Effects of structural factors on the pi-dimerization and/or disproportionation of the cation radical of extended TTF containing thiophene-based pi-conjugated spacers

The electrochemical and chemical oxidation of extended TTF 4 and 5 are analysed by cyclic voltammetry, Visible/NIR and ESR spectroscopies, and the X-ray structures of the new salts 5 x BF(4)(CH(2)Cl(2)) and 4 x ClO(4)(THF)(1/2) are presented. The effects of structural factors on the pi-dimerization or the disproportionation reaction of the cation radical are shown. The oxidation of compound 4 presents the successive formation of stable cation radical and dication species both in dichloromethane (DCM) and in a CH(3)CN/THF mixture. In contrast, for compound 5, the stability of the oxidation states strongly depends on the nature of the solvent. In DCM, the oxidation of 5 proceeds by two close one-electron transfers while in CH(3)CN/THF the dication is directly formed via a two-electron process. The X-ray structures of the two salts reveal the formation of pi-dimers of cation radical. While the dimer (5(2))(2+) is due mainly to pi-pi interactions between the conjugating spacer, the multiplication of the sulfur atoms in compound 4 contributes to stabilize the dimer by the combined effects of S-S and pi-pi interactions. Visible/NIR and ESR experiments confirm the higher tendency of 4(+)(.) to dimerize with the occurrence of dimer and monomer in solution, while for 5(+)(.) only the monomer is detected in DCM. On the other hand, by dissolution of 5 x BF(4)(CH(2)Cl(2)) in CH(3)CN, only the neutral and the dicationic states of compounds 5 are observed owing to the disproportionation reaction.     

Determination of adsorptive properties of clay/water system: methylene blue sorption

In this study, adsorption of methylene blue onto clay was investigated. The effect of adsorption time and temperature on the adsorption process was studied. To reveal the adsorptive characteristics of the clay studied, porosity and BET surface area measurements were made. It was observed that the adsorption capacity decreases with increasing temperature, and adsorption equilibrium was attained within 1 h. It was found that the data fit well to Langmuir, Halsey, Henderson, and Harkins-Jura models but experimental data deviate significantly from BET and Freundlich models at especially high concentrations. Furthermore, isosteric adsorption enthalpy and entropy are calculated as -7.99 kJ mol(-1) and 25.41 JK(-1)mol(-1), respectively.     

Enzymatic bleaching of organosolv sugarcane bagasse pulps with recombinant xylanase of the fungus Humicola grisea and with commercial cartazyme HS xylanase

Organosolv (ethanol/water and acetosolv) pulps were treated with Humicola grisea var. thermoidea and compared with Cartazyme HS xylanase-treated pulp. The ethanol/water pulps treated with H. grisea had the same viscosity as unbleached pulps (8 cP). Ethanol/water pulps treated with Cartazyme had higher viscosity than H. grisea-treated pulps (12 cP). Acetosolv pulps treated with H. grisea and Cartazyme presented a reduction in viscosity; however, the pulps treated with H. grisea had a lower reduction in viscosity than Cartazyme-treated pulps. Ethanol/water pulps treated with H. grisea had a 23% reduction in kappa number in 4 and 8 h of treatment, compared with the unbleached pulps. Cartazyme-treated pulps had a kappa number similar to that of the control pulps for 4 h of treatment. Extending the treatment time to 12 h resulted in a reduction of 33%. The acetosolv pulp treated with H. grisea had a kappa number reduced to 23% in 4 h. Cartazyme treatment resulted in a reduction of 55 and 44% in kappa number for 4 and 8 h of treatment, respectively, when compared with control pulp. Extending the treatment time to 12 h decreased the kappa number 72%. Fourier transform infrared spectra and principal component analysis showed differences among unbleached, H. grisea-treated, and Cartazyme-treated pulps.     

Metal complexes of a homopolymer system containing diethanolamine side group: synthesis and dielectrical behaviors

In this work, 4-diethanolaminomethyl styrene (DEAMSt) monomer was prepared by modification of 4-chloromethyl styrene with diethanolamine. The homopolymerization of styrene modificated was carried out by free radical polymerization method at 60?°C in presence of 1,4-dioxane and AIBN. The metal complexes were prepared by reaction of the homopolymer used as ligand P(DEAMSt)L^l and Ni(II), Co(II) metal ions in presence of ethanol and dilute NaOH at 65?°C for 48?h in pH 6.

The structure of modificated monomer, homopolymer used as ligand and polymer-metal complexes were characterized by (FT-IR), ¹H-NMR, ¹³C-NMR, Raman spectroscopy tecniques, elemental analysis, SEM, XRD and magnetic measurements. Their geometric structures according to magnetic measurements of Co(II) and Ni(II) complexes were estimated that have a tetrahedral structure. P(DEAMSt)L^l polymer has a transition state between amorphous and crystalline, whereas metal complexes (Co(II) and Ni(II) are with a large crystal structure. The molecular weight of P(DEAMSt)L¹ homopolymer was determined by gel permeation chromatography (GPC). The glass transition temperature (Tg) of homopolymer was measured by differantial scanning calorimeter (DSC). The thermal behaviors of both ligand and polymer-metal complexes were investigated by thermogravimetric analysis (TGA) and (DTA). The results obtained were compared with each other. Then, the dielectrical measurements (dielectric constant, dielectric loss and conductivity) of the ligand and polymer-metal complexes were investigated as a function of temperature and frequency. The activation energies (Ea) of the ligand and metal complexes were determined from the conductivity measurements.     

Synthèse énantiospécifique de la (+)-(R)-éthyl-6-dihydro-2,3-méthyl-2-4H-pyranone-4, phéromone de la mite Hepialus hecta L

Enantiospecific Synthesis of (+)-(R)-6-Ethyl-2,3-dihydro-2-methyl-4H-pyran-4-one, Sex-pheromonal Component of the Male Swift Moth Hepialus hecta L . A new synthesis of (+)?(R)-6-ethyl-2,3-dihydro-2-methyl-4H-pyran-4-one ((R)- 8 ), sex-pheromonal component of the male swift moth Hepialus hecta L., has been performed from (?)-(R)-1-(1,3-dithian-2-yl)propan-2-ol with an enantiomeric excess of ? 97%.     

Structure and properties of hydrophobically end-capped poly(ethylene oxide) solutions in the presence of monovalent and divalent cations

Hydrophobically modified poly(ethylene oxide), HMPEO, was studied in concentrated salt solutions. The influence of salts was compared to the effect of temperature on poly(ethylene oxide), PEO. As expected, the addition of monovalent cations (Na(+), K(+)) has the same effect as an increase in temperature in agreement with the thermodynamic properties of PEO: a decrease in solubility, micelle size, and viscosity was observed. Moreover, the intensity of neutron scattering peaks (characteristic of the semi-dilute solutions of these associative polymers) increases due to the collapse of PEO coronae in micelles. Very peculiar behavior was observed in the presence of divalent cations (Ca(2+), Mg(2+)): larger micelle aggregates and higher viscosities, relaxation times, and activation energies were observed by dynamic rheology. This behavior is attributed to interactions between divalent cations and oxygen in PEO backbones close to the micelle core, which may reinforce intermicellar bridges.     

Fullerohelicates: a new class of fullerene-containing supermolecules

A multicomponent array made of a bis-copper(I) helicate core and two peripheral fullerene subunits has been prepared and electron transfer from the photoexcited Cu(I)-complexed unit to C60 occurs.     

Vibrational Spectroscopic Studies on the Hofmann Type Clathrates: M(1,6-diaminohexane)Ni(CN) 4 .G (M = Co, Ni or Cd; G = chlorobenzene, 1,2-, 1,3- or 1,4-dichlorobenzene)

New Hofmann-diaminohexane(dahxn)-type clathrates of the form M(1,6-dahxn)Ni(CN)₄.G (M = Co, Ni or Cd; G = chlorobenzene, 1,2-, 1,3 or 1,4-dichlorobenzene) were prepared inpowder form and their infrared spectra are reported. The spectral data suggest that these compounds are similar in structure to those of the Hofmann-diam-type clathrates. Their structure consists of planar polymeric layers, {M–Ni(CN)₄}, formedfrom Ni(CN)₄ anions coordinated to the bridging 1,6-diaminohexane molecules bound directly to the metal (M). The M atoms are bound to four N atoms of the CN ions and, the Ni atoms are surrounded by four C atoms of the CN groups in a square-planar layer.     

CRYPTATES XIX. Ligands polyaza-polyoxa-macrobicycliques: Synthèse et complexes métalliques

Polyaza-polyoxa macrobicyclic ligands: its synthesis and metal complexes. The synthesis of the polyaza-polyoxa macrobicyclic ligands 1–4 is described. They form complexes with a variety of metal cations, transition metal cations as well as alkali and alkaline-earth cations. These complexes may be formulated as cation inclusion complexes, cryptates, in which the cation is contained in the intramolecular cavity. The properties of the complexes are described. An especially interesting feature is that these ligands, polymines of macrobicyclic topology, provide a means of trapping transition metal cations inside a molecular cavity; thus they impose coordination geometries and may modify the spectral and redox properties of the cations.