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.     

Morphogen gradient from a noisy source

We investigate the effect of time-dependent noise on the shape of a morphogen gradient in a developing embryo. Perturbation theory is used to calculate the deviations from deterministic behavior in a simple reaction-diffusion model of robust gradient formation, and the results are confirmed by numerical simulation. It is shown that such deviations can disrupt robustness for sufficiently high noise levels, and the implications of these findings for more complex models of gradient-shaping pathways are discussed.     

Unusual Corrections to Scaling in the 3-State Potts Antiferromagnet on a Square Lattice

At zero temperature, the 3-state antiferromagnetic Potts model on a square lattice maps exactly onto a point of the 6-vertex model whose long-distance behavior is equivalent to that of a free scalar boson. We point out that at nonzero temperature there are two distinct types of excitation: vortices, which are relevant with renormalization-group eigenvalue 1/2 and non-vortex unsatisfied bonds, which are strictly marginal and serve only to renormalize the stiffness coefficient of the underlying free boson. Together these excitations lead to an unusual form for the corrections to scaling: for example, the correlation length diverges as J/kT according to Ae ² (1+be ^– +···), where b is a nonuniversal constant that may nevertheless be determined independently. A similar result holds for the staggered susceptibility. These results are shown to be consistent with the anomalous behavior found in the Monte Carlo simulations of Ferreira and Sokal.     

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.     

Linking numbers for self-avoiding loops and percolation: application to the spin quantum hall transition

Nonlocal twist operators are introduced for the O(n) and Q-state Potts models in two dimensions which count the numbers of self-avoiding loops (respectively, percolation clusters) surrounding a given point. Their scaling dimensions are computed exactly. This yields many results: for example, the number of percolation clusters which must be crossed to connect a given point to an infinitely distant boundary. Its mean behaves as (1/3sqrt[3] pi) |ln( p(c)-p)| as p-->p(c)-. As an application we compute the exact value sqrt[3]/2 for the conductivity at the spin Hall transition, as well as the shape dependence of the mean conductance in an arbitrary simply connected geometry with two extended edge contacts.     

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.