Flame atomic absorption spectrometric determination of silver after preconcentration on Amberlite XAD-16 resin from thiocyanate solution

A method of silver preconcentration by using a column containing Amberlite XAD-16 resin and this future determination by a flame AAS after elution is proposed. The effect of the factors such as pH, the nature of complexing agent, sample volume, flow rate, the type and concentration of elution solution on the preconcentration efficiency have been investigated. The influence of some matrix elements on the recovery of silver were also examined. It was found, that the quantitative recovery of thiocyanate complex of silver was obtained from nitric acid solution (pH 2) as 99.20+/-0.07% at the 95% confidence level. A preconcentration factor up to 75 could be obtained. The detection limit of silver was 0.047 mg l(-1). The adsorption of silver onto Amberlite XAD-16 can be formally described by a Langmuir equation with maximum adsorption capacity 4.66 mg g(-1) (0.043 mmol g(-1)). The proposed method was applied to determination of silver in standard alloy with relative error 6.25%.     

Sodium 5‐nitro‐2‐pyridonate trihydrate

The title compound, alternatively sodium pyridin‐2‐olate trihydrate, Na⁺·C₅H₃N₂O₃^?·3H₂O, crystallizes in the P space group. It is made up of edge‐shared chains of NaO₆ octahedra with five water mol­ecules and one 5‐nitro‐2‐pyridonate anion. Four of these water mol­ecules are bicoordinating, involved in connecting the adjacent octahedra, and the fifth is coordinated to only one octahedron. The crystal structure is stabilized by a network of strong O—H?O and O—H?N interactions. The organic moieties occupy the space between the chains with an antiparallel alignment.     

Ultrafast dynamics of Cu(I)-phenanthrolines in dichloromethane

Transient absorption spectrometry of Cu(I)-phenanthrolines in CH2Cl2 reveals ligand-independent dynamic processes lasting 15 ps, which are associated with the peculiar structural rearrangements occurring for this class of compounds upon photoexcitation.     

Trimeric perfluoro-ortho-phenylenemercury: a versatile Lewis acidic host

Trimeric perfluoro-ortho-phenylenemercury (1) constitutes one of the simplest trifunctional Lewis acidic hosts. In addition to cooperative effects arising from the proximity of the mercury(II) centers, the electron-withdrawing properties of the backbone and the accessibility of the electrophilic sites lead to the facile complexation of neutral and electron rich substrates. The planarity of the structure as well as its overall polarizability compounded with relativistic effects at mercury also permits the occurrence of non-covalent interactions and accounts for the tendency of this compound to form cofacial dimers. Collectively, the Lewis acidic properties of 1 as well as its ability to engage in non-covalent interactions can be held responsible for its ability to form extended binary supramolecular stacks with arenes. The photoluminescence observed in some of these supramolecular complexes corresponds to the phosphorescence of the aromatic substrate and indicate the occurrence of a mercury heavy atom effect.     

A general strategy for the diastereoselective synthesis of 2,6-diaryl-3,7-dioxabicyclo[3.3.0]octane lignans

A strategy for the stereoselective synthesis of all the possible diastereoisomers of the 2,6-diaryl-3,7-dioxabicyclo[3.3.0]octane (furofuran) lignans from a single dihydrofuran precursor is described. The key steps involve a diastereocontrolled templated cationic cyclization followed by stereoselective reduction of the resulting methyl glycoside.     

Azidopeptide nucleic acid. An alternative strategy for solid-phase peptide nucleic acid (PNA) synthesis

[reaction: see text] A practical and efficient method for PNA synthesis using an azide group to mask the N-terminus is reported. The deprotection was carried out in 5 min, while couplings were complete within 60 min. The near neutral conditions of the phosphine deprotection combined with the base-free coupling using hydroxybenzotriazole-activated monomers make this approach very mild.     

A supramolecular cup-and-ball C60-porphyrin conjugate system

In addition to the ammonium-crown ether recognition, pi-stacking interactions between the C60 sphere and the porphyrin moiety have been evidenced in a supramolecular complex obtained from a porphyrin-crown ether conjugate and a fullerene derivative bearing an ammonium unit.     

Molecular structure-activity relationships for the oxidation of organic compounds using mesoporous silica catalysts derivatised with bis(halogeno)dioxomolybdenum(VI) complexes

Mo K-edge XAFS spectra have been measured for ordered mesoporous silica MCM-41 grafted with the complexes [MoO2X2(thf)2] (X=Cl, Br). For grafting reactions in the absence of triethylamine, materials with 1 wt. % Mo are obtained; the Mo K-edge EXAFS results indicate the co-existence of isolated surface-fixed monomeric species [MoO2[(-O)3SiO]2(thf)(n)] and [MoO2[(-O)3SiO]X(thf)(n)]. When Et3N is used in the grafting reactions, materials with 4 wt. % Mo are obtained. The EXAFS data for the material prepared using [MoO2Cl2(thf)2] and Et3N indicate the presence of dinuclear species with two Mo(VI) centres, each with two Mo=O groups and each linked by one or two oxo bridges (Mo...Mo 3.27 A). The molybdenum centres in the material prepared using the dibromo complex comprise mainly isolated four-coordinate dioxomolybdenum(VI) and trioxomolybdenum(VI) monomeric species, with a small contribution from dimeric species. All materials were further characterised in the solid state by powder X-ray diffraction, N2 adsorption analysis, MAS NMR (13C, 29Si) and FTIR spectroscopy. The derivatised MCMs perform differently as catalysts in the liquid-phase oxidation of various olefins and alcohols with tert-butyl hydroperoxide. The highest alkene epoxidation activity was recorded for the catalysts with low metal loading, whereas the material containing oxo-bridged dimers had the highest activity for oxidation of alcohols. The recyclability of all the catalysts was tested: the catalytic activity of the derivatised materials tended to stabilize with ageing.     

From supramolecular block copolymers to advanced nano-objects

The formation of asymmetric bis-complexes, based on terpyridine ligands and ruthenium ions, is described as a powerful tool for the self-assembly of polymer blocks end-functionalized with terpyridine units. This is illustrated in this contribution for the synthesis of amphiphilic metallo-supramolecular block copolymers, which are further used to produce aqueous micelles. Finally, the reversibility of the supramolecular bond opens new avenues for the preparation and manipulation of these nano-objects.     

Donor-substituted peralkynylated "radiaannulenes": novel all-carbon macrocycles with an intense intramolecular charge-transfer

A novel class of planar, highly conjugated all-carbon macrocycles, which we christened "radiaannulenes", have been prepared based on acetylenic scaffolding using tetraethynylethene (TEE) building blocks; these structures are powerful electron acceptors and, upon peripheral substitution with electron-donating N,N-dialkylanilino groups, display intense intramolecular charge-transfer.