Orbital magnetism and spin-orbit effects in the electronic structure of BaIrO3

The electronic structure and magnetism of Ir 5d5 states in nonmetallic, weakly ferromagnetic BaIrO3 are probed with x-ray absorption techniques. Contrary to expectation, the Ir 5d orbital moment is found to be ~1.5 times larger than the spin moment. This unusual, atomiclike nature of the 5d moment is driven by a strong spin-orbit interaction in heavy Ir ions, as confirmed by the nonstatistical large branching ratio at Ir L(2,3) absorption edges. As a consequence, orbital interactions cannot be neglected when addressing the nature of magnetic ordering in BaIrO3. The local moment behavior persists even as the metallic-paramagnetic phase boundary is approached with Sr doping or applied pressure.     

Allylic disulfide rearrangement and desulfurization: mild, electrophile-free thioether formation from thiols

[reaction: see text] Secondary and tertiary allylic 2-pyridyl and 2-benzothiazolyl disulfides react with thiol groups at room temperature to give secondary and tertiary allyl alkyl disulfides. On the addition of a phosphine, a desulfurative sigmatropic rearrangement takes place at room temperature to give thioethers.     

Structure and solution dynamics of a “P–N–P” ligand attached to calix[4]arene scaffold and its palladium dichloride complex

A new diphosphazane ligand, Ph₂PN(CHMe₂)P(Ph){1,3-dimethoxycalix[4]arene} (2), in which the P–N–P unit is appended to calix[4]arene backbone, and its PdCl₂ complex (3) have been synthesized. The structures of the conformers of both the compounds in solution have been elucidated with the help of two-dimensional NMR experiments. Single crystal X-ray diffraction studies reveal the partial cone and cone conformations of the calixarene unit in the ligand (2) and the Pd-complex (3), respectively.     

Drifting undulations in an achiral smectic C liquid crystal driven by a static electric field

We report a novel dc field-driven propagative instability associated with the thermally induced layer undulations of the smectic C phase in a phenyl benzoate. While the undulations are two-dimensional, the drift is observed only along the wave vector q parallel to the c director; undulations with orthogonal q and c remain stable. The drift, which is nonhysteretic, takes place in a hopping way between equilibrium positions; it has a well-defined threshold in a given region, but the threshold varies rather widely for different regions. The average propagation velocity increases linearly from zero with the control parameter epsilon until epsilon approximately 2 but tends to saturate thereafter. Significantly, the drift direction reverses on switching the field polarity. The mechanism responsible for the drift appears to involve a coupling between the transverse field gradients due to the conductivity anisotropy and the transverse component of the flexoelectric polarization.     

Dynamic exponent in extremal models of pinning

The depinning transition of a front moving in a time-independent random potential is studied. The temporal development of the overall roughness w(L,t) of an initially flat front, , is the classical means to have access to the dynamic exponent. However, in the case of front propagation in quenched disorder via extremal dynamics, we show that the initial increase in front roughness implies an extra dependence over the system size which comes from the fact that the activity is essentially localized in a narrow region of space. We propose an analytic expression for the exponent and confirm this for different models (crack front propagation, Edwards-Wilkinson model in a quenched noise etc.). Received 27 August 1999     

Forty years of hydride reductions

Forty years ago, it was observed that diborane, a hydride, reduces aldehydes and ketones with exceptional ease even at 0°. Since then various hydride reagents have evolved for the convenient reduction of typical organic functional groups. Electrophilic reducing agents such as borane and alane possess markedly different reducing characteristics than those of nucleophilic reducing agents such as sodium borohydride and lithium aluminum hydride. Explorations have revealed means of both enhancing and diminishing the electrophilic character of borane and alane on the one hand and both enhancing and diminishing the nucleophilic character of borohydrides and aluminohydrides on the other. Such derivatives reveal unique characteristics making possible valuable selective reductions, not practical previously. These developments have completely altered the procedures normally used in organic chemistry for the reduction of functional groups.     

Simultaneous identification and verification of Bacillus anthracis

Specific identification of Bacillus anthracis (B. anthracis) is vital for the accurate treatment of afflicted personnel during biological warfare situations and civilian terrorist attacks. In order to accomplish this, we have subjected the lysates from B. anthracis to affinity purification using monoclonal antibodies for the selected antigenic protein present in the bacteria. The bound antigenic protein was identified by multi-dimensional protein identification technology (MudPIT) to be a surface layer protein EA1. The same antigen was identified from the lysates from a few strains of B. anthracis demonstrating the observation to be common for B. anthracis strains. Hence, this presents an effective pathway for the identification of the bacteria present in unknown samples of various origins. Generation of a database containing the EA1 protein has been found to be useful in the database search of unknown samples.