Development and validation of a liquid chromatography-tandem mass spectrometry method for the simultaneous determination of nine corticosteroid residues in bovine liver samples

A liquid chromatography tandem mass spectrometry (LC-MS/MS) confirmatory method for the simultaneous determination of nine corticosteroids in liver, including the four MRL compounds listed in Council Regulation 37/2010, was developed. After an enzymatic deconjugation and a solvent extraction of the liver tissue, the resulting solution was cleaned up through an SPE Oasis HLB cartridge. The analytes were then detected by liquid chromatography-negative-ion electrospray tandem mass spectrometry, using deuterium-labelled internal standards. The procedure was validated as a quantitative confirmatory method according to the Commission Decision 2002/657/EC criteria. The results showed that the method was suitable for statutory residue testing regarding the following performance characteristics: instrumental linearity, specificity, precision (repeatability and intra-laboratory reproducibility), recovery, decision limit (CCα), detection capability (CCβ) and ruggedness. All the corticosteroids can be detected at a concentration around 1 μg kg(-1); the recoveries were above 62% for all the analytes. Repeatability and reproducibility (within-laboratory reproducibility) for all the analytes were below 7.65% and 15.5%, respectively.     

Asymptotic Analysis of Shell-like Inclusions with High Rigidity

We study the problem of an elastic shell-like inclusion with high rigidity in a three-dimensional domain by means of the asymptotic expansion method. The analysis is carried out in a general framework of curvilinear coordinates. After defining a small real adimensional parameter ε, we characterize the limit problems when the rigidity of the inclusion has order of magnitude \frac1e\frac{1}{\varepsilon } and \frac1e³\frac{1}{\varepsilon^{3}} with respect to the rigidities of the surrounding bodies. Moreover, we prove the strong convergence of the solution of the initial three-dimensional problem towards the solution of the simplified limit problem.     

NMR studies of models having the Pt(d(GpG)) 17-membered macrocyclic ring formed in DNA by platinum anticancer drugs: Pt complexes with bulky chiral diamine ligands

The highly distorted Pt(d(G*pG*)) (G* = N7-platinated G) 17-membered macrocyclic ring formed by cisplatin anticancer drug binding to DNA alters the structure of the G*G* base pair steps, canting one base, and increases dynamic motion, complicating solution structural studies. However, the ring appears to favor the HH1 conformation (HH1 denotes head-to-head guanine bases, 1 denotes the normal direction of backbone propagation). Compared to cisplatin, analogues with NH groups in the carrier ligand replaced by bulky N-alkyl groups are more toxic and less active and form less dynamic adducts. To examine the molecular origins for the biological effects of steric bulk, we evaluate Me(4)DABPt(d(G*pG*)) models; the bulk and chirality of Me(4)DAB (N,N,N',N'-tetramethyl-2,3-diaminobutane with S,S or R,R configurations at the chelate ring carbons) impede dynamic motion and enhance the utility of NMR methods for identifying and characterizing conformers. Unlike past studies of adducts with such bulky carrier ligands, in which no HH conformer was found, the Me(4)DABPt(d(G*pG*)) adducts did form the HH1 conformer, providing compelling evidence that the sugar-phosphate backbone can impose constraints sufficient to overcome the alkyl-group steric effects. The HH1 conformer exhibits no significant canting. The (S,S)-Me(4)DABPt(d(G*pG*)) adduct has the least amount of the "normal" HH1 conformer and the greatest amount of the ΔHT1 conformer (ΔHT1 = head-to-tail G* bases with Δ chirality) ever observed (88% under some conditions). Thus, our results lead us to hypothesize that the low activity and high toxicity of analogues of cisplatin having carrier ligands with N-alkyl groups arise from the low abundance and minimal canting of the HH1 conformer and possibly from the adverse effects of an abundant ΔHT1 conformer. The new findings advance our understanding of the chemistry of the Pt(d(G*pG*)) macrocyclic ring and of the effects of carrier-ligand steric bulk on the properties of the ring.     

Linking the historical and chemical definitions of diabatic states for charge and excitation energy transfer reactions in condensed phase

Marcus theory of electron transfer (ET) and Fo?rster theory of excitation energy transfer (EET) rely on the Condon approximation and the theoretical availability of initial and final states of ET and EET reactions, often called diabatic states. Recently [Subotnik et al., J. Chem. Phys. 130, 234102 (2009)], diabatic states for practical calculations of ET and EET reactions were defined in terms of their interactions with the surrounding environment. However, from a purely theoretical standpoint, the definition of diabatic states must arise from the minimization of the dynamic couplings between the trial diabatic states. In this work, we show that if the Condon approximation is valid, then a minimization of the derived dynamic couplings leads to corresponding diabatic states for ET reactions taking place in solution by diagonalization of the dipole moment matrix, which is equivalent to a Boys localization algorithm; while for EET reactions in solution, diabatic states are found through the Edmiston-Ruedenberg localization algorithm. In the derivation, we find interesting expressions for the environmental contribution to the dynamic coupling of the adiabatic states in condensed-phase processes. In one of the cases considered, we find that such a contribution is trivially evaluable as a scalar product of the transition dipole moment with a quantity directly derivable from the geometry arrangement of the nuclei in the molecular environment. Possibly, this has applications in the evaluation of dynamic couplings for large scale simulations.     

On site validation of sound absorption measurements of occupied pews

Laboratory measurements of sound absorption by audiences are known to be scarcely reliable when applied to actual rooms as a consequence of several problems, among which the different area of the “sample” and the different distribution of the reflected sound may play important roles. When dealing with worship places, characterized by a variable degree of occupation and much lower absorption due to unoccupied seats, things become more complicated as absorption seems to be proportional to the number of occupants rather than to the area they cover (as normally accepted in performing spaces). The combination of these variables has been investigated by taking advantage of laboratory measurements and analysing their application to six churches, where on site measurements of reverberation time were carried out with and without occupation. The results are discussed both in terms of simple prediction formulae (Sabine, Eyring, and Arau-Purchades) and of computer simulations, showing that laboratory measurements may be reliably used in computer simulations (at least in the frequency range from 500 Hz on). At low frequencies greater attention must be paid as the absorption coefficients need to be corrected as a function of the actual distribution of the sound field in the room.     

A dimensional split preconditioner for Stokes and linearized Navier-Stokes equations

In this paper we introduce a new preconditioner for linear systems of saddle point type arising from the numerical solution of the Navier-Stokes equations. Our approach is based on a dimensional splitting of the problem along the components of the velocity field, resulting in a convergent fixed-point iteration. The basic iteration is accelerated by a Krylov subspace method like restarted GMRES. The corresponding preconditioner requires at each iteration the solution of a set of discrete scalar elliptic equations, one for each component of the velocity field. Numerical experiments illustrating the convergence behavior for different finite element discretizations of Stokes and Oseen problems are included.     

Are there sterile neutrinos at the eV scale?

New predictions for the antineutrino flux from nuclear reactors suggest that reactor experiments may have measured a deficit in this flux, which can be interpreted in terms of oscillations between the known active neutrinos and new sterile states. We perform a reanalysis of global short-baseline neutrino oscillation data in a framework with one or two sterile neutrinos. While one sterile neutrino is still not sufficient to reconcile the signals suggested by reactor experiments and by the LSND and MiniBooNE experiments with null results from other searches, we find that, with the new reactor flux prediction, the global fit improves considerably when two sterile neutrinos are introduced.     

Intercalant and intermolecular phonon assisted superconductivity in K-doped picene

K(3) picene is a superconducting molecular crystal with a critical temperature of T(c) = 7 or 18 K, depending on the preparation conditions. Using density functional theory we show that electron-phonon interaction accounts for T(c) 3-8 K. The average electron-phonon coupling, calculated by including the phonon energy scale in the electron-phonon scattering, is λ = 0.73 and ω(log) = 18.0 meV. Intercalant and intermolecular phonon modes contribute substantially (40%) to λ as also shown by the isotope exponents of potassium (0.19) and carbon (0.31). The relevance of these modes makes superconductivity in K-doped picene peculiar and different from that of fullerenes.