Computational Investigation (computational + investigation)

Distribution by Scientific Domains
Distribution within Chemistry

Selected Abstracts

Asymmetric Lithiation of Boron Trifluoride-Activated Aminoferrocenes: An Experimental and Computational Investigation

Costa Metallinos
Abstract Tertiary aminoferrocenes complexed to boron trifluoride (BF3) are shown to undergo asymmetric lithiation with alkyllithiums in the presence of bulky chiral 1,2-diaminocyclohexane ligands. This reaction represents the first BF3 -activated asymmetric lithiation of a prochiral aromatic amine and the first such transformation to be mediated by a chiral diamine other than (,)-sparteine. The process provides rapid access to a broad range of enantiomerically enriched 2-substituted-1-aminoferrocenes, including derivatives with uncommon substitution patterns that are of interest in catalysis. The enantioselectivity of the process is high enough (87:13 to 91:9 er) to allow for isolation of single enantiomers of several products after simple recrystallization as either the free aminoferrocenes or their ammonium fluoroborate salts. Both antipodes of the planar chiral 2-substituted-1-aminoferrocene products are accessible, as confirmed by single crystal X-ray diffraction analysis of two compounds with opposite relative stereochemistry. Single-point calculation of thirty-two different transition states of the reaction at the M06-2X/6-311+g(2d,2p) level produced a computational model that correctly predicted both the sense and extent of chiral induction. Three factors appeared to play important roles in determining enantioinduction during lithiation of BF3 -complexed tertiary aminoferrocenes: (i) the maintenance of a highly organized eight-membered ring transition state; (ii) the existence of a strong Li,,,F contact which placed the chiral diamine ligand in close proximity to the ferrocene substrate; (iii) the orientation of the sterically demanding N -alkyl groups of the chiral diamine additives, either away or towards, the aminoferrocene and the alkyllithium. The model may serve as a predictive tool for the rational design of new ligands for this and related asymmetric lithiations. [source]

ChemInform Abstract: [Ir(COD)Cl]2 as a Catalyst Precursor for the Intramolecular Hydroamination of Unactivated Alkenes with Primary Amines and Secondary Alkyl- or Arylamines: A Combined Catalytic, Mechanistic, and Computational Investigation.

CHEMINFORM, Issue 28 2010
Kevin D. Hesp
Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source]

Computational Investigation of HIO and HIO2 Isomers

CHEMINFORM, Issue 16 2004
Nebojsa Begovic
Abstract For Abstract see ChemInform Abstract in Full Text. [source]

Computational Investigation of Hydrogen Adsorption by Alkali-Metal-Doped Organic Molecules: Role of Aromaticity

CHEMPHYSCHEM, Issue 2 2009
Kancharlapally Srinivasu
Abstract Hydrogen storage: Simple organic molecular systems (CnHn, n=4, 5, 6, 8) are proposed for hydrogen storage purposes based on the concept of aromaticity. The adsorption of hydrogen is attributed to pronounced charge transfer from the sodium atom (green, see picture) to the organic systems and the electrostatic interaction between the ion and hydrogen molecules. Theoretical studies on hydrogen adsorption in small organic molecular systems, such as cyclobutadiene (C4H4), the cyclopentadienyl radical (C5H5), benzene (C6H6), and cyclooctatetraene (C8H8) and their metal-doped modifications, are carried out. Our results reveal that the simple van der Waals surfaces of pure organic molecules are not good enough for hydrogen adsorption due to the weak interaction between hydrogen molecules and the organic molecular surface. However, doping of alkali-metal atoms in the above organic molecular systems increases their hydrogen adsorption ability significantly, mainly due to electron transfer from the metal atom to the carbon surface. This charged surface created around the metal atom is found to enhance the hydrogen adsorption capacity of the complex considerably, both in terms of interaction energy and the number of adsorbed hydrogen molecules, with a hydrogen adsorption capacity ranging from 10 to 12 wt,%. The role of aromaticity in such molecular systems is important in stabilizing these ionized organo-alkali-metal complexes. [source]

Computational Investigation of 1,3-H and 1,5-H Shifts in Isomerization of Enol Acetate of 2-Aceto-1,3-cyclohexanedione

Yanhua WANG
Abstract The mechanism of the isomerization of the enol acetate of 2-aceto-1,3-cyclohexanedione has been discussed in detail. The possible 1,3-H and 1,5-H shifts in isomerization were investigated systematically. It seems that this mechanism includes two successive 1,5-sigmatropic shifts, i.e. 1,5-acetyl and 1,5-H shifts. Density functional theory calculations have been performed to evaluate the reasonability of the proposed mechanisms. The effect of the solvent upon the rate-determining steps has been also considered. In addition, the relative stabilities of the reactant, the product as well as the intermediates in the proposed mechanism have been examined and discussed. [source]

An Empirical and Computational Investigation of Perceiving and Remembering Event Temporal Relations

Shulan Lu
Abstract Events have beginnings, ends, and often overlap in time. A major question is how perceivers come to parse a stream of multimodal information into meaningful units and how different event boundaries may vary event processing. This work investigates the roles of these three types of event boundaries in constructing event temporal relations. Predictions were made based on how people would err according to the beginning state, end state, and overlap heuristic hypotheses. Participants viewed animated events that include all the logical possibilities of event temporal relations, and then made temporal relation judgments. The results showed that people make use of the overlap between events and take into account the ends and beginnings, but they weight ends more than beginnings. Neural network simulations showed a self-organized distinction when learning temporal relations between events with overlap versus those without. [source]

Computational Investigations on the General Reaction Profile and Diastereoselectivity in Sulfur Ylide Promoted Aziridination

Deepa Janardanan
Abstract Mechanism and diastereoselectivity of sulfur ylide promoted aziridination reactions were studied by density functional theory with inclusion of solvent effects through the continuum solvation model. The general reaction pathway was modeled for the addition of substituted sulfur ylides (Me2S+CH,R) to an aldimine ((E)-methyl ethylidenecarbamate, MeHCNCO2Me). The nature of the substituents on the ylidic carbon atom substantially affects the reaction profile. The stabilized (R=COMe) and semistabilized (R=Ph) ylides follow a cisoid addition mode leading to trans aziridines via anti betaine intermediates. The simplest model ylide (unstabilized, R=H) underwent cisoid addition in a similar fashion. In the case of stabilized ylides product diastereoselectivity is controlled by the barriers of the elimination step leading to the 2,3- trans aziridine, whereas it is decided in the addition step in the case of semistabilized ylides. The importance of steric and electronic factors in diastereoselective addition (2 and 5) and elimination (5) transition states was established. Comparison of results obtained with the gas-phase optimized geometries and with the fully optimized solvent-phase geometries reveals that the inclusion of solvent effects does not bring about any dramatic changes in the reaction profiles for all three kinds of ylides. In particular, diastereoselectivity for both kinds of ylides was found to be nearly the same in both these approaches. [source]

Computational investigation of the mechanisms of particle separation and "fish-hook" phenomenon in hydrocyclones

AICHE JOURNAL, Issue 7 2010
B. Wang
Abstract The motion of solid particles and the "fish-hook" phenomenon in an industrial classifying hydrocyclone of body diameter 355 mm is studied by a computational fluid dynamics model. In the model, the turbulent flow of gas and liquid is modeled using the Reynolds Stress Model, and the interface between the liquid and air core is modeled using the volume of fluid multiphase model. The outcomes are then applied in the simulation of particle flow described by the stochastic Lagrangian model. The results are analyzed in terms of velocity and force field in the cyclone. It is shown that the pressure gradient force plays an important role in particle separation, and it balances the centrifugal force on particles in the radial direction in hydrocyclones. As particle size decreases, the effect of drag force whose direction varies increases sharply. As a result, particles have an apparent fluctuating velocity. Some particles pass the locus of zero vertical velocity (LZVV) and join the upward flow and have a certain moving orbit. The moving orbit of particles in the upward flow becomes wider as their size decreases. When the size is below a critical value, the moving orbit is even beyond the LZVV. Some fine particles would recircuit between the downward and upward flows, resulting in a relatively high separation efficiency and the "fish-hook" effect. Numerical experiments were also extended to study the effects of cyclone size and liquid viscosity. The results suggest that the mechanisms identified are valid, although they are quantitatively different. 2009 American Institute of Chemical Engineers AIChE J, 2010 [source]

Tris(4-cyanophenyl)amine: Simple Synthesis via Self-assembly; Strong Fluorescence in Solution, Nano/microcrystals, and Solid,

A. Patra
Abstract The threefold symmetric molecule, tris(4-cyanophenyl)amine (TCPA) is synthesized from 4-fluorocyanobenzene by treatment with potassium carbonate in dimethylsulfoxide; the occurrence of the reaction without any amine reagent suggests the involvement of a novel self-assembly process. A reprecipitation strategy provides stable colloids containing highly monodisperse nano/microcrystals with well-defined cubic morphology and sizes tunable from 250 to 500,nm. The solution, colloid, and solid states of TCPA exhibit strong blue fluorescence; the colloid shows dual emission with an unusually small Stokes shift. Computational investigations are carried out on the molecule and supramolecular assemblies derived from the crystal structure. Coupled with detailed spectroscopic studies, they show that the emission in the colloidal and solid states can be attributed to energy levels resulting from the intermolecular interactions within different aggregation motifs in the condensed phase and energy cascades between them. The computations also reveal the presence of cooperative interactions in the molecular crystal contributing to its high thermal stability. The strong light emission exhibited by TCPA, concurrently in the solution, nano/microcrystal, and solid states establishes it as a novel molecular material of potential practical utility; it has led to the exploration of the underlying mechanism that describes the phenomena observed in the different physical states. [source]

Reaction of Carboxylic Acids with Isocyanides: A Mechanistic DFT Study

Tommaso Marcelli
Abstract We present a computational investigation of the reaction between isocyanides and carboxylic acids. Our results indicate that this reaction begins with a stereoselective concerted ,-addition of the acid to the isocyanide, leading exclusively to a Z -acyl imidate. Isomerization to the E isomer and successive rate-limiting 1,3 O,N acyl migration yields an N -formyl imide. The calculated barriers are in good agreement with the experimental reaction conditions. Our results might provide an explanation for the peculiar reactivity observed when this reaction is carried out in a self-assembled capsule. ( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source]

Experimental and computational investigation of three-dimensional mixed-mode fatigue

S. C. Forth
Experimental and computational methods were developed to model three-dimensional (3-D) mixed-mode crack growth under fatigue loading with the objective of evaluating proposed 3-D fracture criteria. The experiments utilized 7075-T73 aluminium forgings cut into modified ASTM E740 surface crack specimens with pre-cracks orientated at angles of 30, 45 and 60 in separate tests. The progress of the evolving fatigue crack was monitored in real time using an automated visualization system. In addition, the amplitude of the loading was increased at prescribed intervals to mark the location of the 3-D crack front for post-test inspection. In order to evaluate proposed crack growth equations, computer simulations of the experiments were conducted using a 3-D fracture model based on the surface integral method. An automatic mesher advanced the crack front by adding a ring of elements consistent with local application of fracture criteria governing rate and direction of growth. Comparisons of the computational and experimental results showed that the best correlation was obtained when KII and KIII were incorporated in the growth rate equations. [source]

Optimizing the formula of rare earth-bearing materials: A computational chemistry investigation

Marjorie Bertolus
Abstract We present a computational investigation into the nature of bonds formed by rare earth elements (REE) in materials. This study focuses on the incorporation of neodymium in minerals called apatites, which are derived from fluorapatite: Ca10(PO4)6F2. These minerals, which allow many substitutions on all three Ca, P, and F sites, are considered as potential host phases for radioactive elements separated from nuclear waste. Nd and trivalent actinides have very similar physical and chemical properties, and Nd is not radioactive and much more easily handled. It is therefore very often used as a surrogate for actinides with oxidation degree three in experimental studies. Several formulas can be considered to substitute Nd3+ to Ca2+ and maintain charge balance of the apatite. Existing experimental and theoretical studies, however, mostly concern the Ca9Nd(PO4)5SiO4F2 formula, where the Nd incorporation is compensated by the replacement of one PO by a SiO group. Moreover, only the cation position has been studied, whereas the silicate position and its influence on stability are unknown. We present a more general investigation of possible charge compensations on the one hand, and of the various resulting configurations on the other. All possible configurations of the two formulas Ca9Nd(PO4)5 SiO4F2 and Ca8NdNa(PO4)6F2 have been considered. Calculations have been performed within the framework of density functional theory (DFT). A computation scheme that permits good accuracy in these systems within reasonable computation times is determined. The results obtained for cohesion energies, geometries, and electronic densities are discussed. As for the formulation, it is shown that the Ca8NdNa(PO4)6F2 formula is less stable than the fluorapatite, while Ca9Nd(PO4)5 SiO4F2 is more stable. For the structures, it is found that Nd substitutes preferably in the second cationic site. Moreover, the most stable structures exhibit the shortest Na,Nd or Nd,Si distances. Local charge balance therefore seems favorable. Then, it is shown that Nd forms covalent bonds both in apatite and in britholite, while Na forms ionic bonds. Finally, a first correlation between the material stability and the covalent character of the bonds formed is established. 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 [source]

Simulation and experiments of mixing and segregation in a tote blender

AICHE JOURNAL, Issue 3 2005
O. S. Sudah
Abstract Experimental and computational investigation of mixing and segregation of granular material in a tote blender was carried out. The discrete element method (DEM) was used to simulate flow of spherical, free-flowing particles where the results of the computations were compared to blending. Computational results are compared to blending experiments of monodisperse and bidisperse systems using spherical glass beads in a 1:1 scale. Although some discrepancies were observed, DEM simulations illustrated good agreement with experimentally measured mixing and segregation rates for different fill levels and loading conditions. The effects of blender geometry on particle velocities and flow patterns were examined using DEM. The presence of a hopper and bin section, as well as the axial offset proved to introduce greater axial mixing rates that would be expected from pure dispersion. Vibrated experiments showed better agreement than not-vibrated experiments, indicating that modeling of friction forces needs to be further improved to enhance the accuracy of DEM methods. 2005 American Institute of Chemical Engineers AIChE J, 51: 836,844, 2005 [source]

Solvent effects on the conformational distribution and optical rotation of ,-methyl paraconic acids and esters,

CHIRALITY, Issue 5 2006
S. Coriani
Abstract A computational investigation of the optical rotatory power of cis and trans 2-methyl-5-oxo-tetrahydro-3-furancarboxylic acids and the corresponding methyl and ethyl esters is presented. Solvent effects on both the conformational space and the rotatory power are analyzed by comparing results obtained in vacuo with those computed,using the Polarizable Continuum Model,in methanol. A comparison with experimental observations for the optical rotatory power of the title compounds in methanol is also carried out, in a few cases also for several wavelengths. Agreement between theory and experiment is in all cases excellent, in particular when solvent effects are included both in the geometry optimization and in the calculation of the OR, thus confirming the validity of the computational procedure adopted, even for this challenging family of floppy molecules. Chirality, 2006. 2006 Wiley-Liss, Inc. [source]

Experimental Physiology ,Review Article: Tissue capillary supply , it's quality not quantity that counts!

Stuart Egginton
This article explores how common misunderstandings about the microcirculation , that capillary supply varies directly with O2 demand, that local capillary supply in muscle is determined by fibre type and that it is appropriate to model capillary distribution as either random or in a fixed geometric pattern , arise from quantifying capillarity by simple measures of quantitative extent, rather than the more functionally relevant qualitative distribution. We show that the latter approach reveals exquisite control of angiogenesis that determines the location of new vessels with astonishing accuracy, motivating a reappraisal of the physiological remodelling process and a new approach to computational investigations into peripheral O2 transport. [source]

The mechanisms of collisional activation of ions in mass spectrometry

Paul M. Mayer
Abstract This article is a review of the mechanisms responsible for collisional activation of ions in mass spectrometers. Part I gives a general introduction to the processes occurring when a projectile ion and neutral target collide. The theoretical background to the physical phenomena of curve-crossing excitation (for electronic and vibrational excitation), impulsive collisions (for direct translational to vibrational energy transfer), and the formation of long-lived collision intermediates is presented. Part II highlights the experimental and computational investigations that have been made into collisional activation for four experimental conditions: high (>100 eV) and intermediate (1,100 eV) center-of-mass collision energies, slow heating collisions (multiple low-energy collisions) and collisions with surfaces. The emphasis in this section is on the derived post-collision internal energy distributions that have been found to be typical for projectile ions undergoing collisions in these regimes. 2009 Wiley Periodicals, Inc., Mass Spec Rev 28:608,639, 2009 [source]

The Stereospecific Ligand Exchange at a Pseudo-Benzylic T -4 Iridium Centre in Planar-Chiral Cycloiridium (,6 -Arene)tricarbonylchromium Complexes

Jean-Pierre Djukic Dr.
Abstract The stereospecificity of ligand exchange at the IrIII centre of a cycloiridium arenetricarbonylchromium complex has been established experimentally by various analytical methods as well as by X-ray diffraction structural analysis and computational investigations. Two new cases of phenyl and methyl iridium(III) complexes have been prepared by reaction of (,)-chlorido{2-[(tricarbonyl)(,6 -phenylene-,C1,)chromium(0)]pyridine-,N}(pentamethylcyclopentadienyl)iridium(III) with PhMgBr and MeMgBr. The determining influence of electrostatic repulsion has been established by means of density functional theory at the Becke,Perdew/TZP(ZORA) level by using, among other means, energy partitioning analysis. It is also shown that the Cr(CO)3 fragment is likely to ease the ionic cleavage of the IrCl bond in chlorido cycloiridium tricarbonylchromium complexes in a way similar to that already established for the solvolysis of benzyl halide complexes, that is, through a direct interaction of the Cr0 centre with the cationic IrIII centre. [source]