Vibrational Fano resonances in dipole-bound anions

This paper explores Fano resonances due to non-adiabatic coupling of vibrational modes and the electron continuum in dipole-bound anions. We adopt a simple one-electron model consisting of a point dipole and an auxiliary potential to represent the electron interaction with the neutral core. Nuclear motion is added by assuming that harmonic vibrations modulate the dipole moment. When the model is parameterized to simulate key features of the water tetramer anion, the resultant photodetachment lineshape closely resembles that observed experimentally and analyzed as a Fano resonance with a parameter q close to -1. Other parameterizations are explored for the model and it is found that large changes in the auxiliary potential are required to change the sign of q. This is consistent with the experimental finding that q is negative for all water cluster sizes studied.     

The structure, thermal properties and phase transformations of the cubic polymorph of magnesium tetrahydroborate

The structure of the cubic polymorph of magnesium tetrahydroborate (γ-Mg(BH(4))(2)) has been determined in space group Ia3[combining macron]d from a structural database of the isoelectronic compound SiO(2); this has been corroborated by DFT calculations. The structure is found to concur with that recently determined by Filinchuk et al. (Y. Filinchuk, B. Richter, T. R. Jensen, V. Dmitriev, D. Chernyshov and H. Hagemann, Angew. Chem. Int. Ed., 2011, DOI: 10.1002/anie.201100675). The phase transformations and subsequent decomposition of γ-Mg(BH(4))(2) on heating have been ascertained from variable-temperature synchrotron X-ray diffraction data combined with thermogravimetric and mass spectrometry measurements. At ～160 °C, conversion to a disordered variant of the β-Mg(BH(4))(2) phase (denoted as β') is observed along with a further unidentified polymorph. There is evidence of amorphous phases during decomposition but there is no direct crystallographic indication of the existence of Mg(B(12)H(12)) or other intermediate Mg-B-H compounds. MgH(2) and finally Mg are observed in the X-ray diffraction data after decomposition.     

Structural basis for efficient chromophore communication and energy transfer in a constructed didomain protein scaffold

The construction of useful functional biomolecular components not currently part of the natural repertoire is central to synthetic biology. A new light-capturing ultra-high-efficiency energy transfer protein scaffold has been constructed by coupling the chromophore centers of two normally unrelated proteins: the autofluorescent protein enhanced green fluorescent protein (EGFP) and the heme-binding electron transfer protein cytochrome b(562) (cyt b(562)). Using a combinatorial domain insertion strategy, a variant was isolated in which resonance energy transfer from the donor EGFP to the acceptor cyt b(562) was close to 100% as evident by virtually full fluorescence quenching on heme binding. The fluorescence signal of the variant was also sensitive to the reactive oxygen species H(2)O(2), with high signal gain observed due to the release of heme. The structure of oxidized holoprotein, determined to 2.75 ? resolution, revealed that the two domains were arranged side-by-side in a V-shape conformation, generating an interchromophore distance of ～17 ? (14 ? edge-to-edge). Critical to domain arrangement is the formation of a molecular pivot point between the two domains as a result of different linker sequence lengths at each domain junction and formation of a predominantly polar interdomain interaction surface. The retrospective structural analysis has provided an explanation for the basis of the observed highly efficient energy transfer through chromophore arrangement in the directly evolved protein scaffold and provides an insight into the molecular principles by which to design new proteins with coupled functions.     

Roots of solvable polynomials of prime degree

An explicit formula for the most general root of a solvable polynomial of prime degree is stated and proved. Such a root can be expressed rationally in terms of a single compound radical determined by the roots of a cyclic polynomial whose degree divides μ−1$\mu -1$, where μ$\mu$ is the prime. The study of such formulas was initiated by a formula of Abel for roots of quintic polynomials that are solvable, and was carried forward by Kronecker and a few others, but seems to have lain dormant since 1924. A formula equivalent to the one given here is contained in a paper of Anders Wiman in 1903, but it seems to have been forgotten.     

On the representation of tight functionals as integrals

We consider a vector lattice $\mathcal L $ of bounded real continuous functions on a topological space $X$ that separates the points of $X$ and contains the constant functions. A notion of tightness for linear functionals is defined, and by an elementary argument we prove with the aid of the classical Riesz representation theorem that every tight continuous linear functional on $\mathcal L $ can be represented by integration with respect to a Radon measure. This result leads incidentally to an simple proof of Prokhorov’s existence theorem for the limit of a projective system of Radon measures.     

Block Copolymer Morphology Formation on Topographically Complex Surfaces: A Self‐Consistent Field Theoretical Study

A self‐consistent field theoretic study is performed to study morphological development of lamellae‐forming diblock copolymers on substrates with a well‐defined roughness, modeled as trenches of varying depth and width engraved into the substrates. There are three possible lamellar orientations observed: horizontal lamellae, vertical lamellae that are parallel to the trench direction, and vertical lamellae that are perpendicular to the trench direction. Which of these three morphologies formed depends upon the trench width and surface affinity; however, trench depth has a relatively insignificant effect on the morphological development. Therefore, tuning trench width, but not trench depth, should allow for a reduction of the morphological defect density in directed self‐assembly of lamellar morphology of diblock copolymers.

     

Molecular dynamics study of reaction kinetics in viscous media

Predicted by stochastic models and observed experimentally in a number of isomerization reactions, viscosity-induced solvent effects manifest themselves in a significant departure of the reaction rates from the values expected on the basis of transition state theory. These effects are well understood within the framework of stochastic models; however, the predictive power of such models is limited by the fact that their parameters are not readily available. Experiment and molecular dynamics (MD) simulations can provide such information and can serve as the testing grounds for various stochastic models. In real solvents, a change in viscosity is inevitably associated with variation of at least one of the three factors – temperature, pressure, or solvent identity, resulting in different solvent–solvent and solvent–solute interactions. A model is proposed in which solvent viscosity is manipulated through mass scaling, which allows one to maintain other factors constant for a series of viscosities. This approach was tested on MD simulations of the kinetics of two model isomerization reactions in Lennard–Jones solvents, whose viscosity was varied over three orders of magnitude. The results reproduce the Kramers turnover and a strong negative viscosity dependence of the reaction rates in the high viscosity limit, somewhat weaker than η ^?1.     

Evidence of tin and other anthropogenic metals in particulate matter in Lisbon, Portugal

Thermal and epithermal neutron activation analysis techniques were used to analyze 27 Teflon air filters which were exposed to ambient air in Lisbon, Portugal, in February 2007. Tin was detected which is strongly suggestive of an anthropogenic source. Arsenic, antimony and copper were shown to be highly correlated, which is also suggestive of anthropogenic pollution. Trace element analysis of short- and medium-lived isotopes was performed yielding concentration information of various elements. Analytical sensitivities were enhanced using a Compton suppression system. Enrichment factor analysis shows that arsenic, tin, zinc, copper and antimony are at elevated concentrations in the Lisbon atmosphere.     

Total synthesis of ionophores the monensin BC-rings via permanganate promoted stereospecific oxidative cyclization

Complex tetrahydrofuran 8, containing the elements of the BC-rings of monensin with four chiral centers, and functionalized for further elaboration, is synthesized via permanganate promoted stereospecific oxidative cyclization of an acyclic, achiral 1,5-diene precursor.