in eastern Ukraine and Islamic terrorist activities in Europe. Consequently the demand for defence in the member states of the European Union has become greater than in previous years.This situation leads to the dilemma when the high level of defence expenditure can hamper the financial support of other sectors of national economy.Therefore it is necessary to increase the efficiency of available financial resources that have been allocated for the defence without a significant increase in defence expenditure. In order to achieve this efficiency the concept of cl…
Acylative Dynamic Kinetic Resolution of Secondary Alcohols: Tandem Catalysis by HyperBTM and Bäckvall's Ruthenium Complex.
2021
Non-enzymatic dynamic kinetic resolution (DKR) of secondary alcohols by enantioselective acylation using an isothiourea-derived HyperBTM catalyst and racemization of slowly reacting alcohol by Backvall's ruthenium complex is reported. The DKR approach features high enantioselectivities (up to 99:1), employs easy-to-handle crystalline 4-nitrophenyl isobutyrate as the acylating reagent, and proceeds at room temperature and under an ambient atmosphere. The stereoinduction model featuring cation-π system interactions between the acylated HyperBTM catalyst and π electrons of an alcohol aryl subunit has been elaborated by DFT calculations.
Palladium-Catalyzed Hydroxycarbonylation of Aryl and Vinyl Bromides by Mixed Acetic Formic Anhydride
2006
The palladium-catalyzed hydroxycarbonylation of aryl and vinyl bromides in the presence of acetic anhydride and lithium formate as a carbon monoxide source has been developed. The combination of palladium(II) acetate with 1,1'-bis(diphenylphosphino)ferrocene (dppf) is an efficient catalytic system when the reaction is carried out at 120 °C.
High affinity of "arbor" iron porphyrins for dioxygen
1998
International audience; The equilibrium rates of dioxygen and carbon monoxide binding have been measured for a series of capped iron porphyrins called "arbor". The affinity for dioxygen of these models is 100-fold higher than the highest previously reported values.
On the physicochemical properties of pyridohelicenes.
2014
A comprehensive study on the physicochemical properties of a series of mono- and diaza[5]helicenes as well as mono- and diaza[6]helicenes is reported. Through the use of both computational and experimental methods, these helically chiral pyridohelicenes with the nitrogen atom(s) in various positions are characterised according to their inversion barriers, protonation constants and redox potentials. By using DFT calculations, kinetic measurements, UV/Vis titrations, cyclic voltammetry and EPR spectroscopy, a self-contained picture of their behaviour under conventional treatment by heat, acids and oxidising/reducing agents is provided.
Acidic Co-Catalysts in Cationic Gold Catalysis.
2016
A systematic study on the effects of Lewis or Bronsted acid co-catalysts in gold-catalyzed reactions was undertaken using representative reactions (O-, N-, and C-nucleophilic additions to alkynes). Through these reactions, it was demonstrated that an acidic co-catalyst can increase the catalyst turnover significantly, enabling practical reaction rates at competitive catalyst loadings (<1 mol %). Further investigation is currently underway to improve the understanding of the subtle principles underlying these experimental observations.
More than a Confinement: “Soft” and “Hard” Enzyme Entrapment Modulates Biological Catalyst Function
2019
Catalysis makes chemical and biochemical reactions kinetically accessible. From a technological point of view, organic, inorganic, and biochemical catalysis is relevant for several applications, from industrial synthesis to biomedical, material, and food sciences. A heterogeneous catalyst, i.e., a catalyst confined in a different phase with respect to the reagents’ phase, requires either its physical confinement in an immobilization matrix or its physical adsorption on a surface. In this review, we will focus on the immobilization of biological catalysts, i.e., enzymes, by comparing hard and soft immobilization matrices and their effect on the modulation of the catalysts’ function. Indeed, …
Mechanism of sulfur transfer across protein-protein interfaces: The cysteine desulfurase model system
2016
CsdA cysteine desulfurase (the sulfur donor) and the CsdE sulfur acceptor are involved in biological sulfur trafficking and in iron-sulfur cluster assembly in the model bacterium Escherichia coli. CsdA and CsdE form a stable complex through a polar interface that includes CsdA Cys328 and CsdE Cys61, the two residues known to be involved in the sulfur transfer reaction. Although mechanisms for the transfer of a sulfur moiety across protein-protein interfaces have been proposed based on the IscS-IscU and IscS-TusA structures, the flexibility of the catalytic cysteine loops involved has precluded a high resolution view of the active-site geometry and chemical environment for sulfur transfer. H…
Structural Origin of Metal Specificity in Isatin Hydrolase from Labrenzia aggregata Investigated by Computer Simulations.
2017
We performed quantum-chemical calculations, ab initio molecular dynamics, hybrid quantum mechanics/molecular mechanics (QM/MM) and enhanced sampling metadynamics simulations to investigate the origin of metal specificity in isatin hydrolase from Labrenzia aggregata. The peculiar octahedral binding geometry of the Mn2+ ion in the Michaelis complex includes both the isatin substrate and the catalytic water within the first coordination shell of the cation. Our calculations show that the same arrangement of the ligands cannot be efficiently achieved in the presence of other small divalent metal cations such as Zn2+ or Cu2+ . On the contrary, bulkier alkaline-earth cations such as Mg2+ , which …