Effects of Fuel Lewis Number on Localised Forced Ignition of Turbulent Mixing Layers

The influences of fuel Lewis number Le _F on localised forced ignition of inhomogeneous mixtures are analysed using three-dimensional compressible Direct Numerical Simulations (DNS) of turbulent mixing layers for Le _F  = 0.8, 1.0 and 1.2 and a range of different root-mean-square turbulent velocity fluctuation u′ values. For all Le _F cases a tribrachial flame has been observed in case of successful ignition. However, the lean premixed branch tends to merge with the diffusion flame on the stoichiometric mixture fraction isosurface at later stages of the flame evolution. It has been observed that the maximum values of temperature and reaction rate increase with decreasing Le _F during the period of external energy addition. Moreover, Le _F is found to have a significant effect on the behaviours of mean temperature and fuel reaction rate magnitude conditional on mixture fraction values. It is also found that reaction rate and mixture fraction gradient magnitude \(\vert \nabla \xi \vert \) are negatively correlated at the most reactive region for all values of Le _F explored. The probability of finding high values of \(\vert \nabla \xi \vert \) increases with increasing Le _F . For a given value of u′, the extent of burning decreases with increasing Le _F . A moderate increase in u′ gives rise to an increase in the extent of burning for Le _F  = 0.8 and 1.0, which starts to decrease with further increases in u′. For Le _F  = 1.2, the extent of burning decreases monotonically with increasing u′. The extent of edge flame propagation on the stoichiometric mixture fraction ξ = ξ _st isosurface is characterised by the probability of finding burned gas on this isosurface, which decreases with increasing u′ and Le _F . It has been found that it is easier to obtain self-sustained combustion following localised forced ignition in case of inhomogeneous mixtures than that in the case of homogeneous mixtures with the same energy input, energy deposition duration when the ignition centre is placed at the stoichiometric mixture. The difficultly to sustain combustion unaided by external energy addition in homogeneous mixture is particularly prevalent in the case of Le _F  = 1.2.     

Testing of Model Equations for the Mean Dissipation using Kolmogorov Flows

Direct Numerical Simulations (DNS) of Kolmogorov flows are performed at three different Reynolds numbers Re _λ between 110 and 190 by imposing a mean velocity profile in y-direction of the form U(y) = F sin(y) in a periodic box of volume (2π)³. After a few integral times the turbulent flow turns out to be statistically steady. Profiles of mean quantities are then obtained by averaging over planes at constant y. Based on these profiles two different model equations for the mean dissipation ε in the context of two-equation RANS (Reynolds Averaged Navier–Stokes) modelling of turbulence are compared to each other. The high Reynolds number version of the k-ε-model (Jones and Launder, Int J Heat Mass Transfer 15:301–314, 1972), to be called the standard model and a new model by Menter et al. (2006), to be called the Menter–Egorov model, are tested against the DNS results. Both models are solved numerically and it is found that the standard model does not provide a steady solution for the present case, while the Menter–Egorov model does. In addition a fairly good quantitative agreement of the model solution and the DNS data is found for the averaged profiles of the kinetic energy k and the dissipation ε. Furthermore, an analysis based on flow-inherent geometries, called dissipation elements (Wang and Peters, J Fluid Mech 608:113–138, 2008), is used to examine the Menter–Egorov ε model equation. An expression for the evolution of ε is derived by taking appropriate moments of the equation for the evolution of the probability density function (pdf) of the length of dissipation elements. A term-by-term comparison with the model equation allows a prediction of the constants, which with increasing Reynolds number approach the empirical values.     

Chemistry at High Dilution: Dinuclear 99 mTc Complexes

The formation of di- or polynuclear complexes at nanomolar concentrations is generally too slow to be observed with ^99mTc. It is reported in this communication that an appropriate choice of potentially bridging ligands, herein thiols HS-R, accelerates the dimerization reaction to an extent that dinuclear complexes are formed at very high dilution. The dinuclear nature of [^99mTc₂(μ₂-SR)₃(CO)₆]⁻ is shown by chromatographic comparison, not only with its rhenium homologue as commonly done, but also with the true ⁹⁹Tc analogue.     

Perturbed Divisible Sandpiles and Quadrature Surfaces

Potential Analysis - The main purpose of the present paper is to establish a link between quadrature surfaces (potential theoretic concept) and sandpile dynamics (Laplacian growth models). For this...     

[(C C)Au(N N)]+ Complexes as a New Family of Anticancer Candidates: Synthesis,Characterization and Exploration of the Antiproliferative Properties

A library of eleven cationic gold(III) complexes of the general formula [(C C)Au(N N)]⁺ when C C is either biphenyl or 4,4’-ditertbutyldiphenyl and N N is a bipyridine, phenanthroline or dipyridylamine derivative have been synthesized and characterized. Contrasting effects on the viability of the triple negative breast cancer cells MDA-MB-231 was observed from a preliminary screening. The antiproliferative activity of the seven most active complexes were further assayed on a larger panel of human cancer cells as well as on non-cancerous cells for comparison. Two complexes stood out for being either highly active or highly selective. Eventually, reactivity studies with biologically meaningful amino acids, glutathione, higher order DNA structures and thioredoxin reductase (TrxR) revealed a markedly different behavior from that of the well-known coordinatively isomeric [(C N C)Au(NHC)]⁺ structure. This makes the [(C C)Au(N N)]⁺ complexes a new class of organogold compounds with an original mode of action.     

Overtone spectra of 2-mercaptoethanol and 1,2-ethanedithiol

Vibrational spectra of vapor-phase 1,2-ethanedithiol and 2-mercaptoethanol were recorded to investigate weak intramolecular interactions. The spectra were recorded with conventional absorption spectroscopy and laser photoacoustic spectroscopy in the 2000-11,000 cm(-1) region. The room temperature spectra of each molecule are complicated by contributions from several conformers. Anharmonic oscillator local-mode calculations of the OH- and SH-stretching transitions have been performed to facilitate assignment of the different conformers in the spectra. We observe evidence of hydrogen-bond-like interactions from OH to S, but not from SH to O or S. The OH to S intramolecular interaction in 2-mercaptoethanol is weak and comparable to that found in the OH to O interaction in ethylene glycol.     

Synthesis and molecular modelling of double-functionalised nucleosides with aromatic moieties in the 5'-(S)-position and minor groove interactions in DNA zipper structures

A series of six double-functionalised nucleosides, in which aromatic moieties were inserted into the 5'-(S)-C-position, were synthesised and incorporated into DNA duplexes. The aromatic moieties were thymine-1-yl, phenyl, 1,2,3-triazol-1-yl, 1,2,3-triazol-4-yl, 4-(uracil-5-yl)-1,2,3-triazol-1-yl and 4-phenyl-1,2,3-triazol-1-yl. The DNA duplexes were studied with UV melting curves, CD spectroscopy and molecular modelling. The results showed that the aromatic moieties in some cases interact in the minor groove forming DNA zipper structures. The strongest specific interaction was found between two thymines or between a thymine and a phenyl group in a crossed (-3)-zipper motif (i.e., with two base pairs interspacing the modifications). Modelling revealed that the interaction is aromatic stacking across the minor groove. Also, the extended uracil-triazole moiety demonstrated zipper contacts in the minor groove as well as binding to the floor of the groove.     

DFT+U study of defects in bulk rutile TiO(2)

We present a systematic study of electronic gap states in defected titania using our implementation of the Hubbard-U approximation in the grid-based projector-augmented wave density functional theory code, GPAW. The defects considered are Ti interstitials, O vacancies, and H dopants in the rutile phase of bulk titanium dioxide. We find that by applying a sufficiently large value for the Hubbard-U parameter of the Ti 3d states, the excess electrons localize spatially at the Ti sites and appear as states in the band gap. At U=2.5?eV, the position in energy of these gap states are in fair agreement with the experimental observations. In calculations with several excess electrons and U=2.5?eV, all of these end up in gap states that are spatially localized around specific Ti atoms, thus effectively creating one Ti(3+) ion per excess electron. An important result of this investigation is that regardless of which structural defect is the origin of the gap states, at U=2.5?eV, these states are found to have their mean energies within a few hundredths of an eV from 0.94 eV below the conduction band minimum.