Microorganic pollutants in the outskirts of Rome

A short field campaign was performed in the outskirts of Rome at four sites located pretty along the four rose wind directions to city centre. Both chlorinated (PCB and PCDD/F) and non-chlorinated (n-alkanes, PAH, nitrated-PAH, n-alkanoic acids) organic micropollutants were investigated for their contents in the atmosphere. Concentrations reached by these pollutants in the outskirts were compared to those found in downtown Rome, both inside and outside of its largest city garden. Although concentrations of organic pollutants found in the outskirts were quite low, however they seemed enough high to induce some health risk in humans. Rural sites were less affected than industrial and waste disposal/treatment areas.     

Blocking Sets of Type (1, k) in a Finite Projective Plane

Following a previous work of Tallini (J. Geom. (1987), 191–199), we investigate the arithmetical properties of a blocking set in a finite projective plane which is met by any line in either 1 or k points, for a fixed number k. The results are then used to give some characterizations of blocking sets of this type which are preserved by a large collineation group of the plane.     

In Silico and In Vitro Analysis of Major Cannabis-Derived Compounds as Fatty Acid Amide Hydrolase Inhibitors

Accumulated evidence suggests that enhancing the endocannabinoid (eCB) tone, in particular of anandamide (N-arachidonoylethanolamine, AEA), has therapeutic potential in many human diseases. Fatty acid amide hydrolase (FAAH) is a membrane-bound enzyme principally responsible for the degradation of AEA, and thus it represents a relevant target to increase signaling thereof. In recent years, different synthetic and natural compounds have been developed and tested on rat FAAH, but little is known of their effect on the human enzyme. Here, we sought to investigate six major cannabis-derived compounds to compare their action on rat and human FAAHs. To this aim, we combined an in silico analysis of their binding mode and affinity, with in vitro assays of their effect on enzyme activity. This integrated approach allowed to disclose differences in efficacy towards rat and human FAAHs, and to highlight the role of key residues involved in the inhibition of both enzymes. This study suggests that the therapeutic efficacy of compounds targeted towards FAAH should be always tested in vitro on both rat and human enzymes.     

Essential dynamics for the study of microstructures in liquids

Essential Dynamics (ED) is a powerful tool for analyzing molecular dynamics (MD) simulations and it is widely adopted for conformational analysis of large molecular systems such as, for example, proteins and nucleic acids. In this study, we extend the use of ED to the study of clusters of arbitrary size constituted by weakly interacting particles, for example, atomic clusters and supramolecular systems. The key feature of the method we present is the identification of the relevant atomic‐molecular clusters to be analyzed by ED for extracting the information of interest. The application of this computational approach allows a straightforward and unbiased conformational study of the local microstructures in liquids, as emerged from semiclassical MD simulations. The good performance of the method is demonstrated by calculating typical observables of liquid water, that is, NMR, NEXAFS O1s, and IR spectra, known to be rather sensitive both to the presence and to the conformational features of hydrogen‐bonded clusters. © 2014 Wiley Periodicals, Inc.     

Twistor spaces and spinors over loop spaces

In this paper two natural twistor spaces over the loop space of a Riemannian manifold are constructed and their equivalence is shown in the Kählerian case. This relies on a detailed study of frame bundles of loop spaces on the one hand and, on the other hand, on an explicit local trivialization of the Atiyah operator family [defined in Atiyah (SMF 131:43–59, 1985)] associated to a loop space. We relate these constructions to the Dixmier-Douady obstruction class against the existence of a string structure, as well as to pseudo - line bundle gerbes in the sense of Brylinski (Loop spaces, characteristic classes and geometric quantization. Birkhäuser, Basel, 1993).     

Optimal quantum circuits for general phase estimation

We address the problem of estimating the phase phi given N copies of the phase-rotation gate uphi. We consider, for the first time, the optimization of the general case where the circuit consists of an arbitrary input state, followed by any arrangement of the N phase rotations interspersed with arbitrary quantum operations, and ending with a general measurement. Using the polynomial method, we show that, in all cases where the measure of quality of the estimate phi for phi depends only on the difference phi-phi, the optimal scheme has a very simple fixed form. This implies that an optimal general phase estimation procedure can be found by just optimizing the amplitudes of the initial state.     

Molecular dynamics simulation of polymer electrolytes based on poly(ethylene oxide) and ionic liquids. II. Dynamical properties

Dynamical properties of polymer electrolytes based on poly(ethylene oxide) (PEO) and ionic liquids of 1-alkyl-3-methylimidazolium cations were calculated by molecular dynamics simulations with previously proposed models [L. T. Costa and M. C. Ribeiro, J. Chem. Phys. 124, 184902 (2006)]. The effect of changing the ionic liquid concentration, temperature, and the 1-alkyl-chain lengths, [1,3-dimethylimidazolium]PF(6) and [1-butyl-3-methylimidazolium]PF(6) ([dmim]PF(6) and [bmim]PF(6)), was investigated. Cation diffusion coefficient is higher than those of anion and oxygen atoms of PEO chains. Ionic mobility in PEO[bmim]PF(6) is higher than in PEO[dmim]PF(6), so that the ionic conductivity kappa of the former is approximately ten times larger than the latter. The ratio between kappa and its estimate from the Nernst-Einstein equation kappa/kappa(NE), which is inversely proportional to the strength of ion pairs, is higher in ionic liquid polymer electrolytes than in polymer electrolytes based on inorganic salts with Li(+) cations. Calculated time correlation functions corroborate previous evidence from the analysis of equilibrium structure that the ion pairs in ionic liquid polymer electrolytes are relatively weak. Structural relaxation at distinct spatial scales is revealed by the calculation of the intermediate scattering function at different wavevectors. These data are reproduced with stretched exponential functions, so that temperature and wavevector dependences of best fit parameters can be compared with corresponding results for polymer electrolytes containing simpler ions.     

Enantioselective synthesis of (s)- and (R)-tolterodine by asymmetric hydrogenation of a coumarin derivative obtained by a Heck reaction

An efficient and short enantioselective synthesis of (S)- and (R)-tolterodine was performed by asymmetric hydrogenation of a coumarin intermediate, easily obtained by a Heck reaction from inexpensive and commercially available starting materials.     

Modulating the M-M distance in dinuclear complexes. New ligand with a 2,2'-Biphenol fragment as key unit: synthesis, coordination behavior, and crystal structures of Cu(II) and Zn(II) dinuclear complexes

The synthesis and characterization of the new polyamino-phenolic ligand 3,3'-bis[N,N-bis(2-aminoethyl)aminomethyl]-2,2'-dihydroxybiphenyl (L) are reported. L contains two diethylenetriamine units linked by a 1,1'-bis(2-phenol) group (BPH) on the central nitrogen atom which allows two separate binding amino subunits in a noncyclic ligand. The basicity and binding properties of L toward Cu(II) and Zn(II) were determined by means of potentiometric measurements in aqueous solution (298.1 +/- 0.1 K, I = 0.15 mol dm-3). L behaves as a pentaprotic base and as a monoprotic acid under the experimental conditions used, yielding the H5L5+ or H-1L- species, respectively. L forms both mono- and dinuclear species with both metal ions investigated; the dinuclear species are largely prevalent in aqueous solution with a L/M(II) molar ratio of 1:2 at pH higher than 7. L shows different behavior in Cu(II) and Zn(II) binding, affecting the dinuclear species formed and the distance between the two coordinated metal ions, which is greater in the Zn(II) than in the Cu(II) dinuclear species. This difference can be attributed to the different degree of protonation of BPH which influences the angle between the phenyl rings in the two systems. In this way, it is possible to modulate the M(II)-M(II) distance by the choice M(II) and to space the two M(II) farther away than was possible with the previously synthesized ligands. L does not saturate the coordination sphere of the coordinated M(II) ions in the dinuclear species, and thus, these latter species are prone to add guests. 1H and 13C NMR experiments carried out in aqueous solution, as well as the crystal structures of the dinuclear Cu(II) and Zn(II) species formed in aqueous solution, aided in elucidating the involvement of L and BPH in Zn(II) and Cu(II) stabilization.     

Bipyridyl ligands as photoactivatable mono- and bis-alkylating agents capable of DNA cross-linking

The photoactivation of 6,6'-bis-CH2X-[2,2']bipyridinyl-5,5'-diol ligands as mono and bis-alkylating agents has been investigated, detecting transient heterocyclic quinone methides.