Search results for "INO"
showing 10 items of 50751 documents
Carbonyl compounds of Tc, Re, and Bh: Electronic structure, bonding, and volatility.
2018
Calculations of molecular properties of M(CO)5 and MH(CO)5, where M = Tc, Re, and Bh, and of the products of their decomposition, M(CO)4 and MH(CO)4, were performed using density functional theory and coupled-cluster methods implemented in the relativistic program suits such as ADF, DIRAC, and ReSpect. The calculated first M—CO bond dissociation energies (FBDEs) of Bh(CO)5 and BhH(CO)5 turned out to be significantly weaker than those of the corresponding Re homologs. The reason for that is the relativistic destabilization and expansion of the 6d AOs, responsible for weaker σ-forth and π-back donations in the Bh compounds. The relativistic FBDEs of M(CO)5 have, therefore, a Λ-shape behavior …
pKa at Quartz/Electrolyte Interfaces.
2016
Acidity of silanol sites at the crystalline quartz/aqueous electrolyte (NaCl, NaI, KCl) interfaces are calculated from ab initio molecular dynamics simulations. pKa’s are found to follow a combination of the cationic and anionic Hofmeister series in the order pKa(neat solution) < pKa(NaCl) < pKa(NaI) < pKa(KCl), in agreement with experimental measurements. Rationalization of this ranking is achieved in terms of the microscopic local solvation of the protonated silanols and their conjugated bases, the silanolates SiO–. The change in the pKa is the result of both water destructuring by alkali halides, as well as of the specific cation/SiO– interaction, depending on the electrolyte. M…
Heterogeneous Interactions between Gas-Phase Pyruvic Acid and Hydroxylated Silica Surfaces: A Combined Experimental and Theoretical Study
2019
The adsorption of gas-phase pyruvic acid (CH3COCOOH) on hydroxylated silica particles has been investigated at 296 K using transmission Fourier transform infrared (FTIR) spectroscopy and theoretical simulations. Under dry conditions (<1% relative humidity, RH), both the trans-cis (Tc) and trans-trans (Tt) pyruvic acid conformers are observed on the surface as well as the (hydrogen bonded) pyruvic acid dimer. The detailed surface interactions were further understood through ab initio molecular dynamics simulations. Under higher relative humidity conditions (above 10% RH), adsorbed water competes for surface adsorption sites. Adsorbed water is also observed to change the relative populations …
Contextuality-by-Default: A Brief Overview of Ideas, Concepts, and Terminology
2016
This paper is a brief overview of the concepts involved in measuring the degree of contextuality and detecting contextuality in systems of binary measurements of a finite number of objects. We discuss and clarify the main concepts and terminology of the theory called “contextuality-by-default,” and then discuss generalizations of the theory to arbitrary systems of arbitrary random variables.
Antineutrino monitoring of spent nuclear fuel
2016
Military and civilian applications of nuclear energy have left a significant amount of spent nuclear fuel over the past 70 years. Currently, in many countries world wide, the use of nuclear energy is on the rise. Therefore, the management of highly radioactive nuclear waste is a pressing issue. In this letter, we explore antineutrino detectors as a tool for monitoring and safeguarding nuclear waste material. We compute the flux and spectrum of antineutrinos emitted by spent nuclear fuel elements as a function of time, and we illustrate the usefulness of antineutrino detectors in several benchmark scenarios. In particular, we demonstrate how a measurement of the antineutrino flux can help to…
Determination of the chemical warfare agents Sarin, Soman and Tabun in natural waters employing fluorescent hybrid silica materials
2017
[EN] A novel mesoporous silica material containing boron-dipyrromethene (BODIPY) moieties (I) is employed for the detection of nerve agent simulants (NASs) and the organophosphate nerve or chemical warfare agents (CWAs) Sarin (GB), Soman (GD), and Tabun (GA) in aqueous environments. The reactive BODIPY dye with an optimum positioned hydroxyl group undergoes acylation reactions with phosph(on)ate substrates, yielding a bicyclic ring. Due to aggregation of the dyes in water, the sensitivity of the free dye in solution is very low. Only after immobilization of the BODIPY moieties into the silica substrates is aggregation inhibited and a sensitive determination of the NASs diethyl cyanophosphon…
Catalytic epoxidation using dioxidomolybdenum(VI) complexes with tridentate aminoalcohol phenol ligands
2019
Reaction of the tridentate aminoalcohol phenol ligands 2,4-di-tert-butyl-6-(((2 hydroxyethyl)(methyl)amino)methyl)phenol (H2L1) and 2,4-di-tert-butyl-6-(((1-hydroxybutan-2-yl)amino)methyl)phenol (H2L2) with [MoO2(acac)2] in methanol solutions resulted in the formation of [MoO2(L1)(MeOH)] (1) and [MoO2(L2)(MeOH)] (3), respectively. In contrast, the analogous reactions in acetonitrile afforded the dinuclear complexes [Mo2O2(μ-O)2(L1)2] (2) and [Mo2O2(μ-O)2(L2)2] (4). The corresponding reactions with the potentially tetradentate ligand 3-((3,5-di-tert-butyl-2-hydroxybenzyl)(methyl)amino)propane-1,2-diol (H3L3) led to the formation of the mononuclear complex [MoO2(L3)(MeOH)] (5) in methanol whi…
Oxidovanadium(V) amine bisphenolates as epoxidation, sulfoxidation and catechol oxidation catalysts
2017
Air-stable oxidovanadium(V) complexes with tetradentate amine bisphenolate ligands were made by the reaction of VOSO4·xH2O and ligand precursors in MeOH solutions. Isolated compounds were studied as catechol oxidase models as well as catalysts for epoxidation and sulfoxidation reactions. All compounds can catalyse such oxidation reactions without notable structure-activity correlations. The 51V NMR studies indicate that the complexes turn to the number of different species during the catalytic experiments. peerReviewed
Enantioselective synthesis of 4H-pyranonaphthoquinones via sequential squaramide and silver catalysis
2015
Chemical communications 52(8), 1669-1672(2016). doi:10.1039/C5CC09592A
Phosphasalen group IV metal complexes: synthesis, characterization and ring opening polymerization of lactide.
2020
International audience; We report the synthesis of a series of Zr and Ti complexes bearing phosphasalen which differs from salen by the incorporation of two P atoms in the ligand backbone. The reaction of phosphasalen proligands (1a-1c)H2 with Zr(CH2Ph)4 led to different products depending on the nature of the N,N-linker in the ligand. In case of ethylene-linked phosphasalen, octahedral Zr complex 2a formed as a single stereoisomer in trans geometry. With the phenylene linker, it was shown by dynamic NMR spectroscopy that complex 2b exists as a mixture of trans and cis-β isomers in solution, both enantiomers (Δ and Λ) of the cis-β isomer being in fast equilibrium with respect to the NMR tim…