Search results for "TRIP"
showing 10 items of 2134 documents
Influence of lipid physical state on the in vitro digestibility of emulsified lipids.
2008
The objective of this study was to investigate the influence of the physical state of emulsified lipids on their in vitro digestibility by pancreatic lipase. A 10 wt % tripalmitin oil-in-water emulsion stabilized by sodium dodecyl sulfate (0.9 wt % SDS) was prepared at a temperature (>70 degrees C) above the melting point of the lipid phase (T(m) approximately 60 degrees C). A portion of this emulsion was cooled to a temperature (0 degrees C for 15 min) well below the crystallization temperature of the emulsified lipid (T(c) approximately 22 degrees C) and then warmed to 37 degrees C so as to have completely solid lipid particles. Another portion of the emulsion was directly cooled from 70 …
Assessment of the Potential Energy Hypersurfaces in Thymine within Multiconfigurational Theory: CASSCF vs. CASPT2
2016
The present study provides new insights into the topography of the potential energy hypersurfaces (PEHs) of the thymine nucleobase in order to rationalize its main ultrafast photochemical decay paths by employing two methodologies based on the complete active space self-consistent field (CASSCF) and the complete active space second-order perturbation theory (CASPT2) methods: (i) CASSCF optimized structures and energies corrected with the CASPT2 method at the CASSCF geometries and (ii) CASPT2 optimized geometries and energies. A direct comparison between these strategies is drawn, yielding qualitatively similar results within a static framework. A number of analyses are performed to assess t…
Characterization of Pumice-Supported Ag–Pd and Cu–Pd Bimetallic Catalysts by X-Ray Photoelectron Spectroscopy and X-Ray Diffraction
1999
Bimetallic Ag–Pd and Cu–Pd catalysts supported on pumice have been prepared in order to be used in the selective hydrogenation of dienes. The catalysts were obtained by the classical impregnation method and in the case of the Cu–Pd system also by organometallic precursors. They were analysed by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). XPS allowed us to determine the surface distribution and chemical state of the two elements; XRD yielded the lattice parameters and allowed us to establish the possible formation of alloys. The two bimetallic systems behave differently. In the case of the Ag-Pd catalysts, Pd particles covered by silver atoms along with highly dispers…
Evidence of intramolecular electron transfer between two metallic atoms in a bimetallic complex by electrochemical methods
2005
The electrochemical properties of the monomeric complex [(η5-C5H5)(μ-η5:η1-C5H4(CH2)2P(C6H5)2TiCl2] 1 and the heterobimetallic complex [(η5-C5H5)(μ-η5:η1-C5H4(CH2)2P(C6H5)2TiCl2][RuCl2(C6H4(CH3)(C3H7))] 2 have been studied by cyclic voltammetry, controlled potential electrolysis and rotating disk electrode voltammetry. An unexpected electron transfer between the two heterobimetallic atoms has been observed. This transfer takes place via an intramolecular interaction, hence via a chloride bridge. Electrochemical simulation has been carried out to verify experimental results and to obtain the kinetic constant of the proposed square scheme.
A hollow tetrahedral cage of hexadecagold dianion provides a robust backbone for a tuneable sub-nanometer oxidation and reduction agent via endohedra…
2007
We show, via density functional theory calculations, that dianionic Au16(2-) cluster has a stable, hollow, Td symmetric cage structure, stabilized by 18 delocalized valence electrons. The cage maintains its robust geometry, with a minor Jahn-Teller deformation, over several charge states (q = -1,0,+1), forming spin doublet, triplet and quadruplet states according to the Hund's rules. Endohedral doping of the Au16 cage by Al or Si yields a geometrically robust, tuneable oxidation and reduction agent. Si@Au16 is a magic species with 20 delocalized electrons. We calculate a significant binding energy for the anionic Si@Au16/O2- complex and show that the adsorbed O2 is activated to a superoxo-s…
On the relaxation mechanisms of 6-azauracil
2011
The nonadiabatic photochemistry of 6-azauracil has been studied by means of the CASPT2//CASSCF protocol and double-ζ plus polarization ANO basis sets. Minimum energy states, transition states, minimum energy paths, and surface intersections have been computed in order to obtain an accurate description of several potential energy hypersurfaces. It is concluded that, after absorption of ultraviolet radiation (248 nm), two main relaxation mechanisms may occur, via which the lowest (3)(ππ*) state can be populated. The first one takes place via a conical intersection involving the bright (1)(ππ*) and the lowest (1)(nπ*) states, ((1)ππ*/(1)nπ*)(CI), from which a low-energy singlet-triplet crossin…
On the electronic structure of a dianion, a radical anion, and a neutral biradical (HB)11CCCC(BH)11 carborane dimer
2009
Abstract The electronic structure of a neutral, a radical anion, and a dianion carborane dimer connected via an acetylenic bridge unit (HB) 11 C C C C(BH) 11 is analyzed by quantum chemical methods. Geometries, relative stabilities, and singlet–triplet gaps are determined in the neutral and dianion species for the lowest-lying singlet and triplet states and for the doublet ground state in the radical anion. As for the recently studied biradical compounds derived from o -carborane, m -carborane and p -carborane [J. Chem. Theory Comput. 4 (2008) 1338] via double hydrogen abstraction, the neutral dimeric compound displays a biradical ground-state structure in which both singlet and triplet sta…
Molecule Isomerism Modulates the Diradical Properties of Stable Singlet Diradicaloids
2019
Inclusion of quinoidal cores in conjugated hydrocarbons is a common strategy to modulate the properties of diradicaloids formed by aromaticity recovery within the quinoidal unit. Here we describe an alternative approach of tuning of diradical properties in indenoindenodibenzothiophenes upon anti → syn isomerism of the benzothiophene motif. This alters the relationship of the S atom with the radical center from linear to cross conjugation yet retains the same 2,6-naphtho conjugation pattern of the rearomatized core. We conduct a full comparison between the anti and syn derivatives based on structural, spectroscopic, theoretical, and magnetic measurements, showing that these systems are stabl…
Ultraviolet luminescence of ScPO4, AlPO4 and GaPO4 crystals.
2013
The luminescence of self-trapped excitons (STEs) was previously observed and described for the case of tetragonal-symmetry ScPO4 single crystals. The subject band in this material is situated in the UV spectral range of ?210?nm or ?5.8?eV. In the present work, we are both expanding this earlier luminescence study and seeking to identify similar luminescence phenomena in other orthophosphate crystals, i.e., AlPO4 and GaPO4. These efforts have proven to be successful?in spite of the structural differences between these materials and ScPO4. Specifically we have found that for AlPO4 and GaPO4, in addition to an ?-quartz-like STE, there is a UV luminescence band that is similar in position and d…
Self-trapped exciton luminescence in crystalline α-quartz under two-photon laser excitation
2003
Abstract The luminescence of pure crystalline α-quartz is studied under pulsed ArF laser excitation. The luminescence parameters obtained correspond well with those of self-trapped excitons (STEs) in α-quartz, indicating that the excitation process is two-photon. The efficiency of two-photon excitation is of the same order of magnitude as the one-photon excitation of sodium salicylate. The STE luminescence decay kinetics and their temperature dependence under photoexcitation were recorded with higher accuracy than previously. Changes in the decay kinetics with temperature are explained by the splitting of the STE triplet state in zero magnetic field and are analyzed with the assumption of t…