Search results for "EFF"

The substituent effect of π-electron delocalization in N-methylamino-nitropyridine derivatives: crystal structure and DFT calculations

2020

AbstractThe crystal and molecular structures of 3-(N-methylamino)-2-nitropyridine, 5-(N-methylamino)-2-nitropyridine and 2-(N-methylamino)-5-nitropyridine have been characterized by X-ray diffraction. To perform conformational analysis, the geometries of the compounds as well as their conformers and rotamers were optimized at the B3LYP/6-311++G(3df,3pd) level. The resulting data were used to analyze the π-electron delocalization effect in relation to the methylamino group rotation in ortho-, meta- and para-substitution positions. Quantitative aromaticity indices were calculated based on which we estimated the electronic structures of the analyzed compounds. The substituent effect of the met…

2020

The course of organic chemical reactions is efficiently modelled through the concepts of “electrophiles” and “nucleophiles” (meaning electron-seeking and nucleus-seeking reactive species). On the one hand, an advanced approach of the correlation of the nucleophilicity parameters N and electrophilicity E has been delivered from the linear free energy relationship log k (20 °C) = s(N + E). On the other hand, the general influence of the solvent mixtures, which are very often employed in preparative synthetic chemistry, has been poorly explored theoretically and experimentally, to date. Herein, we combined experimental and theoretical studies of the solvent influence on pyrrolidine nucleophili…

A Molecular Electron Density Theory Study of the Role of the Copper Metalation of Azomethine Ylides in [3 + 2] Cycloaddition Reactions.

2018

The copper metalation of azomethine ylides (AYs) in [3 + 2] cycloaddition (32CA) reactions with electron-deficient ethylenes has been studied within the Molecular Electron Density Theory (MEDT) at the MPWB1K/6-311G(d,p) level, in order to shed light on the electronic effect of the metalation in the course of the reaction. Analysis of the Conceptual Density Functional Theory reactivity indices indicates that the metalation of AYs markedly enhances the nucleophilicity of these species given the anionic character of the AY framework. These 32CA reactions take place through stepwise mechanisms characterized by the formation of a molecular complex. Both nonmetalated and metalated 32CA reactions …

Tetrasubstituted Thieno[3,2- b]thiophenes as Hole-Transporting Materials for Perovskite Solar Cells

2019

Three hole-transporting materials (HTMs) were prepared following a straightforward synthetic route by cross-linking arylamine-based ligands with a simple thieno[3,2-b]thiophene (TbT) core. The novel HTMs were fully characterized with standard techniques to gain insight into their optical and electrochemical properties and were incorporated in solution-processed mesoporous (FAPbI3)0.85(MAPbBr3)0.15 perovskite-based solar cells. The similar molecular structure of the synthesized HTMs was leveraged to investigate the role that the bridging units between the conjugated TbT core and the peripheral arylamine units plays on their properties and thereby on the photovoltaic response. A remarkable po…

Solvent effects on the dimensionality of oxamato-bridged manganese(II) compounds

2018

Two new oxamate-containing manganese(II) complexes, [{Mn(H2edpba)(H2O)2}2]n (1) and [Mn(H2edpba)(dmso)2]∙dmso∙CH3COCH3∙H2O (2) (H4edpba = N,N′-ethylenediphenylenebis(oxamic acid) and dmso = dimethylsulfoxide), have been synthesized and the structures of 1 and 2 were characterized by single crystal X-ray diffraction. The structure of 1 consists of neutral honeycomb networks in which each manganese(II) is six-coordinate by one H2edpba2− ligand and two carboxylate–oxygens from two other H2edpba2− ligands building the equatorial plane. Each manganese is connected to its nearest neighbor through two carboxylate(monoprotonated oxamate) bridges in an anti-syn conformation. A dmso solution of singl…

Dietary and Household Sources of Prenatal Exposure to Polybrominated Diphenyl Ethers (PBDEs) in the INMA Birth Cohort (Spain)

2016

This study looked at predictors of exposure to polybrominated diphenyl ethers (PBDEs) with a focus on dietary and household-level factors. Concentrations of BDE-47, -99, -153, and -209 and their sum (∑PBDEs) were measured in cord serum. Spanish women (n = 541) completed two semiquantitative food frequency questionnaires during the first and third trimesters of pregnancy. The daily mean intake (grams) of eggs, dairy products, meat, cereals and pasta, vegetables and pulses, fruits, shellfish and cephalopods, and fish, and the weekly mean intake (servings) of lean, large oily, other oily, and other fish from both questionnaires were averaged. Information on house size, curtains and carpets at …

Annually resolved δ13Cshell chronologies of long-lived bivalve mollusks (Arctica islandica) reveal oceanic carbon dynamics in the temperate North Atl…

2011

Abstract The ability of the ocean to absorb carbon dioxide is likely to be adversely affected by recent climate change. However, relatively little is known about the spatiotemporal variability in the oceanic carbon cycle due to the lack of long-term, high-resolution dissolved inorganic carbon isotope ( δ 13 C DIC ) data, especially for the temperate North Atlantic, which is the major oceanic sink for anthropogenic CO 2 . Here, we report shell carbon isotope values ( δ 13 C shell ), a potential proxy for δ 13 C DIC , of old-grown specimens of the long-lived bivalve mollusk, Arctica islandica . This paper presents the first absolutely dated, annually resolved δ 13 C shell record from surface …

Dimensionless Stage-Discharge Relationship for a Non-Linear Water Reservoir: Theory and Experiments

2020

In the field of hydrology, stage&ndash

Digital thermal monitoring of the Amazon forest: an intercomparison of satellite and reanalysis products

2015

Remote sensing and climate digital products have become increasingly available in recent years. Access to these products has favored a variety of Digital Earth studies, such as the analysis of the impact of global warming over different biomes. The study of the Amazon forest response to drought has recently received particular attention from the scientific community due to the occurrence of extreme droughts and anomalous warming over the last decade. This paper focuses on the differences observed between surface thermal anomalies obtained from remote sensing moderate resolution imaging spectroradiometer (MODIS) and climatic (ERA-Interim) monthly products over the Amazon forest. With a few e…

Influence of Wind on Suspended Matter in the Water of the Albufera of Valencia (Spain)

2021

Wind is one of the factors that has a great influence on suspended matter in lakes, especially in shallow lagoons. In order to know how wind affects the water in Albufera of Valencia, a shallow coastal lagoon, the measured variables of turbidity and transparency have been correlated with the estimates by processing Sentinel-2 satellite images with the Sen2Cor processor. Data from four years of study show that most of them are light to gentle easterly breezes and moderate to fresh westerly breezes. The results obtained show significant correlations between the measured variables and those obtained from the satellite images for total suspended matter and water transparency and with the averag…