Search results for "LOAD"
showing 10 items of 1967 documents
Transient and Steady-State Radiation Response of Phosphosilicate Optical Fibers: Influence of H2 Loading
2019
The radiation response of a phosphorus-doped multimode optical fiber is investigated under both transient (pulsed X-rays) and steady-state ( $\gamma $ - and X-rays) irradiations. The influence of a H2 preloading on the fiber radiation-induced attenuation (RIA) in the 300–2000-nm wavelength range has been characterized. To better understand the impact of this treatment, online behaviors of fiber samples containing different amounts of gas are compared from glass saturation (100%) to less than 1%. In addition to these in situ experiments, additional postirradiation spectroscopic techniques have been performed such as electron paramagnetic resonance or luminescence measurements to identify the…
Understanding the role of the Lewis acid catalyst on the 1,3-dipolar cycloaddition of N-benzylideneaniline N-oxide with acrolein: a DFT study
2007
Abstract The Lewis acid (LA) catalyzed 1,3-dipolar cycloaddition of N -benzylideneaniline N -oxide with acrolein has been studied using DFT calculations. Coordination of AlCl 3 to the acrolein oxygen atom produces a drastic change in the mechanism along the more favorable meta reactive channel. The process is characterized by a strong nucleophile/electrophile interaction allowing the formation of a zwitterionic intermediate, a Michael-type addition. The subsequent ring closure constitutes the rate-determining step. The energies obtained with the inclusion of solvent effect by means of the polarizable continuum model are in good agreement with experimental findings. Analysis of the global an…
A condensed-to-atom nucleophilicity index. An application to the director effects on the electrophilic aromatic substitutions
2009
Abstract The local nucleophilicity of simple substituted aromatic systems is shown to be described on a quantitative basis by using a condensed-to-atoms nucleophilicity index. This quantity constitutes an extension of the global nucleophilicity descriptor, N introduced for reagents in cycloaddition reactions and other organic molecules [Journal of Organic Chemistry 73 (2008) 4615–4624; Journal of Molecular Structure (THEOCHEM) 865 (2008) 68–72]. The local projection N k is performed on the basis of the normalization condition of the Fukui functions. It is shown that such a simple index provides useful clues about the director effects of the substituents on the electrophilic aromatic substit…
Coupling of Azomethine Ylides with Nitrilium Derivatives ofcloso-Decaborate Clusters: A Synthetic and Theoretical Study
2012
The azomethine ylides p-R3C5H4N+CH−COC6H4R2-p (3 a: R3=H, R2=H, X=Br; 3 b: R3=H, R2=Me, X=I; 3 c: R3=H, R2=OMe, X=I; 3 d: R3=H, R2=F, X=I; 3 e: R3=Me, R2=Me, X=Br) react with the nitrile functionality of the closo-decaborate clusters [Bun4N][B10H9(NCR1)] (1 a: R1=Me; 1 b: R1=Et; 1 c: R1=Ph) in a CH3NO2 solution under mild conditions (20–25 °C, 2 min) to afford selectively products of the nucleophilic addition (ca. quantitative yields based on NMR analysis in [D6]DMSO, 71–87 % yield of isolated products). These products are the borylated enamino ketones as the salts bearing exclusively a tetrabutylammonium cation [Bun4N][B10H9{NCR1=C(N+C5H4R3-p)COC6H4R2-p}] (4 a–h,k–n) or the mixed salts [Bu…
1,4-Benzoquinones with Styryl Substituents
2002
2-Styryl-1,4-benzoquinone (1) and compounds 2 and 3 containing 1 as a substructure all proved to be highly reactive towards thermal or photochemical [4π + 2π] cyclodimerization reactions. Chemo-, regio- and stereoselective processes lead to dimers (compounds 1−10), which can undergo secondary reactions consisting of the addition of nucleophiles combined with a twofold keto-enol tautomerism (10 ⇄ 12). An alternative process is dehydrogenation/oxidation followed by an intramolecular [4π + 2π] cycloaddition (10 ⇄ 11). The same selective [4π + 2π] cyclodimerization can be observed in solution upon irradiation (e.g., 1a ⇄ 10a), in contrast to irradiation in the crystalline state which yields a […
A DFT study of the domino reactions between imidazole NHC, ketenimines and DMAD or MP acetylene derivatives yielding spiro-pyrroles
2014
Abstract The domino reactions of imidazole carbene 9, ketenimine 10 and DMAD 5 or MP 7 to yield the formal [3+2] cycloadducts 12 or 14 have been investigated using DFT methods at the B3LYP/6-31G* level. These domino reactions are initialized by the nucleophilic attack of imidazole 9 on ketenimine 10 to yield the zwitterionic intermediate 11. The second reaction is a formal [3+2] cycloaddition (32CA) reaction between the zwitterionic intermediate 11 and acetylene carboxylates DMAD 5 or MP 7 yielding spiro-pyrroles 12 and 14. These formal 32CA reactions are initialized by the nucleophilic attack of the N3 nitrogen of intermediate 11 on the most electrophilic centres of these acetylene derivat…
MANAGEMENT OF PSYCHOSOCIAL RISKS IN THE EDUCATIONAL SECTOR OF LATVIA
2019
Risk management is gaining acknowledgement in organisational management due to the benefits it brings with it, such as ability of managers to forecast possible threats and plan the most appropriate prevention measures. Psychosocial risk group is one of the largest risk group types and is related to the aspects of staff overburning, lack of employee motivation, health problems due to stress, etc. Study carried in Latvia about risk management showed that psychosocial risks are significant for educational institutions. Empirical research carried out in Latvia has shown that the top risks perceived by the education sector professionals in Latvia are overloading of employees and lack of employee…
A correction method for the analysis of continuous linear one-dimensional systems under moving loads
2008
A new correction procedure for dynamic analysis of linear, proportionally damped, continuous systems under traveling concentrated loads is proposed; both cases of non-parametric (moving forces) and parametric (moving mass) loads are considered. Improvement in the evaluation of the dynamic response is obtained by separating the contribution of the low-frequency (LF) modes from that of the high-frequency (HF) modes. The former is calculated, as usual, by classical modal analysis, while the latter is taken into account using a new series expansion of the corresponding particular solution. The advantage of the suggested method is immediately shown in the calculation of the stress distribution s…
Seagrass ecosystem response to long-term high CO2 in a Mediterranean volcanic vent
2014
We examined the long-term effect of naturally acidified water on a Cymodocea nodosa meadow growing at a shallow volcanic CO2 vent in Vulcano Island (Italy). Seagrass and adjacent unvegetated habitats growing at a low pH station (pH = 7.65 ± 0.02) were compared with corresponding habitats at a control station (pH = 8.01 ± 0.01). Density and biomass showed a clear decreasing trend at the low pH station and the below- to above-ground biomass ratio was more than 10 times lower compared to the control. C content and delta 13C of leaves and epiphytes were significantly lower at the low pH station. Photosynthetic activity of C. nodosa was stimulated by low pH as seen by the significant increase in…
Homogeneous Metal-Based Catalysis in Supercritical Carbon Dioxide as Reaction Medium
2016
Above 31.1 degrees C and 73.8 bar, carbon dioxide reaches the supercritical state, being transformed into a fluid (scCO(2)) that has attracted interest in the last few decades as reaction medium for several transition-metal-catalyzed organic transformations. The main feature of this fluid rests on its capability to dissolve large amounts of other gases such as hydrogen, carbon monoxide, ethylene, or even methane and light alkanes. In this manner, very high concentrations of these reactants are available for catalysis. In this contribution a review of the main achievements of the use of transition-metal complexes as catalysts in scCO(2) is presented.