Synthesis of a Naphthalimide Functionalized Calix[4]arene; A Host Type Fluorophore for Inclusion Compounds in Organic Medium

This article reports the synthesis and the properties of 5,11,17,23-tetra(t-butyl)-25,27-bis-(ethoxy-1,8-naphthalimide)-26,28-hidroxy-calix[4]arene and the formation of an inclusion compound in organic medium. This functionalized calix[4]arene was conceived as the association of a potential host species with a good fluorophore for optical sensoring purposes. Calix[4]-NI as we will call it, maintains its ‘cone-pinched’ configuration and exhibits typical naphthalimide fluorescence bands in non-polar solvents. Its ability to interact with guest species via hydrogen bonding in its endo-hydrophilic cavity to form inclusion compounds was verified with absorption and fluorescence measurements using N-ethanol-1,8-naphthalimide as guest species, which was projected to fit exactly the host cavity and to interact with its naphthalimide π electrons. For this reason, it was possible to follow the formation of the inclusion compound with electronic spectroscopy.     

A trinuclear bis(dioximate)(chloro)(nitrosyl)ruthenium(II) complex containing two (2,2′-bipyridine)copper(II) groups

A trinuclear bis(cyclohexanedioximate)(chloro)(nitrosyl)ruthenium(II) complex containing two (2,2-bipyridine)-copper(II) groups has been synthesized and its electronic and electrochemical properties investigated. According to ZINDO/S calculations, the electronic structure of the ruthenium(dioximate)(nitrosyl) moiety is strongly delocalized. The electrochemical behavior has been interpreted with the aid of spectroelectrochemical measurements. In the trinuclear complex, it has been shown that the copper(II) ions can promote the oxidation of the NO species generated electrochemically, and also mediate the redox reactions of the complex, under a dioxygen atmosphere.     

Kink instability in applied-field magneto-plasma-dynamic thrusters

Measurements of magnetic and electrostatic fluctuations in an applied field magneto-plasma-dynamic thruster have shown that a m/n=1/1 kink mode becomes unstable whenever the Kruskal-Shafranov limit is violated. A positive correlation is established between the kink and performance degradation at high current, which has until now prevented the use of this kind of thruster in space missions.     

FTIR Spectroelectrochemical Investigation of the trans-[Ru(NO)(dimethylglyoximate)2Cl] Complex: Vibrational Characterization of the NO+/0 and RuIII/II Redox Couples

Abstract

This paper deals with the spectroelectrochemical characterization of the Ru^III/II and N0^+/0 oxidation states of the trans-[Ru(NO)(dmgH)₂Cl] complex (dmgH = dimethylglyoximate ion). The cyclic voltammograms of the complex in acetonitrile solution exhibited a reversible wave at -0.09 V versus SHE, and two less intense waves at 1.19 and 1.41 V. Visible-UV spectra were recorded at -0.4 and 1.5 V, however, the absorption bands collapsed into a single tail, providing little information on the redox states involved. In contrast, in the FTIR measurements at -0.4 V, the v(NO) peak shifted from 1878 to 1855cm^?1, without changing the vibrational peaks of the dmgH ligand, indicating an electrochemical process involving the NO^+/0 redox couple. At 1.5 V, the changes in the vibrational peaks of the NO and dig lagans indicated a redox process associated with the Ru^III/II redox'couple. The existence of an open and a cyclic hydrogen bridged configuration was proposed, in order to explain the occurrence of two electrochemical waves at positive potentials.     

Conical cavitands as second coordination spheres and protecting environments. Towards metal-centred, intra-cavity reactions

Metallocavitands are coordination compounds based on rigidified molecular cavities which possess at least one entry. Those in which the metal centre is rigidly held above the entrance are particularly promising for the study of host-guest interactions between metal-bonded substrates and the internal part of a cavity. Such systems also open the way to highly selective intra-cavity reactions. The present review focusses on conical cavities derived from calixarenes and cyclodextrins and examines their possible use as second coordination sphere ligands.     

Detection of the EPR spectra of NO. in ruthenium(II) complexes

The EPR of NO. can be detected in the liquid and solid states when crystal fields are sufficient to remove the axial symmetry and separate the (pi*)x and (pi*)y orbitals by a few hundred reciprocal centimeters. The theory of the EPR spin Hamiltonian of bound NO. is reviewed, further developed, and then applied to the observed frozen-liquid spectra of NO. bound to Ru(II) obtained from RuIINO+ complexes by reduction. Comparisons to earlier reports on the observation of the EPR spectra of NO. are made.     

Poloidal Magnetic Field Measurements in a Reversed Field Pinch Plasma by a Far‐Infrared Polarimeter

A multichannel farinfrared (FIR) polarimeter has been installed in RFX, a Reversed Field Pinch (RFP) plasma experiment, to measure the poloidal magnetic field profile. The polarimeter uses a CH₃OH FIR laser operating at =118.8 m. Faraday rotation measurements on five of six parallel diagnostic chords are used in preliminary investigations of poloidal field profiles. The experimental results are generally found in good agreement with the &p model predictions. The choice of the profile of = ₀ j·B/B² is discussed. For the reconstruction of the magnetic field profiles a numerical filamentary current equilibrium code is described, where polarimetric data are included as constraints. An alternative method based on the bestfit of a threeparameter profile to the polarimetric data is also reported. Both methods provide reliable reconstructions of the plasma magnetic field and the results indicate the existence in RFX of hollow profiles.     

Synthesis of a Naphthalimide Functionalized Calix[4]arene; A Host Type Fluorophore for Inclusion Compounds in Organic Medium

This article reports the synthesis and the properties of 5,11,17,23-tetra(t-butyl)-25,27-bis-(ethoxy-1,8-naphthalimide)-26,28-hidroxy-calix[4]arene and the formation of an inclusion compound in organic medium. This functionalized calix[4]arene was conceived as the association of a potential host species with a good fluorophore for optical sensoring purposes. Calix[4]-NI as we will call it, maintains its ‘cone-pinched’ configuration and exhibits typical naphthalimide fluorescence bands in non-polar solvents. Its ability to interact with guest species via hydrogen bonding in its endo-hydrophilic cavity to form inclusion compounds was verified with absorption and fluorescence measurements using N-ethanol-1,8-naphthalimide as guest species, which was projected to fit exactly the host cavity and to interact with its naphthalimide π electrons. For this reason, it was possible to follow the formation of the inclusion compound with electronic spectroscopy.in final form: 17 November 2004.This revised version was published online in July 2005 with a corrected issue number.     

Study of color centers produced in thulium doped YLF crystals irradiated by electron beam and femtosecond laser pulses

In this work, we report the influence of the presence of photochromic and color centers in the photobleaching of thulium ions blue emission in YLF (YLiF₄) crystals doped with 1 mol% Tm (3+). The samples were irradiated at room temperature both with electron beam and high intensity ultrashort pulses from a Ti:Sapphire CPA laser system. In both irradiations the production of photochromic and color centers was observed via the absorption bands in the UV and visible ranges. Pure LiF and pure and oxygen doped YLF crystals were used to identify the color centers produced and their optical properties. From a phenomenological model it was possible to study the interaction between color centers and thulium ions, and their effect in photobleaching and photodarkening behaviors. Finally, the blue up laser level population was computed using a rate equation analysis.     

Investigation of the ETA-BETA II plasma edge by surface analysis of collector probes

To investigate the ion flux escaping from the plasma and the impurity flux released by the wall, collector probes made of graphite, silicon and titanium have been exposed to the deuterium plasma confined in the toroidal device ETA BETA II. The damages on the collector surfaces have been surveyed by a scanning electron microscopy (SEM) apparatus. The deuterium and impurity retention have been measured by elastic recoil detection (ERD) and Rutherford backscattering spectroscopy (RBS) techniques respectively. The implantation build-up has been investigated as a function of the exposure time. The deuterium dose in graphite saturates after a few discharges, whereas the metal impurities exhibit a linear increase in time. The deuterium flux and its radial dependence, inferred from the implanted concentrations, have been compared with those measured by Langmuir probes. Metal impurities have been identified and their relative abundances have been compared with the material wall composition. The impurity flux is found consistent with the global content in the plasma derived by spectroscopic measurements. The deuterium dose measured in different samples has been related to the backscattering coefficient of the materials. Finally, to investigate the damage on sample probes facing the plasma particle flow, erosion probes made of vitreous graphite with silver implanted at a fixed depth have been exposed to the plasma and the thickness change after exposure recovered.