Mn(III)-initiated facile oxygenation of heterocyclic 1,3-dicarbonyl compounds

The Mn(III)-initiated aerobic oxidation of heterocyclic 1,3-dicarbonyl compounds, such as 4-alkyl-1,2-diphenylpyrazolidine-3,5-diones, 1,3-dialkylpyrrolidine-2,4-diones, 3-alkyl-1,5-dimethylbarbituric acids, and 3-butyl-4-hydroxy-2-quinolinone gave excellent to good yields of the corresponding hydroperoxides, which were gradually degraded by exposure to the metal initiator after the reaction to afford the corresponding alcohols. The synthesis of 30 heterocyclic 1,3-dicarbonyl compounds, the corresponding hydroperoxides and the 10 alcohols, their characterization, and the limitations of the procedure are described. In addition, the mechanism of the hydroperoxidation and the redox decomposition of the hydroperoxides are discussed.     

Exact Solutions of Compressible Flow Equations with Spherical Symmetry

In this paper, we construct spherically symmetric solutions of the equations of compressible flow, which are important in the theory of explosion waves in air, water, and other media. Following McVittie [ 1 ], we write a general solution form, in terms of velocity potential, as a product of a function of time and a function of a similarity variable. First, we find solutions to the equations of motion and continuity without reference to adiabatic or isentropic relation. These solutions are quite general and can be applied to nonadiabatic motions, such as the motions of interstellar gas clouds that lose energy by radiation. All the solutions found by McVittie [ 1 ] have linear velocity profile with respect to distance. We introduce a nonlinear form of the velocity function containing an arbitrary function of the similarity variable. Adiabatic conditions lead to a second-order ODE, which we discuss in some detail. We relate our work to the earlier investigations of Taylor [ 2 ], McVittie [ 1 ], and Keller [ 3 ].     

g-factor of the first excited 4+ states in156Gd and158Gd

Relative g-factor of the first 2⁺ and 4⁺ states have been measured with the transient field technique in¹⁵⁶Gd and¹⁵⁸Gd. The precession of gamma rays depopulating the levels under study were observed, after passing through thin polarized gadolinium. The observed values agree with the predictions of the rotational model, i.c. g(4⁺)= g(2⁺), while contrasting the hypothesis that in¹⁵⁶Gd the g-factor of the 4⁺ is reduced with respect to the 2⁺, because of rotational alignment.     

Substituent effect on ionisation potential in a series of related molecules: A theoretical study in a molecular orbital framework

The effect of replacing the hydrogen atoms in thioformaldehyde by halogen atoms (F, Cl) on the ionisation potential of the non-bonding electron is analysed by using the Hellman-Feynman theorem, regarding the nuclear charge of the substituent as a parameter in the many-electron Hamiltonian. The trends predicted by our theory nicely agree with the relevant ionisation potentials computed either by applying Koopmans’ theorem or by the ΔE _SCF method. For the carbonyls, avaible experimental data indicate the reliability of our prediction.     

An asymmetric total synthesis of vitamin d3 (cholecalciferol)

The total synthesis of cholecalciferol $\text{via}$ an intramolecular Diels-Alder approach is described.     

Effects of electric fields on thermal convection in gases

Summary Extensive measurements of the coefficient of electroconvective heat transfer have been carried out in gases: air, Ar, N₂, O₂, freon-12 and freon-22, using a single platinum wire mounted along the axis of a copper cylinder. The diameter of the cylinder was 53 mm, while that of the wire was 0.025 mm. Electroconvective heat transfer coefficients have been measured as a function of electric field, pressure, orientation and frequency of the applied electric field in the earth's gravitational field. The results reveal a complicated interaction between the electric-field gradient and thermal convection. The present work indicates that the Senftleben mechanism alone cannot account for the observed phenomena.     

Filter-paper test for microgram detection of aliphatic amines

A new simple, sensitive and selective test for the detection of microgram amounts of aliphatic amines with diphenylcarbazide-soaked Whatman No. 1 filter paper as the detection medium is described. A feature of the study is the observation that the reaction does not take place in solution in the absence of the filter paper.     

Deformation of a trapped Fermi gas with unequal spin populations

The real-space densities of a polarized strongly interacting two-component Fermi gas of 6Li atoms reveal two low-temperature regimes, both with a fully paired core. At the lowest temperatures, the unpolarized core deforms with increasing polarization. Sharp boundaries between the core and the excess unpaired atoms are consistent with a phase separation driven by a first-order phase transition. In contrast, at higher temperatures the core does not deform but remains unpolarized up to a critical polarization. The boundaries are not sharp in this case, indicating a partially polarized shell between the core and the unpaired atoms. The temperature dependence is consistent with a tricritical point in the phase diagram.     

Interface engineering for solid-state dye-sensitised nanocrystalline solar cells: the use of an organic redox cascade

We demonstrate the formation of a charge transfer cascade at a nanostructured TiO2/dye/polymer/molecular hole transport multilayer interface. Charge recombination dynamics at this interface are shown to be retarded when the ionisation potential of the polymer layer exceeds that of the molecular hole transport layer.     

Photochemical energy conversion: from molecular dyads to solar cells

Photochemical approaches to solar energy conversion are currently making rapid progress, increasing not only academic but also commercial interest in molecular-based photovoltaic solar cells. This progress has been achieved not only by increased understanding of the physics and physical chemistry of device function but also through advances in chemical and materials synthesis and processing, which now allows the design and fabrication of increasingly sophisticated device structures organised on the nanometer length scale. In this feature article, we review some progress in this field, focusing in particular upon the electron-transfer dynamics which underlie the function of dye-sensitised, nanocrystalline solar cells. The article starts by building upon the parallels between the function of such devices and the function of simple donor/acceptor molecular systems in solution. We then go on to discuss the optimisation of device function, and in particular the use of self-assembly-based strategies to control interfacial electron-transfer kinetics.