Spontaneous dissolution of a single-wall carbon nanotube salt

Upon reduction with alkali metals, single-wall carbon nanotubes (SWNTS) are shown to form polyelectrolyte salts that are soluble in polar organic solvents without any sonication, use of surfactants, or functionalization whatsoever, thus forming true thermodynamically stable solutions of naked SWNTs.     

UV index experimental values during the years 2000 and 2001 from the Spanish broadband UV-B radiometric network

An analysis is made of experimental ultraviolet erythemal solar radiation data measured during the years 2000 and 2001 by the Spanish UV-B radiation evaluation and prediction network. This network consists of 16 Robertson-Berger type pyranometers for evaluating solar erythemal radiation and five Brewer spectroradiometers for evaluating the stratospheric ozone. On the basis of these data the Ultraviolet Index (UVI) was evaluated for the measuring stations that are located either in coastal regions or in the more densely populated regions inland on the Iberian Peninsula. It has been checked that in most cases the maximum irradiance values corresponded to solar noon, although there were exceptions that could be explained by cloudiness. The maximum experimental values of the UVI were around 9 during the summer, though frequently passing this value at the inland measurement stations. The annual accumulated dose of irradiation on a horizontal plane has also been studied, as well as the evolution through the year in units of energy, standard erythemal doses and minimum erythemal doses, according to different phototypes.     

Conformational behaviour of 2,2′-bipyrrole

The rotational potential around the interannular bond in 2,2-bipyrrole has been calculated making use of standard minimal STO-3G and split valence 4-31G basis sets. Geometrical optimization concerning the most significant interannular internal parameters has been performed with both basis sets. The trans conformer is predicted to be more stable than the cis. The minimal basis set predicts the existence of a cisoid-gauche minimum which after limited optimization becomes very shallow and it seems to be an artifact of the rigid rotor approximation. At 4-31G level, both the trans and cis conformers represent maxima in the potential curve and two gauche minima appear at =46.0° and =147.6°, the latter being the absolute minimum. The absolute maximum of the potential curve corresponds to the cis conformer.     

Cover Picture

The cover picture shows the structure, determined crystallographically, of the tetrakis(trimethylstannyl)phosphonium cation that is formed with surprising ease from the reaction of P(SnMe(3))(3) with Me(3)SnOTf (OTf=OSO(2)CF(3)) and is isolated as the OTf salt. It is the first completely substituted main group organometallic phosphonium derivative, and, in contrast to the more common tetraorganic-substituted phosphonium cations is only stable in the solid state; in solution it functions as a masked Me(3)Sn(+) reagent. More about this chameleonlike ion and the N(SnMe(3))(4) cation homologue, which is equally dynamic in solution and has unusual long Sn-N bond lengths, is reported by M. Driess et al. on p. 3684 ff.     

Approximate transferability in alkanenitriles

The atomic and bond properties of a series of alkanenitriles were calculated in order to analyze the transferability of the CN, methyl, and methylene groups. The calculations were carried out using the atoms in molecules (AIM) theory on RHF/6‐31++G**// RHF/6‐31G** wave functions obtained for compounds CN–R (R ranging from H to C₁₁H₂₃). Linear correlations between L(Ω) and N(Ω) were used to establish N(CH₂) and N(CH₃) nearly transferable values. Average values and maximum differences to the mean value of several properties were used for classifying the CN group. It shows a transferable behavior along the CN–R series for R>Et. The methyl group presents specific properties when R<Pr. The methylene groups can be classified considering both their position with respect to the end of the chain and the position with respect to the CN group. The atomic energy displays a dependence on the molecular size. Although this behavior does not allow to consider this property as transferable, both the ab initio total electronic molecular energies and the experimental heats of formation can be fitted, by linear regression analysis, as a function of the number of methylene groups. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001     

Orbital-band interactions and the reactivity of molecules on oxide surfaces: from explanations to predictions

 The surface chemistry of oxides is relevant for many technological applications: catalysis, photoelectrolysis, electronic-device fabrication, prevention of corrosion, sensor development, etc. This article reviews recent theoretical works that deal with the surface chemistry of oxides. The account begins with a discussion of results for the adsorption of CO and NO on oxides, systems which have been extensively studied in the literature and constitute an ideal benchmark for testing the quality of different levels of theory. Then, systematic studies concerned with the behavior of adsorbied alkali metals and sulfur-containing molecules are presented. Finally, a correlation between the electronic and chemical properties of mixed-metal oxides is analyzed and basic principles for designing chemically active oxides are introduced. Advances in theoretical methods and computer capabilities have made possible a fundamental understanding of many phenomena associated with the chemistry of molecules on oxide surfaces. Still many problems in this area remain as a challenge, and the approximate nature of most theoretical methods makes necessary a close coupling between theory and experiment. Following this multidisciplinary approach, the importance of band-orbital interactions for the reactivity of oxide surfaces has become clear. Simple models based on band-orbital mixing can explain trends found for the interaction of many adsorbates with oxide surfaces. These simple models provide a conceptual framework for modifying or controlling the chemical activity of pure oxides and for engineering mixed-metal oxides. In this respect, theoretical calculations can be very useful for predicting the best ways for enhancing the reactivity of oxide systems and reducing the waste of time, energy and materials characteristic of an empirical design. Received: 21 June 2001 / Accepted: 8 October 2001 / Published online: 1 February 2002     

Syntheses d'oxazolidines substituees par l'adamantane et de nitroxydes oxazolidines stables derives de l'adamantane

Adamantane oxazolidine derivatives have been prepared. The corresponding mono and biradicals have molecular shapes well suited to the study of the motion anisotropy in solution.     

Selective crystallization of calcium salts by poly(acrylate)-grafted chitosan

The biopolymer chitosan was chemically modified by grafting polyacrylamide or polyacrylic acid in a homogeneous aqueous phase using potassium persulfate (KPS) as redox initiator system in the presence of N,N-methylene-bis-acrylamide as a crosslinking agent. The influence of the grafted chitosan on calcium salts crystallization in vitro was studied using the sitting-drop method. By using polyacrylamide grafted chitosan as substrate, rosette-like CaSO4 crystals were observed. This was originated by the presence of sulfate coming from the initiator KPS. By comparing crystallization on pure chitosan and on grafted chitosan, a dramatic influence of the grafted polymer on the crystalline habit of both salts was observed. Substrates prepared by combining sulfate with chitosan or sulfate with polyacrylamide did not produce similar CaSO4 morphologies. Moreover, small spheres or donut-shaped CaCO3 crystals on polyacrylic acid grafted chitosan were generated. The particular morphology of CaCO3 crystals depends also on other synthetic parameters such as the molecular weight of the chitosan sample and the KPS concentration.     

Pollutants leaching behaviour from solidified wastes: a selection of adapted various models

Leaching tests are essential in the environmental assessment of stabilized wastes. Research programmes were conducted on their interpretation in order to develop tools for the evaluation of long term release of pollutants contained in solidified wastes. Models for the leaching of porous materials are discussed in this paper according to the specificity of the chemical species (i.e. transport model with total dissolution of species-diffusional model; transport model with progressive dissolution of species due to limitation of solubility-shrinking core model; and the model coupling transport and chemical phenomena). The leaching behaviour of pollutants (i.e. lead) solidified in a cement matrix was studied under different chemical conditions. Results have shown that the release of species whose solubilities depend on the physico-chemical conditions, and especially the pH (e.g. amphoteric metals), is governed by the solubility of the species in the pore water at local conditions and by the pH evolution within the matrix. A coupled dissolution/diffusion model was developed to describe the release of chemically complex species contained in a porous medium in contact with water. Leaching tests of cement matrices and artificial porous matrices containing calcium hydroxide and pollutants were conducted in order to validate the coupled dissolution/diffusion model. A good assessment of the retention of some pollutants contained in cement matrices could then be obtained by the association of two tests: solubilization of the pollutants related to the chemical context (pH) under steady state conditions and monolithic long term dynamic leaching tests in order to characterize the evolution of the chemical context (pH) and consequently the release of pollutants. The objective is to integrate this approach in the standardization process (CEN TC 292- WG 6, in progress).     

A pyrimidine thiolate Rh(I) complex: structure, bonding and one-dimensional interactions in solid and in solution

The reaction of [Rh(micro-Cl)(COD)]2 with 4,6-dimethyl-pyrimidinethiolate (Me2-pymt) and subsequent substitution of COD by CO yields [Rh(Me2-pymt)(CO)2]. The stacking pattern found in this compound is in contradiction with previously studied comparable square-planar complexes of type d8-[M(chelate)(monodentate)2] in which each ligand has different pi-acidic character. A theoretical study of the intermolecular interactions and conformation of the title compound has been carried out, combining semi-empirical band calculations on the real chains and ab initio(MP2 level) calculations on a model dimer. The combination of electronic and steric effects determines the rotation of the successive monomers and the deviation from linearity of the one-dimensional stacks. Its behaviour in solution is also special, developing a blue colour and forming micelles, when adding water to acetone solutions.