Enantiospecific synthesis of tricyclo5.2.1.0(4,8)]decanes via acid catalysed rearrangement of isotwistanes

An acid catalysed rearrangement was employed for the enantiospecific conversion of isotwistanol to tricyclo5.2.1.0(4.8)]-decanes, which provided support for the proposed biosynthesis of allopupukeananes from pupukeananes. The strategy has been further extended to the enantiospecific synthesis of a homobrexane. (c) 2005 Elsevier Ltd. All rights reserved.

Probing disorder in cubic pyrochlore Bi-1 Zn-5(1) Nb-0(1) O-5(7) (BZN) thin films

The dielectric response of pulsed laser ablated Bi-1 Zn-5(1) Nb-0(1) O-5(7) (BZN) thin films are investigated within the temperature range of 300-660 K and frequency range of 100 Hz-100 kHz Thin film exhibited a strong dielectric relaxation behavior A sharp rise in dielectric constant of BZN thin film at high temperatures is related to disorder in canon and anion lattices Observed dielectric relaxation implies a redistribution of charges within the unit cell This phenomenon suggests that the large change in dielectric constant is due to a dynamical rise of dipolar fluctuations in the unit cell XPS spectra of BZN (A(2)B(2)O(6)O') cubic pyrochlore confirm that the relaxation corresponds to the ionic hopping among the A and O' positions of several local potential minima Barrier height for hopping is distributed between 0 and 0 94 eV The O is spectrum confirms presence of two types of oxygen in BZN thin film The disorder in charge neutralized thin film is correlated with XPS spectra (C) 2010 Elsevier Ltd All rights reserved

Stereospecific construction of multiple contiguous quaternary carbons. Total synthesis of (±)-cis,anti,cis-1,8,12,12-tetramethyl-4-oxatricyclo[6.4.0.02,6]dodecan-3-ol, a thapsane isolated from Thapsia villosa var minor

The details of the first total synthesis of a natural thapsane lg containing three contiguous quaternary carbon atoms, starting from cyclogeraniol (9) '5 described. The Claisen rearrangement of 9 with methoxypropene in the presence of a catalytic amount of propionic acid produced ketone 10. Rhodium acetate-catalyzed intramolecular cyclopropanation of a-diazo-&keto ester 12, obtained from 10 via 8-keto ester 8, furnished cyclopropyl keto ester 7. Lithium in liquid ammonia reductive cleavage of cyclopropyl compound 7 gave a 1:l mixture of hydrindanone 6 and keto1 13. Wittig methylenation of 6 furnished ester 21. Epoxidation of 21, followed by BF3-OEt2-catalyzed rearrangement of epoxide 23 afforded hemiacetal 25. Treatment of hemiacetal 25 with triethylsilane in trifluoroacetic acid furnished lactone 22, a degradation product of various thapsanes. Finally, DIBAH reduction of lactone 22 generated the thapsane

Formation of a single, rotated-Brass (1 1 0)< 5 5 6 > texture by hot cross-rolling of an Al-Zn-Mg-Cu-Zr alloy

The present work describes the evolution of a strong, single-component rotated-Brass ((1 1 0) < 5 5 6 >) texture in an Al-Zn-Mg-Cu-Zr alloy by an uneven hot cross-rolling with frequent interpass annealing. This texture development is unique because hot rolling of aluminum alloys results in orientation distribution along the ``beta-fibre''. It has been demonstrated that the deformation by cross-rolling of a partially recrystallized grain structure having rotated-Cube and Goss orientations, and the recrystallization resistance of near-Brass-oriented elongated grains play a critical role in development of this texture. (C) 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Dynamics of I-asterisk(P-2(1/2)) production inthe ultraviolet photodissociation of alkyn iodides

The relative quantum yields, phi*, for the production of I*(P-2(1/2)) at 266, 280, and similar to 305 nm are reported for a series of primary alkyl iodides using the technique of two-photon laser-induced fluorescence for the detection of I(P-2(3/2)) and I*(P-2(1/2)) atoms. Results are analyzed by invoking the impulsive energy disposal model, which summarizes the dynamics of dissociation as a single parameter. Comparison of our data with those calculated by a more sophisticated time-dependent quantum mechanical model is also made. Near the red edge of the alkyl iodide A band, absorption contribution from the (3)Q(1) state is important and the dynamics near the (3)Q(0)-(1)Q(1) curve-crossing region seem to be influenced by the kinematics of the dissociation process

Synthesis based on cyclohexadienes: Part 10 synthesis of 5,5-dimethyl-7-methoxy-4-oxatricyclo[4.3.1.0]decan-2-ones

Synthesis of 5, 5-dimethyl- 7-methoxy-4 -oxatricyclo[4,3,1,0(3,7)]- decan-2-one 3a, a novel heterocyclic ring system present in morellin 1, and its 3-substituted derivatives 3b-e, is described from the Diels-Alder adducts 7, available from 1-methoxycyclohexa-1,4-dienes 4. Two routes, which involved the halocyclisation and the oxidative addition, were investigated for the conversion of the adducts 7 into 3. While the halocyclisation method resulted in mixtures, excellent yields of the target molecule were obtained by the second method. Solvolysis of the bromoether 9 resulted in a mixture of rearranged products 10, 13, 15 and 16.

Solution structure of BTK-2, a novel hK(v)1.1 inhibiting scorpion toxin, from the eastern Indian scorpion Mesobuthus tamulus

The three dimensional structure of a 32 residue three disulfide scorpion toxin, BTK-2, from the Indian red scorpion Mesobuthus tamulus has been determined using isotope edited solution NMR methods. Samples for structural and electrophysiological studies were prepared using recombinant DNA methods. Electrophysiological studies show that the peptide is active against hK(v)1.1 channels. The structure of BTK-2 was determined using 373 distance restraints from NOE data, 66 dihedral angle restraints from NOE, chemical shift and scalar coupling data, 6 constraints based on disulfide linkages and 8 constraints based on hydrogen bonds. The root mean square deviation (r.m.s.d) about the averaged co-ordinates of the backbone (N, C-alpha, C') and all heavy atoms are 0.81 +/- 0.23 angstrom and 1.51 +/- 0.29 angstrom respectively. The backbone dihedral angles (phi and psi) for all residues occupy the favorable and allowed regions of the Ramachandran map. The three dimensional structure of BTK-2 is composed of three well defined secondary structural regions that constitute the alpha-beta-beta, structural motif. Comparisons between the structure of BTK-2 and other closely related scorpion toxins pointed towards distinct differences in surface properties that provide insights into the structure-function relationships among this important class of voltage-gated potassium channel inhibiting peptides. (C) 2011 Elsevier B.V. All rights reserved.

H-1 MAS NMR study of protonic conduction in layered HNbWO6 center dot xH(2)O (x=1.5, 0.5)

H-1 Magic Angle Spinning (MAS) NMR of layered HNbWO6 . xH(2)O (x = 1.5, 0.5) is carried out at room temperature and at various spinning speeds (1-12 kHz). Results on the fully hydrated sample (x = 1.5) are consistent with the model of diffusion of H3O+ ions within the layers. In the partially dehydrated sample (x = 0.5) an exchange between the distinctly present cage protons and H3O+ protons leads to protonic conduction.

Dielectric function and optical conductivity of TiOx (0.8

Reflection electron energy-loss spectra are reported for the family of compounds TiOx over the entire homogeneity range (0.8 < a: < 1.3). The spectra exhibit a plasmon feature on the low-energy side, while several interband transitions are prominent at higher energies. The real and imaginary parts of dielectric functions and optical conductivity for these compounds are determined using the Kramers-Kronig analysis. The results exhibit systematic behavior with varying oxygen stoichiometry.

Structural and vibrational studies of the layered structure solid Fe1 ? xNixPS3 (1 greater-or-equal, slanted x greater-or-equal, slanted 0)

We report here the results of structural and vibrational studies on the solid solution Fe1 ? xNixPS3 (1 greater-or-equal, slanted x greater-or-equal, slanted 0) systems. From the structural analysis, we show that there is a lattice compaction as the composition x is varied from 0 to 1, the basic lattice symmetry being maintained. We find that the compaction is more in the basal plane. These subtle structural changes are also reflected in the vibrational bands. We observed splitting of certain bands due to these small changes in the lattice constants, which we explained as arising from a correlation splitting. These changes in the vibrational bands have also been seen on cooling where there is a preferential thermal compaction in the basal plane compared to that perpendicular to the plane.

Superconductivity of La2?ySryCu1?xNixO4+? (y = 0.1, 0.2; 0less-than-or-equals, slantxless-than-or-equals, slant0.5) The hole-compensating effect of Ni

Magnetization measurements below 50 K on ceramic La2?ySryCu1?xNixO4+? (y = 0.1, 0.2; 0less-than-or-equals, slantxless-than-or-equals, slant0.5) show a progressive diminution of superconducting properties with increasing x. The larger suppressive action of Ni in the y=0.1 system than that for y=0.2 is attributed to the hole-compensating effect of Ni3+. The assumption that nickel is in the 3+ state satisfactorily explains: (1) the reduction in hole concentration, (2) a right-shift of the Tc versus y curve with x, and (3) the low magnetic moment carried by Ni atoms, in the La2?ySryCu1?xNixO4+? system.

Stereospecific solid-state NaBH4-promoted reduction of 1-methylpentacyclo[5.4.0.0(2,6).0(3,10).0(5,9)]undecane-8,11-dione

NaBH4 reduction of a cage dione proceeds in a stereospecific fashion to give the endo,endo-diol. This reactivity is related to the crystal structure.

Synthesis based on cyclohexadienes. Part-27. Synthesis of functionalized tricyclo[5.2.2.0(1,5)]undecanes

A new methodology for the construction of tricyclo[5.2.2.0(1,5)]undecanes is described from indane-4-carboxylic acids. Birch reduction of indane-4-carboxylic acids followed by conjugation and cycloaddition with alpha-chloroacrylonitrile and hydrolysis lead to the tricyclic compounds 36 and 48 which are intermediates in the eremolactone synthesis.

LiSr1.65 square 0.35B1.3B ' O-1.7(9) (B = Ti, Zr; B ' = Nb, Ta): New lithium ion conductors based on the perovskite structure

We describe the design and synthesis of new lithium ion conductors with the formula, LiSr(1.65)rectangle(0.35)B(1.3)B'O-1.7(9) (rectangle = vacancy; B = Ti, Zr; B' = Nb, Ta), on the basis of a systematic consideration of the composition-structure-property correlations in the well-known lithium-ion conductor, La-(2/3-x)Li(3x)rectangle((1/3)-2x)TiO3 (I), as well as the perovskite oxides in Li-A-B,B'-O (A = Ca, Sr, Ba; B = Ti, Zr; B' = Nb, Ta) systems. A high lithium-ion conductivity of ca. 0.12 S/cm at 360 degrees C is exhibited by LiSr(1.65)rectangle(0.35)Ti(1.3)Ta(1.7)O(9) (III) and LiSr(1.65)rectangle(0.35)Zr(1.3)Ta(1.7)O(9) (IV), of which the latter containing stable Zr(IV) and Ta(V) oxidation states is likely to be a candidate electrolyte material for all-solid-state lithium battery application. More importantly, we believe the approach described here could be extended to synthesize newer, possibly better, lithium ion conductors.

Magneto-structural correlation in (mu-alkoxo/hydroxo)(mu-carboxylato)dicopper(II) systems: Synthesis, X-ray structure and magnetic properties of aquo(mu-hydroxo) (mu-arylcarboxylato)bis(N,N,N ',N '-tetramethylethane-1,2-diamine)dicopper(II) diperchlorate

Asymmetrically dibridged dicopper(II) complexes, [Cu-2(OH)(O2CC6H4-p-Me)(tmen)(2)(H2O)](ClO4)(2) (1) and [Cu-2(OH)(O2CC6H4-p-OMe)(tmen)(2)(H2O)](ClO4)(2) (2) (tmen = N,N,N',N'-tetramethylethane-1,2-diamine), were prepared and structurally characterized. Complex 1 crystallizes in the monoclinic space group P2(1)/a with a = 17.718(2), b = 9.869(1), c = 19.677(2) Angstrom, beta = 115.16(1)degrees, V = 3114.3(6) Angstrom(3) and Z = 4. The structure was refined to R(wR(2)) = 0.067(0.178). Complex 2 crystallizes in the monoclinic space group P2(1)/a with a = 17.695(3), b = 9.574(4), c = 20.104(2) Angstrom, beta = 114.18(1)degrees, V = 3107(1) Angstrom(3) and Z = 4. The final residuals are R(wR(2)) = 0.067(0.182). The complexes have a [Cu-2(mu-OH)(mu-OH)(mu-O2CAr)](2+) core with tmen Ligands occupying the terminal sites of the core. In addition, one copper is axially bound to a water molecule. The Cu ... Cu distances and the Cu-OH Cu angles in the core are 3.394(1) Angstrom, 124.4(2)degrees for 1 and 3.374(1) Angstrom, 123.3(3)degrees for 2. The complexes show axial X-band EPR spectral features in methanol glass at 77 K giving g(perpendicular to) = 2.02, g(parallel to) = 2.3 (A(parallel to) = 165 x 10(-4) cm(-1)) and a visible band near similar to 630 nm in methanol. The complexes are weakly antiferromagnetic. A theoretical fit of the magnetic susceptibility data in the temperature range 40-295 K gives -J = 10 cm(-1), g = 2.05 for 1 and -J = 10 cm(-1), g = 2.0 for 2. Plots of -2J versus the Cu-OH-Cu angle (phi) in this class of asymmetrically dibridged dicopper(II) complexes having d(x2-y2)-d(x2-y2) magnetic orbitals show a linear magneto-structural correlation: -2J(cm(-1)) = 11.48 phi(deg) - 1373.