μ- spin rotation studies on graphite and its second-stage rubidium intercalation compound. Evidence for a paramagnetic chemical shift

The precession frequencies of negative-muon spin rotation in highly oriented pyrolytic graphite and its second stage Rb compound were measured at room temperature. The results showed that a μ^- C-C bond is formed from sp² hybrid orbitals involving the partially filled p_z orbital and that intercalation influences the σ as well as the π bonds.     

Microscopic Studies of 2H-NbSe2 Probed by Positive Muon

Abstract

The microscopic state of the positively charged light particle in the transition metal dichalcogenide 2H-NbSe₂ was studied using the muon spin relaxation method (μ⁺SR) and muon level crossing resonance method (μ-LCR). Muons are expected to stay at interlayer position and behaves as a hydrogen like intercalant. We discuss the relation between conduction electron properties and the muon's behavior.     

Lithium ion conductive glass–ceramics with Li3Fe2(PO4)3 and YAG laser-induced local crystallization in lithium iron phosphate glasses

The glasses with the composition of 37.5Li₂O–(25 − x)Fe₂O₃–xNb₂O₅–37.5P₂O₅ (mol%) (x = 5,10,15) are prepared, and it is found that the addition of Nb₂O₅ is effective for the glass formation in the lithium iron phosphate system. The glass–ceramics consisting of Nasicon-type Li₃Fe₂(PO₄)₃ crystals with an orthorhombic structure are developed through conventional crystallization in an electric furnace, showing electrical conductivities of 3 × 10^− 6 Scm^− 1 at room temperature and the activation energies of 0.48 eV (x = 5) and 0.51 eV (x = 10) for Li⁺ ion conduction in the temperature range of 30–200 °C. A continuous wave Nd:YAG laser (wavelength: 1064 nm) with powers of 0.14–0.30 W and a scanning speed of 10 μm/s is irradiated onto the surface of the glasses, and the formation of Li₃Fe₂(PO₄)₃ crystals is confirmed from XRD analyses and micro-Raman scattering spectra. The crystallization of the precursor glasses is considered as new route for the fabrication of Li₃Fe₂(PO₄)₃ crystals being candidates for use as electrolyte materials in lithium ion secondary batteries.     

Total Biosynthesis of Melleolides from Basidiomycota Fungi: Mechanistic Analysis of the Multifunctional GMC Oxidase Mld7

Mushroom terpenoids are biologically and chemically diverse fungal metabolites. Among them, melleolides are representative sesquiterpenoids with a characteristic protoilludane skeleton. In this study, we applied a recently established hot spot knock-in method to elucidate the biosynthetic pathway leading to 1α-hydroxymelleolide. The biosynthesis of the sesquiterpene core involves the cytochrome P450 catalyzing stepwise hydroxylation of the Δ⁶-protoilludene framework and a stereochemical inversion process at the C5 position catalyzed by short-chain dehydrogenase/reductase family proteins. The highlight of the biosynthesis is that the flavoprotein Mld7 catalyzes an oxidation-triggered double-bond shift accompanying dehydration and acyl-group-assisted substitution with two different nucleophiles at the C6 position to afford the Δ⁷-protoilludene derivatives, such as melleolide and armillarivin. The complex reaction mechanism was proposed by DFT calculations. Of particular importance is that product distribution is regulated by interaction with the cell membrane.     

Periodic porous stripe patterning in a polymer blend film induced by phase separation during spin-casting

A periodic striping pattern with microscale pore size is observed on the surface of thin films prepared by spin-casting from a polystyrene (PS) and polyethylene glycol (PEG) blend solution. The pattern is created by the convection generated by thermal gradients in the solution between the substrate and film solution during solvent evaporation, the radial flow of the spin-coated solution, and the primary and secondary phase separation of the PS and PEG solutions. The formation mechanism of the periodic porous stripe pattern is discussed, wherein the effects of the polymer blend weight ratio, polymer concentration, and drying rate on the formation of the periodic porous striping pattern are investigated using scanning electron and atomic force microscopy.     

μ+SR Study of Ordering Phenomena in the Heavy-Fermion State of Ce3Pd20Ge6

Magnetic and quadrupolar ordering phenomena in a Ce₃Pd₂₀Ge₆ single crystal have been investigated by muon spin rotation/relaxation (μ⁺SR) spectroscopy. We have observed spontaneous precession of muons in zero-field below T _N =0.7 K in the antiferromagnetic state. The precession frequency follows the power law: ν(T)=ν(0)(1−T/T _N ) ⁿ . The exponent n=0.43(2) is close to the mean-field value of 0.5. The muon longitudinal spin relaxation rate 1/T ₁ is found to be nearly independent of temperature in the range of 0.3 to 2 K, i.e., across either T _N or T _Q =1.2 K, the quadrupolar ordering temperature. Two likely mechanisms for the temperature independent behavior of 1/T ₁ are suggested. This revised version was published online in September 2006 with corrections to the Cover Date.     

First-Principles Theory of Muon and Muonium Trapping in the Protein Chain of Cytochrome c and Associated Hyperfine Interactions

The microscopic details of the electron transfer in cytochrome c (cyt c) are being investigated by the Muon Spin Relaxation (μSR) technique. We are using the Hartree–Fock Cluster Procedure to determine the most likely trapping sites for μ⁺ and muonium (Mu) in the protein chain, and have performed extensive calculations in single amino acid molecules of the protein chain of cyt c. The double-bonded oxygen atom of the carboxyl group was identified as the trapping site for both μ⁺ and Mu. Utilizing the wave functions we obtained from the Hartree–Fock calculations, we have determined the hyperfine field that the μ⁺ in Mu experiences while the latter is trapped at the oxygen. This revised version was published online in September 2006 with corrections to the Cover Date.     

Determination of Easy Axis in a Chemical Ferromagnet, 4-(p-Chlorobenzylideneamino)–TEMPO (TEMPO=2,2,6,6-Tetramethylpiperidin-1-Oxyl)

The trapping sites for muon and muonium in ferromagnetic p-Cl–Ph–CH=N–TEMPO [(4-(p-chlorobenzylideneamino)–TEMPO (TEMPO = 2,6,6-tetramethyl-piperidin-1-yloxyl)] and the hyperfine interaction tensors for these sites are obtained using first-principles Unrestricted Hartree–Fock theory. The calculated hyperfine interactions are used to compare the calculated zero field muon spin rotation (μSR) frequencies for different choices for the easy axis and the observed frequency. It has been concluded that the two trapping centers that can best explain the observed μSR frequency are a trapped singlet muonium near the radical oxygen and a trapped muon site near the chlorine. The direction of the easy axis also is determined to be the b-axis of the monoclinic lattice. This direction for the easy axis is confirmed by determining the direction of the distributed magnetization in the molecular solid which leads to a minimum dipole–dipole interaction energy. The consequences of this agreement for the easy axis direction by two independent procedures are discussed. This revised version was published online in September 2006 with corrections to the Cover Date.     

Appearance of magnetic long range order in the spin ladder compound LaCuO2.5

We report here the two current topics in the ladder compounds. 1. The new ladder compound LaCuO_2.5 recently discovered by Hiroi and Takano shows a clear sign of magnetic long range order at around 125 K observed by μ⁺SR technique. This result demonstrates that the ground state of LaCuO_2.5 is not a spin liquid state, but a magnetically ordered state. 2. Superconductivity has been found in the ladder material (Sr,Ca)₁₄Cu₂₄O₄₁ under high pressure between 3 GPa and 4.5 GPa. The superconducting transition temperatures T_c (onset) are 12 K and 9 K at 3 GPa and 4.5 GPa, respectively. This revised version was published online in July 2006 with corrections to the Cover Date.