Noble metals in polyoxometalates

Polyoxometalates containing noble metal ions, such as ruthenium, osmium, rhodium, palladium, platinum, silver and gold, are a structurally diverse class of compounds. They include both classical heteropolyanions (vanadates, molybdates, tungstates) in which noble metals are present as heteroatoms, as well as the recently discovered class of polyoxometalates with noble metal "addenda" atoms. The focus of this Review is on complexes that should, in principle, exist as discrete molecular species in solution, and which are therefore of interest for their reactivity, their future synthetic utility and potential applications, for example, in catalysis or nanoscience.     

Biologically compatible, phosphorescent dimetallic rhenium complexes linked through functionalized alkyl chains: syntheses, spectroscopic properties, and applications in imaging microscopy

A range of luminescent, dimetallic complexes based upon the rhenium fac-tricarbonyl diimine core, linked by aliphatic chains of varying lengths and functionality, have been synthesized and their photophysical properties examined. Each complex displays characteristic (3)M(Re)L(diimine)CT emission in aerated acetonitrile solution, with long lifetimes in the range of 129-248 ns and corresponding quantum yields in the range 3.2-8.0%. In aqueous solution, as opposed to acetonitrile, the complexes generally show a small hypsochromic shift in λ(em) and an extension of the (3)MLCT lifetime, attributed to a hydrophobically driven association of the alkyl chains with the rhenium-bound diimine units. In live cell imaging experiments using MCF7 cells the complexes all show good uptake by non-energy dependent mechanisms without endosomal entrainment, and with varying propensity to localize in organelles. The degrees of uptake and localization properties are discussed in terms of the length and chemical nature of the linkers, and in terms of the likely interactions between these and the various cellular components encountered.     

Proposed mechanisms for the fragmentation of doubly allylic alkenamides (tingle compounds) by low energy collisional activation in a triple quadrupole mass spectrometer

Tingle compounds are a class of alkenamides with organoleptic properties that include a numbing or a pins and needles effect that is generally perceived on the lips and in the mouth when consumed. They occur in nature in a number of botanical species. Spilanthol and Pellitorine are important examples of tingle compounds. A number of homologs and analogs were synthesized to study the effect of chain length, double bond location, and amide moiety on the tingle effect. This also provided the opportunity to study the behavior of these compounds in the collision cell of a triple quadrupole mass spectrometer. The doubly allylic 2E,6Z-alkenamides, which made up the largest class studied, fragmented in a characteristic way to produce a distonic radical cation and a cyclopropene cation. Mechanisms for the formation of these ions are proposed. The mechanisms are supported by energy-resolved mass spectrometric data, the analysis of deuterated analogs and homologs that are not doubly allylic, and exact mass measurements. Exceptions to the proposed mechanisms are also presented. These data represent the first attempt to apply mechanistic principles to the product ions observed in the MS/MS spectra of these compounds. The authors believe the results of this study will facilitate the identification of these and similar compounds and contribute to the fundamental understanding of the behavior of alkenamides in the collision cell of a triple quadrupole mass spectrometer.     

A second-order Monte Carlo method for the solution of the Ito stochastic differential equation

A difference approximation that is second-order accurate in the time step his derived for the general Ito stochastic differential equation. The difference equation has the form of a second-order random walk in which the random terms are non-linear combinations of Gaussian random variables. For a wide class of problems, the transition pdf is joint-normal to second order in h; the technique then reduces to a Gaussian random walk, but its application is not limited to problems having a Gaussian solution. A large number of independent sample paths are generated in a Monte Carlo solution algorithm; any statistical function of the solution (e.g., moments or pdf's) can be estimated by ensemble averaging over these paths     

Expected utility versus the changes in knowledge ahead

We present a decision theory appropriate for use in serious choices such as insurance. It extends standard decision theories like expected utility or cumulative prospect theory which are atemporal single stage theories. Instead it employs stages of knowledge ahead to track satisfactions and dissatisfactions. In the first stage of the risk, the uninsured face dissatisfactions of worries and planning difficulties (avoided by the insured), also perhaps positive satisfactions of thrills (missed out by the insured). In the second stage when the risk is past, the uninsured may face the dissatisfactions of ridicule and blame if they learn that they were unlucky. From experimental and questionnaire data, 80% of our subjects are influenced by such secondary satisfactions. Only five percent of our participants employ the usage of integrated quantitative aggregation rules for evaluating acts as assumed under expected utility theory.     

A LES/PDF simulator on block-structured meshes

A block-structured mesh large-eddy simulation (LES)/probability density function (PDF) simulator is developed within the OpenFOAM framework for computational modelling of complex turbulent reacting flows. The LES/PDF solver is a hybrid solution methodology consisting of (i) a finite-volume (FV) method for solving the filtered mass and momentum equations (LES solver), and (ii) a Lagrangian particle-based Monte Carlo algorithm (PDF solver) for solving the modelled transport equation of the filtered joint PDF of compositions. Both the LES and the PDF methods are developed and combined to form a hybrid LES/PDF simulator entirely within the OpenFOAM framework. The in situ adaptive tabulation method [S.B. Pope, Computationally efficient implementation of combustion chemistry using in situ adaptive tabulation, Combust. Theory Model. 1 (1997), pp. 41–63; L. Lu, S.R. Lantz, Z. Ren, and B.S. Pope, Computationally efficient implementation of combustion chemistry in parallel PDF calculations, J. Comput. Phys. 228 (2009), pp. 5490–5525] is incorporated into the new LES/PDF solver for efficient computations of combustion chemistry with detailed reaction kinetics. The method is designed to utilise a block-structured mesh and can readily be extended to unstructured grids. The three-stage velocity interpolation method of Zhang and Haworth [A general mass consistency algorithm for hybrid particle/finite-volume PDF methods, J. Comput. Phys. 194 (2004), pp. 156–193] is adapted to interpolate the LES velocity field onto particle locations accurately and to enforce the consistency between LES and PDF fields at the numerical solution level. The hybrid algorithm is fully parallelised using the conventional domain decomposition approach. A detailed examination of the effects of each stage and the overall performance of the velocity interpolation algorithm is performed. Accurate coupling of the LES and PDF solvers is demonstrated using the one-way coupling methodology. Then the fully two-way coupled LES/PDF solver is successfully applied to simulate the Sandia Flame-D, and a turbulent non-swirling premixed flame and a turbulent swirling stratified flame from the Cambridge turbulent stratified flame series [M.S. Sweeney, S. Hochgreb, M.J. Dunn, and R.S. Barlow, The structure of turbulent stratified and premixed methane/air flames I: Non-swirling flows, Combust. Flame 159 (2012), pp. 2896–2911; M.S. Sweeney, S. Hochgreb, M.J. Dunn, and R.S. Barlow, The structure of turbulent stratified and premixed methane/air flames II: Swirling flows, Combust. Flame 159 (2012), pp. 2912–2929]. It is found that the LES/PDF method is very robust and the results are in good agreement with the experimental data for both flames.     

A Simple Approach for Specifying Velocity Inflow Boundary Conditions in Simulations of Turbulent Opposed-Jet Flows

A new methodology is developed to specify inflow boundary conditions for the velocity field at the nozzle exit planes in turbulent counterflow simulations. The turbulent counterflow configuration consists of two coaxial opposed nozzles which emit highly-turbulent streams of varying species compositions depending on the mode considered. The specification of velocity inflow boundary conditions at the nozzle exits in the counterflow configuration is non-trivial because of the unique turbulence field generated by the turbulence generating plates (TGPs) upstream of the nozzle exits. In the method presented here, a single large-eddy simulation (LES) is performed in a large domain that spans the region between the TGPs of the nozzles, and the time series of the velocity fields at the nozzle exit planes are recorded. To provide inflow boundary conditions at the nozzle exit planes for simulations under other conditions (e.g., different stream compositions, bulk velocity, TGP location), transformations are performed on the recorded time series: the mean and r.m.s. (root-mean-square) quantities of velocity, as well as the longitudinal integral length scale on the centerline, at the nozzle exits in simulations are matched to those observed in experiments, thereby matching the turbulent Reynolds number R e _t . The method is assessed by implementing it in coupled large-eddy simulation/probability density function (LES/PDF) simulations on a small cylindrical domain between the nozzle exit planes for three different modes of the counterflow configuration: N ₂ vs. N ₂; N ₂ vs. hot combustion products; and C H ₄/N ₂ vs. O ₂. The inflow method is found to be successful as the first and second moments of velocity from the LES/PDF simulations agree well with the experimental data on the centerline for all three modes. This simple yet effective inflow strategy can be applied to eliminate the computational cost required to simulate the flow field upstream of the nozzle exits. It is also emphasized that, in addition to the predicted time series data, the availability of experimental data close to the nozzle exit planes plays a key role in the success of this method.     

Turbulent piloted partially-premixed flames with varying levels of O2/N2: stability limits and PDF calculations

This paper reports measured stability limits and PDF calculations of piloted, turbulent flames of compressed natural gas (CNG) partially-premixed with either pure oxygen, or with varying levels of O₂/N₂. Stability limits are presented for flames of CNG fuel premixed with up to 20% oxygen as well as CNG–O₂–N₂ fuel where the O₂ content is varied from 8 to 22% by volume. Calculations are presented for (i) Sydney flame B [Masri et al. 1988] which uses pure CNG as well as flames B15 to B25 where the CNG is partially-premixed with 15–25% oxygen by volume, respectively and (ii) Sandia methane–air (1:3 by volume) flame E [Barlow et al. 2005] as well as new flames E15 and E25 that are partially-premixed with ‘reconstituted air’ where the O₂ content in nitrogen is 15 and 25% by volume, respectively. The calculations solve a transported PDF of composition using a particle-based Monte Carlo method and employ the EMST mixing model as well as detailed chemical kinetics. The addition of oxygen to the fuel increases stability, shortens the flames, broadens the reaction zone, and shifts the stoichiometric mixture fraction towards the inner side of the jet. It is found that for pure CNG flames where the reaction zone is narrow (～0.1 in mixture fraction space), the PDF calculations fail to reproduce the correct level of local extinction on approach to blow-off. A broadening in the reaction zone up to about 0.25 in mixture fraction space is needed for the PDF/EMST approach to be able to capture these finite-rate chemistry effects. It is also found that for the same level of partial premixing, increasing the O₂/N₂ ratio increases the maximum levels of CO and NO but shifts the peak to richer mixture fractions. Over the range of oxygenation investigated here, stability limits have shown to improve almost linearly with increasing oxygen levels in the fuel and with increasing the contribution of release rate from the pilot.     

Computational study of lean premixed turbulent flames using RANSPDF and LESPDF methods

A computational study is performed on a series of four piloted, lean, premixed turbulent jet flames. These flames use the Sydney Piloted Premixed Jet Burner (PPJB), and with jet velocities of 50, 100, 150 and 200 m/s are denoted PM150, PM1100, PM1150 and PM1200, respectively. Calculations are performed using the RANSPDF and LESPDF methodologies, with different treatments of molecular diffusion, with detailed chemistry and flamelet-based chemistry modelling, and using different imposed boundary conditions. The sensitivities of the calculations to these different aspects of the modelling are compared and discussed. Comparisons are made to experimental data and to previously-performed calculations. It is found that, given suitable boundary conditions and treatment of molecular diffusion, excellent agreement between the calculations and experimental measurements of the mean and variance fields can be achieved for PM150 and PM1100. The application of a recently developed implementation of molecular diffusion results in a large improvement in the computed variance fields in the LESPDF calculations. The inclusion of differential diffusion in the LESPDF calculations provides insight on the behaviour in the near-field region of the jet, but its effects are found to be confined to this region and to the species CO, OH and H₂. A major discrepancy observed in many previous calculations of these flames is an overprediction of reaction progress in PM1150 and PM1200, and this discrepancy is also observed in the LESPDF calculations; however, a parametric study of the LESPDF mixing model reveals that, with a sufficiently large mixing frequency, calculations of these two flames are capable of yielding improved reaction progress in good qualitative agreement with the mean and RMS scalar measurements up to an x/D of 30. Lastly, the merits of each computational methodology are discussed in light of their computational costs.     

Effects of vapor pressure on thermodynamic equilibrium in multiphase flow for thermochemical hydrogen production

This paper examines the effects of H₂O vapor pressure on the equilibrium conditions of a CuCl₂ hydrolysis reactor in the thermochemical Cu–Cl cycle of hydrogen production. A new predictive model is developed to determine the minimum steam requirement in the reactor based on the chemical equilibrium condition, reactor pressure and fraction of gaseous reactant. Experimental data, at three separate vapour pressures of steam, compared well with the new predictive formulation.