Covalent-ionic nature of the potential energy surface of the Li-CO2 complex

Unrestricted Hartree-Fock calculations with large basis sets, including d-functions, and the estimation of the correlation energy, show that the potential energy surface for the Li-CO₂ complex is built from the crossing of two states, each of them corresponding to a different electron arrangement. One has a strong ionic character and the other is of van der Waals type. Each portion of the energy surface presents a minimum, which is stable in respect to the dissociation limit.     

Investigation of anthropic effects connected with metal ions concentration, organic matter and grain size in Bormida river sediments

An investigation on the sediment composition and grain size was carried out along the Bormida river (Piedmont, Northern Italy). The samples were taken both in the riverbed and on its banks. Multivariate statistical exploratory methods permitted to identify possible sources of primary pollution. In particular, principal component analysis (PCA) showed that there are probably at least three anthropogenic main causes of pollution, one connected with Cr, Ni and Sn, the second with cadmium and the last one with mercury. Some correlations were found between heavy metal ion concentrations and organic matter and/or the sediment grain size. Differences between the samples collected in the riverbed and on the banks were identified and the relationships between the principal components and the distance of the samples from the riverbed and from the hot spot represented by the ACNA industrial site were also analyzed.     

The state of conservation of painted surfaces in the presence of accelerated ageing processes monitored by use of FT-Raman spectroscopy and multivariate control charts

A new method has been developed for monitoring the degradation of paintings. Two inorganic pigments (ultramarine blue and red ochre) were blended with linseed oil and spread on canvas. Each canvas was subjected to simulated accelerated ageing in the presence of typical degradation agents (UV radiation and acidic solution). Periodically the painted surfaces were analysed by FT-Raman, to investigate the status of the surface. The data obtained were analysed by principal component analysis (PCA). Finally the Shewhart and cumulative sum control charts based on the relevant principal components (PC) and the so called scores monitoring and residuals tracking (SMART) charts were built. The method based on the use of PC to describe the process was found to enable identification of the presence of relevant modification occurring on the surface of the samples studied.Electronic supplementary material Supplementary material is available for this article at     

ANVAS: Artificial Neural Variables Adaptation System for descriptor selection

A new algorithm model-oriented for variable selection is presented in this study. It is based on the combination of genetic algorithms (GA) for hyperspace exploration, and counterpropagation artificial neural network (CP ANN) for deriving the fitness score. The proposed method performed very well on both well defined synthetic data sets and real academic data sets.     

Uncharged water-soluble Co(II)-porphyrin: a receptor for aromatic alpha-amino acids

Changes in the UV-vis spectra and induced circular dichroism (ICD) signals observed, in correspondence with the porphyrin Soret region, for aqueous solutions of achiral 5,10,15,20-tetrakis{p-[omega-methoxy poly(oxy-ethylene)]phenyl}porphyrin cobalt (II) (Co-P) and aromatic alpha-L-amino acids (Trp and Phe) give direct evidence for the coordination between the Co-P and amino acids. Considering that Co-P, besides the Co atom (one-fixation-point system), does not contain in the molecule active ligand groups and that no ICD signals have been observed in the case of Co-P/Ala, it has been concluded that hydrophobic interactions or stacking interactions between the aromatic rings of the porphyrin and those of Trp or Phe, acting as further amino acid (AA) fixation points, can strongly reduce the mobility of the chiral guest, thus permitting the generation of ICD signals. The effects of changes of both pH (in the range 2-9) and amino acid structure on the ICD phenomenon have also been investigated. In particular, the following have been observed: (i) strong ICD signals for all of the Co-P/N-acetyl amino acid aqueous solutions at pH 7, (ii) an unexpected ICD band with a bisignate form for the Co-P/Ala solution at pH 9 after long aging, and (iii) an opposite ICD signal when alpha-D-Phe and alpha-D-Trp enantiomers have been used. The data reported in this paper show how the binding mechanism between receptor and AAs changes by modulating properly the pH or the molecular structures and indicate that in these aqueous solutions the coordination Co-N is not the fundamental mechanism giving rise to the formation of the complexes and that the binding can be driven by hydrophobic interactions. These occurrences, through the analysis of the spectroscopic response (and, in particular, the form of the ICD band), can allow the recognition of AAs.     

Carboxylate-bridged copper(II)-lanthanide(III) complexes [(Cu(3)Ln(2)(oda)(6)(H(2)O)(6)).12H(2)O](n)(Ln = Dy,Ho, Er,Y; oda = oxydiacetate)

The hydrothermal reaction of Ln(2)O(3) (Ln = Dy and Ho), Cu(OAc)(2).2H(2)O, and oxydiacetic acid in the approximate mole ratio of 1:3:8 resulted in the formation of two new members of the isostructural series of polymers formulated as [(Cu(3)Ln(2)(oda)(6)(H(2)O)(6)).12H(2)O](n), crystallizing in the hexagonal crystal system, space group P6/mcc (No. 192). Temperature-dependent magnetic susceptibilities and EPR spectra are reported for the heterometallic compounds Cu-Dy 1, Cu-Ho 2, Cu-Er 3, and Cu-Y 4. The results are discussed in terms of the structure of the compounds, the electronic properties of the lanthanide ions, and the exchange interactions between the magnetic ions.     

New dirhenium(III) compounds bridged by carboxylate ligands: N(C(4)H(9))(4)[Re(2)(OOCCF(3))Cl(6)] and Re(2)(OOCCCHCo(2)(CO)(6))(4)Cl(2)

The solvothermal reaction of (N(C(4)H(9))(4))(2)[Re(2)Cl(8)] with trifluoroacetic acid and acetic anhydride leads to the new rhenium trifluoroacetate dimer N(C(4)H(9))(4)[Re(2)(OOCCF(3))Cl(6)] (1) and to the rhenium carbonyl dimer Re(2)(mu(2)-Cl)(2)(CO)(8) as the rhenium-reduced byproduct. The reaction of the precursor complex, N(C(4)H(9))(4)[Re(2)(OOCCF(3))Cl(6)] (1), with the organometallic carboxylic acid (CO)(6)Co(2)HCCCOOH leads to the cluster of clusters compound Re(2)(OOCCCHCo(2)(CO)(6))(4)Cl(2) (2), which has the dimer structure of Re(2)(OOCR)(4)Cl(2). Cyclic voltammetric measurements show that Re(2)(OOCCCHCo(2)(CO)(6))(4)Cl(2) (2) has one reduction centered on the dirhenium core and a reduction centered on the cobalt atoms. DFT calculations have been used to rationalize the observed displacements of the voltammetric signals in Re(2)(OOCCCHCo(2)(CO)(6))(4)Cl(2) (2) compared to the parent ligand (CO)(6)Co(2)HCCCOOH and rhenium pivalate.     

Determination of oxytetracycline in urine and human serum by differential pulse polarography

Summary A differential pulse polarographic method for the determination of oxytetracycline in urine and human serum in acid media (HClO₄ of pH 2) is proposed. The effects of the amount of sample taken and the concentration of HClO₄ present were investigated. The detection limit was 5.5×10^–6 mol/l. The standard deviation of the determination of 5.5×10^–5 mol/l of oxytetracycline in 2 ml of urine was 1.7×10^–6 mol/l and that of the determination of 5.5×10^–5 mol/l of oxytetracycline in 2 ml of human serum was 1.9×10^–6 mol/l.

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Bestimmung von Oxytetracyclin in Urin und Humanserum durch Differential-Pulspolarography

     

Ratios between content of fatty acids as markers for mixture of cow and goat milk

The fat of mixture of goat and cow milk, extracted by di-ethylic ether, was gas chromatographically analysed in order to propose an analytical procedure suitable to reveal small additions of cow milk to goat milk. The obtained results show evident differences in the percentages of some fatty acids. An attempt to apply the peak area ratios, corresponding to the methyl esters of fatty acids, suggested by the literature for cow milk did not yield good results. Other ratios suitable to reveal even the presence of low percentages (up to 5 %) of cow milk in goat milk were found and proposed in this paper. Such ratios are sensitive and can be defined markers towards cow or goat milk and also towards extraneous fat like lard or colza seeds oil.