Addition reaction of azido-exTTFs to C60: synthesis of fullerotriazoline and azafulleroid electroactive dyads

[structure: see text] The addition reaction of azido-exTTFs to C(60) affords electroactive fullerotriazoline and azafulleroid dyads, which behave as amphoteric redox systems. Fluorescence experiments and transient absorption spectroscopy reveal that excitation of the fullerene moiety leads to radical pair lifetimes that are 2 orders of magnitude higher than those previously reported for related fullerotriazolines.     

Influence of the Meniscus at the Bottom of the Solid Plate on Imbibition Experiments

The analysis of the experiments on liquid imbibition into porous solids carried out by using the increase of weight technique proves the influence that meniscus formation has on the experimental increase of weight when the bottom of the porous layer is put in contact with the free surface of the liquid used to perform the penetration experiments. This process (meniscus onset) has a temporary dependence due to the change of the distance between the inferior base of the plate and the free surface of the liquid as a result of the imbibition. We have also found the proper experimental conditions under which such temporary dependence can be minimized after a short time after the start of contact between the porous layer and the free surface of the liquid utilized in the penetration procedure. Thus, the weight increase because of the meniscus formation can be assumed as a constant during the greatest part of the experiments, allowing the use of the proper mathematical form of Washburn's equation in order to describe the imbibition of the liquid into the pores of the solid. Copyright 2001 Academic Press.     

Effects of cetylpyridinium bromide micelles on the spectrofluorimetric characteristics of polycyclic aromatic hydrocarbons

The presence of a micellar medium of cetylpyridinium bromide (CPB) causes, in relation to the aqueous medium, important bathochromic shifts in the excitation spectra of a considerable number of polycyclic aromatic hydrocarbons (PAHs). Furthermore, the CPB acts as a quencher, provoking inhibitions of the fluorescence intensity emitted by PAHs. The micellar inhibition factors show that, generally, the quenching affects alternant hydrocarbons to a greater extent. Some interesting relationships between the hydrocarbon structure and both the characteristic wavelengths of fluorescence spectra and the values of Deltalambda are established.     

Determination of polycyclic aromatic hydrocarbons in seawater by high-performance liquid chromatography with fluorescence detection following micelle-mediated preconcentration

In this work, the nonionic surfactant polyoxyethylene-10-lauryl ether has been used for the extraction and preconcentration of 14 polycyclic aromatic hydrocarbons, classified as priority pollutants by the US Environmental Protection Agency, from seawater samples. The cloud-point preconcentration previous separation by HPLC and quantification using fluorimetric detection and wavelength programming allow to determine these pollutants with detection limits ranging from 1.0 to 1.5 x 10(2) ng/l with RSDs better than 10.4%. The methodology is evaluated using well-established extraction and preconcentration methods and GC-MS.     

Determination of linuron in soil by stripping voltammetry with a carbon fiber microelectrode

A carbon fiber microelectrode was used for the electroanalytical determination of Linuron (LIN) in soil extracts. The microelectrode was subjected to an electrochemical pretreatment in order to improve the herbicide adsorption on the electrode surface. With this preconcentration step, detection limits of 80 ng ml⁻¹ and determination limits of 260 ng ml⁻¹ were reached. Optimal conditions with respect to accumulation time and potential, scan rate and pH were established. The LIN was determined in a soil sample with the method proposed and the results found were comparable to those obtained by HPLC.     

Biotreatment of tannin-rich beer-factory wastewater with white-rot basidiomycete Coriolopsis gallica monitored by pyrolysis/gas chromatography/mass spectrometry

Some fractions of beer-factory wastewaters represent an important environmental concern owing to their high content of polyphenols and dark-brown color. The capacity of Coriolopsis gallica to preferentially degrade lignin has been successfully applied in our laboratory to the biotreatment and decolorization of paper-industry effluents. In this work, the ability of this white-rot fungus to degrade high-tannin-containing wastewaters is evaluated. Under all the conditions studied, effluent decolorization and chemical oxygen demand reduction achieved by C. gallica at day 12 of incubation were close to 50 and 65%, respectively. No adhesion of dark color to the fungal mycelium was observed suggesting that decolorization could be ascribed to C. gallica degradation systems. Mycelium dry-weight values showed that C. gallica is tolerant to relatively high tannin content present in the effluent samples. In the sample containing the highest effluent concentration (60% v/v), dry-weight values suggested an inhibition of fungal growth at day 6 of incubation and a further adaptation of the fungus to the stressing tannin effect at day 12 of fungal treatment. Pyrolysis/gas chromatography/mass spectrometry results showed a decrease of polyphenols pyrolysis products, mainly phenol and guaiacol, with the incubation time. All these results indicate the potential use of C. gallica in bioremediation of tannin-containing industrial wastewaters and in other applications where a reduction in polyphenols content is required.     

Product distributions, rate constants, and mechanisms of LiH+H reactions

We present a quantum-mechanical investigation of the LiH depletion reaction LiH+H-->Li+H2 and of the H exchange reaction LiH+H'-->LiH'+H. We report product distributions, rate constant, and mechanism of the former, and rate constant and mechanism of the latter reaction. We use the potential-energy surface by Dunne et al. [Chem. Phys. Lett. 336, 1 (2001)], the real-wave-packet method by Gray and Balint-Kurti [J. Chem. Phys. 108, 950 (1998)], and the J-shifting approximation. The 1H2 nuclear-spin statistics and progressions of vib-rotational states (v',j') rule both initial-state-resolved and thermal product distributions, which have saw-toothed shapes with odd j' preferred with respect to even j'. At high collision energies and temperatures, we obtain a regular 3-to-1 intensity alternation of rotational states. At low collision energies and temperatures, the degeneracy and density of many H2 levels can, however, give more irregular distributions. During the collision, the energy flows from the reactant translational mode to the product vibration and recoil ones. The rate constants of both reactions are not Arrhenius type because the reactions are barrier-less. The low-temperature, LiH depletion rate constant is larger than the H exchange one, whereas the contrary holds at high temperature. The real-time mechanisms show the nuclear rearrangements of the nonreactive channel and of the reactive ones, and point out that the LiH depletion is preferred over the H exchange at short times. This confirms the rate-constant results.     

Solid-phase extraction-liquid chromatography-fluorimetry for organotin speciation in natural waters

Summary A method is reported for the determination of dibutyltin (DBT), diphenyltin (DPhT), tributyltin (TBT), and triphenyltin (TPhT) species at the nanogram per litre concentration level in natural water samples. Analytes were isolated from samples by solid-phase extraction and analysed both off-line and on-line by reversed-phase high-performance liquid chromatography with post-column derivatization and fluorimetric detection. Several SPE cartridges and eluents were evaluated; C₁₈ enrichment and elution with a mixture of methanol, acetic acid, and water was found most suitable. Preconcentration factors up to 250 can be achieved when a 500-mL sample is processed. Detection limits, recovery rates, and the precision of the whole process have been determined. The method has been applied to the determination of organotin species in spiked natural water samples collected on the NW Mediterranean coast. Recovery rates range from 75 to 110% and detection limits are at the low ng L⁻¹ level (1–3 ng Sn L⁻¹ for DPhT, DBT, and PhT and 40 ng Sn L⁻¹ for TBT when 250 mL spiked sea water is processed.)     

Antiparallel triple helices. Structural characteristics and stabilization by 8-amino derivatives

The structural, dynamical, and recognition properties of antiparallel DNA triplexes formed by the antiparallel d(G#G.C), d(A#A.T), and d(T#A.T) motifs (the pound sign and dot mean reverse-Hoogsteen and Watson-Crick hydrogen bonds, respectively) are studied by means of "state of the art" molecular dynamics simulations. Once the characteristics of the helix are defined, molecular dynamics and thermodynamic integration calculations are used to determine the expected stabilization of the antiparallel triplex caused by the introduction of 8-aminopurines. Finally, oligonucleotides containing 8-aminopurine derivatives are synthesized and tested experimentally using several approaches in a variety of systems. A very large stabilization of the triplex is found experimentally, as predicted by simulations. These results open the possibility for the use of oligonucleotides carrying 8-aminopurines to bind single-stranded nucleic acids by formation of antiparallel triplexes.     

Density and Sound Velocity Studies of Aqueous Solutions of Tetradecyltrimethylammonium Nitrate at Different Temperatures

The density and ultrasound velocity of aqueous solutions of tetradecyltrimethylammonium nitrate were measured in the temperature range of 15 to 35°C in 5°C intervals. The concentration range covered the premicellar and micellar regimes. By assuming a pseudophase separation model for the micellar system, we applied the densitometric data to estimate the apparent molar volumes and the apparent thermal expansibility coefficients of the surfactant in monomeric and micellar forms. Ultrasound velocity and density data enabled us to estimate the isentropic compressibility of the surfactant in both forms. The results are compared with relevant literature data for alkyltrimethylammonium bromides.