Commensurability oscillations in NdBa2Cu3Oy single crystals

Commensurability between inter-vortex distance and crystal lattice constant is investigated by angular dependent magnetization in very pure twinned and twin-free NdBa₂ Cu₃ O_y single crystals. With increasing temperature the incommensurate states split up and become finally commensurate with half the vortex distance. These new commensurate states are related to a substructure of the intrinsic pinning potential within the unit cell and discussed with respect to temperature, field, anisotropy, and twin structure.     

Determining a 'safe' high-mass limit in matrix-assisted laser desorption/ionisation time-of-flight mass spectra of coal derived materials with reference to instrument noise

Three methods for determining a 'safe' estimate for high-mass limits of MALDI spectra of coal derived liquids were explored, using a sample of coal-tar pitch and its pyridine-insoluble fraction. Co-addition of increasing numbers of single-shot spectra (10, 30, 50 and 100 pulses) showed visually observable reductions in noise levels, consistent with robust and statistically meaningful signals. Three separate types of post-acquisition calculation were used to identify high-mass limits of the spectra. (i) A literature method indicated high-mass limits similar to those observed visually-as a shift from baseline at the highest masses, nearly 350 000 u for the coal tar pitch and about 390 000 u for its pyridine insoluble fraction. (ii) Comparing instrument signal with pre-selected multiples of the standard deviation, upper mass estimates of between 40-60 000 u for the coal-tar pitch and about 95 000 u for its pyridine-insoluble fraction were found. (iii) Calculation of the slope was used to identify 'lift-off' of the spectrum from baseline. The angle between the smoothed spectrum and the baseline was matched to a pre-selected value (e.g. 0.5 degrees and 1 degrees ). However, the arbitrary specification of the key parameter did not establish this last method on a firm basis. The choice of a criterion for estimating high-mass limits of MALDI spectra remains a semi-quantitative procedure; a reasonably conservative high-mass limit may be estimated by comparison of signal with five times the standard deviation. However, evaluation of size exclusion chromatograms of the present samples using polystyrene standards suggests that molecular mass distributions of pitch samples arrived at by MALDI mass spectrometry are, at least partly, determined by the limitations of available instruments. Copyright 1999 John Wiley & Sons, Ltd.     

Highly Crystalline and Semiconducting Imine-Based Two-Dimensional Polymers Enabled by Interfacial Synthesis

Single-layer and multi-layer 2D polyimine films have been achieved through interfacial synthesis methods. However, it remains a great challenge to achieve the maximum degree of crystallinity in the 2D polyimines, which largely limits the long-range transport properties. Here we employ a surfactant-monolayer-assisted interfacial synthesis (SMAIS) method for the successful preparation of porphyrin and triazine containing polyimine-based 2D polymer (PI-2DP) films with square and hexagonal lattices, respectively. The synthetic PI-2DP films are featured with polycrystalline multilayers with tunable thickness from 6 to 200 nm and large crystalline domains (100–150 nm in size). Intrigued by high crystallinity and the presence of electroactive porphyrin moieties, the optoelectronic properties of PI-2DP are investigated by time-resolved terahertz spectroscopy. Typically, the porphyrin-based PI-2DP 1 film exhibits a p-type semiconductor behavior with a band gap of 1.38 eV and hole mobility as high as 0.01 cm² V⁻¹ s⁻¹, superior to the previously reported polyimine based materials.     

Metal promoted vinylcyclopropane-cyclopentene rearrangements: Reactions ripe for mechanism-based catalyst design

This brief review describes experimental and theoretical data relevant to the mechanisms of transition metal promoted vinylcyclopropane-cyclopentene rearrangements. In particular, reactions utilizing Pd(0), Rh(I), and Ni(0) are highlighted and compared to analogous reactions not involving transition metals.     

Mutually Independent Hamiltonian Connectivity of (n, k)-Star Graphs

A graph G is hamiltonian connected if there exists a hamiltonian path joining any two distinct nodes of G. Two hamiltonian paths and of G from u to v are independent if u = u ₁ = v ₁, v = u _v(G) = v _v(G) , and u _i ≠ v _i for every 1 < i < v(G). A set of hamiltonian paths, {P ₁, P ₂, . . . , P _k }, of G from u to v are mutually independent if any two different hamiltonian paths are independent from u to v. A graph is k mutually independent hamiltonian connected if for any two distinct nodes u and v, there are k mutually independent hamiltonian paths from u to v. The mutually independent hamiltonian connectivity of a graph G, IHP(G), is the maximum integer k such that G is k mutually independent hamiltonian connected. Let n and k be any two distinct positive integers with n–k ≥ 2. We use S _n,k to denote the (n, k)-star graph. In this paper, we prove that IHP(S _n,k ) = n–2 except for S _4,2 such that IHP(S _4,2) = 1.      

A highly selective rearrangement of a housane-derived cation radical: an electrochemically mediated transformation

To utilize housane-derived cation radicals as intermediates for the synthesis of the bicyclo (n.3.0) framework of natural products, a highly regioselective [1,2] shift of carbon to either a radical or an electron-deficient site is required. Herein we describe how this has been accomplished, provide a set of guidelines to assess housane oxidizability prior to its synthesis, and describe a synthesis of housane 18 that capitalizes upon the facility of [1,5] hydrogen shifts in substituted cyclopentadienes. The catalytic electrochemically mediated oxidation of 18 leads to a cation radical that engages in a rearrangement leading to the (4.3.0) adduct 23. The appearance of a catalytic current in the cyclic voltammogram of a solution containing the tris(aryl)amine and housane 18 is an excellent indicator that the amminium cation radical 14*+ is able to oxidize the housane and return the mediator to the original redox couple. DFT calculations show electron density on both the aryl and strained sigma framework in the HOMO of housane 18. From the spin density and electrostatic potential map for the cation radical, a picture where the spin resides on the side that is distal to the substituent emerges, while the hole is proximal to it. Both experiment and theory show that the rearrangement is best characterized as a [1,2] carbon shift toward an electron-deficient site and that migration toward the substituent-bearing carbon is much preferred over the alternative pathway.     

Selective stabilization of transition state structures for cope rearrangements of semibullvalene and barbaralane through interactions with halogens

A new means-discovered through quantum chemical studies (B3LYP/6-31G(d))-of selectively stabilizing the delocalized forms of unsubstituted semibullvalene and barbaralane is described. Calculations indicate that complexation of delocalized semibullvalene and barbaralane Cope rearrangement transition structures by halogen-containing molecules (homo- and heteronuclear diatomics and Lewis acids) can reduce the barrier significantly, in many cases causing it to disappear entirely.     

Bromination of silatranyl-, germatranyl-, silyl-, and germyl-phenylacetylenes

Reactions of element-substituted alkynes R₃MCCPh (R₃M = Me₃Si, Et₃Si, Ph₃Si, Et₃Ge, n-Bu₃Sn, N(CH₂CH₂O)₃Si, N(CH₂CH₂O)₃Ge, N(CH₂-CHMeO)₃Ge, and N(CH₂CH₂O)₂(CH₂CHPhO)Ge) with bromine, tetra-n-butylammonium tribromide (TBAT), and N-bromosuccinimide (NBS)/DMSO were investigated. The Z,E-ratio of isomeric dibromoalkenes formed in bromination reaction with Br₂ and TBAT are discussed. The crystal structures of N(CH₂CH₂O)₃SiCCPh and N(CH₂CHMeO)₃GeX (X = C CPh, C(Br)C(Br)Ph, C(Br₂)C(O)Ph), and Ph₃SiC(Br)C(Br)Ph are reported. © 2003 Wiley Periodicals, Inc. 15:43–56, 2004; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/.hc10211     

Obliquely propagating ion-acoustic shock waves in a degenerate quantum plasma

A theoretical investigation has been carried out on the propagation of non-linear ion-acoustic shock waves (IASHWs) in a magnetized degenerate quantum plasma system composed of inertial non-relativistic positively charged light and heavy ions, inertialess non-relativistically or ultra-relativistically degenerate electrons and positrons. The reductive perturbation method has been employed to derive the Burgers' equation. It has been observed that under consideration, our plasma model supports only positive potential shock structure. It is also found that the amplitude and steepness of the IASHWs have been significantly modified by the variation of ion kinematic viscosity, oblique angle, number density, and charge state of the plasma species. The results of our present investigation will be helpful for understanding the propagation of IASHWs in white dwarfs and neutron stars.