Generation of a heterobimetallic FeMoS system containing intermediate spin [FeIIN4S2] functionality: Synthesis,characterisation and redox chemistry of [(N–N)2FeS2MoS2] (N–N=bipy or phen)

Tetrathiomolybdate reacts with iron (II) in the presence of bidentate ligands to form neutral binuclear complexes [Fe(N–N)₂MoS₄] [N–N=2-2bipyridine(bipy) and 1,10-phenanthroline(phen)] showing intermediate spin character for Fe^II. The spin state of the complexes has been examined by variable temperature magnetic moment (VTM) measurements and by variable temperature Mössbauer spectroscopy. The Mössbauer spectra indicate the presence of two iron sites: one of intermediate spin and the other of low spin at room temperature. The low spin site predominates over the intermediate spin as the temperature is lowered. The structural features of the complexes are supported by i.r., Raman, electronic and FAB mass spectra and by X-ray powder diffraction data. Substitution of one bipy/phen ligand in [Fe(N–N)₃]²⁺ by MS₄ ^2– ligands does not impart any major effect towards the size of the redox potentials of the tris-bipy/phen complexes, although the reversible nature of their cyclic voltammetric response is affected.     

Excess volumes of isomeric butanols with di-n-butyl ether

The excess volumes of four isomeric butanols with di-n-butyl ether were determined at 30°C. The isomeric effect was distinctly observed in the excess volume profiles. 1-Butanol and 2-methyl-l-propanol systems exhibited negative excess volumes throughout the concentration range. The 2-butanol system had positive excess volumes up to 0.9 mol fraction of alcohol after which it became negative, while the 2-methyl-2-propanol system exhibited positive excess volumes throughout the concentration range. NCL Communication No. 4678     

A Plane-Symmetric Inhomogeneous Cosmological Model of Perfect Fluid Distribution with Electromagnetic Field I

A plane-symmetric inhomogeneous cosmological model of perfect fluid distribution with electro-magnetic field is obtained. F12 is the non-vanishing component of electromagnetic field tensor. To get a deterministic solution, we assume the free gravitational field is Petrov type-Ⅱ non-degenerate. Some physical and geometric properties of the model are also discussed.     

Photo-gated charge transfer of organized assemblies of CdSe quantum dots

The electronic conductivity of tri-n-octylphosphineoxide (TOPO)-protected CdSe quantum dots (QDs) was studied at the air-water interface using the Langmuir technique within the context of photochemical and photophysical excitation. It was found that, upon photoirradiation with photon energies higher than that of the absorption threshold, the voltammetric currents increased rather substantially with a pair of voltammetric peaks at positive potentials. However, the photoconductivity profiles exhibited a dynamic transition, which was ascribed to the strong affinity of oxygen onto the CdSe surface and the consequent trapping of the photogenerated electrons. The resulting excess of holes led to photocorrosion of the particle cores. The oxygen adsorption and photoetching processes were found to be reversible upon cessation of the photoexcitation. In contrast, only featureless voltammetric responses were observed when the particle monolayers were deposited onto the electrode surface and the film conductance was measured in a vacuum (the overall profiles were analogous to that of a Coulomb blockade). A comparative study was also carried out with a CdSe dropcast thick film immersed in acetonitrile, where the photoconductivity profiles were reversible and almost linear. The latter was attributed to the separation of photogenerated electrons and holes which were subsequently collected at the electrodes under voltammetric control. In the dropcast system, the oxygen effects were minimal which was ascribed to the acetontrile medium that limited the access to oxygen and thus the particles were chemically intact. These studies suggest that chemical environment plays an important role in the determination of the chemical stability and electronic conductivity of CdSe QD thin films.     

Origin of threefold symmetric torsional potential of methyl group in 4-methylstyrene

To understand the effect of the para position vinyl group substitution in toluene on methyl torsion, we investigated 4-methylstyrene, a benchmark molecule with an extended pi conjugation. The assignment for a 33 cm(-1) band in the excitation spectrum to the 3a(2) torsional transition, in addition to the assignments suggested previously for the other bands in the excitation spectrum, leads to the model potentials for the ground as well as excited states with V(3) (")=19.6 cm(-1), V(6) (")=-16.4 cm(-1) and V(3) (')=25.6 cm(-1), V(6) (')=-30.1 cm(-1), respectively. These potentials reveal that both in ground and excited states, the methyl group conformations are staggered with a 60 degrees phase shift between them. MP2 ab initio calculations support the ground state conformations determined from experiments, whereas Hartree-Fock calculations fail to do so. The origin of the modified ground state potential has been investigated by partitioning the barrier energy using the natural bond orbital (NBO) theoretical framework. The NBO analysis shows that the local delocalization (bond-antibond hyperconjugation) interactions of the methyl group with the parent molecule is sixfold symmetric. The threefold symmetric potential, on the other hand, stems from the interaction of the vinyl group and the adjacent ring pi bond. The threefold symmetric structural energy arising predominantly from the pi electron contribution is the barrier forming term that overwhelms the antibarrier contribution of the delocalization energy. The observed 60 degrees phase shift of the excited state potential is attributed to the pi(*)-sigma(*) hyperconjugation between out of plane hydrogens of the methyl group and the benzene ring.     

Amyotrophic lateral sclerosis with predominant pyramidal signs -- early diagnosis by magnetic resonance imaging

OBJECTIVE: To evaluate the role of magnetic resonance imaging (MRI) in the early diagnosis of amyotrophic lateral sclerosis (ALS) with predominant upper motor neuron (UMN) signs in the initial stage of the disease. PATIENTS AND METHOD: Two patients with ALS were found to have spastic quadriparesis with no wasting or fasciculation in the limbs in the early stage of the disease. Both were subjected to MRI of the head and cervical spine to look for any specific diagnostic feature. Both of them were followed with clinical evaluation and electroneuromyography (ENMG) for the definitive diagnosis of ALS. RESULTS: Magnetic resonance imaging showed selective degeneration of the pyramidal tracts in the contiguous axial cuts from subcortical white matter to cerebral peduncles. The finding was more visible in the coronal section. In addition, there was T1 hyperintensity visible along the anterior aspect of the spinal cord in the cervical region. These findings were suggestive of ALS, the diagnosis that was subsequently confirmed by serial clinical follow-up and ENMG. CONCLUSION: It is difficult to diagnose ALS in the early stage of the disease especially if the pyramidal signs predominate over the lower motor neuron (LMN) signs; MRI might be useful in such cases.     

Ligand-stabilized metal nanoparticles in organic solvent

This critical review reports the fundamental behavior of metal nanoparticles in different organic solvents, i.e., metal organosol. An overview on metal organosol and then their smart synthetic approaches, characterization, and potential applications in the fields of catalysis and spectroscopy with special emphasis on SERS are embodied. Aspects of organosol fabrication, stabilization, morphology control, growth mechanisms, and physical properties as mono- and bimetallic nanoparticles are discussed. The article inspires the repetitive usage of metal nanoparticles as stable deliverable organic and molecular compounds.