Novel thermolytic transformations of n-benzoyl 2-aza 3-oxa bicyclo(2.2.1)hept-5-ene and n-benzoyl 2-aza 3-oxa bicyclo(2.2.1)heptane

Novel thermolytic pathways were encountered in careful studies with N-benzoyl 2-aza 3-oxa bicyclo (2.2.1)heptene (1) and N-benzoyl 2-aza 3-oxa bicyclo(2.2.1)heptane (2). Compound 1 thermally fragments by four major pathways, namely, (3,3)-sigmatropic shift, (4 + 2) cycloreversion, N-O rupture and C-N homolysis. The (3,3)-sigmatropic shift provides a novel route to unusual, bicyclic heterocycles. Electron withdrawing aryl groupings tend to promote the (3,3)-sigmatropic shift pathway over others. The (4 + 2)-cycloreversion of 1 leads to nitroso carbonyl benzene and cyclopentadiene. The weak σ bonds of PhCONO undergo ready homolysis. The intermediate arising from N-O rupture leads to a cyclopentenone radical similar to that involved in the PG endoperoxide → PGE change. This radical either combines with benzoyl radical leading to 4-dibenzoylamino cyclopentenone or is transformed to an enamide by loss of hydrogen, which, in turn, undergoes (4 + 2)-cycloaddition with cyclopentadiene leading to a novel spiro adduct. The C-N rupture leads to the formation of benzanilide.Nitrosocarbonyl benzene is a powerful electrophile. With cyclohexene it forms a hydroximic ester, initiated by nucleophile acceptance at the CO oxygen. In contrast, it reacts with P(OMe)₃ leading to diphenylurea via nucleophile acceptance at NO oxygen. Thermolysis of 2 proceeds largely by N-O rupture, similar to that normally observed in the PG endoperoxide → PGE change.     

Intrinsic ferromagnetism in insulating cobalt doped anatase TiO2

Using complementary experiments we show that the room temperature ferromagnetism observed in anatase Co:TiO(2) films is not carrier mediated, but coexists with the dielectric state. TEM and x-ray absorption spectroscopy reveal a solid solution of Co in anatase, where Co is not metallic but in the +2 state substituting for Ti. Measurements at 300 K yield a M(S) of 1.1 mu(B)/Co atom, while all films are highly insulating. The evidence of intrinsic ferromagnetism in the dielectric ground state of Co:TiO(2) leads to new considerations for the origin of ferromagnetism in transition metal doped oxides.     

The temporal effect in listeners with mild to moderate cochlear hearing impairment

This study examines the relationship between a temporal masking effect and cochlear hearing impairment. The threshold level of a long-duration broadband masker needed to mask a short-duration tonal signal was measured for signals presented 2 ms (short-delay) or 202 ms (long-delay condition) after masker onset. The difference between these thresholds is the temporal effect. In two previous studies with normal-hearing listeners, estimates of gain of the cochlear active process derived from such data suggested a decrease in gain during the course of the masker. This hypothesis was further examined in the present study by testing listeners with mild to moderate cochlear hearing impairment. Results are consistent with a decrease in gain in the short-delay condition with increasing hearing impairment, and also less change in gain with increasing hearing impairment.     

Effect of the Radiation Power Density on the Sensitivity of a Diamond Detector

This paper presents the results of an experimental study of the sensitivity of a detector made of natural diamond of the IIa type as a function of the power density of the radiation of a pulsed xenon lamp. It has been shown that the sensitivity of the detector depends on the power density of the xenon lamp radiation and equals about (1–6)·10^–4 A/W. A monotonic decrease in sensitivity of the detector during a radiation pulse has been detected. The minimum resistance of the diamond crystal with an irradiated face of area 3 mm², placed 7 mm away from the axis of the xenon lamp, was 300 , which corresponds to a specific conductivity of 2.2 ^–1·m^–1.     

Syntheses of stereochemically diverse nine-membered ring-containing biaryls

[reaction: see text] A library of nine-membered, biaryl-containing rings has been synthesized in parallel on polystyrene macrobeads. Dimeric medium rings were shown to be accessible via a regio- and stereoselective double cyclization.     

Long-range molecular resonances in a cold Rydberg gas

We present evidence for molecular resonances in a cold dense gas of rubidium Rydberg atoms. Single UV photon excitation from the 5s ground state to np Rydberg states (n=50-90) reveals resonances at energies corresponding to excited atom pairs (n-1)d+ns. We attribute these normally forbidden transitions to avoided crossings between the long-range molecular potentials of two Rydberg atoms. These strong van der Waals interactions result in avoided crossings at extremely long range, e.g., approximately 58 000 times the Bohr radius (a(0)) for n=70.     

One-step transformation of tricyclopentabenzene (trindane, C(15)H(18)) to bicyclo(10.3.0)pentadec-1(12)ene- 2,6,7,11-tetrone (C(15)H(18)O(4)) and its aldol product, 12-hydroxy-16-oxatetracyclo(10.3.1.0.(1,5)0(7,11))hexadec-7(11)ene-2,6-dione (C(15)H(18)O(4))

[reaction: see text] Ozonolysis of 1 largely results in 2 and 3, having features similar to several classes of natural products. The retention of the C(15) pericycle suggests preference for the cleavage of pi-bonds endo to the cyclopentane ring. This unique property of trindane offers opportunities for synthesis of complex natural products from this hydrocarbon that can be made in quantity by acid-catalyzed trimerization of cyclopentanone.     

Direct evidence for block-by-block growth in high-temperature superconductor ultrathin films

Charge neutrality and stoichiometry impose severe restrictions on the mechanisms of epitaxial growth of complex oxides. The fundamental question arises of what is the minimum growth unit when sample thickness is reduced beyond the size of the unit cell. We have investigated the growth mechanism of YBa2Cu3O7 cuprate superconductor, using a consistent approach based on the growth of noninteger numbers of YBa2Cu3O7 layers in YBa(2)Cu(3)O(7)/PrBa(2)Cu3O7 superlattices. Ex situ chemical and structural analysis evidence a 2D block-by-block mechanism in which the minimum growth units are complete unit cell blocks, growing coherently over large lateral distances.     

Thin Nd:YAG slab laser pumped by lens duct coupled diode laser stacks

High power continuous wave operation of a diode face-pumped thin Nd:YAG slab laser is reported. A novel pumping geometry for a thin Nd:YAG slab using cylindrical lens duct coupled diode laser stacks is demonstrated. In a close-coupled resonator, a maximum laser output power of 260 W in multimode operation is obtained. This corresponds to a slope efficiency of 34% and an optical-to-optical efficiency of 27%, respectively. In high-brightness operation, a polarized laser output of 70 W has been obtained with a beam quality factor close to 4 in both directions. The polarization contrast ratio is >100. PACS 42.55.Xi; 42.60.Pk; 42.60.By