Rapid qualitative analysis of metallic alloys by electrospot chromatography

Summary Electrography and paper chromatography were combined to analyse rapidly metallic alloys in an almost non destructive technique. Using anodic dissolution the sample is applied on the start point of the chromatographic paper. Known ketones-HCl-water mixtures are usually used as solvents to analyse electrospots of different alloys and metal coatings and a separate electrospottest is recommended for Cr. Results of qualitative analysis of some steels, Cu–Ni, and Pb alloys are presented.     

Influence of Al2O3 Nanoparticles on the Thermal Stability of Ultra-Fine Grained Copper Prepared by High Pressure Torsion

Summary.  Ultra-fine grained (UFG) Cu (grain size 80 nm) containing 0.5 wt.% Al₂O₃ nanoparticles (size 20 nm) was prepared by high pressure torsion (HPT). Positron lifetime spectroscopy was employed to characterize the microstructure of this material, especially with respect to types and concentration of lattice defects. The evolution of microstructure with increasing temperature was studied by positron lifetime spectroscopy and X-ray diffraction measurements. The thermal stability of the Cu + 0.5 wt.% Al₂O₃ nanocomposite was compared with that of pure UFG Cu prepared by the same technique. The processes taking place during thermal recovery of the initial nanoscale structure in both studied materials are described. Received October 5, 2001. Accepted (revised) December 20, 2001     

Effective interactions in the colloidal suspensions from hypernetted-chain theory

The hypernetted-chain (HNC) Ornstein-Zernike integral equations are used to determine the properties of simple models of colloidal solutions where the colloids and ions are immersed in a solvent considered as a dielectric continuum and have a size ratio equal to 80 and a charge ratio varying between 1 and 4000. At an infinite dilution of colloids, the effective interactions between colloids and ions are determined for ionic concentrations ranging from 0.001 to 0.1 mol/l and compared to those derived from the Poisson-Boltzmann theory. At finite concentrations, we discuss on the basis of the HNC results the possibility of an unambiguous definition of the effective interactions between the colloidal molecules.     

Buffer layer effect in nanostructured tin electrodeposition on insulating and conducting substrates

The electroplating techniques for metal aggregates and films deposition commonly use an electric current to reduce metal ions in solution, but are restricted to conducting substrate. This new electrochemical technique permits coating of insulating or conducting substrates with metals having controlled aggregate size and growth speed. The basis of our approach is the progressive outward growth of the metal from an electrode in contact with the substrate, with the cell geometry chosen in such a way that the electron current providing the reduction passes through the growing deposit. The nanostructured deposit is composed of branched nanoaggregates from a quasi-continuous film to a more dendritic morphology dependant on current conditions. This approach has been used to elaborate tin electrodeposited thin films composed of a homogeneous distribution of nanoparticles on conducting or insulating substrates. In our works, when a non-continuous buffer gold coating is used, spontaneous mixing of tin atoms into AuSn nanoparticles takes place even at room temperature forming a nanostructured fractal film, if the substrate is conducting or insulating. Without a gold buffer layer, the deposit is composed of large pure tin micro-crystals with a large size distribution, less adapted to tin oxide nanoparticle formation. Indeed, from these tin metal deposits, the final goal is to elaborate functional nanostructured tin oxide films by oxidation for gas sensor applications.     

Study of the segmental dynamics in semi-crystalline poly(lactic acid) using mechanical spectroscopies

The glass transition of poly(L-lactic acid) (PLLA) occurs not far above typical service temperatures (room or body temperatures) which has consequences on the material properties during its use, such as damping or the occurrence of structural relaxation. This work aims at characterising the glass transition dynamics of a semi-crystalline PLLA using both dynamic mechanical analysis (DMA) and thermally stimulated recovery (TSR). The main viscoelastic parameters have been characterised at 1 Hz using DMA and the master curve obtained after isothermal experiments at different temperatures provided a full picture of the solid-state rheological behaviour throughout a wide frequency range. The activation energies calculated from the shift factors agree with the TSR ones, exhibiting a maximum near the T(g). Above the T(g), the results can be described with the WLF model. In the glassy state, the activation energy decreases with decreasing temperatures being always higher than the prediction of the Adam and Gibbs theory, at least down to temperatures 30 degrees C below the T(g). This suggests the existence of non-arrested degrees of freedom in the glassy state, being consistent with the existence of a significant degree of cooperativity in the TSR results.     

N,N'-ethylenebis(pyridoxylideneiminato) and N,N'-ethylenebis(pyridoxylaminato): synthesis, characterization, potentiometric, spectroscopic, and DFT studies of their vanadium(IV) and vanadium(V) complexes

The Schiff base N,N'-ethylenebis(pyridoxylideneiminato) (H(2)pyr(2)en, 1) was synthesized by reaction of pyridoxal with ethylenediamine; reduction of H(2)pyr(2)en with NaBH(4) yielded the reduced Schiff base N,N'-ethylenebis(pyridoxylaminato) (H(2)Rpyr(2)en, 2); their crystal structures were determined by X-ray diffraction. The totally protonated forms of 1 and 2 correspond to H(6)L(4+), and all protonation constants were determined by pH-potentiometric and (1)H NMR titrations. Several vanadium(IV) and vanadium(V) complexes of these and other related ligands were prepared and characterized in solution and in the solid state. The X-ray crystal structure of [V(V)O(2)(HRpyr(2)en)] shows the metal in a distorted octahedral geometry, with the ligand coordinated through the N-amine and O-phenolato moieties, with one of the pyridine-N atoms protonated. Crystals of [(V(V)O(2))(2)(pyren)(2)].2 H(2)O were obtained from solutions containing H(2)pyr(2)en and oxovanadium(IV), where Hpyren is the "half" Schiff base of pyridoxal and ethylenediamine. The complexation of V(IV)O(2+) and V(V)O(2) (+) with H(2)pyr(2)en, H(2)Rpyr(2)en and pyridoxamine in aqueous solution were studied by pH-potentiometry, UV/Vis absorption spectrophotometry, as well as by EPR spectroscopy for the V(IV)O systems and (1)H and (51)V NMR spectroscopy for the V(V)O(2) systems. Very significant differences in the metal-binding abilities of the ligands were found. Both 1 and 2 act as tetradentate ligands. H(2)Rpyr(2)en is stable to hydrolysis and several isomers form in solution, namely cis-trans type complexes with V(IV)O, and alpha-cis- and beta-cis-type complexes with V(V)O(2). The pyridinium-N atoms of the pyridoxal rings do not take part in the coordination but are involved in acid-base reactions that affect the number, type, and relative amount of the isomers of the V(IV)O-H(2)Rpyr(2)en and V(V)O(2)-H(2)Rpyr(2)en complexes present in solution. DFT calculations were carried out and support the formation and identification of the isomers detected by EPR or NMR spectroscopy, and the strong equatorial and axial binding of the O-phenolato in V(IV)O and V(V)O(2) complexes. Moreover, the DFT calculations done for the [V(IV)O(H(2)Rpyr(2)en)] system indicate that for almost all complexes the presence of a sixth equatorial or axial H(2)O ligand leads to much more stable compounds.     

Highly stereoselective and efficient total synthesis of (+)-laurencin

A highly stereoselective and efficient asymmetric total synthesis of (+)-laurencin (1) has been accomplished from the known oxazolidinone 5 in 15 steps. The route features an efficient internal alkylation to form oxocene 3 from 4 and a novel use of acetonitrile anion as a two-carbon acetaldehyde equivalent for direct synthesis of ketone 2 from alpha-alkoxy amide 3.     

A new binucleating macrocycle incorporating exocyclic oxime groups and its polynuclear complexes

A new binucleating macrocycle incorporating four exocyclic oxime groups, 6,6′-methylene-bis[1,12–di(hydroximino)-2,3;9,10–dibenzo-1,11–diaza-4,8–dithiacyclotridecane] (LH4) has been synthesized, its mononuclear CoIII and hetropolynuclear CoIII-PdII complexes have been prepared. LH4 and its metal complexes have been characterized by elemental analysis, 1H- and 13C-n.m.r., i.r. and mass spectral studies. The elemental analysis, stoichiometry and the spectroscopic data of the mononuclear CoIII complex indicate that the CoIII ions are coordinated by the oxime nitrogen atoms (C=N); PdII ions in the latter complex are coordinated through diaza-dithia moiety on the macrocycle. The mononuclear CoIII complex of LH4 has a 1:1 metal:ligand ratio. All spectral data support the proposed structure of LH4 and its complexes. This revised version was published online in June 2006 with corrections to the Cover Date.     

The effect of pH on the reactions of catalytically important RhI complexes in aqueous solution: reaction of [RhCl(tppms)3] and trans-[RhCl(CO)(tppms)2] with hydrogen (TPPMS = mono-sulfonated triphenylphosphine).

Hydrolysis and hydrogenation of [RhCl(tppms)3] (1) and trans-[RhCl(CO)(tppms)2] (2) was studied in aqueous solutions in a wide pH range (2 < pH < 11) in the presence of excess TPPMS (3-diphenylphosphinyl-benzenesulfonic acid sodium salt). In acidic solutions hydrogenation of 1 yields a mixture of cis-mer- and cis-fac-[RhClH2(tppms)3] (3a,b) while in strongly basic solutions [RhH(H2O)(tppms)3] (4) is obtained, the midpoint of the equilibrium between these hydride species being at pH 8.2. The paper gives the first successful 1H and 31P NMR spectroscopic characterization of a water soluble rhodium(I)-monohydride (4) bearing only monodentate phosphine ligands. Hydrolysis of 2 is negligible below pH 9 and its hydrogenation results in formation of [Rh(CO)H(tppms)3] (5), which is an analogue to the well known and industrially used hydroformylation catalyst [Rh(CO)H(tppts)3] (6) (TPPTS = 3,3',3'-phosphinetriyltris(benzenesulfonic acid) trisodium salt). It was shown by pH-potentiometric measurements that formation of 5 is strongly pH dependent in the pH 5-9 range, this gives an explanation for the observed but previously unexplained pH dependence of several hydroformylation reactions. Conversely, the effect of pH on the rate of hydrogenation of maleic and fumaric acid catalyzed by 1 in the 2 < pH < 7 range can be adequately described by considering solely the changes in the ionization state of these substrates. All these results warrant the use of buffered (pH-controlled) solutions for aqueous organometallic catalysis.