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.     

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.     

TEM study of the origin of the surface microroughness in DSL photoetched Si-implanted GaAs wafers

TEM has been used to study the origin of the surface microroughness that formed in both ²⁹Si as-implanted and rapid thermal annealed LEC undoped GaAs wafers after DSL photoetching. The degree of microroughness increased as the implant dose increased from 3 × 10¹² to 3 × 10¹⁴ atoms/cm². It has been found that such a microroughness is due to the fine-scale damage induced by the implantation in the as-implanted wafers and to interstitial dislocation loops in the implanted and then annealed wafers. Microroughness appears during DSL etching because such defects are effective recombination centres for the holes involved in the dissolution of the GaAs surface so that the wafers etch slower at the point-defect clusters and dislocation loops.     

Homo-epitaxial GaN growth on exact and misoriented single crystals: suppression of hillock formation

GaN single crystals were used as substrates for MOCVD growth. The ( ) plane of the substrate crystals was polished to obtain off-angle orientations of 0, 2, and 4° towards the [ ] direction. The highest misorientation resulted in a reduction of the hexagonal hillock density by nearly two orders of magnitude as compared with homo-epitaxial films grown on the exact ( ) surface. The features that are still found on the 4° off-angle sample after growth can be explained by a model involving the interaction of steps, introduced by the misorientation, and the hexagonal hillocks during the growth process. Following from this explanation it could be concluded that surface diffusion is found to be not important during growth on the N-side. The material quality of the N-side was examined by photoluminescence (PL) measurements. The PL spectrum measured at 5 K shows dominant donor bound excitons with a FWHM of 1.4 meV as well as free excitonic transitions.     

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.     

Photoluminescence study of homoepitaxial N-polar GaN grown on differently misoriented single crystal substrates

We report results of a photoluminescence (PL) study of homoepitaxial N-polar GaN films grown by metal-organic chemical vapour deposition on vicinal GaN single crystal substrates. Off-angles of 2° and 4° towards the direction as well as 4° in the direction were investigated. Along with a remarkable improvement of the epilayer morphology, a significant reduction of the unintentional/intrinsic donor concentration is achieved for all considered misorientations. As a consequence, PL spectra with narrow bound and free excitonic lines were observed. The misorientation of 4° towards the direction results in an N-polar epilayer of the best optical quality.