Catalytic activity of a ceria-lanthana system for 4-methylpentan-2-ol dehydration

A ceria-lanthana catalytic system prepared by the sol-gel technique proved to be active in 4-methylpentan-2-ol conversion, mainly leading to 4-methylpent-1-ene, a monomer for manufacturing polymers of high technological properties. The product distribution strongly depends on the acid-base features of the catalyst. The catalytic behavior of the samples was examined in the light of their acid-base properties. This revised version was published online in June 2006 with corrections to the Cover Date.     

Lower Rim Substituted p-tert-Butyl Calix[4]arenes (V). Synthesis of New 5,11,17,22-tetrakis-p-tert-Butyl-25,27-bis(methoxy)- 26,28-bis(dialkoxyphosphorylmethoxy)calix[4]arenes and Cation Complexation Studies in Ion-Selective Membrane Electrodes

The synthesis and characterization of the lower rim bis-phosphorylatedtetrakis-p-tert-butyl-25,27-bis(methoxy)calix[4]arenas(compounds 2–4) is presented. The studied compounds were examined as ionophores in ion-selective membrane electrodes, showing selectivity for rubidium, potassium, and for the large and flat guanidinium cations (G⁺). The correlation wasstudied between the stereochemical structure of the ligands andpotentiometrically determined ion-selectivity. Complex formationconstants in the PVC/BEHS (bis(ethyl)hexyl sebacate) membranes weredetermined. The crystal and molecular structures of compound 4 have been determined by single crystal X-ray diffraction study.     

Low-temperature IR and NMR studies of the interaction of group 8 metal dihydrides with alcohols

The reactions of the octahedral dihydrido complexes [MH(2)(PP(3))] [M=Fe, Ru, Os; PP(3)=P(CH(2)CH(2)PPh(2))(3)] with a variety of weak ROH acids have been studied by IR and NMR methods in either CH(2)Cl(2) or THF in the temperature range from 190 to 290 K. This study has allowed the determination of the spectral and thermodynamic properties associated with the formation of dihydrogen bonds (DHB) between the terminal hydrides and the OH group. Both the DHB enthalpy values and the hydride basicity factors (E(j)) have been found to increase in the order Fe < Ru < Os. The proton transfer process, leading to the DHB complexes, and eventually to eta(2)-H(2) products, has been found to depend on the acidic strength of the alcohol as well as the nature of the solvent. Low temperature IR and NMR techniques have been used to trace the complete energy profile of the proton transfer process involving the osmium complex [OsH(2)(PP(3))] with trifluoroethanol.     

The preparation of hexasilsesquioxane (T6) cages by "non aqueous" hydrolysis of trichlorosilanes

Hexasilsesquioxane cages (T6) have been prepared from a range of alkyl and aryl trichlorosilanes using a "non aqueous" hydrolysis with dimethyl sulfoxide.     

Synthesis of a eta 2-2,3-diphosphabutadiene complex of zerovalent platinum from the corresponding eta 2-phosphaalkyne complex

Hydrozirconation of the eta 2-phosphaalkyne complex [Pt(dppe)(eta 2-tBuCP)] with [ZrHCl(eta 5-C5H5)2], followed by treatment with the chlorophosphaalkene ClP=C(SiMe3)2 affords the eta 2-2,3-diphosphabutadiene complex [Pt(dppe)(eta 2-tBuC(H)=PP=C(SiMe3)2]. In the presence of [Pt(PPh3)2] the latter undergoes an addition reaction with water to afford the structurally characterised Pt(II) complex [Pt(dppe)(tBuCH2P(O)HPC(SiMe3)2].     

Synthetic peptides in the diagnosis of HIV infection

Peptide-based enzyme-linked immunosorbent assays have been found to be enough sensitive and specific for the diagnosis of human immunodeficiency virus specific antibodies in acquired immunodeficiency syndrome patients. This review provides an overview of the most important peptides developed for use as synthetic antigens in immunodiagnosis of HIV-infected patients. In particular, many studies have been devoted to discriminate between the two retroviruses HIV-1 and HIV-2, as well as different subtypes.     

Labeling of organic biomolecules with ethynylferrocene

The Sonogashira coupling reaction of ethynylferrocene with adenine, uracil, tyrosine and steroid derivatives was studied; with the exception of tyrosine it was proved to be a good route for the attachment of ferrocene to these representative biomolecules. In addition the transformation of alkynyl uracil to furanopyrimidone derivatives was investigated and the formation of the furanopyrimidone ring was confirmed by an X-ray crystallographic analysis carried out on product 16.     

NMR and theoretical investigations on the structures and dynamics of octahedral bis(chelate)dichloro V(III) compounds isolated by an unusual reduction of non-oxo V(IV) species

Reaction of the non-oxo V(IV) species [V(IV)Cl(2)(L(OO))(2)] [L(OO) = acetylacetonate (acac(-)) or benzoylacetonate (bzac(-))] with a chelate nitrogen-donor ligand L(NN) in acetonitrile leads to the reduction of V(IV) to V(III) and the formation of the mononuclear V(III) compounds of the general formula [V(III)Cl(2)(L(OO))(L(NN))] (L(OO) and L(NN) are acac(-) and bipy for 1; acac- and 5,5'-me(2)bipy for 2; acac(-) and 4,4'-tb(2)bipy for 3; acac(-) and phen for 4; bzac(-) and bipy for 5; bzac(-) and phen for 6). The reduction of the V(IV) complexes was monitored by GC-MS and (1)H NMR spectroscopy. Both one- and two-dimensional (2D COSY and 2D EXSY) (1)H NMR techniques were used to assign the observed (1)H NMR resonances of 1-6 in CD(2)Cl(2) or CDCl(3) solution. It appeared that in solution these V(III) complexes form two isomers which are in equilibrium: cis-[V(III)Cl(2)(L(OO))(L(NN))] <==> trans-[V(III)Cl(2)(L(OO))(L(NN))]. 2D EXSY cross-peaks were clearly observed between bipy- and acac-hydrogen atoms of the two geometrical isomers of 1-3 as well as between bipy and acac(-) protons of the cis isomer, indicating a dynamic process that corresponds to cis-trans isomerization and a cis-cis racemization. The thermodynamic and kinetic parameters of the equilibrium between these two isomers were calculated for compounds 1 and 2 by using variable temperature (VT) NMR data. Both cis-trans isomerization and cis-cis racemization processes probably proceed with an intramolecular twist mechanism involving a trigonal prismatic transition state. Density functional calculations (DFT) also indicated such a rearrangement mechanism.     

Application of electrochemical reactors for industrial waste-water treatment

The effectiveness of electrochemical reactors for industrial wastewater treatment has been improved since three-dimensional electrodes have been introduced; in fact, limitations of mass transfer can arise, due to the low concentrations of pollutants which may be involved in the process. Three-dimensional electrodes offer a very high electrode area per unit electrode volume and they can act as turbulence promoters or give rise to high linear electrolyte velocity, resulting in high values of mass transport coefficient. However, careful selection of operative parameters is needed in order to obtain high performance. This paper examines the results obtained in our laboratory on the cathodic reduction of copper at RVC electrodes; in particular the interference of dissolved oxygen is studied during the removal of copper from extremely diluted solutions (C < 10 ppm). Some results are also discussed on the removal of organic pollutants by electrochemical oxidation at three-dimensional anode consisting of a fixed bed of carbon pellets.     

Experimental study of the pH influence on the transport mechanisms of phenols in soil

The study of the transport mechanisms connected to solid-liquid interactions is fundamental in the determination of the extension of the pollution of a site and in the evaluation of the best remediation process to be applied. The sorption of hydrophobic ionizable organic contaminants from the groundwaters is supervised not only by the physico-chemical properties of soil and pollutants, but also by the groundwaters pH, which deeply influences their solubility in the aqueous media, and consequently their transport mechanisms in the aquifer. In this work an experimental study of the sorption of phenol and 2-nitrophenol on two soils, different in particle-size distribution, CEC and organic carbon content, was realized. The sorption potential of the soils was evaluated by means of a physical, mineralogical and chemical characterization. The experimental data coming from some batch tests, performed at pH values equal to 4, 7 and 10 were fitted by means of linear, Freundlich and Langmuir isotherms models. The soil-contaminants interaction mechanisms that influence the isotherms shapes were then analyzed and discussed, and a comparison between the theoretical and experimental values of the partitioning coefficient KD was performed.