Preparation and properties of solid state selenite ion selective electrodes and their applications

A new selenite ion selective electrode using solid salts of Ag(2)Se and Cu(2)S has been developed. Detailed information is provided concerning the composition, working pH and conditioning of the electrode. The change of potential with concentration is found to be linear in the range of 10(-5)-10(-2) M, the slope of the linear portion is 28 mV/10-fold change in selenite concentration. The effect of other ions on selenite response is evaluated and selenium content of anodic slime is determined.     

Electroreductive polymerization of trans-[RuCl 2(vpy) 4] on Nd-Fe-B magnets: electrochemical impedance spectroscopy interpretation, Raman spectroscopy, X-ray photoelectron spectroscopy and scanning electron microscopy analysis

The electropolymerization of trans-[RuCl₂(vpy)₄] (vpy=4-vinylpyridine) monomer on Nd-Fe-B magnets was studied by electrochemical impedance spectroscopy (EIS). Impedance diagrams obtained during the polymerization process were used to monitor film formation. The EIS results gave insight into the electrochemical phenomena occurring at the magnet surface as the polymerization process progressed. The film structure and morphology were also studied by X-ray photoelectron spectroscopy, scanning electron microscopy and Raman spectroscopy. The Raman spectroscopy results showed that the polymerization takes place at the vinyl groups of the monomer and also that the redox polymer structure is very similar to that of the monomer. The ratio of the intensity of the XPS peaks for fluorine (from the electrolyte PF₆ ^–) and ruthenium present in the film showed that the polymer on Nd-Fe-B contained an equal proportion of Ru²⁺ and Ru³⁺, indicating that part of the film is positively charged, i.e. {[RuCl₂(vpy)₄]⁺} _n .     

Development of quantitative vitellogenin-ELISAs for fish test species used in endocrine disruptor screening

The yolk protein precursor vitellogenin (Vtg) in plasma has proved to be a simple and sensitive biomarker for assessing exposure of fish to environmental estrogens. Within international bodies such as the Organization for Economic Cooperation and Development (OECD) work is ongoing to develop screening and testing programmes for endocrine disrupting effects of new chemicals, and in the focus of this development are the fish test species common carp (Cyprinus carpio), fathead minnow (Pimephales promelas), zebrafish (Danio rerio) and Japanese medaka (Oryzias latipes). In this study we have developed quantitative enzyme linked immunosorbent assays (ELISAs) for Vtg in common carp/fathead minnow, zebrafish and Japanese medaka. The assays were developed using a combination of monoclonal and polyclonal fish Vtg antibodies in a sandwich format, using stabilized Vtg from the test species as a standard. The carp Vtg ELISA has a working range of 1–63 ng/mL, a minimal detection limit of 0.6 ng/mL, and may also be used for quantification of Vtg in fathead minnow. In fathead minnow whole-body homogenate samples, the practical detection limit is 400 ng/mL due to the matrix effect. The zebrafish Vtg ELISA has a working range of 0.5–63 ng/mL, a minimal detection limit of 0.4 ng/mL, and a practical detection limit of 200 ng/mL in whole-body homogenate samples. The medaka Vtg ELISA has a working range of 0.25–16 ng/mL, a minimal detection limit of 0.1 ng/mL, and a practical detection limit of 125 ng/mL in whole-body homogenate samples. The intra- and inter-assay variations were below 20% for all assays. The assays were evaluated with sets of representative samples spanning the wide dynamic range of Vtg-levels found in fish exposed to environmental estrogens, and all three assays are currently undergoing international inter-laboratory validation.     

Analysis of the essential oil from aerial parts of Eupatorium cannabinum subsp. corsicum (L.) by gas chromatography with electron impact and chemical ionization mass spectrometry

Eupatorium cannabinum subsp. corsicum (L.), an aromatic plant, is an endemic subspecies from Corsica. The essential oil from aerial parts of E. cannabinum subsp. corsicum was studied by GC, GC/MS and 13C NMR. One hundred and forty-seven components were identified representing 93.6% of the total amount. The main constituents are germacrene D (28.5%), alpha-phellandrene (19.0%) and para-cymene (5.2%). A particularity of this essential oil is the presence of monoterpene esters derived from nerol, lavandulol, borneol, thymol and 8,9-dehydrothymol. These compounds have been investigated using GC/MS in different ionization modes like electron impact (EI), positive chemical ionization (PCI) and negative chemical ionization (NCI).     

Characterization of a Thermotolerant and Alkalotolerant Xylanase from a Bacillus sp.

In a recent screening for thermophilic bacteria from Azores hot springs, a Bacillus sp strain 3M, exhibiting cellulase-free extracellular xylanolitic activity, was isolated. Further enzyme characterization from liquid cultures grown on birchwood xylan revealed that the endo-l,4-βxylanase retains 100% of activity for at least 3 d at 55°C. At 80°C, it retains 47% of its maximal activity, and the enzyme is still active at 90°C. The optimum pH of the enzyme has a broad pH range, between 6.0 and 7.5, and it is remarkably active for the alkaline region, exhibiting 89% of relative activity at pH 9.O. The enzyme was partially inactivated by different divalent metal ions. Because of its tolerance for high temperature and pH conditions, and the absence of contaminating cellulase activity, the xylanase produced byBacillus sp 3M appears to be attractive for use in the pulp and paper industry. Indeed, the efficiency of the enzyme application to the kraftEucalyptus pulp was studied for bleaching pretreatment, resulting in a moderate increase of pulp bleachability.     

Investigations for Modification of Polyacrylamide-Bentonite by Phytic Acid and its Usability in Fe3+, Zn2+ and UO2 2+ Adsorption

Composite of polyacrylamide-bentonite (PAA-B) was prepared by direct polymerisation of PAA in a suspension of bentonite (B). Adsorption and thermodynamic features of phytic acid (Phy) adsorption onto B, PAA and PAA-B, and those of Fe³⁺, Zn²⁺, UO₂ ²⁺ adsorption onto PAA-B and its modification by Phy (PAA-B-Phy) have been investigated. The reusability, storagability, ion selectivity and recoverability of sorbed ions with 1 M HCl have also been considered.The chemical and physical structure of adsorbents has been characterised by means of FT-IR and XRD. All adsorption isotherms for Phy and the ions were L-type of the Giles classification except, the one which is S type for adsorption of Phy onto PAA. The maximum adsorption capacities for the ions adsorbed were in order of UO₂ ²⁺ > Fe³⁺ > Zn²⁺ for PAA-B and Zn²⁺ > Fe³⁺ > UO₂ ²⁺ for PAA-B-Phy. Langmuir equilibrium constants for the adsorption of ions onto PAA-B-Phy were significantly higher than those found for PAA-B; the magnitude of increase for UO₂ ²⁺ was about 100. The thermodynamic parameters indicated that adsorption reactions are spontaneous in terms of adsorption free enthalpy.The chemical structure of PAA-B-Phy was not changed at the end of the studies of reusability and storagability. The composite was selective for UO₂ ²⁺ of the ions of interest.The composite of PAA-B and its modification by Phy have been used for the first time in this investigation. It is proposed that the composites can be practically used in the investigations and applications of adsorption.     

Hydrogen activation on Mo-based sulfide catalysts,a periodic DFT study

Hydrogen adsorption on Mo[bond]S, Co[bond]Mo[bond]S, and Ni[bond]Mo[bond]S (10 1 macro 0) surfaces has been modeled by means of periodic DFT calculations taking into account the gaseous surrounding of these catalysts in working conditions. On the stable Mo[bond]S surface, only six-fold coordinated Mo cations are present, whereas substitution by Co or Ni leads to the creation of stable coordinatively unsaturated sites. On the stable MoS(2) surface, hydrogen dissociation is always endothermic and presents a high activation barrier. On Co[bond]Mo[bond]S surfaces, the ability to dissociate H(2) depends on the nature of the metal atom and the sulfur coordination environment. As an adsorption center, Co strongly favors molecular hydrogen activation as compared to the Mo atoms. Co also increases the ability of its sulfur atom ligands to bind hydrogen. Investigation of surface acidity using ammonia as a probe molecule confirms the crucial role of sulfur basicity on hydrogen activation on these surfaces. As a result, Co[bond]Mo[bond]S surfaces present Co[bond]S sites for which the dissociation of hydrogen is exothermic and weakly activated. On Ni[bond]Mo[bond]S surfaces, Ni[bond]S pairs are not stable and do not provide for an efficient way for hydrogen activation. These theoretical results are in good agreement with recent experimental studies of H(2)[bond]D(2) exchange reactions.     

Vilsmeier formylation of 5,10,15-triphenylcorrole: expected and unusual products

5,10,15-Triphenylcorrole (1) reacts with the Vilsmeier reagent (POCl(3)/DMF) to give the corresponding 3-formyl derivative 3 as the major product. The regioselectivity of the reaction was proven by X-ray crystallography and only traces of the 2-formyl isomer were observed. A more polar product is also observed and this compound becomes the major product when an excess of DMF is used for the preparation of the Vilsmeier reagent, while the formation of the 3-formyl isomer is almost completely suppressed. X-ray crystallography allowed us to identify this compound as the fully substituted N-ethane bridged derivative 4, formed from the attack of the Vilsmeier reagent at the inner core of the macrocycle. This compound is unique among porphyrinoid macrocycles, and further confirms the peculiarity of corrole chemistry.     

Removal of strontium ions by a crosslinked copolymer containing methacrylic acid functional groups</p> </p>

Summary A tail-made polymer matrix is proposed to remove strontium ions from aqueous solutions. The removal behavior of strontium ions on a crosslinked copolymer containing methacrylic acid as functional groups was investigated as a function of sorptive concentration, time, temperature and pH. It was observed that an increase of these parameters enhanced the removal of Sr(II) ions from aqueous solution. It is found that a maximum adsorption of Sr(II) ions can be obtained on the crosslinked copolymer after 30 minutes and at pH 8. The increase of Sr(II) ion concentration in the solution resulted in an increase in the amount of Sr(II) ions adsorbed on the crosslinked copolymer containing methacrylic acid as functional groups. However, after a maximum of Sr(II) concentration in the solution, the percentage of adsorbed Sr(II) ions decreased. The adsorption data are well represented by the Freundlich, Langmuir and Dubinin-Radushkevich (D-R) isotherms. The adsorption capacity of the copolymer and the free energy change were calculated by using the D-R isotherm. For the adsorption of Sr(II) ions on the crosslinked copolymer the thermodynamic parameters (DH°,DS° andDG°) were calculated.</p> </p>     

An Infrared Spectroscopic Study on the Hofmann-diam-type 1,12-Diaminododecanemetal(II) Tetracyanonickelate(II)-aromatic Guest Clathrates: M(H2N(CH2)12NH2)Ni(CN)4ċG(M=Co, Ni or Cd; G = Benzene, Naphthalene, Anthracene, Phenanthrene or Biphenyl)

Three Hofmann-diaminododecane-type clathrates of the form M(1,12-diaminododecane) Ni(CN)₄G (M = Co, Ni or Cd; G = benzene, naphthalene, anthracene, phenanthrene or biphenyl) have been prepared in powder form. The 1,12-diaminododecane molecules in the host lattice permit the inclusion of bulky guest molecules. The spectral features suggest that these compounds are similar in structure to the other Hofmann-diam-type clathrates.