Phase Transitions and Spatio-Temporal Fluctuations in Stochastic Lattice Lotka–Volterra Models

We study the general properties of stochastic two-species models for predator-prey competition and coexistence with Lotka–Volterra type interactions defined on a d-dimensional lattice. Introducing spatial degrees of freedom and allowing for stochastic fluctuations generically invalidates the classical, deterministic mean-field picture. Already within mean-field theory, however, spatial constraints, modeling locally limited resources, lead to the emergence of a continuous active-to-absorbing state phase transition. Field-theoretic arguments, supported by Monte Carlo simulation results, indicate that this transition, which represents an extinction threshold for the predator population, is governed by the directed percolation universality class. In the active state, where predators and prey coexist, the classical center singularities with associated population cycles are replaced by either nodes or foci. In the vicinity of the stable nodes, the system is characterized by essentially stationary localized clusters of predators in a sea of prey. Near the stable foci, however, the stochastic lattice Lotka–Volterra system displays complex, correlated spatio-temporal patterns of competing activity fronts. Correspondingly, the population densities in our numerical simulations turn out to oscillate irregularly in time, with amplitudes that tend to zero in the thermodynamic limit. Yet in finite systems these oscillatory fluctuations are quite persistent, and their features are determined by the intrinsic interaction rates rather than the initial conditions. We emphasize the robustness of this scenario with respect to various model perturbations.     

Conversion of γ-substituted bicyclo[2.2.1] (Z)-vinylsulfones to the corresponding (E)-allylsulfones

The preparation of bicyclo[2.2.1] (E)-allylsulfones starting from the corresponding (Z)-vinylsulfones is described. Starting from 2,3-bis(phenylsulfonyl)norbornadiene 1, the Michael addition of organometallic reagents followed by the base catalyzed isomerization affords (E)-allylsulfones in high yields. The procedure allows to obtain vinylidenic norbornenes which are characteristic nuclei of valuable biologically active compounds.     

Ultrasound‐Assisted Synthesis of Hybrid Vanadium Oxide/Polyaniline Nanowires

A single‐step sonochemical procedure to synthesize hybrid vanadium oxide/polyaniline nanowires starting from crystalline V₂O₅ and aniline in aqueous medium is presented. The synthesis explores the effect of high power ultrasounds on heterogeneous solid–aqueous phases, which leads to 30 nm width wires of 5 to 10 µm in length. Monomer intercalation and oxidative polymerization within the inorganic matrix proceed simultaneously with morphological changes. The electronic conductivity of hybrid nanowires reaches 0.8 S · cm⁻¹ at room temperature.

     

Tricarbonyl rhenium(I) complexes containing a bridging 2,5-diphenyl-1,3,4-oxadiazole ligand: structural, spectroscopic, electrochemical, and computational characterization

The three complexes [Re2(mu-X1)(mu-X2)(CO)6(mu-ppd-kappaN3:kappaN4)] (X1, X2 ) H, 1; X1 ) H, X2 ) Cl, 2; X1, X2 ) Cl, 3; ppd) 2,5-diphenyl-1,3,4-oxadiazole) have been synthesized by different routes, involving the reaction of [Re4(mu3-H)4(CO)12]with ppd for 1, the reaction of 1 with HCl for 2, and the reaction of [ReCl(CO)5] with ppd for 3. The three complexes possess a different number of valence electrons, so the formal Re-Re bond order varies from 2 to 1 to 0 in complexes 1, 2, and 3, respectively. This is reflected in the Re-Re bond distance (277.9, 297.9, and 358.5 pm in the same series)and in the stability of the complexes in the coordinating solvent acetonitrile (t1/2 for ppd displacement 13.6, 4.5, and 3.7 h,for 1, 2, and 3, respectively). Both experimental and calculated structures indicates that coordination induces a distortion from planarity of the diphenyloxadiazole moiety due to the interaction of the equatorial carbonyls with the bridging ppd,which increases on going from 1 to 2 to 3 (dihedral angle between the oxadiazole and the phenyl rings 18.4 degrees, 23.3 degrees, and 45.0 degrees, respectively). The UV spectra show pi-pi* transitions of the oxadiazole ligand (which shift to higher energy on increasing the distortion from the planarity, from 252 to 267 nm) and metal-to-ligand charge transfer absorptions (from 300 to 362 nm). Upon irradiation between 340 and 380 nm, complex 2 only features a weak broad emission at 527 nm(phi)0.02%), whereas upon excitation at 300 nm, the emission typical of free ppd is observed, suggesting photodissociation.Cyclic voltammetry investigations in acetonitrile showed that the three complexes exhibit ligand-centered irreversible reduction peaks (from -1.83 to -1.93 V vs Fc+|Fc), shifted to more positive values with respect to free ppd (-2.50 V). The shift however is smaller than in the analogous derivatives containing 1,2-diazines, suggesting a smaller electron depletion of the heterocycle ligand upon coordination. The complexes also show a metal-centered, bi-electronic, irreversible oxidation peak (from 1.05 to 1.37 V vs Fc+/Fc). A combined density functional and time-dependent density functional (TD DFT)study allowed us to understand the factors affecting the stability of the three complexes and to rationalize their electrochemical and photophysical properties in terms of their electronic structure.     

Identification and Quantification of Polycyclic Aromatic Hydrocarbons in Polyhydroxyalkanoates Produced from Mixed Microbial Cultures and Municipal Organic Wastes at Pilot Scale

Polyhydroxyalkanoates (PHAs) are well-known biodegradable plastics produced by various bacterial strains, whose major drawback is constituted by the high cost of their synthesis. Producing PHAs from mixed microbial cultures and employing organic wastes as a carbon source allows us to both reduce cost and valorize available renewable resources, such as food waste and sewage sludge. However, different types of pollutants, originally contained in organic matrices, could persist into the final product, thus compromising their safety. In this work, the exploitation of municipal wastes for PHA production is evaluated from the environmental and health safety aspect by determining the presence of polycyclic aromatic hydrocarbons (PAHs) in both commercial and waste-based PHA samples. Quantification of PAHs by gas chromatography-mass spectrometry on 24 PHA samples obtained in different conditions showed very low contamination levels, in the range of ppb to a few ppm. Moreover, the contaminant content seems to be dependent on the type of PHA stabilization and extraction, but independent from the type of feedstock. Commercial PHA derived from crops, selected for comparison, showed PAH content comparable to that detected in PHAs derived from organic fraction of municipal solid waste. Although there is no specific regulation on PAH maximum levels in PHAs, detected concentrations were consistently lower than threshold limit values set by regulation and guidelines for similar materials and/or applications. This suggests that the use of organic waste as substrate for PHA production is safe for both the human health and the environment.     

Stability constants of iron(II) sulfate complexes

The complex formation equilibria between iron(II) and sulfate ions have been studied at 25 degrees C in 3 M NaClO4 ionic medium by measuring with a glass electrode the competition of Fe2+ and H+ ions for the sulfate ion. The concentrations of the metal and of the ligand were varied in the ranges 0.01 to 0.125 and 0.01 to 0.250 M, respectively. The analytical concentration of strong acid was chosen to be 0.01 or 0.03 M. The potentials of the glass electrode, corrected for the effect of replacement of medium ions with reagent species, have been interpreted with the equilibria [formula: see text] Stability constants valid in the infinite dilution reference state, logK zero = 1.98 +/- 0.16, log beta 1 zero = 2.1(5) +/- 0.2 and log beta 2 = 2.5 +/- 0.2, have been estimated by assuming the validity of the specific interaction theory.     

Molecular dynamics and conformational behaviour of mesogenic resorcinarenes

The dynamic and conformational behaviour of four mesogenic resorcinarenes exhibiting columnar mesophases have been studied by a combination of broadband dielectric spectroscopy and deuterium solid state NMR. Broadband dielectric spectroscopy provided evidence for two relaxation processes present both in the mesophase and in the isotropic liquid. The high frequency process II, common to all mesogens, has been assigned to the libration of the carbonyl groups of the ester junctions between the core and the side chains. The low frequency process I, present in conformationally mobile mesogens 1 and 2, has been attributed to the ring inversion process of the macrocyclic core associated with dipole inversion along the columnar axis. Deuterium solid state NMR performed on 4, the deuteriated analogue of 1, confirmed the molecular dynamics attribution for process I, assigning the ring inversion to the interconversion of the two equivalent crown conformations.     

Modifying LnHPDO3A Chelates for Improved T1 and CEST MRI Applications

The new ligand HPDO3MA [(R,R,R,R)-10-(2-hydroxypropyl)-α,α′,α′′-trimethyl-1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid] was designed to combine and optimize the chemical properties of the macrocyclic ligands HPDO3A and DOTMA. The presence of the methyl groups on the acetic pendant arms of HPDO3A is expected to rigidify the structure of the ligand and favor an increase of the kinetic inertness of the Ln complexes. ¹H NMR spectra of Eu(HPDO3MA) displayed the presence of two pairs of diastereoisomers: SAP (square antiprismatic) and TSAP (twisted square antiprismatic) isomers (56 and 44 %, respectively). In addition, ¹H and ¹⁷O relaxometric NMR studies of Gd(HPDO3MA) showed approximately a 10 % increase in relaxivity and a faster water exchange rate with respect to Gd(HPDO3A). Moreover, a detailed chemical exchange saturation transfer (CEST) characterization of Yb(HPDO3MA) displayed a sensitivity about two times larger than that of Yb(HPDO3A) both in phantom and in cell labeling experiments. Finally, the kinetic inertness of Yb(HPDO3MA) was measured to be twice as high as that of Yb(HPDO3A), with a dissociation half-life at physiological pH of about 2500 years.