Oscillations in the dark energy equation of state: New MCMC lessons

We study the possibility of detecting oscillating patterns in the equation of state (EoS) of the dark energy using different cosmological datasets. We follow a phenomenological approach and study three different oscillating models for the EoS, one of them periodic and the other two damped (proposed here for the first time). All the models are characterized by the amplitude, the center and the frequency of oscillations. In contrast to previous works in the literature, we do not fix the frequency to a fiducial value related to the time extension of chosen datasets, but consider a discrete set of values, so to avoid arbitrariness and try to detect any possible time period in the EoS. We test the models using a recent collection of SNeIa, direct Hubble data and Gamma Ray Bursts data. Main results are: I. even if constraints on the amplitude are not too strong, we detect a trend of it versus the frequency, i.e. decreasing (and even negatives) amplitudes for higher frequencies; II. the center of oscillation (which corresponds to the present value of the EoS parameter) is very well constrained, and phantom behavior seems statistically disfavored; III. the frequency is hard to constrain, showing similar statistical validity for all the values of the discrete set chosen, but the best fit of all the considered scenarios is associated with a period which is in the redshift range depicted by our cosmological data. The “best” oscillating models are compared with ΛCDM using different dimensionally consistent and Bayesian-based information criteria; the conclusion is reached that at present, data cannot discriminate between a cosmological constant and oscillating equation of state.     

A general protocol for temperature calibration of MAS NMR probes at arbitrary spinning speeds

A protocol using (207)Pb NMR of solid lead nitrate was developed to determine the temperature of magic-angle spinning (MAS) NMR probes over a range of nominal set temperatures and spinning speeds. Using BioMAS and FastMAS probes with typical sample spinning rates of 8 and 35 kHz, respectively, empirical equations were devised to predict the respective sample temperatures. These procedures provide a straightforward recipe for temperature calibration of any MAS probe.     

Non-centrosymmetric coordination polymers based on thallium and acetylenedicarboxylate

Single crystals of anhydrous thallium acetylenedicarboxylate (Tl₂(C₄O₄), 1) and thallium acetylenedicarboxylate oxalate (Tl₄(C₄O₄)(C₂O₄), 2) precipitated from aqueous solutions containing thallium(I)-acetate and the respective organic acids. Both compounds crystallize in non-centrosymmetric space groups (1: P2₁2₁2₁; 2: C2) and contain stereochemically active lone pairs at Tl(I). The crystal structures of 1 and 2 show some similarities. Tl atoms are organized in corrugated layers, which are connected by the respective carboxylate anions. Upon heating 1 decomposes at 195 °C to form elemental pyrophorous thallium powder. 2 starts decomposing at approx. 150 °C forming elemental thallium next to another compound, which could not be identified up to now. TlHADC was also synthesized, but its crystal structure could not be solved either from powder or single crystal diffraction data. Upon heating it decomposes to form 1.     

RNA-binding residues in sequence space: Conservation and interaction patterns

RNA-binding proteins (RBPs) perform fundamental and diverse functions within the cell. Approximately 15% of proteins sequences are annotated as RNA-binding, but with a significant number of proteins without functional annotation, many RBPs are yet to be identified. A percentage of uncharacterised proteins can be annotated by transferring functional information from proteins sharing significant sequence homology. However, genomes contain a significant number of orphan open reading frames (ORFs) that do not share significant sequence similarity to other ORFs, but correspond to functional proteins. Hence methods for protein function annotation that go beyond sequence homology are essential. One method of annotation is the identification of ligands that bind to proteins, through the characterisation of binding site residues. In the current work RNA-binding residues (RBRs) are characterised in terms of their evolutionary conservation and the patterns they form in sequence space. The potential for such characteristics to be used to identify RBPs from sequence is then evaluated.In the current work the conservation of residues in 261 RBPs is compared for (a) RBRs vs. non-RBRs surface residues, and for (b) specific and non-specific RBRs. The analysis shows that RBRs are more conserved than other surface residues, and RBRs hydrogen-bonded to the RNA backbone are more conserved than those making hydrogen bonds to RNA bases. This observed conservation of RBRs was then used to inform the construction of RBR sequence patterns from known protein–RNA structures. A series of RBR patterns were generated for a case study protein aspartyl-tRNA synthetase bound to tRNA; and used to differentiate between RNA-binding and non-RNA-binding protein sequences. Six sequence patterns performed with high precision values of >80% and recall values 7 times that of an homology search. When the method was expanded to the complete dataset of 261 proteins, many patterns were of poor predictive value, as they had not been manipulated on a family-specific basis. However, two patterns with precision values ≥85% were used to make function predictions for a set of hypothetical proteins. This revealed a number of potential RBPs that require experimental verification.     

Characterization of smokeless powders using nanoelectrospray ionization mass spectrometry (nESI-MS)

Smokeless powder is one of the most common types of explosives used in civilian ammunition and, hence, its detection and identification is of great forensic value. Based on comparison of physical properties, extraction yield in methanol, and the spectra obtained using nanoelectrospray ionization and multistage tandem mass spectrometry (MS/MS) in a quadrupole ion trap mass spectrometer, a method was developed to identify and differentiate unburned smokeless powders from different brands of ammunition. The mass spectrometry method was optimized for the simultaneous detection of the organic stabilizers commonly present in smokeless powders: methyl centralite, ethyl centralite, and diphenylamine. All but two of the powders were differentiated; however, the two that were not differentiated were produced by the same manufacturer. Gunshot residue from the cartridges was deposited on cotton cloth and collision-induced dissociation MS/MS was used to identify low levels of ethyl centralite in the residue, despite the presence of contaminants.     

Das neue ternäre Borid Mg8Pt4B und die neue intermetallische Verbindung PtMg2

The New Ternary Boride Mg₈Pt₄B and the New Intermetallic Compound PtMg₂ The new magnesium platinum boride Mg₈Pt₄B was obtained from a reaction of the elements in sealed niobium tubes. It crystallizes isotypically with Mg₈Rh₄B in the cubic space group with a =12.2481(1) Å and can be structurally derived from the Ti₂Ni structure type, where boron occupies cavities, which are formed by four magnesium and four platium atoms. The new intermetallic compound PtMg₂ was also prepared by reaction of the elements in a sealed Nb container and adopts the tetragonal CuAl₂ type structure, space group I4/mcm with a = 6.334(1) Å and c = 5.621(1) Å.     

Effective manipulation of the electronic effects and its influence on the emission of 5-substituted tris(8-quinolinolate) aluminum(III) complexes

The unique electron-transport and emissive properties of tris(8-quinolinolate) aluminum(III) (Alq(3)) have resulted in extensive use of this material for small molecular organic light-emitting diode (OLED) fabrication. So far, efforts to prepare stable and easy-to-process red/green/blue (RGB)-emitting Alq(3) derivatives have met with only a limited success. In this paper, we describe how the electronic nature of various substituents, projected via an arylethynyl or aryl spacer to the position of the highest HOMO density (C5), may be used for effective emission tuning to obtain blue-, green-, and red-emitting materials. The synthetic strategy consists of four different pathways for the attachment of electron-donating and electron-withdrawing aryl or arylethynyl substituents to the 5-position of the quinolinolate ring. Successful tuning of the emission color covering the whole visible spectrum (lambda=450-800 nm) was achieved. In addition, the photophysical properties of the luminophores were found to correlate with the Hammett constant of the respective substituents, providing a powerful strategy with which to predict the optical properties of new materials. We also demonstrate that the electronic nature of the substituent affects the emission properties of the resulting complex through effective modification of the HOMO levels of the quinolinolate ligand.     

Monomeric azaheterofullerene derivatives RC59N: influence of the R moiety on spectroscopic and photophysical properties

We have synthesised nine monomeric azaheterofullerene (AZA) derivatives, RC(59)N, with a wide variety of different side chains R and investigated their spectroscopic and photophysical properties in toluene and o-dichlorobenzene (ODCB). Measurements include their ground-state absorption spectra, molar absorption coefficient (epsilon(G)), fluorescence spectra, fluorescence quantum yields (Phi(F)), singlet-state lifetimes (tau(F)), triplet-state absorption spectra, triplet molar absorption coefficients (epsilon(T)), singlet oxygen (Phi(Delta)), and triplet state (Phi(T)) quantum yields. The replacement of a carbon by a nitrogen atom in the C(60) sphere strongly affects most of the spectroscopic and photophysical properties. The chemical nature of the R moiety has definite effects on these properties in contrast with minor effects on the chemical nature of the addends in [6,6]-ring bridged monoadduct methano[60]fullerene derivatives. These effects concern properties of the ground state, singlet excited state, and triplet states of our nine RC(59)N derivatives and in particular the values of photophysical parameters epsilon(G), epsilon(T), Phi(Delta), and Phi(T), which are significantly lower than those of analogous monoadduct [6,6]-ring bridged methano[60]fullerene derivatives.     

Unraveling the origin of band shapes in infrared spectra of N2O-12CO2 and 12CO2-13CO2 ice particles

Band structures in the region of strong infrared absorption bands for different N2O-12CO2 and 12CO2-13CO2 composite particles are investigated by combining quantum mechanical exciton calculations with systematic experimental investigations. The ice particles are generated by collisional cooling and characterized with rapid-scan infrared spectroscopy. The size of the particles lies between approximately 10 and 100 nm. The calculated spectra show excellent agreement with the experimental data. This work leads to a detailed understanding on a molecular level of shape effects in pure and statistically mixed particles as well as of the characteristic features observed for core-shell particles.