Delocalized fermions in underdoped cuprate superconductors

Low-temperature heat transport was used to investigate the ground state of high-purity single crystals of the lightly doped cuprate YBa2Cu3O6.33. Samples were measured with doping concentrations on either side of the superconducting phase boundary. We report the observation of delocalized fermionic excitations at zero energy in the nonsuperconducting state, which shows that the ground state of underdoped cuprates is a thermal metal. Its low-energy spectrum appears to be similar to that of the d-wave superconductor, i.e., nodal. The insulating ground state observed in underdoped La2-xSrxCuO4 is attributed to the competing spin-density-wave order.     

Polyethylene glycol in copper electrodeposition onto a rotating disk electrode

Many of the proprietary additive formulations that have been proposed to control the properties of metal electrodeposits include water soluble macromolecules. Among these are the hydrodynamically interesting polyethylene glycols ‘Polyox’. In the course of a rotating disk electrode study of the effects of additives in copper electrodeposition the present authors had cause to try the effects of low concentrations of Polyox in an acid copper sulphate plating solution. In the presence of an essential trace of chloride ion Polyox very strongly inhibited deposition below a critical overpotential at which current density rises extremely rapidly with increasing overpotential. These results suggest that below the critical overpotential chloride ions hold a film of Polyox onto the electrode surface and may also give the film some lateral cohesion. The film may be a Polyox-cuprous chloride complex. Striking spiral patterns form at the critical overpotential. Their characteristics are explained as the consequences of electrodeposition on a surface containing submicroscopic protrusions and depressions in conditions where current density increases very rapidly with potential.     

Phenolic compounds,essential oil composition,and antioxidant activity of Angelica purpurascens (Avé-Lall.) Gill

In this study, methanol extracts (MEs) and essential oil (EO) of Angelica purpurascens (Avé-Lall.) Gill obtained from different parts (root, stem, leaf, and seed) were evaluated in terms of antioxidant activity, total phenolics, compositions of phenolic compound, and essential oil with the methods of 2,2-azino-bis(3ethylbenzo-thiazoline-6-sulfonic acid (ABTS•⁺), 2,2-diphenyl-1-picrylhydrazil (DPPH•) radical scavenging activities, and ferric reducing/antioxidant power (FRAP), the Folin–Ciocalteu, liquid chromatography−tandem mass spectrometry (LC−MS/MS), and gas chromatography-mass spectrometry (GC−MS), respectively. The root extract of A. purpurascens exhibited the highest ABTS•⁺, DPPH•, and FRAP activities (IC₅₀: 0.05 ± 0.0001 mg/mL, IC₅₀: 0.06 ± 0.002 mg/mL, 821.04 ± 15.96 µM TEAC (Trolox equivalent antioxidant capacity), respectively). Moreover, EO of A. purpurascens root displayed DPPH• scavenging activity (IC₅₀: 2.95 ± 0.084 mg/mL). The root extract had the highest total phenolic content (438.75 ± 16.39 GAE (gallic acid equivalent), µg/mL)). Twenty compounds were identified by LC−MS/MS. The most abundant phenolics were ferulic acid (244.39 ± 15.64 μg/g extract), benzoic acid (138.18 ± 8.84 μg/g extract), oleuropein (78.04 ± 4.99 μg/g extract), and rutin (31.21 ± 2.00 μg/g extract) in seed, stem, root, and leaf extracts, respectively. According to the GC−MS analysis, the major components were determined as α-bisabolol (22.93%), cubebol (14.39%), α-pinene (11.63%), and α-limonene (9.41%) among 29 compounds. Consequently, the MEs and EO of A. purpurascens can be used as a natural antioxidant source.     

Thermal and mechanical properties of radiation crosslinked poly(tetrafluoroethylene-co-perfluoromethyl vinyl ether)

The effect of irradiation temperature on the polymer properties was investigated for the fluoroelastomer poly(tetrafluoroethylene-co-perfluoromethylvinyl ether) (TFE/PMVE). TFE/PMVE samples were γ-irradiated to 150 kGy at temperatures ranging from 77 K to 373 K. Analysis of the sol/gel behaviour, tensile properties, and glass transition temperatures indicated that crosslinking commenced in the temperature range 195 to 263 K, for a dose of 150 kGy. The latter temperature was 13 K below the glass transition temperature. Crosslinking remained relatively constant to higher temperatures. Chain scission reactions were found to occur well below the glass transition temperature and increased at higher temperatures. The optimum temperature for the radiation crosslinking of TFE/PMVE, for the temperatures investigated, was 263 K.     

Half-integer spin heptanuclear single-molecule magnet with an unusual Mn(III)6Mn(II) exchange-coupled core

The synthesis, X-ray crystallography, magnetic properties, and high-field electron paramagnetic resonance (HFEPR) of a new heptanuclear manganese complex [Mn(7)(heamp)(6)](ClO(4))(2)·4CH(2)Cl(2)·H(2)O (complex 2), in which heampH(3) is 2-[N,N-di(2-hydroxyethyl)aminomethyl]phenol (compound 1), is reported. Complex 2 has a hexagonal, disk-shaped topology and contains six Mn(III) ions and a central Mn(II) ion. It crystallizes in the monoclinic space group P2(1)/c with two molecular orientations. Consideration of the cluster topology, together with variable-temperature and variable-field DC magnetic susceptibility data, suggest that complex 2 exists in a half-integer, S = (19)/(2) ± 1 spin ground state, with appreciable uniaxial zero-field splitting (D = -0.16 cm(-1)). AC magnetic susceptibility measurements clearly show out-of-phase signals, which are frequency- and temperature-dependent, indicating slow magnetization relaxation behavior. An analysis of the relaxation data employing the Arrhenius formula yielded an effective relaxation barrier of 12.9 cm(-1). Simulations of HFEPR studies agree with the assignment of an S ≈ (19)/(2) spin ground state, with g = 1.96, D = -4.71 GHz (-0.16 cm(-1)), and a longitudinal fourth-order zero-field splitting parameter B(4)(0) = -2.7 × 10(-4) GHz (-9.0 × 10(-6) cm(-1)).     

Derivation of class II force fields. VIII. Derivation of a general quantum mechanical force field for organic compounds

A class II valence force field covering a broad range of organic molecules has been derived employing ab initio quantum mechanical "observables." The procedure includes selecting representative molecules and molecular structures, and systematically sampling their energy surfaces as described by energies and energy first and second derivatives with respect to molecular deformations. In this article the procedure for fitting the force field parameters to these energies and energy derivatives is briefly reviewed. The application of the methodology to the derivation of a class II quantum mechanical force field (QMFF) for 32 organic functional groups is then described. A training set of 400 molecules spanning the 32 functional groups was used to parameterize the force field. The molecular families comprising the functional groups and, within each family, the torsional angles used to sample different conformers, are described. The number of stationary points (equilibria and transition states) for these molecules is given for each functional group. This set contains 1324 stationary structures, with 718 minimum energy structures and 606 transition states. The quality of the fit to the quantum data is gauged based on the deviations between the ab initio and force field energies and energy derivatives. The accuracy with which the QMFF reproduces the ab initio molecular bond lengths, bond angles, torsional angles, vibrational frequencies, and conformational energies is then given for each functional group. Consistently good accuracy is found for these computed properties for the various types of molecules. This demonstrates that the methodology is broadly applicable for the derivation of force field parameters across widely differing types of molecular structures. Copyright 2001 John Wiley & Sons, Inc. J Comput Chem 22: 1782-1800, 2001     

Recent developments in the chemistry of stable silylenes

This paper reviews progress in the field of thermally stable silylenes since 2000. Developments in the synthesis and characterization of new stable silylenes are discussed, followed by a summary of recent theoretical calculations upon model silylenes. The main part of the article concerns the reactivity patterns displayed by silylenes 1-4, which are discussed in terms of their behavior toward radical, organic, inorganic, and organometallic species.     

Temporally resolved laser induced plasma diagnostics of single crystal silicon — Effects of ambient pressure

Laser-Induced Breakdown Spectroscopy of silicon was performed using a nanosecond pulsed frequency doubled Nd:YAG (532 nm) laser. The temporal evolution of the laser ablation plumes in air at atmospheric pressure and at an ambient pressure of ∼ 10^− 5 mbar is presented. Electron densities were determined from the Stark broadening of the Si (I) 288.16 nm emission line. Electron densities in the range of 6.91 × 10¹⁷ to 1.29 × 10¹⁹ cm^− 3 at atmospheric pressure and 1.68 × 10¹⁷ to 3.02 × 10¹⁹ cm^− 3 under vacuum were observed. Electron excitation temperatures were obtained from the line to continuum ratios and yielded temperatures in the range 7600–18,200 K at atmospheric pressure, and 8020–18,200 K under vacuum. The plasma morphology is also characterized with respect to time in both pressure regimes.     

Crystal structure and DFT calculations of Cp2NbH(SiIMe2)(SiFMe2): an asymmetric bis(silyl) niobocene hydride complex

An asymmetric bis(silyl) niobocene hydride complex, namely, bis(η⁵-cyclopentadienyl)(fluorodimethylsilyl)hydrido(iododimethylsilyl)niobium, [Nb(C₅H₅)₂(C₂H₆FSi)(C₂H₆ISi)H] or Cp₂NbH(SiIMe₂)(SiFMe₂), has been studied to determine the effect of the silyl ligand on the position of the hydride attached to the Nb atom. It has been shown that when a Group 17 atom is substituted onto one of the silyl ligands, there is a greater interaction between the hydride and this ligand, as demonstrated by a shorter Si…H distance. In the present work, we have investigated the effect when the silyl ligands are substituted by different Group 17 atoms. We present here the structure and DFT calculations of Cp₂NbH(SiIMe₂)(SiFMe₂), showing that the position of the hydride is located between the two silyl ligands. The results from our investigation show that the hydride is closer to the silyl ligand that is substituted by fluorine.