Electron affinity of exotic systems under Debye plasma

Electron affinity of plasma embedded muonium (μ⁺e^?) and pionium (π⁺e^?) has been estimated using a general three‐body formalism within variational framework. Electron correlation is taken care of using extended Hylleraas basis sets. The stability of the three‐body systems have been studied under the Debye screening model of the plasma, which changes the Coulombic potential to the screened Coulomb one. The electron affinity of the muonium and pionium is maximum for free systems, and it decreases gradually toward zero with increase of the plasma strength, which tends to push the three‐body system toward gradual instability. The electron correlation contribution to the affinity has been analyzed. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

Effect of core charge density on the electrophoresis of a soft particle coated with polyelectrolyte layer

The electrophoresis of a charged soft particle with charged rigid core is considered under a weak imposed field condition. The rigid core of the soft particle is considered to have a finite dielectric permittivity and a fixed volume charge density. The electric potential distribution is determined by solving the Poisson-Boltzman equation out side the rigid core and a Poisson equation within the core along with continuity conditions on the core-shell interface. We have extended the analytic expression of Ohshima (Electrophoresis 27:526–533, 2006) for the electrophoretic mobility of a soft particle with a charged shell to include the effect of the volume charge density of the rigid core. Mobility based on the present expression matches exactly with the existing analytical solutions for a soft particle with an uncharged core. We have also made a comparison of our solution for mobility with an uncharged rigid core with the existing experimental results. The impact of the core charge density on the soft particle mobility is analyzed.     

Mechanistic Studies on the Oxidation of Nitrite by a μ‐Oxodiiron(III,III) Complex in Aqueous Acidic Media

Examined in this study is the kinetics of a net 2e⁻ transfer between [Fe₂(μ‐O)(phen)₄(H₂O)₂]⁴⁺ ( 1 ) and its hydrolytic derivatives [Fe₂(μ‐O)(phen)₄(H₂O)(OH)]³⁺ ( 2 ) and [Fe₂(μ‐O)(phen)₄(OH)₂]²⁺ ( 3 ) with in aqueous media and in presence of excess 1,10‐phenanthroline (phen). The reaction is quantitative with a 1 : 1 stoichiometry between the oxidant and reductant to produce ferroin ([Fe(phen)₃]²⁺) and . The order of reactivity of the oxidant species is 1 > 2 > 3 , in agreement with the progressive cationic charge reduction. The reactions appear to be inner‐sphere where the initial one‐electron proton‐coupled redox (1e⁻, 1H⁺; electroprotic) seems to be rate‐determining.     

A heteropolynuclear R2[S2WS2Re(O)(Cl)S2WS2] (R = PPh4 and Et4N) complex. The first example of a tetrathiometalate ligand co-ordinated to an oxo-metal core

A solution of [ReOCl3(PPh3)2] in benzene reacts with solid (NH4)2WS4, in the presence of traces of H2O, to give [ReOCl(WS4)2]2–, isolated as its PPh4 (1) and NEt4 (2) salts. Both (1) and (2) exhibit (Re=O) at ca. 930, (Re=Cl) at ca. 330 (W=S)t at ca. 495 and (W–S–Re) bridging vibration at ca. 460cm–1. The FAB mass spectrum of (1) shows a peak for [ReO(WS4)2]+(m/z=826 amu) in the positive mode and that for PPh4[ReOCl(WS4)]– (m/z=889amu) in the negative mode, confirming the suggested composition. This is the second example of a d2 metal ion forming a tetrathiometalate complex and also the first example of an oxometal ion (excepting those of W and Mo) forming a molecular complex with tetrathio- tungstate or -molybdate ligands.     

Structural features of some small carbonyls in the 1,3nπ states: An mcscf study

Structural features of a series of tetraatomic carbonyls in the ^1,3nπ* states are studied by using a recently proposed MCSCF algorithm at the INDO/2 level. The computed geometrical parameters and the inversion barrier heights agree quite well with the available experimental or ab initio theoretical data. The calculated transition energies turn out to be somewhat lower than the experimental counterparts. The specific MCSCF algorithm used is found to have excellent convergence properties.     

Tetrahalidometallate(II) Ionic Liquids with More than One Metal: The Effect of Bromide versus Chloride

Fifteen N-butylpyridinium salts – five monometallic [C₄Py]₂[MBr₄] and ten bimetallic [C₄Py]₂[M_0.5^aM_0.5^bBr₄] (M=Co, Cu, Mn, Ni, Zn) – were synthesized, and their structures and thermal and electrochemical properties were studied. All the compounds are ionic liquids (ILs) with melting points between 64 and 101 °C. Powder and single-crystal X-ray diffraction show that all ILs are isostructural. The electrochemical stability windows of the ILs are between 2 and 3 V. The conductivities at room temperature are between 10⁻⁵ and 10⁻⁶ S cm⁻¹. At elevated temperatures, the conductivities reach up to 10⁻⁴ S cm⁻¹ at 70 °C. The structures and properties of the current bromide-based ILs were also compared with those of previous examples using chloride ligands, which illustrated differences and similarities between the two groups of ILs.     

Adsorption of several tracer cations and separation of234Th from238U and113mIn from113Sn on tin dioxide

The uptake of 22 cations at tracer concentrations has been studied over hydrous tin dioxide exchanger material. A granular variety of tin dioxide was prepared from the reaction of tin(IV) chloride with NaOH solution, and the formula of the material was ascertained to be SnO₂·1.7 H₂O. Radiochemical separation of carrier-free²³⁴Th from²³⁸U and^113mIn from¹¹³Sn was achieved over a tin dioxide column. The separated products were of high radionuclidic purity. The overall separation procedures are very simple and quick with quantitative yield.     

Degeneracy in one dimension: Role of singular potentials

That the bound energy eigenstates of one-dimensional quantum systems can be degenerate in the presence of specific singular or supersingular potentials is demonstrated by choosing a family of bistable and other oscillators. Relevance of our study to spectroscopic observations is noted. Quasi-degeneracy is found even in the absence of any singularity in the potential and the importance of tunneling is highlighted in this context to analyze the general nature of such potentials leading to double degeneracy. Additionally, the case of spiked oscillators is discussed with particular reference to the “Klauder phenomenon,” revealing clearly that the mere presence of singularity in the potential is not a sufficient criterion for the occurrence of degeneracy. © 1996 John Wiley & Sons, Inc.     

An Organoruthenium Anticancer Agent Shows Unexpected Target Selectivity For Plectin

Organometallic metal(arene) anticancer agents require ligand exchange for their anticancer activity and this is generally believed to confer low selectivity for potential cellular targets. However, using an integrated proteomics-based target-response profiling approach as a potent hypothesis-generating procedure, we found an unexpected target selectivity of a ruthenium(arene) pyridinecarbothioamide (plecstatin) for plectin, a scaffold protein and cytolinker, which was validated in a plectin knock-out model in vitro. Plectin targeting shows potential as a strategy to inhibit tumor invasiveness as shown in cultured tumor spheroids while oral administration of plecstatin-1 to mice reduces tumor growth more efficiently in the invasive B16 melanoma than in the CT26 colon tumor model.     

Electrokinetic actuation of an uncharged polarizable dielectric droplet in charged hydrogel medium

Electrokinetic transport of an uncharged nonconducting microsized liquid droplet in a charged hydrogel medium is studied. Dielectric polarization of the liquid drop under the action of an externally imposed electric field induces a non-homogeneous charge density at the droplet surface. The interactions of the induced surface charge of the droplet with the immobile charges of the hydrogel medium generates an electric force to the droplet, which actuates the drop through the charged hydrogel medium. A numerical study based on the first principle of electrokinetics is adopted. Dependence of the droplet velocity on its dielectric permittivity, bulk ionic concentration, and immobile charge density of the gel is analyzed. The surface conduction is significant in presence of charged gel, which creates a concentration polarization. The impact of the counterion saturation in the Debye layer due to the dielectric decrement of the medium is addressed. The modified Nernst–Planck equation for ion transport and the Poisson equation for the electric field is considered to take into account the dielectric polarization. A quadrupolar vortex around the uncharged droplet is observed when the gel medium is considered to be uncharged, which is similar to the induced charge electroosmosis around an uncharged dielectric colloid in free-solution. We find that the induced charge electrokinetic mechanism creates a strong recirculation of liquid within the droplet and the translational velocity of the droplet strongly depends on its size for the dielectric droplet embedded in a charged gel medium.