Co-ordination chemistry of amino pendant arm derivatives of 1,4,7-triazacyclononane

The binding properties of 1,4,7-triazacyclononane ([9]aneN3) to metal cations can be adapted through sequential functionalisation of the secondary amines with aminoethyl or aminopropyl pendant arms to generate ligands with increasing numbers of donor atoms. The new amino functionalised pendant arm derivative of 1,4,7-triazacyclononane ([9]aneN3), L1, has been synthesised and its salt [H2L1]Cl2 characterised by X-ray diffraction. The protonation constants of the ligands L1-L4 having one, two or three aminoethyl or three aminopropyl pendant arms, respectively, on the [9]aneN3 framework, and the thermodynamic stabilities of their mononuclear complexes with CuII and ZnII have been investigated by potentiometric measurements in aqueous solutions. In order to discern the protonation sites of ligands L1-L4, 1H NMR spectroscopic studies were performed in D2O as a function of pH. While the stability constants of the CuII complexes increase on going from L1 to L2 and then decrease on going from L2 to L3 and L4, those for ZnII complexes increase from L1 to L3 and then decrease for L4. The X-ray crystal structures of the complexes [Cu(L1)(Br)]Br, [Zn(L1)(NO3)]NO3, [Cu(L2)](ClO4)2, [Ni(L2)(MeCN)](BF4)2, [Zn(L4)](BF4)2.MeCN and [Mn(L4)](NO3)2.1/2H2O have been determined. In both [Cu(L1)(Br)]Br and [Zn(L1)(NO3)]NO3 the metal ion is five co-ordinate and bound by four N-donors of the macrocyclic ligand and by one of the two counter-anions. The crystal structures of [Cu(L2)](ClO4)2 and [Ni(L2)(MeCN)](BF4)2 show the metal centre in slightly distorted square-based pyramidal and octahedral geometry, respectively, with a MeCN molecule completing the co-ordination sphere around NiII in the latter. In both [Zn(L4)](BF4)2.MeCN and [Mn(L4)](NO3)2.1/2H2O the metal ion is bound by all six N-donors of the macrocyclic ligand in a distorted octahedral geometry. Interestingly, and in agreement with the solution studies and with the marked preference of CuII to assume a square-based pyramidal geometry with these types of ligands, the reaction of L4 with one equivalent of Cu(BF4)2.4H2O in MeOH at room temperature yields a square-based pyramidal five co-ordinate CuII complex [Cu(L6)](BF4)2 where one of the three propylamino pendant arms of the starting ligand has been cleaved to give L6.     

Chemical composition and in vitro activity of plant extracts from Ferula communis and Dittrichia viscosa against postharvest fungi

F. communis and D. viscosa are perennial Mediterranean weeds that have been used for different therapeutic purposes in traditional pharmacopeia. Plant extracts were obtained from air dried D. viscosa young shoots (DvA) and F. communis aerial part (FcA) and roots (FcR) with n-hexane. The chemical compositions of the extracts were analyzed by HPLC-DAD, LC-MS (ESI) and LC-Q-TOF techniques. Two sesquiterpene lactones (inuviscolide, tomentosin) and three sesquiterpene acids (costic acid, hydroxycostic acid, ilicic acid) were identified from the D. viscosa extract, while in F. communis extracts three daucane sesquiterpenes (acetoxyferutinin, oxojaeskeanadioyl anisate, fertidin) and one coumarin (ferulenol) derivates were found. Biological activities of plant extracts were studied in in vitro experiments on the colonies and conidia of Botryotinia fuckeliana, Penicillium digitatum, P. expansum, Monilinia laxa, M. fructigena and Aspergillus spp. Extracts showed varying degree of antifungal activities on colony growth and conidia germination. The extract from FcA showed the least effect, while DvA extract had the strongest fungitoxic effects. FcR extract presented a fungitoxic effect on the colony growth, but it was not able to inhibit the conidia germination. These distinctions can be attributed to the differences in chemical composition of plant extracts.     

Sulle funzioni di più variabili a variazione limitata

Memoria presentata da G. Fichera     

A characterization of Denniston's maximal arcs

Our main result is the following characterization of Denniston's maximal arcs: If a maximal arcK in PG(2,q),q even, is invariant under a linear collineation group of PG(2,q) which is cyclic and has orderq+1, thenK is a Denniston's maximal arc.This work was partially supported by a grant of M.P.I. (Research project Strutture geometriche combinatorie e loro applicazioni).     

Electrolytic Oxidation of Thiocyanate and Selenocyanate Salts and the Photoelectrochemical Effect.

New photosensitive materials can be obtained by electrochemical oxidation of thiocyanate and selenocyanate salts. Using (K,Na)SCN eutectic melt, the formation of an electrodic deposit, with photoelectrochemical properties, has already been reported by us. To improve the photoelectrochemical characteristics of the deposit, futher investigations were carried out in the following sistems: selenocyanate ammoniate, KSCH-Acetamide eutectic mixture and KSCN ethylene carbonate solution:. Attempts to obtain a massive deposit in the ammoniate solution were unsuccessful due to ammonia oxidation. Measurements performed on the other KSCN systems show that temperature is a parameter of remarkable importance. In fact, lowering the temperature one obtains a decrease on formation of parathiocyanogen on behalf of the polytrithiocyanogen, the species that gives rise to the photoeffect.     

Stereoselective synthesis of 2,3-epoxy alcohols mediated by a remote sulfinyl group

The influence of the sulfinyl group as a chiral auxiliary in the stereoselective addition of oxiranyllithiums to (S)-2-p-tolylsulfinylbenzaldehyde has been studied. All reactions evolve with retention of configuration at the starting lithiated carbon. Completely stereoselective additions have been observed when configurations at sulfur and the lithiated carbon are different (matched pair), whereas variable dr's values (ranging between 52:48 and >99:<1%) when they are identical (mismatched pair).     

Solvent and TMEDA effects on the configurational stability of chiral lithiated aryloxiranes

The employment of hexane/N,N,N',N'-tetramethylethylenediamine (TMEDA) dramatically hinders the racemization of those lithiated styrene oxides (trifluoromethyl-, chloro-, and phenylthio-substituted) that have been proven to be configurationally unstable in THF on the timescale of their reactions. The barriers to inversion and the activation parameters, calculated (Eyring equation) for reactions performed in THF, THF/TMEDA, and hexane/TMEDA, suggest the intervention of particular enantiomerization mechanisms for each case. The role of TMEDA in both coordinating and noncoordinating solvents has also been questioned and discussed in light of the kinetic data gathered and a model for deprotonation in hexane/TMEDA has also been proposed. The synthetic benefits of our results became apparent on establishing an asymmetric synthesis of an industrially important antifungal agent.     

Thermodynamic and dynamic anomalies in a one-dimensional lattice model of liquid water

We investigate the occurrence of waterlike thermodynamic and dynamic anomalous behavior in a one dimensional lattice gas model. The system thermodynamics is obtained using the transfer matrix technique and anomalies on density and thermodynamic response functions are found. When the hydrogen bond (molecules separated by holes) is more attractive than the van der Waals interaction (molecules in contact) a transition between two fluid structures is found at null temperature and high pressure. This transition is analogous to a 'critical point' and intimately connects the anomalies in density and in thermodynamic response functions. Monte Carlo simulations were performed in the neighborhood of this transition and used to calculate the self diffusion constant, which increases with density as in liquid water.