Search results for "Quantum"

The Influence of the Amide Linkage in the FeIII-Binding Properties of Catechol-Modified Rosamine Derivatives

2015

The two new fluorescent ligands RosCat1 and RosCat2 contain catechol receptors connected to rosamine platforms through an amide linkage and were synthesized by using microwave-assisted coupling reactions of carboxyl- or amine-substituted rosamines with the corresponding catechol units and subsequent deprotection. RosCat1 possesses a reverse amide, whereas RosCat2 has the usual oriented amide bond (HNCO vs. CONH, respectively). The ligands were characterized by means of NMR spectroscopy, mass-spectrometry, and DFT calculations and X-ray crystallography studies for RosCat1. The influence of the amide linkage on the photophysical properties of the fluorescent ligands was assessed in different …

The Nonlocal Correlation Density Functional VV10

2015

Abstract In this chapter, we review the most relevant attempts to merge the Vydrov and van Voorhis nonlocal density-dependent functional kernel (VV10) with modern density functionals to accurately describe van der Waals interactions with a reasonable computational cost. The chapter is organized by providing first an introduction of the relevance of van der Waals interactions and the difficulties of common density functionals to describe these forces. Second, the historical developments that eventually give rise to the most modern formulation of the nonlocal density functional VV10 are briefly addressed. Then, an overview of its technical formulation, adjustable parameters, and implementatio…

Influence of operational variables on the photodegradation kinetics of Monuron in aqueous titanium dioxide dispersions

1994

The degradation of Monuron [N′—(4-chlorophenyl)—N, N dimethyl urea] in aqueous TiO 2 dispersions irradiated in the near-UV region has been investigated using a Pyrex batch photoreactor. The influence on the degradation kinetics of pH, initial Monuron concentration and catalyst concentration has been studied. The mineralization of the pollutant was also investigated. Measurements of photon absorbed flows allowed to determine the quantum yield values; they were found to increase by increasing the initial pH of the dispersion.

Quantum-chemistry calculations of surface complex and orbital control in para/ortho toluene alkylation catalyzed by big pore zeolites

1994

Summary By means of MNDO-PM3 semiempirical quantum-chemistry calculations, the mechanism for alkylation of toluene by methanol on two zeolite clusters with Al and Ga as T III has been studied. The process variables controlled through the hypersurface of the reaction were: the distances of methyl group to the cluster of zeolite and to the toluene molecule; and the distances of the hydrogen atom of the toluene to be transfered to the zeolite cluster and to the toluene. The energetic factor associated with the electronic interaction between the molecular orbitals (LUMO of the zeolite-methoxy and HOMO of toluene) have been calculated by a PMO analysis for two geometries: the transition state an…

Extraction Chromatographic Behavior of Rf, Zr, and Hf in HCl Solution with Styrenedivinylbenzene Copolymer Resin Modified by TOPO (trioctylphosphine …

2010

It is of great interest to study chemical properties of the transactinide elements with atomic numbers (Z) ≥ 104. One of the most important subjects is to establish the position of the elements at the extreme end of the periodic table. To this end we perform studies of chemical properties of these transactinides and compare them with those of their lighter homologues and with the ones expected from extrapolations in the periodic table. So far, chromatographic studies of the transactinides have provided experimental proof of placing rutherfordium (Rf, Z = 104) through hassium (Hs, Z = 108) into groups 4 to 8, respectively. 1-10 Quite recently, copernicium (Cn, Z = 112) has been shown to be a…

Steady-state fluorescence emission studies on polyazacyclophane macrocyclic receptors and on their adducts with hexacyanocobaltate(III)

1995

The steady-state fluorescence emission spectra of the azacyclophanes 2,5,8,11-tetraaza[12] paracyclophane (L1), 2,6,9,13-tetraaza[14]paracyclophane (L2), 14,15,17,18-tetramethyl-2,5,8,11-tetraaza[12]paracyclophane (L3) and 16,17,19,20-tetramethyl-2,6,9,13-tetraaza[14]paracyclophane (L4) as a function of pH have been measured. The fully protonated species of each cyclophane gives the highest fluorescence-emission quantum yield. The shapes of the titration curves have been explained by the existence of an electron-transfer quenching effect from a non-protonated amine to the benzene chromophore. This effect is greater for macrocycles in which the first deprotonated amine group is closer to the…

(1Z,3Z)-1,4-Di(pyridin-2-yl)buta-1,3-diene-2,3-diol:  The Planar Highly Conjugated Symmetrical Enediol with Multiple Intramolecular Hydrogen Bonds

2002

1H, (13)C, and (15)N NMR spectral data show that in chloroform solution (1Z,3Z)-1,4-di(pyridin-2-yl)buta-1,3-diene-2,3-diol, OO, is in ca. 9:1 equilibrium with (3Z)-3-hydroxy-1,4-di(pyridin-2-yl)but-3-en-2-one, OK, while no 1,4-di(pyridin-2-yl)-2,3-butanedione, KK, was detected. The species present in the tautomeric mixture were identified by comparing their experimental chemical shifts with those known for similar compounds as well as with the theoretically calculated (GIAO-HF/DFT) values. Ab initio calculations show that OK and especially the highly conjugated OO forms are preferred in the tautomeric mixtures both in vacuo and in chloroform solution. Comparison of experimental (Arrhenius)…

Recent Advances in the Field of Naturally Occurring 5,6-Dihydropyran-2-ones

2013

Micellar fluorescence enhancement of carbamate pesticides

1990

Abstract Different studies have been carried out on the interaction of carbamate pesticides, such as carbofuran and carbaryl, with nonionic and anionic surfactants. Micellar fluorescence enhancements (MEF) of 15–20 for carbofuran in the presence of fatty alcohol ethylene oxide condensates, and of 3.7–8.6 in the presence of anionic surfactants at neutral pH have been obtained. Carbaryl does not interact with surfactants, but when it is hydrolysed to 1-naphthol, MEF values of the order of 2 are obtained in the presence of nonylphenol ethylene oxide condensates. The experimental parameters have been optimized in order to obtain maximum fluorescence. The mechanisms involved in the fluorescence …

NIR laser scanning microscopy for photophysical characterization of upconversion nanoparticles and nanohybrids

2021

Photophysical characterization of upconversion nanoparticles (UCNPs) and nanohybrids (UCNHs) is more challenging than that of down-conversion nanomaterials. Moreover, it is still difficult to gain knowledge about the homogeneity of the sample and colocalization of emissive chromophores and nanoparticles in nanohybrids. Near infrared laser scanning microscopy (NIR-LSM) is a well-known and useful imaging technique, which enables excitation in the NIR region and has been extensively applied to optical fluorescence imaging of organic fluorophores and nanomaterials, such as quantum dots, which exhibit a short-lived emission. NIR-LSM has recently been used to determine the empirical emission life…