Leucascandrolide A,a New Type of Macrolide: The first powerfully bioactive metabolite of calcareous sponges (Leucascandra caveolata,a new genus from the coral sea)

Leucascandrolide A ((+)- 1 ), a doubly O-bridged 18-membered macrolide of a new type, i.e., showing little C₁-branching vs. extensive 1,3-dioxygenation and a peculiar side chain, was isolated from a calcareous sponge of a new genus, Leucascandra caveolata BOROJEVIC and KLAUTAU from the Coral Sea. Transesterification of (+)- 1 gave the methyl ester 3 , derived from the side chain, and the 5-hydroxy derivative (+)- 2 , derived from the macrolide portion and with the natural configuration at C(5) (axial). Mosher's MTPA esters 4 and 5 obtained from (+)- 2 showed scattered Δδ = (δ(S) ? δ(R)) data. However, inversion of the configuration at C(5) led, via ketone (+)- 6 , to the less encumbered 5-equatorial hydroxy derivative (+)- 7 , whose MTPA esters 8 and 9 gave consistent Δδ data, allowing the assignment of the absolute configuration of (+)- 7 , and hence of (+)- 1 . The structural novelty of (+)- 1 and its powerful antifungal and cytotoxic activities are likely to renew interest in calcareous sponges, previously limited to scarcely biologically active 2-aminoimidazoles.     

Synthesis,catalytic properties and biological activity of new water soluble ruthenium cyclopentadienyl PTA complexes [(C5R5)RuCl(PTA)2] (R = H,Me; PTA = 1,3,5-triaza-7-phosphaadamantane)

The new water soluble ruthenium complexes [(C5R5)RuCl(PTA)2] (R = H, Me; PTA = 1,3,5-triaza-7-phosphaadamantane) were synthesised and characterised. Their evaluation as regioselective catalysts for hydrogenation of unsaturated ketones in aqueous biphasic conditions and as cytotoxic agents towards the TS/A adenocarcinoma cell line is briefly presented.     

The CuII−CuI−Cu0(Hg) system in the presence of benzotriazole: Part I. A polarographic investigation

A polarographic investigation of Cu^II electroreduction from solutions of benzotriazole (BTA) of pH from 1 to 3 at a dropping mercury electrode shows the presence of two successive adsorption waves of equal height (waves Ic and IIIc) due, respectively, to the formation and to the subsequent dissolution of an adsorbed film of a Cu^I compound. The dependence of the half-wave potential of wave IIIc, which is polarographically reversible, upon pH and BTA concentration indicates that the adsorbed film has the composition [Cu^I(BTA^?)], where BTA^? denotes the deprotonated anionic form of benzotriazole. Moreover, the maximum height of wave IIIc indicates that this film is one monolayer thick. A third cathodic wave (wave IIc), lying between waves Ic and IIIc, stems from the reduction to the metal state of the Cu^II ions diffusing from the bulk solution. Copper(0) oxidation at dropping amalgam electrodes in BTA solutions yields two successive adsorption waves (waves Ia and IIa). Wave Ia is due to the same electrode process, Cu⁰ (Hg)+BTA?Cu^I(BTA^?)+H⁺+e, responsible for the cathodic wave IIIc. On the other hand, wave IIa is due to the formation of roughly two adsorbed monolayers of [Cu^I(BTA^?)] upon that formed along wave Ia.     

Ionization enthalpy of benzoic acid in water—dimethylsulfoxide mixtures

The ionization enthalpy of benzoic acid has been measured calorimetrically at 25°C in H₂ODMSO mixtures ranging from pure water to a maximum DMSO molar ratio X_DMSO = 0.80. With the increase of DMSO content, the ionization becomes more and more endothermic, and for X_DMSO = 0.8 the ionization enthalpy is about 6 kcal mol^?1 higher than in water. By also measuring the solution enthalpy of crystalline benzoic acid in the mixtures, it has been shown that the solvation of the undissociated molecule is the main cause for the increase of the dissociation enthalpy. A comparison has been made between the relative enthalpies of benzoic and hydroxide ions in H₂ODMSO mixtures.     

Three applications toSO(4) invariant systems of a theorem of L. Michel relating extremal points to invariance properties

We consider a theorem due to Michel [1] which relates the invariance properties in peculiar directions in a linear space on which we represent a Lie groupG to the extremal points of an arbitrary smoothG-invariant function. The group we are interested in isSO(4) and we apply the mathematical results to the following problems:

1. mixed linear Stark Zeeman effect in a hydrogen atom,
2. perturbation of a finite Robertson-Walker metric,
3. gas evolutions preserving angular momentum and vorticity.

     

The (N=1) Supersymmetric Sine-Gordon model in two dimensions. I

In this paper and its companion (II) we prove that the SupersymmetricN=1 massless Sine-Gordon field theory, at finite (space) volume, exists and is analytic in the coupling constant . Moreover at finite (space) volume is Witten index is=1.     

Thiourea-linked upper rim calix[4]arene neoglycoconjugates: synthesis,conformations and binding properties

The thiourea group has been exploited to link two or four carbohydrate units at the upper rim of tetrapropoxycalix[4]arene derivatives in the cone conformation. Two synthetic methodologies were used, the first one consisting of the condensation of di- and tetraminocalix[4]arenes with the isothiocyanate of monosaccharides in dry CH2Cl2 at room temperature and the second one exploiting the condensation of an aminolactoside with a calixarene isothiocyanate. The first method allows the glycoconjugates to be obtained in 75-80% overall yields. The disfunctionalized derivatives exist in a closed flattened cone conformation in CDCl3 and CD3OD due to the formation of intramolecular hydrogen bonds involving the thiourea groups which are broken in DMSO-d6 to give an open flattened cone conformation. The thiourea groups act not only as linkers but also as binding units for anionic substrates as evidenced by solution 1H NMR and ESI-MS experiments. Turbidimetric analysis indicates that the tetraglucoside and tetragalactoside clusters give specific interactions with Concanavalin A (Con A) and peanut lectin (PNA), respectively. Both features show that the neoglycoconjugates could also be used as site specific molecular delivery systems.     

Perfluoropolyether-Silica Hybrids: Preparation and Surface Characterization

,-Triethoxysilane terminated perfluoropolyether-polycaprolactone block copolymers, TXCL(x)Si, were synthesised, characterised and subsequently reacted with tetraethoxysilane to prepare transparent organic-inorganic hybrid materials by using the sol–gel process. Surface characterization was carried out through contact angle measurements. All the materials investigated (independently on both the reaction time of the sol–gel reaction before coating application and the bulk organic-inorganic ratio) showed a strong hydrophobic character when compared with non-fluorinated and fully inorganic control materials. The highest water contact angles were obtained when TXCL(x)Si oligomer used for the preparation of the hybrid contained short hydrogenated polycaprolactone segments. In all cases, the surface tension values indicated that the very surface at the air-coating interface showed almost completely perfluoropolyether segments.     

A theoretical study of the nitrogen—graphite system

The chemisorption of atomic and molecular nitrogen on the basal plane of graphite has been studied by both semiempirical and non-empirical Hartree—Fock methods employing finite cluster models.

Geometric and energetic parameters obtained by semiempirical and non-empirical methods are generally in good agreement. Among the different chemisorption sites considered, nitrogen atoms are found to prefer a two-fold coordination site, and only in this case has any evidence been found for an exothermic process. No evidence of dissociative chemisorption has been found in the case of molecular nitrogen, whose preferred orientation changes from nearly vertical to nearly horizontal on approaching the surface. Molecular adsorption is strongly endothermic at the Hartree—Fock level, so that the only possible interaction occurs through dispersion forces, which are not taken into account in our computations, but can be well represented by model potentials.