Determination of ammonia based on the electro-oxidation of hydroquinone in dimethylformamide or in the room temperature ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

The results detail a novel methodology for the electrochemical determination of ammonia based on its interaction with hydroquinone in DMF. It has been shown that ammonia reversibly removes protons from the hydroquinone molecules, thus facilitating the oxidative process with the emergence of a new wave at less positive potentials. The analytical utility of the proposed methodology has been examined with a linear range from 10 to 95 ppm and corresponding limit-of-detection of 4.2 ppm achievable. Finally, the response of hydroquinone in the presence of ammonia has been examined in the room temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluormethylsulfonyl)imide, [EMIM][N(Tf)₂]. Analogous voltammetric waveshapes to that observed in DMF were obtained, thereby confirming the viability of the method in either DMF or [EMIM][N(Tf)₂] as solvent.     

Synthesis and pharmacological evaluation of new 16-methyl pregnane derivatives

The pharmacological activity of several new pregnane derivatives 15-19 were determined on gonadectomized male hamster flank organs, seminal vesicles and in vitro conversion of testosterone (T) to dihydrotestosterone (DHT) as 5alpha-reductase inhibitors. Steroids 15-19 decreased the diameter of the pigmented spot in the flank organs as compared to the T treated animals; in this model, steroids 16 and 19 showed a higher activity than the commercially available finasteride 3. Injection of T increased the weight of the seminal vesicles. Compounds 15-19 when injected together with T decreased the weight of the seminal vesicles thus showing an antiandrogenic effect. The trienone 19 exhibited a considerably higher activity than finasteride. Steroids 15-19 inhibited the in vitro metabolism of [3H]T to [3H]DHT in seminal vesicles homogenates of gonadectomized male hamsters. Compounds 18 and 19 showed a much higher antiandrogenic effect than finasteride. This enhancement of the biological activity could probably be attributed to the coplanarity of the steroidal skeleton as previously observed by our group. The high antiandrogenic activity of the epoxy compound 16 is probably the result of the ring opening of the oxiran ring with the nucleophilic part of the enzyme 5alpha-reductase thus leading to a stable adduct with concomitant deactivation of this enzyme.     

The properties of the metal complex hydrides

The essential features (geometries of the minima and of the saddle points, energy barriers) of the potential energy surface of the four hydrides YXH₄ mentioned in the title have been determined with two basis sets, of minimal and DZ quality respectively. The importance of the different extent of the deformation of the XH₄ group in the different structures of the four hydrides is brought out and discussed. The aspects of charge distribution and bonding are examined drawing on population analysis, comparison of the electrostatic molecular potentials and decomposition of the interaction energy (this last referred to the Y⁺ + XH ₄ ^– YXH₄ process). The capability of XH₃ in effecting the etherolytic disruption of the Y-H bond is finally brought out.     

Theoretical and experimental studies of asymmetric organozinc additions to benzaldehyde catalyzed by flexible and constrained gamma-amino alcohols

The cis-decalin based gamma-amino alcohols, 1-5, were synthesized, resolved, and employed as catalysts in the addition of organozincs to benzaldehyde. Despite large facial differentiation in the RZn adducts of the ligands, the enantioselectivities were found to be moderate. Transition structure calculations were done using several quantum chemical methods to examine the underlying causes of the selectivity for three gamma-amino alcohols, 1, 2, and 3. The tricyclic mu-oxo (6/4/4), rather than the bicyclic six-membered (6/6), transition structures were found to explain the observed enantioselectivity for 2 and 3. MP2 calculations gave the best correlation to the experimental results compared to B3LYP and HF calculations. The conformational flexibility of the chiral ligands was found to be an important factor in the selectivity.     

Aλδ-calculus with an algorithmicδ

In this paper we propose a system, based on-calculus, where the restriction of Church's to normal forms is dropped, while the monotony properties are weakened. The main feature of such a system is that the Church-Rosser property is maintained and all provable equalities between closed terms are semidecidable within it.     

ICP-MS multi-element analysis of wine samples - a comparative study of the methodologies used in two laboratories

A comparison of the performance of the methodologies used in two distinct laboratories (Lab A and Lab B) for multi-element analysis in different wines was carried out. ICP-MS apparatus (quadrupole mass analyzers) of different brands as well as different wine pre-treatments were used. At Lab A, a pre-treatment by UV-irradiation was performed. At Lab B, a micro-concentric nebulizer was used for direct analysis of the wine. Twenty-six elements (Li, V, Co, Ni, Cu, Zn, Ga, As, Rb, Sr, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Pb) were measured in common at the two labs in three different wine samples (red and white Bordeaux table wines and Port wine) and the results were compared. The two methodologies provided similar LODs and similar precisions, with RSDs of 0.5-5%, for most of the elements. The recovery percentages were 85-120% at Lab A for the three wines, and 78-119% at Lab B for the Bordeaux wines, validating the accuracy of the methods used. Comparable results were obtained at both labs for ten elements (Li, V, Co, Ni, Cu, Zn, Rb, Sr, Ba, and Pb) in the three selected wines; the differences were lower than 10% in most cases. For REEs, the differences observed were slightly higher, but still in the acceptable range due to the sub-ppb levels involved. The results obtained for As and Ga were not comparable, due to methodological influence. A comparison through linear least-squares adjustment indicated that the results obtained by the two labs were linearly correlated (correlation coefficient =0.997) but statistically different as the slope was slightly, but significantly different from one, for a confidence level of 95% (the intercept was statistically identical to zero in any case). In the future, strictly more identical results can be achieved by using a reference wine sample.     

Is the A-ring of sparteine essential for high enantioselectivity in the asymmetric lithiation-substitution of N-Boc-pyrrolidine?

The simplest chiral portion of sparteine, N,N'-dimethyl-2-endo-methylbispidine, was prepared and evaluated in the asymmetric lithiation-substitution of N-Boc-pyrrolidine. The results indicate that the complete A-ring of sparteine is essential for high levels of asymmetric induction. DFT-QSSR analyses of the diamine/Li(+) complexes and DFT calculations of the pertinent i-PrLi/diamine/N-Boc-pyrrolidine complexes are predictive and provide complementary pictures of the stereochemical features critical to this transformation.     

Self-assembled monolayers on Au microelectrodes

Long chain alkanethiols self-assembled monolayers (SAMs) formed on Au microelectrodes showed higher sensitivity towards defects than the same monolayers on macroelectrodes. The analysis of cyclic voltammetry and electrochemical impedance spectroscopy (EIS) experiments performed on covered microelectrodes were consistent with the formation of pinholes of about 10 nm in diameter. Moreover, the EIS data exhibited a specific behavior that was interpreted invoking the short circuiting of the pinholes impedance by the surrounding surface of the microelectrode in the high frequency domain, whereas in the low frequencies, the surface covered by the SAM was assume to act as an insulator.     

Configuration-interaction calculations for the ground state of OF2, NO 2 − , CN−: Canonical orbitals and exclusive orbitals

The C.I. method is applied to already published double- SCF wave functions for OF₂, NO ₂ ^– and CN^–. All doubly excited configurations are considered. The second order approximation values presented for those cases are compared with the exact energy values in some minor cases. An attempt has been made to improve the rate of convergency of the process by transforming the canonical SCF occupied orbitals into localized ones and the virtual canonical orbitals into a particular type of localized orbitals. These latter show also an intuitively acceptable spatial conformation.

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Zusammenfassung Die CI Methode wird auf bereits bekannte Doppel-Zeta-SCF-Wellenfuntionen für die Systeme OF₂, NO ₂ ^– und CN^– angewandt. Dabei werden alle doppelt angeregten Konfigurationen berücksichtigt. Um die Konvergenz zu verbessern, werden versuchsweise die kanonischen und besetzten SCF-Orbitale in lokalisierte Orbitale und die virtuellen kanonischen Orbitale in einen besonderen Typ von lokalisierten Orbitalen transformiert. Die letzteren zeigen eine besonders geeignete räumliche Anpassung.

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Résumé Pour un calcul de intéraction de configurations, comprenant toutes le configurations à double excitation, on a employé des fonctions d'onde SCF sur une base doublée. Pour le calcul complet on a essayé des formules d'approximation, qu'on a pu vérifier avec le calcul exact sur des cas réduits.Pour améliorer la vélocité de convergence du procés on a transformé les orbitales canoniques SCF en orbitales localisées et aprés on a construit, selon un procedé particulier, des orbitales virtuelles localisées qui montrent une conformation dans l'espace qui est intuitivement satisfaisante.

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Work supported by the Consiglio Nazionale delie Ricerche.