Infrared and Raman spectroscopic investigation of Eu3+-doped mono and Di-urethanesil hybrid siliceous materials

The general features of two series of sol-gel derived materials, designatedurethanesils (Ut), have been investigated by infrared and Raman spectroscopies with the goal of elucidating the chemical environment of the Eu³⁺ cations. The host frameworks of the two families of ormolytes studied have been represented by m-Ut(350) and d-Ut(300), where m stands for mono, d stands for di, 350 and 300 are the average molecular weights of the organic precursors (poly(ethylene glycol) methyl ether, PEGME, and poly(ethylene glycol), PEG, respectively). The hybrid matrix of the mono-xerogels is composed by a siliceous backbone bonded by means of urethane linkages (-NHC (=O)O-) to pendant methyl end capped oligopolymer chains with approximately 7 oxyethylene units, whereas that of the di-xerogels is based on a siliceous network grafted through urethane groups to both ends of poly(oxyethylene) segments containing about 6 (OCH₂CH₂) repeat units. Both classes of materials have been doped with europium triflate (Eu(CF₃SO₃)₃). The doped samples have been identified by m-Ut(350)_nEu(CF₃SO₃)₃ and d-Ut(300)_nEu(CF₃SO₃), where n is the molar ratio of (OCH₂CH₂) repeat units per Eu³⁺ ion. Materials with n ranging from ∞ to 5 have been analyzed. The spectral data obtained provide evidence that the cations begin to coordinate to the ether oxygen atoms of the oligopolymer chains at n=40 in the mono-urethanesils and at n=10 in the di-urethanesils. In mono-urethanesils samples with n>40 and in di-urethanesils materials with n>10, the Eu³⁺ coordinate exclusively to the carbonyl oxygen atoms of the urethane linkages. Paper presented at the 8th EuroConference on Ionics, Carvoeiro, Algarve, Portugal, Sept. 16–22, 2001.     

First measurement of the ϱ spectral function in nuclear collisions

The NA60 experiment at the CERN SPS has studied low-mass muon pairs in 158 A GeV In–In collisions. A strong excess of pairs is observed above the yield expected from neutral meson decays. The unprecedented sample size close to 400000 events and the good mass resolution of about 2% made it possible to isolate the excess by subtraction of the decay sources. The shape of the resulting mass spectrum shows some non-trivial centrality dependence, but is largely consistent with a dominant contribution from π⁺π^-→ϱ→μ⁺μ^- annihilation. The associated ϱ spectral function exhibits considerable broadening, but essentially no shift in mass. The p_T-differential mass spectra show the excess to be much stronger at low p_T than at high p_T. The results are compared to theoretical model predictions; they tend to rule out models linking hadron masses directly to the chiral condensate. PACS 25.75.-q; 12.38.Mh; 13.85.Qk     

Voltammetric sizing of a sphere.

The size of a glass sphere positioned in the center of a microdisk electrode is determined by using a simple electrochemical procedure and is confirmed, additionally, by a microscopical measurement of the sphere at the time of the electrochemical measurement. The cyclic voltammetric response of the naked electrode and of the electrode with the sphere positioned in its center is recorded over a wide range of scan rates (0.002-1.5 V s(-1)). The size of the sphere is then determined by comparison of the experimental voltammogram with simulations for each individual scan rate.     

New example of a non-heme mononuclear iron(IV) oxo complex. Spectroscopic data and oxidation activity

The green complex S=1 [(TPEN)FeO]2+ [TPEN=N,N,N',N'-tetrakis(2-pyridylmethyl)ethane-1,2-diamine] has been obtained by treating the [(TPEN)Fe]2+ precursor with meta-chloroperoxybenzoic acid (m-CPBA). This high-valent complex belongs to the emerging family of synthetic models of Fe(IV)=O intermediates invoked during the catalytic cycle of biological systems. This complex exhibits spectroscopic characteristics that are similar to those of other models reported recently with a similar amine/pyridine environment. Thanks to its relative stability, vibrational data in solution have been obtained by Fourier transform infrared. A comparison of the Fe=O and Fe=(18)O wavenumbers reveals that the Fe-oxo vibration is not a pure one. The ability of the green complex to oxidize small organic molecules has been studied. Mixtures of oxygenated products derived from two- or four-electron oxidations are obtained. The reactivity of this [FeO]2+ complex is then not straightforward, and different mechanisms may be involved.     

A short synthesis of 4-amino-3-hydroxybutyric acid (GABOB) via allyl cyanide

4-Amino-3-hydroxybutyric acid was synthesized from allyl cyanide in four steps in an overall yield of 38%. Ultrasonically promoted epoxidation of allyl cyanide with m-chloroperoxybenzoic acid giving oxiranylacetonitrile was used as a key step.     

Sensitive stripping voltammetry of heavy metals by using a composite sensor based on a built-in bismuth precursor

A new graphite-epoxy composite electrode (GECE) containing Bi(NO(3))(3) as a built-in bismuth precursor for simultaneous and individual anodic stripping analysis of heavy trace metals like lead and cadmium is reported. The developed Bi(NO(3))(3)-GECE is compatible with bismuth film electrodes reported previously including the composite electrodes (Bi-GECE) recently reported by our group. Bi(NO(3))(3)-GECE displays the ability for the detection of both individual and simultaneous determination of heavy trace metals and exhibits well defined, reproducible and sharp stripping signals. The sensitive response is combined with the minimal toxicity of Bi(NO(3))(3). This novel sensor would be an appropriate alternative tool to sensors using bismuth in solution during their utilization in environmental quality monitoring as well as other applications.     

Structural and electronic comparative analysis of aminopyridazines showing anti-GABA activity. Crystal structure of 2-(carboxy-3′-propyl)-3-amino-6-cyclohexylpyridazinium bromide.Ab initio Mulliken population analysis of the 6-phenyl-substituted analog compared to GABA

The crystal structure of 2-(carboxy-3-propyl)-3-amino-6-cyclohexylpyridazinium bromide has been determined by single-crystal X-ray diffraction techniques and refined by full-matrix least squares. The compound crystallized in the tri-clinic space groupP ¯1 witha=10.275(1),b=11.215(1),c=7.082(1) Å,=91.84(1),=102.21(1), =106.77(1)°, andZ=2. FinalR-factor is 0.045. The main structural results are very similar to the ones observed for the 6-phenyl analog. These two compounds are GABA-A antagonists.Ab initio molecular orbital calculations, with STO-3G and 4-31G basis sets, suggest that the exocyclic nitrogen accurately mimics the nitrogen atom of GABA.     

Cooperative effects in phospholipid monolayers induced by a peptide from HIV-1 capsid protein

The study of interactions between biological molecules and model membranes is essential for the understanding of a number of physiological mechanisms involved in viral infections and dissemination. In this paper, the analysis of the interaction between a peptide from the p24 protein of Human Immunodeficiency Virus type 1 (HIV-1) and a phospholipid monolayer has pointed to a cooperative response in which very small amounts of peptide p24-1 (e.g. 0.05 mol%) can lead to measurable effects. Monolayer surface pressure and surface potential isotherms were affected for peptide concentrations as low as 0.05 mol%, with saturation at 0.5 mol%. The expansion effect from p24-1 is confirmed by changes in morphology of the monolayers using Brewster angle microscopy. Even though p24-1 is disordered in aqueous solutions, the interaction with dipalmitoyl phosphatidylcholine (DPPC) causes it to adopt an alpha-helix structure, as shown by circular dichroism (CD) data for multilamellar vesicles (MLV). The expansion of the phospholipid monolayer in a cooperative way may imply that p24-1 has potential antiviral activity, by participating in the cell rupture, with no need of specific receptors in the membrane.