Supramolecular Assemblies in Silver Complexes: Phase Transitions and the Role of the Halogen Bond

Weak interactions (hydrogen bonds, halogen bonds, CH···πand Ï€-πstacking) can play a significant role in the formation of supramolecular assemblies with desired structural features. In this contribution, we report a systematic investigation on how a halogen bond (XB) can modulate the structural arrangement of silver supramolecular complexes. The complexes are composed of X-phenyl(bispyrazolyl)methane (X = Br, I) and I-alkynophenyl(bispyrazolyl)methane ligands functionalized in meta (L3Br, L3I) and para (L4Br, L4I, L4CCI) positions on a phenyl ring with the purpose of providing different directionalities of the X function with respect to the N,N coordination system. The obtained [Ag(L)2]+ moieties show remarkable geometric similarities, and the L4Br, L4I, and L4CCI ligands exhibit the most conserved types of supramolecular arrangement that are sustained by XB. The increased σ-hole in L4CCI with respect to L4I leads to an occurrence of short (and strong) XB interactions with the anions. [Ag(L4I)2]PF6 and [Ag(L4I)2]CF3SO3 are characterized by the presence of three different phases, and the single-crystal evolution from phase-1 (a honeycomb structure with large 1D cavities) to phase-3 (solventless) occurs by a stepwise decrease in the crystallization solvent content, which promotes an increase in XB interactions in the lattice. The present paper aims to provide useful tools for the selection of appropriate components for the use of coordination compounds to build supramolecular systems based on the halogen bond

Experimental study of the delayed threshold phenomenon in a semiconductor laser

An experimental study of the delayed threshold phenomenon in a Vertical Extended Cavity Semiconductor Emitting Laser is carried out. Under modulation of the pump power, the laser intensity exhibits a hysteresis behavior in the vicinity of the threshold. The temporal width of this hysteresis is measured as a function of the modulation frequency, and is proved to follow the predicted scaling law. A model based on the rate equations is derived and used to analyze the experimental observations. A frequency variation of the laser around the delayed threshold and induced by the phase-amplitude coupling is predicted and estimated

“Bottled” Spiro-Doubly Aromatic Trinuclear [Pd2Ru]+ Complexes

Following an ongoing interest in the study of transition metal complexes with exotic bonding networks, we report herein the synthesis of a family of heterobimetallic triangular clusters involving Ru and Pd atoms. These are the first examples of trinuclear complexes combining these nuclei. Structural and bonding analyses revealed both analogies and unexpected differences for these [Pd2Ru]+ complexes compared to their parent [Pd3]+ peers. Noticeably, participation of the Ru atom in the π-aromaticity of the coordinated benzene ring makes the synthesized compound the second reported example of ‘bottled’ double aromaticity. This can also be referred to as spiroaromaticity due to the participation of Ru in two aromatic systems at a time. Moreover, the [Pd2Ru]+ kernel exhibits unprecedented orbital overlap of Ru dz2 AO and two Pd dxy or dx2−y2 AOs. The present findings reveal the possibility of synthesizing stable clusters with delocalized metal–metal bonding from the combination of non-adjacent elements of the periodic table which has not been reported previously

L-Idose: an attractive substrate alternative to d-glucose for measuring aldose reductase activity

Although glucose is one of the most important physio-pathological substrates of aldose reductase, it is not an easy molecule for in vitro investigation into the enzyme. In many cases alternative aldoses have been used for kinetic characterization and inhibition studies. However these molecules do not completely match the structural features of glucose, thus possibly leading to results that are not fully applicable to glucose. We show how aldose reductase is able to act efficiently on L-idose, the C-5 epimer of D-glucose. This is verified using both the bovine lens and the human recombinant enzymes. While the kcat values obtained are essentially identical to those measured for D-glucose, a significant decrease in KM was observed. This can be due to the significantly higher level of the free aldehyde form present in L-idose compared to D-glucose. We believe that L-idose is the best alternative to D-glucose in studies on aldose reductase

Cadmium uptake, localization and stress-induced morphogenic response in the fern Pteris vittata.

Cadmium uptake, tissue localization and structural changes induced at cellular level are essential to understand Cd tolerance in plants. In this study we have exposed plants of Pteris vittata to different concentrations of CdCl2 (0, 30, 60, 100 μM) to evaluate the tolerance of the fern to cadmium. Cadmium content determination and its histochemical localization showed that P. vittata not only takes up, but also transports and accumulates cadmium in the aboveground tissues, delocalizing it mainly in the less bioactive tissues of the frond, the trichomes and the scales. Cadmium tolerance in P. vittata was strictly related to morphogenic response induced by the metal itself in the root system. Adaptive response regarded changes of the root apex size, the developmental pattern of root hairs, the differentiation of xylem elements and endodermal suberin lamellae. All the considered parameters suggest that, in our experimental conditions, 60 μM of Cd may represent the highest concentration that P. vittata can tolerate; indeed this Cd level even improves the absorbance features of the root and allows good transport and accumulation of the metal in the fronds. The results of this study can provide useful information for phytoremediation strategies of soils contaminated by Cd, exploiting the established ability of P. vittata to transport, delocalize in the aboveground biomass and accumulate polluting metals

Elastic Pion Scattering on the Deuteron in a Multiple Scattering Model

Pion elastic scattering on deuterium is studied in the KMT multiple scattering approach developed in momentum space. Using a Paris wave function and the same methods and approximations as commonly used in pion scattering on heavier nuclei excellent agreement with differential cross section data is obtained for a wide range of pion energies. Only for $T_{\pi}>250$ MeV and very backward angles, discrepancies appear that are reminiscent of disagreements in pion scattering on $^3$He, $^3$H, and $^4$He. At low energies the second order corrections have been included. Polarization observables are studied in detail. While tensor analyzing powers are well reproduced, vector analyzing powers exhibit dramatic discrepancies.Comment: 25 pages LATEX and 9 postscript figures in a self-extracting uufile archiv

Rifiuti spiaggiati: problema ambientale e di sanità pubblica

L’accumulo sulle spiagge di materiale naturale o antropico raramente è stato esplorato da una prospettiva “One Health”, che ne consideri l’impatto ambientale e sanitario. In questo lavoro, il modello concettuale Determinanti - Pressioni - Stato - Impatti - Risposte (DPSIR) è stato adattato al problema dei rifiuti spiaggiati, ed applicato ad un comune costiero italiano (Nord Toscana) a forte vocazione turistica

Detriti spiaggiati come possibile veicolo di virus: contaminazione e sopravvivenza

Le spiagge sono interessate dall’accumulo di biomassa e rifiuti antropici. Ciò comporta non solo un impatto ambientale ed economico ma anche effetti sulla salute derivanti dall’esposizione a microorganismi potenzialmente patogeni. La contaminazione microbica delle spiagge è stata studiata principalmente considerando funghi e batteri, mentre esistono pochi dati sui virus. Nel presente lavoro, gli aspetti legati al rischio virale per la salute sono stati affrontati valutando la presenza di virus nel materiale spiaggiato e nella sabbia sottostante e la loro sopravvivenza nella sabbia e nell’acqua di mare

Low levels of fruit nitrogen as drivers for the evolution of Madagascar's primate communities

The uneven representation of frugivorous mammals and birds across tropical regions – high in the New World, low in Madagascar and intermediate in Africa and Asia – represents a long-standing enigma in ecology. Several hypotheses have been proposed to explain these differences but the ultimate drivers remain unclear. Here, we tested the hypothesis that fruits in Madagascar contain insufficient nitrogen to meet primate metabolic requirements, thus constraining the evolution of frugivory. We performed a global analysis of nitrogen in fruits consumed by primates, as collated from 79 studies. Our results showed that average frugivory among lemur communities was lower compared to New World and Asian-African primate communities. Fruits in Madagascar contain lower average nitrogen than those in the New World and Old World. Nitrogen content in the overall diets of primate species did not differ significantly between major taxonomic radiations. There is no relationship between fruit protein and the degree of frugivory among primates either globally or within regions, with the exception of Madagascar. This suggests that low protein availability in fruits influences current lemur communities to select for protein from other sources, whereas in the New World and Old World other factors are more significant in shaping primate communities