On the topological complexity of DC-sets

A DC-set is a set defined by means of convex constraints and one additional inverse convex constraint. Given an arbitrary closed subsetM of the Euclideann-space, we show that there exists a DC-set in (n+1)-space being homeomorphic to the given setM. Secondly, for any fixedn2, we construct a compactn-dimensional manifold with boundary, which is a DC-set and which has arbitrarily large Betti-numbersr _k fork n–2.     

Highly stereoselective synthesis of homoallylic amines based on addition of allyltrichlorosilanes to benzoylhydrazones

Allyltrichlorosilanes reacted with benzoylhydrazones in DMF without the use of any catalyst to afford the corresponding homoallylic benzoylhydrazines in good to high yields. The reactions proceeded at 0 degrees C to room temperature under mild conditions. In addition, it was found that the reactions tolerated well the steric hindrance of hydrazones and allyltrichlorosilanes. Indeed, ketone-derived benzoylhydrazones reacted with allyltrichlorosilane smoothly to afford the corresponding N'-tert-alkyl-N-benzoylhydrazines in high yields. In crotylation with (E)- and (Z)-crotyltrichlorosilanes, syn- and anti-adducts were stereospecifically obtained, respectively. These reactions are most likely to proceed via a cyclic chairlike transition state where the R group takes an axial position. When alpha-heteroatom-substituted chiral benzoylhydrazones were used, high anti-diastereoselectivities were observed. These adducts can be readily converted to homoallylic amines in high yields without epimerization.     

Interstitial superstructures in the TaD system

Ordered deuterium arrangements and order-disorder transformations of the tantalum deuterides in the range TaD_0.50TaD_0.78 have been studied by neutron diffraction and calorimetry at temperatures between ?170 and 120°C. In addition to the disordered phase (α), three ordered phases based on the superstructures Ta₂D_1+x (β₁), Ta₄D₃, (γ), and TaD (δ) are clarified. The Ta₂D_1+x structure is a nonstoichiometric from of the Ta₂D superstructure over the rangex < 0.5. The γ-phase is formed below ?70°C near Ta₄D₃, and transforms into theβ₁and δ-phases, respectively, in the hypo and hyperstoichiometric compositions. The δ-phase that exists beyond TaD_0.75 changes to the disordered α-phase around 100°C.     

First Ritter-type reaction of alkylbenzenes using N-hydroxyphthalimide as a key catalyst

The first Ritter-type reaction of alkylbenzenes with nitriles has been successfully achieved by the use of N-hydroxyphthalimide (NHPI) as a key catalyst. Thus, treatment of ethylbenzene with ammonium hexanitratocerate(IV) (CAN) in the presence of a catalytic amount of NHPI in EtCN under argon produced the corresponding amide in good selectivity.     

Optically active seleninate esters: isolation, absolute configuration, racemization mechanism, and transformation into chiral selenoxide

Optically active seleninate esters were obtained for the first time by chromatographic resolution on an optically active column. The absolute configurations of the optically active seleninate esters were determined by comparing their chiroptical properties with those of two analogous sulfinate esters, the absolute configuration of one of which is known and that of the other was determined by X-ray crystallographic analysis. The optically active seleninate esters were found to racemize in solution. Kinetic studies of the racemization, the oxygen exchange reaction with H(2)(18)O, and theoretical studies clarified that the racemization of the optically active seleninate esters in solution proceeded via an achiral hypervalent selenurane intermediate that was formed by the reaction with water. The reaction of the optically active seleninate ester and the sulfinate ester having bulky substituents with Grignard reagents was found to proceed with the retention of stereochemistry to give an optically active selenoxide and sulfoxides, respectively.     

Dynamic polarization potential of 12C+12C system at molecular-resonance energies

The nuclear reaction dynamics leading to the formation of recently discovered resonance in the mutual-0₂ ⁺ channel of the ¹²C+¹²C inelastic scattering around E _c.m.≃ 32 MeV is studied in terms of the dynamic polarization potential (DPP) induced by the channel coupling among various excited states in ¹²C. The microscopic 3α cluster-model wave functions are used to generate the ¹²C−¹²C diagonal and coupling potentials in the double-folding model. It is found that DPP for the 0₂ ⁺+ 0₂ ⁺ channel is an unusually strong attractive potential which even exceeds the zeroth-order folding-model potential of this channel around the nuclear surface region and that the strong coupling between the 0₂ ⁺ and 2₂ ⁺ states is predominantly responsible for the unusual DPP in this channel. The effective potential, the sum of the original folding-model potential and the attractive DPP, is found to generates resonance states in the same energy region as that of the resonance states generated by the original folding-model potential but the former states are found to be higher-nodal states having four additional radial nodes. Similar but more moderate property of DPP is also found in the entrance (elastic) channel. These results suggest that the reaction dynamics of generating the resonance in the ¹²C(0₂ ⁺) +¹²C(0₂ ⁺) channel may rather differ from that of the simple crossing of the zeroth-order molecular band generated by the potentials in the entrance and exit channels suggested by the standard band-crossing model. Received: 17 December 1998 / Revised version: 1 March 1999     

Structural analysis of O-glycopeptides employing negative- and positive-ion multi-stage mass spectra obtained by collision-induced and electron-capture dissociations in linear ion trap time-of-flight mass spectrometry

Structural analyses of various glycans attached to proteins and peptides are highly desirable for elucidating their biological roles. An approach based on mass spectrometry (MS) combining both collision-induced dissociation (CID) and electron-capture dissociation (ECD) in the positive- and negative-ion modes has been proposed as a simple and direct method of assigning an O-glycan without releasing it from the peptide and of determining the amino acid sequence of the peptide and glycosylation site. The instrument used is an electrospray ionization (ESI) linear ion trap (LIT) time-of-flight (TOF) mass spectrometer with tandem LITs for CID by He gas and ECD. The proposed approach was tested with two synthetic O-glycopeptides binding a sialyl Lewis x (sLe(x)) oligosaccharide and a 3'-sialyl N-acetyllactosamine (3'-SLN) on a serine (S) residue. In the negative-ion mode, the CID MS(2) spectra of O-glycopeptides showed a relatively abundant glycoside-bond cleavage between the core N-acetylglucosamine (GlcNAc) and serine (S) that yields deprotonated C(3)-type fragment ions of O-glycan and deprotonated Z(0)-type peptide ions. The structure of the sLe(x) (3'-SLN) oligosaccharide was simply assigned by comparing the CID MS(3) spectrum derived from the C(3)-type fragment ion with the CID MS(2) spectra of the sLe(x) and sLe(a) (3'- and 6'-SLN) standards (i.e., negative-ion MS(n) spectral matching). The amino acid sequence of the peptide including the glycosylation site was determined from the ECD MS(2) spectrum in the positive-ion mode.     

Angle-resolved photoemission study of insulating and metallic Cu-O chains in PrBa2Cu3O7 and PrBa2Cu4O8

We compare the angle-resolved photoemission spectra of the hole-doped Cu-O chains in PrBa2Cu3O7 (Pr123) and in PrBa2Cu4O8 (Pr124). While, in Pr123, a dispersive feature from the chain takes a band maximum at k(b) (momentum along the chain) approximately pi/4 and loses its spectral weight around the Fermi level, it reaches the Fermi level at k(b) approximately pi/4 in Pr124. Although the chains in Pr123 and Pr124 are approximately 1/4 filled, they show contrasting behaviors: While the chains in Pr123 have an instability to charge ordering, those in Pr124 avoid it and show an interesting spectral feature of a metallic coupled-chain system.     

Fatigue effect in luminescence of glow discharge amorphous silicon at low temperatures

Fatigue in the luminescence was observed in glow discharge amorphous silicon at 4.2 K and 77 K. This fatigue was not recovered by infra-red illumination, but by heating the sample at higher temperatures. These results are interpreted in terms of enhancement of non-radiative recombination associated with dangling bonds created by high optical excitation.