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.     

Temporary threshold shifts and recovery following noise exposure in the Atlantic bottlenosed dolphin (Tursiops truncatus)

Behaviorally determined hearing thresholds for a 7.5-kHz tone for an Atlantic bottlenosed dolphin (Tursiops truncatus) were obtained following exposure to fatiguing low-frequency octave band noise. The fatiguing stimulus ranged from 4 to 11 kHz and was gradually increased in intensity to 179 dB re 1 microPa and in duration to 55 min. Exposures occurred no more frequently than once per week. Measured temporary threshold shifts averaged 11 dB. Threshold determination took at least 20 min. Recovery was examined 360, 180, 90, and 45 min following exposure and was essentially complete within 45 min.     

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.     

Echolocation in the Risso's dolphin,Grampus griseus

The Risso's dolphin (Grampus griseus) is an exclusively cephalopod-consuming delphinid with a distinctive vertical indentation along its forehead. To investigate whether or not the species echolocates, a female Risso's dolphin was trained to discriminate an aluminum cylinder from a nylon sphere (experiment 1) or an aluminum sphere (experiment 2) while wearing eyecups and free swimming in an open-water pen in Kaneohe Bay, Hawaii. The dolphin completed the task with little difficulty despite being blindfolded. Clicks emitted by the dolphin were acquired at average amplitudes of 192.6 dB re 1 microPa, with estimated sources levels up to 216 dB re 1 microPa-1 m. Clicks were acquired with peak frequencies as high as 104.7 kHz (Mf(p) = 47.9 kHz), center frequencies as high as 85.7 kHz (Mf(0) = 56.5 kHz), 3-dB bandwidths up to 94.1 kHz (M(BW) = 39.7 kHz), and root-mean-square bandwidths up to 32.8 kHz (M(RMS) = 23.3 kHz). Click durations were between 40 and 70 micros. The data establish that the Risso's dolphin echolocates, and that, aside from slightly lower amplitudes and frequencies, the clicks emitted by the dolphin were similar to those emitted by other echolocating odontocetes. The particular acoustic and behavioral findings in the study are discussed with respect to the possible direction of the sonar transmission beam of the species.     

Synthesis and Diels-Alder Reactions of a New Kind of Chiral Dienophiles: Cyclic Vinyl-p-tolylsulfilimines

A new kind of chiral dienophiles, cyclic vinyl-p-tolylsulfilimines (2a and 2b), were obtained from the corresponding (Z)-sulfinylacrylonitriles with HBF(4) and methanol. The asymmetric Diels-Alder reaction of optically pure 2a with cyclopentadiene under mild thermal or catalyzed conditions afforded only the endo-4a adduct with complete endo and pi-facial selectivities. The ability of the sulfilimine moiety to enhance the dienophilic reactivity of the double bond is similar to that of the sulfinyl group.