Asymmetric Carboxycyanation of Aldehydes by Cooperative AlF/Onium Salt Catalysts: from Cyanoformate to KCN as Cyanide Source

Asymmetric 1,2-additions of cyanide yield enantioenriched cyanohydrins as versatile chiral building blocks. Next to HCN, volatile organic cyanide sources are usually used. Among them, cyanoformates are more attractive on technical scale than TMSCN for cost reasons, but catalytic productivity is usually lower. Here, the development of a new strategy for cyanations is described, in which this activity disadvantage is overcome. A Lewis acidic Al center cooperates with an aprotic onium moiety within a remarkably robust bifunctional Al–F–salen complex. This allowed for unprecedented turnover numbers of up to 10⁴. DFT studies suggest an unexpected unique trimolecular pathway in which the ammonium bound cyanide attacks the aldehyde, which itself is activated by the carbonyl group of the cyanoformate binding to the Al center. In addition, a novel practical carboxycyanation method was developed that makes use of KCN as the sole cyanide source. The use of a pyrocarbonate as carboxylating reagent provided the best results.     

A divergence-conforming hybridized discontinuous Galerkin method for the incompressible Reynolds-averaged Navier-Stokes equations

We present a hybridized discontinuous Galerkin (HDG) method for the incompressible Reynolds-averaged Navier-Stokes equations coupled with the Spalart-Allmaras one-equation turbulence model. The method extends upon an HDG method recently introduced by Rhebergen and Wells for the incompressible Navier-Stokes equations. With a special choice of velocity and pressure spaces for both element and trace degrees of freedom (DOFs), the method returns pointwise divergence-free mean velocity fields and properly balances momentum and energy. We further examine the use of different polynomial degrees and meshes to see how the order of the scalar eddy viscosity affects the convergence of the mean velocity and pressure fields, specifically for the method of manufactured solutions. As is standard with HDG methods, static condensation can be employed to remove the element DOFs and thus dramatically reduce the global number of DOFs. Numerical results illustrate the effectiveness of the proposed methodology.     

Simulating bubble dynamics in a buoyant system

Multiphase flows are critical components of many physical systems; however, numerical models of multiphase flows with large parameter gradients can be challenging. Here, two different numerical methods, volume of fluid (VOF) and smoothed particle hydrodynamics (SPH), are used to model the buoyant rise of isolated gas bubbles through quiescent fluids for a range of Bond and Reynolds numbers. The VOF is an Eulerian grid–based method, whereas the SPH is Lagrangian and mesh free. Each method has unique strengths and weaknesses, and a comparison of the two approaches as applied to multiphase phenomena has not previously been performed. The VOF and SPH simulations are compared, verified, and validated. Results using two-dimensional VOF and SPH simulations are similar to each other and are able to reproduce numerical benchmarks and experimental results for sufficiently large Morton and Reynolds numbers. It is also shown that at low Reynolds numbers, the two methods, SPH and VOF, diverge in the transient regime of the bubble rise. Regimes that require simulations capable of representing three-dimensional drag are identified as well as regimes in which results from VOF and SPH diverge.     

Enantiodivergent [4+2] Cycloaddition of Dienolates by Polyfunctional Lewis Acid/Zwitterion Catalysis

Diels–Alder reactions have become established as one of the most effective ways to prepare stereochemically complex six-membered rings. Different catalysis concepts have been reported, including dienophile activation by Lewis acids or H-bond donors and diene activation by bases. Herein we report a new concept, in which an acidic prodiene is acidified by a Lewis acid to facilitate deprotonation by an imidazolium–aryloxide entity within a polyfunctional catalyst. A metal dienolate is thus formed, while an imidazolium–ArOH moiety probably forms hydrogen bonds with the dienophile. The catalyst type, readily prepared in few steps in high overall yield, was applied to 3-hydroxy-2-pyrone and 3-hydroxy-2-pyridone as well as cyclopentenone prodienes. Maleimide, maleic anhydride, and nitroolefin dienophiles were employed. Kinetic, spectroscopic, and control experiments support a cooperative mode of action. High enantioselectivity was observed even with unprecedented TONs of up to 3680.     

Performing solvation free energy calculations in LAMMPS using the decoupling approach

Journal of Computer-Aided Molecular Design - The decoupling approach to solvation free energy calculations requires scaling the interactions between the solute and the solution with all...     

Auditory filter shapes at low center frequencies in young and elderly hearing-impaired subjects.

Auditory filter shapes were measured for two groups of hearing-impaired subjects, young and elderly, matched for audiometric loss, for center frequencies (fc) of 100, 200, 400, and 800 Hz using a modified notched-noise method [B. R. Glasberg and B. C. J. Moore, Hear. Res. 47, 103-138 (1990)]. Two noise bands, each 0.4fc wide, were used; they were placed both symmetrically and asymmetrically about the signal frequency to allow the measurement of filter asymmetry. The overall noise level was either 77 or 87 dB SPL. Stimuli were delivered monaurally using Sennheiser HD424 earphones. Although auditory filters for the hearing-impaired subjects were generally broader than for normally hearing subjects [Moore et al., J. Acoust. Soc. Am. 87, 132-140 (1990)], some hearing-impaired subjects with mild losses had normal filters. The filters tended to broaden with increasing hearing loss. There were not any clear differences in filter characteristics between young and elderly hearing-impaired subjects. The signal-to-noise ratios at the outputs of the auditory filters required for threshold (K) tended to be lower than normal for the young hearing-impaired subjects, but were not significantly different from normal for the elderly hearing-impaired subjects. The lower K values for the young hearing-impaired subjects may occur because broadened auditory filters reduce the deleterious effects on signal detection of fluctuations in the noise.     

Universality Under Conditions of Self-tuning

We study systems with a continuous phase transition that tune their parameters to maximize a quantity that diverges solely at a unique critical point. Varying the size of these systems with dynamically adjusting parameters, the same finite-size scaling is observed as in systems where all relevant parameters are fixed at their critical values. This scheme is studied using a self-tuning variant of the Ising model. It is contrasted with a scheme where systems approach criticality through a target value for the order parameter that vanishes with increasing system size. In the former scheme, the universal exponents are observed in naïve finite-size scaling studies, whereas in the latter they are not.     

Tensor Approximation of Generalized Correlated Diffusions and Functional Copula Operators

In this paper we develop a class of applied probabilistic continuous time but discretized state space decompositions of the characterization of a multivariate generalized diffusion process. This decomposition is novel and, in particular, it allows one to construct families of mimicking classes of processes for such continuous state and continuous time diffusions in the form of a discrete state space but continuous time Markov chain representation. Furthermore, we present this novel decomposition and study its discretization properties from several perspectives. This class of decomposition both brings insight into understanding locally in the state space the induced dependence structures from the generalized diffusion process as well as admitting computationally efficient representations in order to evaluate functionals of generalized multivariate diffusion processes, which is based on a simple rank one tensor approximation of the exact representation. In particular, we investigate aspects of semimartingale decompositions, approximation and the martingale representation for multidimensional correlated Markov processes. A new interpretation of the dependence among processes is given using the martingale approach. We show that it is possible to represent, in both continuous and discrete space, that a multidimensional correlated generalized diffusion is a linear combination of processes originated from the decomposition of the starting multidimensional semimartingale. This result not only reconciles with the existing theory of diffusion approximations and decompositions, but defines the general representation of infinitesimal generators for both multidimensional generalized diffusions and, as we will demonstrate, also for the specification of copula density dependence structures. This new result provides immediate representation of the approximate weak solution for correlated stochastic differential equations. Finally, we demonstrate desirable convergence results for the proposed multidimensional semimartingales decomposition approximations.     

Numerical simulation and laser-based imaging of mixture formation, ignition, and soot formation in a diesel spray

Laser-based imaging of fuel vapor distribution, ignition, and soot formation in diesel sprays was carried out in a high-pressure, high-temperature spray chamber under conditions that correspond to temperature and pressure in a diesel engine. Rayleigh scattering and laser-induced incandescence are used to image fuel density and soot volume fraction. The experimental results provide data for comparison with numerical simulations. An interactive cross-sectionally averaged spray model based on Eulerian transport equations was used for the simulation of the spray, and the turbulence-chemistry interaction was modeled with the representative interactive flamelet (RIF) concept. The flamelet calculation is coupled to the Kiva3V computational fluid dynamics (CFD) code using the scalar dissipation rate and pressure as an input to the RIF-code. The flamelet code computes the instationary flamelet profiles for every time step. These profiles were integrated over mixture fraction space using a prescribed β-PDF to obtain mean values, which are passed back to the CFD-code. Thereby, the temperature and the relevant species in each CFD-cell were obtained. The fuel distribution, the average ignition delay as well as the location of ignition are well predicted by the simulation. Furthermore, simulations show that the experimentally observed injection-to-injection variations in ignition delay are due to temperature inhomogeneities. Experimental and simulated spatial soot and fuel vapor density distributions are compared during and after second stage ignition.