N,O-Nucleoside Analogues: Metabolic and Apoptotic Activity

Two new families of N,O-nucleoside analogues containing the anthracene moiety introduced through the nitrosocarbonyl ene reaction with allylic alcohols were prepared. The core structure is an isoxazolidine heterocycle that introduces either atom either a phenyl ring or dimethyl moiety at the C3 carbon. Different heterobases were inserted at the position 5 of the heterocyclic ring. One of the synthesized compounds demonstrated a good capacity to induce cell death and an appreciable nuclear fragmentation was evidenced in treated cells.     

Accurate Modelling of Group Electrostatic Potential and Distributed Polarizability in Dipeptides

Within the scope of accurate structure-property correlations in biomolecules, this work investigates how conformations and electronic configurations of biologically relevant macromolecules affect their intermolecular potentials. With the purpose of testing the suitability of a simple and universal model, the dipeptides are made from the assembly of their building blocks, namely the amino acid residuals or, more finely tuned, the individual functional groups. The model makes use of functional-group electrostatic potentials (GEP) and distributed polarizabilities (GDP), which enable an in depth analysis of the correlation between structural features and property build-up. GEPs and GDPs are calculated for various conformers and protonation states of L-alanyl-L-alanine, glycyl-L-alanine, L-alanylglycine, and glycylglycine, which are prototypic molecules to model the pertinent functional groups. The model provides GEPs that reproduce the exact potential to an average accuracy of ca. 0.05 au. The good agreement between the properties estimated with the simple model and those calculated with state-of-the-art quantum chemical methods encourages further testing of the predictive power of this model, simulating for example interaction energies and optoelectronic properties.     

Universality in lattice models of dynamic arrest: introduction of an order parameter

We introduce an order parameter for dynamical arrest. Dynamically available volume (unoccupied space that is available to the motion of particles) is expressed as holes for the simple lattice models we study. Near the arrest transition the system is dilute in holes, so we expand dynamical quantities in a series of hole density. Unlike the situation when presented in particle density, all cases of simple models that we examine have a quadratic dependence of the diffusion constant on hole density. This observation implies that in certain regimes ideal dynamical arrest transitions may possess a hitherto unnoticed degree of universality.     

Methylpyridylbenz-X-azoles. lH NMR Study

The shielding parameters of benz-X-azolyl substituents in various positions of the pyridine nucleus were determined by means of a regression analysis procedure. Analogously the shielding contributions of pyridyl substituents on homocyclic protons of benz-X-azoles were derived. The results evidence some interactions between the two heterocyclic systems when the benz-X-azolyl substituents are linked at the pyridine α-position.     

Strong oscillations in molecular valence photoemission intensities

Photoemission from the two outermost ionizations [highest occupied molecular orbitals (HOMO and HOMO-1)] of Mg(eta(5)-C(5)H(5))(2) has been studied with synchrotron radiation in the gas phase. Strong oscillations in the HOMO-1/HOMO ratio, qualitatively similar to those well-known for fullerenes, are found. Excellent agreement with the experimental ratio is provided by accurate cross section calculations both at the density-functional theory and time-dependent density-functional theory level, indicating that a many electron response has a minor role for this effect. A comparison with the calculated values for other metal sandwich compounds indicate that the presence of oscillations is a widespread phenomenon, and a potential source of interesting information on the structural and electronic properties of the target molecule.     

Dynamics of alkoxy-oligothiophene ground and excited states in nanochannels

Two oligothiophenes, 4,4'-dipentoxy-2,2'-dithiophene and 4,4"-dipentoxy-2,2':5',2":5",2' '-tetrathiophene, have been included in the nanochannels of the autoassembling host TPP (tris-o-phenylenedioxycyclotriphosphazene). The effect of the confinement on the structure and properties of the two dyes, as conformational arrangements, dynamics, and photophysical behavior, was addressed by the combination of high spinning speed solid-state NMR and time-resolved EPR spectroscopy. We compared the conformations of the dyes in their ground and photoexcited triplet states and described in detail the dynamics of the supramolecular adducts from 4 K to room temperature. Above 200 K surprisingly fast spinning rates of the dithiophene core were discovered, while the side chains show far slower reorientation motion, being in bulky gauche-rich conformations. These lateral plugs keep the planar core as appended in the space like a nanoscale gyroscope, allowing a reorientation in the motion regime of liquids and a long triplet lifetime at unusually high temperature. The nuclear magnetic properties of the guest dyes are also largely affected by the aromatic rings of the neighboring host, imparting an impressive magnetic susceptibility effect (2 ppm proton shift). The high mobility is due to the formation of a nanocage in a channel where aliphatic and aromatic functions isolate the thiophene moieties. Instead, two conformers of the tetrathiophene twisted on the central bond are stabilized by interaction with the host. They interconvert fast enough to be averaged in the NMR time scale.     

MR enteroclysis using iron oxide particles (ferristene) as an endoluminal contrast agent: an open phase III trial

To evaluate efficacy and safety of a superparamagnetic iron oxide contrast agent (ferristene) as an endoluminal contrast medium for magnetic resonance (MR) enteroclysis in a phase III trial. Twenty-three patients with history of known or suspected small bowel Crohn's disease underwent MR imaging of the abdomen at 0.5 T unit. The imaging protocol included two phases: the first one without administration of any contrast agent and the second one, where the small bowel was filled by enteroclysis with 800 ml of the luminal iron oxide contrast medium and Gd-DTPA (0.1 mmol/Kg) was administered intravenously. Axial Spin-Echo (SE) T1-weighted (T1w), proton-density and T2w images, sagittal and coronal SE T1w and Short TI Inversion Recovery (STIR) sequences were subsequently obtained. Three investigators blindly evaluated images to determine small bowel distribution of ferristene, presence of artifacts, delineation of bowel lesion/wall and the diagnostic value of ferristene combined with gadolinium. Pre- and postcontrast signal intensity measurements of bowel lesion/wall, bowel lumen and background noise were also calculated. Three patients withdrew before the procedure, therefore 20 patients were effectively included in the study. No significant difference between the three investigators' evaluations of the improvement of the diagnostic information was found (percentage of improvement of 90% with 95% confidence limits of 68% and 99%). A statistically significant difference between the first and third investigators was found for grading of quality of delineation of bowel lesion/wall. Signal intensity measures showed a significant increase of the bowel lesion/wall and background noise/lesion for the SE T1w images. No serious adverse event was reported in our series. MR enteroclysis using ferristene as an endoluminal contrast agent appears to be a safe and efficient procedure for the study of the small bowel.