Additions of enantiopure alpha-sulfinyl carbanions to (S)-N-sulfinimines: asymmetric synthesis of beta-amino sulfoxides and beta-alphamino alcohols

The addition of the lithium anions derived from (R)- and (S)-methyl and -ethyl p-tolyl sulfoxides to (S)-N-benzylidene-p-toluenesulfinamide provides an easy access route to enantiomerically pure beta-(N-sulfinyl)amino sulfoxides. Stereoselectivity can be achieved when the configurations at the sulfur atoms of the two reagents are opposite (matched pair), thus resulting in only one diastereoisomer, even for the case in which two new chiral centers are created. The N-sulfinyl group primarily controls the configuration of the carbon bonded to the nitrogen, whereas the configuration of the alpha-sulfinyl carbanion seems to be responsible for the level of asymmetric induction, as well as for the configuration of the new stereogenic C-SO carbon in the reactions with ethyl p-tolyl sulfoxides. An efficient method for transforming the obtained beta-(N-sulfinyl)amino sulfoxides into optically pure beta-amino alcohols, based on the stereoselective non-oxidative Pummerer reaction, is also reported.     

(Z)-3-p-tolylsulfinylacrylonitrile as a chiral dienophile: diels-alder reactions with furan and acyclic dienes

The behavior of (Z)-3-p-tolylsulfinylacrylonitrile (1) as a chiral dienophile has been evaluated from its reactions with furan and acyclic dienes. Electrostatic interactions of the cyano group with the sulfinyl one restrict the conformational mobility around the C-S bond, thus controlling the pi-facial selectivity, which is almost complete in all cases, the approach of the diene from the less-hindered face of the dienophile (that bearing the lone electron pair) in the predominant rotamer being the favored one. The regioselectivity is also completely controlled by the cyano group. Additionally, the reactivity of compound 1 as well as its endo-selectivity are both higher than those observed for the corresponding (Z)-3-sulfinylacrylates, thus proving the potential of sulfinylnitriles as chiral dienophiles.     

Walls inhibit chaotic mixing

We report on experiments of chaotic mixing in a closed vessel, in which a highly viscous fluid is stirred by a moving rod. We analyze quantitatively how the concentration field of a low-diffusivity dye relaxes towards homogeneity, and we observe a slow algebraic decay of the inhomogeneity, at odds with the exponential decay predicted by most previous studies. Visual observations reveal the dominant role of the vessel wall, which strongly influences the concentration field in the entire domain and causes the anomalous scaling. A simplified 1D model supports our experimental results. Quantitative analysis of the concentration pattern leads to scalings for the distributions and the variance of the concentration field consistent with experimental and numerical results.     

Spin-singlet clusters in the ladder compound NaV2O5

The space group of alpha(')-NaV2O5 turns below T(c) = 34 K from Pmmn with all V sites equivalent, into Fmm2 with three independent vanadium sites per layer. This is incompatible with models of charge ordering into V4+ and V5+. Our structure determination indicates that the phase transition consists of a charge ordering with three distinct valence states, formally V4+, V4.5+, and V5+. The singlet formation is not associated with dimerization on the spin ladder, but with the formation of spin clusters. Finally, we ascribe the quadrupling of the c axis to the large polarizability of the V2O5 skeleton.     

Dependence of pulser driving responses on electrical and motional characteristics of NDE ultrasonic probes

Acoustic performance in ultrasonic transmitters can be improved by means of a suitable electrical driving response and matching/tuning networks. It is important to predict this electrical response, but doing so is not easy because it departs notably from the nominal pattern with the loading probes. In practice, the analysis of HV pulser spikes in NDE applications requires fairly complex models in the transient regime and, in addition, non-linear problems could arise, especially in the case of tuned transmitters. In this paper, the most relevant influences of loading characteristics of NDT ultrasonic probes on the pulser electrical driving responses are evaluated in time and frequency domains. Conventional pulse generators and typical NDE pulsers are considered. Driving responses are analysed across commercial ultrasonic probes and, alternatively, across similar purely electrical loads. Distinct influences on pulser responses from electrical and motional sections of the probes are identified. All these aspects are studied on the basis of experimental and computer results.     

Optimizing the source distribution in fluid mixing

A passive scalar is advected by a velocity field, with a nonuniform spatial source that maintains concentration inhomogeneities. For example, the scalar could be temperature with a source consisting of hot and cold spots, such that the mean temperature is constant. Which source distributions are best mixed by this velocity field? This question has a straightforward yet rich answer that is relevant to real mixing problems. We use a multiscale measure of steady-state enhancement to mixing and optimize it by a variational approach. We then solve the resulting Euler-Lagrange equation for a perturbed uniform flow and for simple cellular flows. The optimal source distributions have many broad features that are as expected: they avoid stagnation points, favour regions of fast flow, and their contours are aligned such that the flow blows hot spots onto cold and vice versa. However, the detailed structure varies widely with diffusivity and other problem parameters. Though these are model problems, the optimization procedure is simple enough to be adapted to more complex situations.     

A Stokesian viscoelastic flow: Transition to oscillations and mixing

To understand observations of low Reynolds number mixing and flow transitions in viscoelastic fluids, we study numerically the dynamics of the Oldroyd-B viscoelastic fluid model. The fluid is driven by a simple time-independent forcing that, in the absence of viscoelastic stresses, creates a cellular flow with extensional stagnation points. We find that at O(1) Weissenberg number, these flows lose their slaving to the forcing geometry of the background force, become oscillatory with multiple frequencies, and show continual formation and destruction of small-scale vortices. This drives flow mixing, the details of which we closely examine. These new flow states are dominated by a single-quadrant vortex, which may be stationary or cycle persistently from cell to cell.     

Phase Separation in the Advective Cahn–Hilliard Equation

The Cahn–Hilliard equation is a classic model of phase separation in binary mixtures that exhibits spontaneous coarsening of the phases. We study the Cahn–Hilliard equation with an imposed advection term in order to model the stirring and eventual mixing of the phases. The main result is that if the imposed advection is sufficiently mixing, then no phase separation occurs, and the solution instead converges exponentially to a homogeneous mixed state. The mixing effectiveness of the imposed drift is quantified in terms of the dissipation time of the associated advection–hyperdiffusion equation, and we produce examples of velocity fields with a small dissipation time. We also study the relationship between this quantity and the dissipation time of the standard advection–diffusion equation.