Synthesis of reduced complex oxides of molybdenum by fused salt electrolysis

Fused salt electrolysis has been used to prepare a number of reduced oxides of molybdenum with lanthanum, neodymium, and yttrium in single crystal or oriented polycrystalline form. The average valence of molybdenum in the various compounds ranged from 5.67 to 3.50. Previously unreported compounds include La₅Mo₄O₁₆ (triclinica = 5.64 Å,b = 20.7 0Å,c = 5.64 Å, α = 86.55°, β = 90.0°, γ = 93.45°); La₂Mo₂O₇ (orthorhombic,a = 12.19 Å,b = 6.05 Å,c = 3.87 Å); LaMo₂O₅ (hexagonal,a = 8.378 Å,c = 19.26 Å). In addition, single crystal specimens have been prepared of Y₂MoO₅,Ln₅Mo₃O₁₆(Ln =La, Nd) and metal atom cluster compounds of theA₂Mo₃O₈ type (A = Mg, Co, Ni, Zn).     

Identification of a minimal subset of receptor conformations for improved multiple conformation docking and two-step scoring

Docking and scoring are critical issues in virtual drug screening methods. Fast and reliable methods are required for the prediction of binding affinity especially when applied to a large library of compounds. The implementation of receptor flexibility and refinement of scoring functions for this purpose are extremely challenging in terms of computational speed. Here we propose a knowledge-based multiple-conformation docking method that efficiently accommodates receptor flexibility thus permitting reliable virtual screening of large compound libraries. Starting with a small number of active compounds, a preliminary docking operation is conducted on a large ensemble of receptor conformations to select the minimal subset of receptor conformations that provides a strong correlation between the experimental binding affinity (e.g., Ki, IC50) and the docking score. Only this subset is used for subsequent multiple-conformation docking of the entire data set of library (test) compounds. In conjunction with the multiple-conformation docking procedure, a two-step scoring scheme is employed by which the optimal scoring geometries obtained from the multiple-conformation docking are re-scored by a molecular mechanics energy function including desolvation terms. To demonstrate the feasibility of this approach, we applied this integrated approach to the estrogen receptor alpha (ERalpha) system for which published binding affinity data were available for a series of structurally diverse chemicals. The statistical correlation between docking scores and experimental values was significantly improved from those of single-conformation dockings. This approach led to substantial enrichment of the virtual screening conducted on mixtures of active and inactive ERalpha compounds.     

Preparation of some silyl esters and study of their vibration spectra in gas and condensed phases

A new preparative route for silyl esters is described, involving reaction of silyl bromide and trisalkyltin esters. The far infrared spectrum of some simple esters are reported; an investigation of the shifts in the carbonyl stretching band on condensation shows no significant differences in behaviour between methyl and silyl esters.

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Darstellung einiger Silylester und Untersuchung der Vibrationsspektren in der Gasphase und in kondensierter Phase

Zusammenfassung Es wird ein neuer präparativer Weg (über Silylbromid und Trisalkylzinnester) für die Synthese von Silylestern beschrieben. Das ferne IR einiger Ester wird angeführt; eine Untersuchung der Verschiebung der Carbonyl-Streck-Frequenz bei Kondensation zeigt keine signifikanten Unterschiede zwischen Methyl- und Silyl-Estern.

     

A chemical inhibitor reveals the role of Raf kinase inhibitor protein in cell migration

Raf kinase inhibitor protein (RKIP) is a modulator of cell signaling that functions as an endogenous inhibitor of multiple kinases. We demonstrate here a positive role for RKIP in the regulation of cell locomotion. We discovered that RKIP is the relevant cellular target of locostatin, a cell migration inhibitor. Locostatin abrogates RKIP's ability to bind and inhibit Raf-1 kinase, and it acts by disrupting a protein-protein interaction, an uncommon mode of action for a small molecule. Small interfering RNA-mediated silencing of RKIP expression also reduces cell migration rate. Overexpression of RKIP converts epithelial cells to a highly migratory fibroblast-like phenotype, with dramatic reduction in the sensitivity of cells to locostatin. RKIP is therefore the compound's valid target and a key regulator of cell motility.     

Post-source decay in the analysis of polystyrene by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Various secondary series are observed in matrix-assisted laser desorption/ionization (MALDI) time-of-flight mass spectra of polystyrene. The number and positions of the series depend on the choice of matrix and added cation. For a given treatment, series observed in linear mode are not necessarily observed in reflectron mode, and vice versa. Post-source decay analysis was used to determine that the secondary series arise at least in part from formation and decay of adducts of polystyrene with matrix species. There is some treatment-to-treatment variation, but adduct formation and decay were observed for all tested treatments. The multiplicity of secondary series makes it unclear whether post-source decay occurs for the main series (polystyrene + cation)⁺ ions under the conditions normally used for polystyrene analysis. Such ions do undergo post-source decay at laser fluences greater than normally used. Although only polystyrene was investigated in this work, other polymers may also produce adduct and decay series in MALDI analysis. Their presence can mask the presence of minor components in a sample, but at least as observed here, do not have a strong influence on molecular mass determinations.     

The correlation of vibrational broadening of core lines in x-ray photoelectron spectra with valence bond resonance structures

When core ionization of an atom in a molecule causes significant changes in bond orders, the core-hole ion is formed in a strained configuration. This strain causes vibrational broadening of the core line. The core-hole ion can be represented as an ordinary chemical species by applying the equivalent cores approximation. Then simple rules of classical valence bond theory can be used to predict changes in the weighting of resonance structures and corresponding changes in bond orders. Thus qualitative changes in relative linewidths can be predicted.     

Neolemnane and eremophilane sesquiterpenoids from the pacific soft coral lemnalia africana

Two new sesquiterpenoids of the unprecedented neoiemnane ring system, and one eremophflane-derived sesquiterpene diol have been isolated from the pacific soft-coral Lemnalia africana. The structure of the novel neolemnane compounds, 4 and 5, were confirmed by X-ray crystallography, and the diol, 6, has been described based upon spectral analysis and chemical modification.     

The role of kinetic energy in chemical binding

The wavefunctions and various partitions of the energy are examined for a variety of small molecules (H₂, H₃, H₄, HeH, HeH₂, He₂, LiH, and BH) in order to isolate the factors crucial for bond formation. We find that a natural partition of the energy leads to the conclusion that the crucial factor is the exchange, or nonclassical, part of the kinetic energy, T ^x. The change in T ^xupon pushing the atoms towards one another is the dominant term in the binding energy; it is negative when the resulting molecule is stable and positive when it is unstable. We show that T ^x is related to the interference kinetic energy considered by Ruedenberg.

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Zusammenfassung Die Wellenfunktionen und verschiedene Zerlegungen der Energie werden für eine Reihe kleiner Moleküle untersucht (H₂, H₃, H₄, HeH, HeH₂, He₂, LiH und BH), um die Faktoren zu finden, die für die Bindungsbildung ausschlaggebend sind. Die natürliche Zerlegung der Energie läßt die Folgerung zu, daß der bestimmende Faktor der Austauschanteil T ^x(oder nichtklassische Anteil) der kinetischen Energie ist. Die Änderung von T ^xbeim Zusammenführen der Atome ist der dominierende Term für die Bindungsenergie; er ist negativ, wenn das resultierende Molekül stabil ist, und positiv, falls es instabil ist. Es wird gezeigt, daß T ^x im Zusammenhang zum Wechselwirkungsanteil der kinetischen Energie nach Ruedenberg steht.

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Partially supported by a grant (GP-15423) from the National Science Foundation. This paper is based on a portion of the PhD thesis (California Institute of Technology, 1970) by CWW.

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National Science Foundation Predoctoral Trainee.

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Alfred P. Sloan Foundation Research Fellow.

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Contribution No. 3917.     

Rigorous information-theoretic derivation of quantum-statistical thermodynamics. II

Part I of the present work outlined the rigorous application of information theory to a quantum mechanical system in a thermodynamic equilibrium state. The general formula developed there for the best-guess density operator \(\hat \rho\) was indeterminate because it involved in an essential way an unspecified prior probability distribution over the continuumD _H of strong equilibrium density operators. In Part II mathematical evaluation of \(\hat \rho\) is completed after an epistemological analysis which leads first to the discretization ofD _H and then to the adoption of a suitable indifference axiom to delimit the set of admissible prior distributions. Finally, quantal formulas for information-theoretic and thermodynamic entropies are contrasted, and the entire work is summarized.     

Preparation and reactions of [2,2-bis(carbethoxy)propyl]cyclopentadienyldicarbonyliron

Although

, (Fp  η-C₅H₅Fe(CO)₂) (I) is stable and characterizable, the lower homologue FpCH₂CH(CO₂CH₃)₂ (II) is not; this we attribute to a facile elimination reaction resulting from the relatively acidic β-hydrogen of II. Formation of I from Fp^? and XCH₂CE₂CH₃ (X  Br, Cl; E  CO₂CH₂CH₃) and cleavage of its FeC bonds (using H⁺, Br₂, Ce^IV and Hg^II) occur without major amounts of ester group migrations, even though ·CH₂CE₂CH₃ radicals are involved in some of these reactions.