Sidewall functionalization of single-walled carbon nanotubes through electrophilic addition

Electrophilic addition of chloroform to SWNTs followed by hydrolysis resulted in the addition of hydroxy groups to the surface of the nanotubes; further esterification with propionyl chloride led to the corresponding ester derivatives, which allowed us to identify their structure, also providing better solubility in organic solvents.     

Poly(ethylene glycol)-supported tetrahydroxyphenyl porphyrin: a convenient,recyclable catalyst for photooxidation reactions

[reaction: see text] A new poly(ethylene glycol)-supported porphyrin has been prepared and its ability as a promoter in photooxidation reactions has been studied. The PEG-supported catalyst exhibits high activity, comparable to that of a nonanchored sensitizer, and it is easily removable by filtration from the reaction mixture. The polymer-bound porphyrin has been recycled up to six times with no loss of chemical and stereochemical efficiency.     

Generic structure of externally driven tearing modes instabilities

A major limit to steady state and advanced high operation of tokamaks of reactor class is due to the onset of tearing modes that develop magnetic and may cause loss of energy confinement or a major disruption. Here the structure of a classical problem about the effects of external control helical fields is analysed and it is shown to offer a general paradigm of response of low order classical and neoclassical tearing modes to a wide class of external perturbations. New results of principle on the structural stability of the response model are obtained, leading to a clear interpretation of the role of “seed islands" in the onset of neo-classical tearing modes and the role of finite ion larmor radius corrections to Ohm's law. Received 12 November 2001 and Received in final form 4 January 2002     

Principio di massimo generalizzato e valutazione del primo autovalore per problemi ellittici del secondo ordine di tipo variazionale

Summary I prove a generalized maximum principle and an evaluation of the first eingenvalue for linear second order elliptic partial differential equations in divergence form with discontinuous coefficients.

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Lavoro eseguito nell'ambito del Centro di ricerca di matematica e fisica teorica del Consiglio Nazionale delle Ricerche presso l'Università di Genova.

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Entrata in Redazione il 14 luglio 1970.     

First-principles studies of vanadia-titania catalysts: beyond the monolayer

Periodic density functional calculations have been used to investigate the structure and stability of epitaxial vanadium oxide films grown on the TiO(2)(001) anatase surface. The formation energy of films of V(2)O(5) stoichiometry, initially low, is found to rapidly increase with the film thickness, at variance to what is obtained for reduced pseudomorphic VO(2) films. This is in tune with results of oxygen-assisted molecular beam epitaxy. The oxidation of thick, viz. >2 monolayers (ML), VO(2) films yields a c(2 x 2) reconstructed surface, in agreement with low energy electron diffraction. These films are composed by partially reduced inner V atoms in a distorted-octahedral environment, and by isolated surface dioxovanadium centers exhibiting a distorted trigonal-bipyramidal coordination. Single scattering simulations of X-ray photoelectron diffraction patterns have also been performed, taking both 2- and 3-ML surface surface-oxidized films as models. Results are in fair agreement with experiments referring to films grown in oxidizing conditions, which suggests that coherent vanadia ultrathin films could be formed in vanadia-titania catalysts. The electronic structure of the films has been finally studied, finding that the terminal oxygens carried by the surface dioxovanadium species have a strong nucleophilic character, which makes them potential active centers for selective oxidation catalysis.     

A new linker for anchoring/masking primary amines on solid support

A polymer-supported diketone was synthesized and used to fully protect/mask primary amines by the formation of a pyrrole ring. Various reactions can be performed on this system which then can be cleaved with full restoration of the amine functionality. The resin can also be recycled at least once without loss of purity of the final compound. [structure: see text]     

Analysis of uranium and isotopic ratio measurement in fish and marine invertebrates from the North Adriatic Sea by inductively coupled plasma mass spectrometry

Uranium analysis in fish, echinoderms and shellfish samples collected in the north part of the Adriatic Sea is presented. The aim of the work was to evaluate uranium concentrations in samples of this kind, and also to investigate possible contamination from depleted uranium (DU) in consequence of the war operations previously conducted in that area. DU contamination was checked by measuring the (235)U/(238)U isotope ratio. The samples were dissolved according to the EPA 3052 procedure, and the determinations were performed by inductively coupled plasma mass spectrometry (ICP-MS), optimized in order to perform isotope ratio measurements with good precision. The method was validated by evaluating the recovery from spiked samples; results in the range 93-107% were obtained. The isotope ratio measurement was evaluated in terms of accuracy and precision by analyzing the certified reference materials IAEA 326 and GBW 07305, and good agreement with the certified values was obtained here also. The concentration of uranium was higher in invertebrate samples than in fish (0.3-2 microg/g of U vs. 0.05-0.1 microg/g, respectively). The isotope ratio measurements for all the samples gave values very similar to the natural ratio, permitting exclusion of the presence of DU.     

Nature of urea-fluoride interaction: incipient and definitive proton transfer

1,3-bis(4-nitrophenyl)urea (1) interacts through hydrogen bonding with a variety of oxoanions in an MeCN solution to give bright yellow 1:1 complexes, whose stability decreases with the decreasing basicity of the anion (CH3COO- > C6H5COO- > H2PO4- > NO2- > HSO4- > NO3-). The [Bu4N][1.CH3COO] complex salt has been isolated as a crystalline solid and its molecular structure determined, showing the formation of a discrete adduct held together by two N-H...O hydrogen bonds of moderate strength. On the other hand, the F- ion first establishes a hydrogen-bonding interaction with 1 to give the most stable 1:1 complex, and then on addition of a second equivalent, induces urea deprotonation, due to the formation of HF2-. The orange-red deprotonated urea solution uptakes carbon dioxide from air to give the tetrabutylammonium salt of the hydrogencarbonate H-bond complex, [Bu4N][1.HCO3], whose crystal and molecular structures have been determined.