Thermally induced ortho-metalation of dicarbomethoxyacetylenebis(triphenylphosphine)platinum

Heating a toluene solution of dicarhomethoxyacetylenebis(triphenylphosphine)platinum(0) at 130°C gives the ortho-metalated complex (Ph₃P)(Ph₂$\text{PC}{}_6\text{H}{}_4\text{)P}$t-trans-(COOMe)CCHCOOMe.     

Real-time detection of DNA interactions with long-period fiber-grating-based biosensor

Using an optical biosensor based on a dual-peak long-period fiber grating, we have demonstrated the detection of interactions between biomolecules in real time. Silanization of the grating surface was successfully realized for the covalent immobilization of probe DNA, which was subsequently hybridized with the complementary target DNA sequence. It is interesting to note that the DNA biosensor was reusable after being stripped off the hybridized target DNA from the grating surface, demonstrating a function of multiple usability.     

Structural changes within the plastic phase of diamantane

Structural changes within the pre-melting plastic phase of diamantane have been revealed from high-temperature X-ray powder diffraction data. A gradual transition to a more disordered state is suggested, and hexagonal symmetry ($\text{a = 14.1}\text{A}\text{?}\text{, c = 11.0}\text{A}\text{?}$) for the plastic phase is firmly established.     

Simplified determination of the normal paraffin content of petroleum fractions

Summary A greatly simplified method for the determination of the total normal paraffin content in petroleum fractions is described where the use of open-tubular columns and up-to-date data handling contribute to the criterion of separation before quantitation.     

Embeddable transversal designs

The embeddability of certain (group) divisible designs in symmetric 2-designs is investigated. These designs are symmetric resolvable transversal designs. It is proved that all such transversal designs with v = 2k are embeddable and some necessary and sufficient conditions for other cases are given.     

The perception of entropy in rapidly moving sparse dot arrays: a nonlinear dynamic perspective

In visual fields composed of dots spatially randomly distributed but moving rigidly, the percept of coherent motion is lost once D_max is exceeded, resulting in an incoherent, random percept. We have investigated this transition both from a psychophysics perspective and in the development of a dynamic model of the visual system based on a spatially coupled array of nonlinear damped mass-springs cells. We present results of experiments using rigidly moving arrays of dots of different levels of sparseness and differing displacement magnitudes. Results show that the perception of randomness can be reliably judged and displays a transition from coherent to non-coherent motion as the motion amplitude is increased. Using standard psychophysical just noticeable difference (JND) judgements, we noted that the threshold JND was a function of displacement magnitude and sparseness and could not be explained by extant spatiotemporal filtering models. Our model qualitatively explains the important features of the data, reproducing the experimental D_max and entropy perception effects with increased stimuli motion amplitude at different spatial sparseness levels. We have then performed some numerical simulations of the model when the masses in the array are randomly distributed. Results show that sparseness plays different role if close or far from D_max in terms of motion coherence discrimination.     

Pulay forces from localized orbitals optimized in situ using a psinc basis set

In situ optimization of a set of localized orbitals with respect to a systematically improvable basis set independent of the position of the atoms, such as psinc functions, would theoretically eliminate the correction due to Pulay forces from the total ionic forces. We demonstrate that for strict localization constraints, especially with small localization regions, there can be non-negligible Pulay forces that must be calculated as a correction to the Hellmann-Feynman forces in the ground state. Geometry optimization calculations, which rely heavily upon accurate evaluation of the total ionic forces, show much better convergence when Pulay forces are included. The more conventional case, where the local orbitals remain fixed to pseudo-atomic orbital multiple-ζ basis sets, also benefits from this implementation. We have validated the method on several test cases, including a DNA fragment with 1045 atoms.     

Dithiolene complexes and the nature of molybdopterin

The development of the coordination chemistry of dithiolene ligands is summarised, together with a consideration of the electronic structure of complexes of these ‘non-innocent’ ligands. This information provides a context for a consideration of the role of dithiolenes in natural systems, i.e. as the ligand that binds molybdenum (or tungsten) at the catalytic centre of an extensive series of enzymes. These enzymes catalyse the transfer of an oxygen atom to or from the substrate: e.g. the sulfite oxidases catalyse the conversion of sulfite to sulfate and the nitrate reductases catalyse the conversion of nitrate to nitrite. The nature of the catalytic centres of several of these enzymes has been determined and each involves one or two ‘molybdopterin’ (MPT) cofactors bound to a mononuclear metal centre via their dithiolene group. The biosynthesis of MPT is described and, given its nature, possible roles for this moiety in the function of the oxotransferase enzymes are discussed. The review concludes with a consideration of the coordination chemistry that has been stimulated by the present knowledge of the nature and function of the catalytic centres of these enzymes.     

Accurate and efficient method for the treatment of exchange in a plane-wave basis

We describe an accurate and efficient extension of Chawla and Voth's [J. Chem. Phys. 108, 4697 (1998)] plane-wave based algorithm for calculating exchange energies, exchange energy densities, and exchange energy gradients with respect to wave-function parameters in systems of electrons subject to periodic boundary conditions. The theory and numerical results show that the computational effort scales almost linearly with the number of plane waves and quadratically with the number of k vectors. To obtain high accuracy with relatively few k vectors, we use an adaptation of Gygi and Baldereschi's [Phys. Rev. B 34, 4405 (1986)] method for reducing Brillouin-zone integration errors.