On the parallel between normality and extremal disconnectedness

Several familiar results about normal and extremally disconnected (classical or pointfree) spaces shape the idea that the two notions are somehow dual to each other and can therefore be studied in parallel. This paper investigates the source of this ‘duality’ and shows that each pair of parallel results can be framed by the ‘same’ proof. The key tools for this purpose are relative notions of normality, extremal disconnectedness, semicontinuity and continuity (with respect to a fixed class of complemented sublocales of the given locale) that bring and extend to locale theory a variety of well-known classical variants of normality and upper and lower semicontinuities in an illuminating unified manner. This approach allows us to unify under a single localic proof all classical insertion, as well as their corresponding extension results.     

Nonlinear reduced-order model for vertical sloshing by employing neural networks

The aim of this work is to provide a reduced-order model to describe the dissipative behavior of nonlinear vertical sloshing involving Rayleigh–Taylor instability by means of a feed forward neural network. A 1-degree-of-freedom system is taken into account as representative of fluid–structure interaction problem. Sloshing has been replaced by an equivalent mechanical model, namely a boxed-in bouncing ball with parameters suitably tuned with performed experiments. A large data set, consisting of a long simulation of the bouncing ball model with pseudo-periodic motion of the boundary condition spanning different values of oscillation amplitude and frequency, is used to train the neural network. The obtained neural network model has been included in a Simulink®  environment for closed-loop fluid–structure interaction simulations showing promising performances for perspective integration in complex structural system.

     

Comparative metabolomic study of transgenic versus conventional soybean using capillary electrophoresis-time-of-flight mass spectrometry

In this work, capillary electrophoresis-time-of-flight mass spectrometry (CE-TOF-MS) is proposed to identify and quantify the main metabolites found in transgenic soybean and its corresponding non-transgenic parental line both grown under identical conditions. The procedure includes optimization of metabolites extraction, separation by CE, on-line electrospray-TOF-MS analysis and data evaluation. A large number of extraction procedures and background electrolytes are tested in order to obtain a highly reproducible and sensitive analytical methodology. Using this approach, a large number of metabolites were tentatively identified based on the high mass accuracy provided by TOF-MS analyzer, together with the isotopic pattern and expected electrophoretic mobility of these compounds. In general, the same metabolites and in similar amounts were found in the conventional and transgenic variety. However, significant differences were also observed in some specific cases when the conventional variety was compared with its corresponding transgenic line. The selection of these metabolites as possible biomarkers of transgenic soybean is discussed, although a larger number of samples need to be analyzed in order to validate this point. It is concluded that metabolomic procedures based on CE-MS can open new perspectives in the study of transgenic foods in order to corroborate (or not) the equivalence with their conventional counterparts.     

The separation of the enantiomers of diquats by capillary electrophoresis using randomly sulfated cyclodextrins as chiral selectors

Diquats, derivatives of the widely used herbicide diquat, represent a new class of functional organic molecules. A combination of their special electrochemical properties and axial chirality could potentially result in their important applications in supramolecular chemistry, chiral catalysis, and chiral analysis. However, prior to their practical applications, the diquats have to be prepared in enantiomerically pure forms and the enantiomeric purity of their P- and M-isomers has to be checked. Hence, a chiral capillary electrophoresis (CE) method has been developed and applied for separation of P- and M-enantiomers of 11 new diquats. Fast and better than baseline CE separations of enantiomers of all 11 diquats within a short time 5–7 min were achieved using acidic buffer, 22 mM NaOH, 35 mM H₃PO₄, pH 2.5, as a background electrolyte, and 6 mM randomly sulfated α-, β-, and γ-cyclodextrins as chiral selectors. The most successful selector was sulfated γ-cyclodextrin, which baseline separated the enantiomers of all 11 diquats, followed by sulfated β-cyclodextrin and sulfated α-cyclodextrin, which baseline separated enantiomers of 10 and nine diquats, respectively. Using this method, a high enantiopurity degree of the isolated P- and M-enantiomers of three diquats with a defined absolute configuration was confirmed and their migration order was identified.     

Induced Riemannian structures on null hypersurfaces

Given a null hypersurface L of a Lorentzian manifold, we construct a Riemannian metric on it from a fixed transverse vector field ζ. We study the relationship between the ambient Lorentzian manifold, the Riemannian manifold and the vector field ζ. As an application, we prove some new results on null hypersurfaces, as well as known ones, using Riemannian techniques.     

Stannylated polynorbornenes as new reagents for a clean Stille reaction

New functionalized polynorbornenes have been obtained in good yields by vinylic copolymerization of norbornene with a (norbornenyl)SnBu(2)Cl monomer, catalyzed by [Ni(C(6)F(5))(2)(SbPh(3))(2)]. Subsequent functionalization produces a wide variety of polymers with different --SnBu(2)R groups (R=aryl, vinyl, alkynyl). The polymers can be used as R-transfer reagents in Stille couplings, thereby providing easy workup and separation of the polymeric tin byproducts from the coupling products. Tin contents of around 0.05 wt % are found in the Stille products. The stannylated polymers can be recycled and reused with good efficiency.     

Solvent effects on the spectroscopic properties of 4-hexylresorcinol

A study was made on the spectroscopic properties of 4-hexylresorcinol (4HR) in several solvents at room temperature. Absorption and emission spectra were slightly affected by solvent polarity. Stokes' shifts were small (approximately 3000 cm(-1)) and the fluorescence quantum yields varied between 0.05 and 0.68, depending on the solvent. The spectral shifts were correlated with different solvent scales. Multiple regression analysis indicates that both non-specific solute-solvent interactions as well as specific solute-solvent interactions (such as hydrogen bonding) play an important role in the position of the Stokes' shift and on the fluorescence quantum yield in the solvents under study.     

Nitrosation of N-methylhydroxylamine by nitroprusside. A kinetic and mechanistic study

The kinetics of the reaction between aqueous solutions of Na(2)[Fe(CN)(5)NO].2H(2)O (sodium pentacyanonitrosylferrate(ii), nitroprusside, SNP) and MeN(H)OH (N-methylhydroxylamine, MeHA) has been studied by means of UV-vis spectroscopy, using complementary solution techniques: FTIR/ATR, EPR, mass spectrometry and isotopic labeling ((15)NO), in the pH range 7.1-9.3, I = 1 M (NaCl). The main products were N-methyl-N-nitrosohydroxylamine (MeN(NO)OH) and [Fe(CN)(5)H(2)O](3-), characterized as the [Fe(CN)(5)(pyCONH(2))](3-) complex (pyCONH(2) = isonicotinamide). No reaction occurred with Me(2)NOH (N,N-dimethylhydroxylamine, Me(2)HA) as nucleophile. The rate law was: R = k(exp) [Fe(CN)(5)NO(2-)] x [MeN(H)OH] x [OH(-)], with k(exp) = 1.6 +/- 0.2 x 10(5) M(-2) s(-1), at 25.0 degrees C, and DeltaH(#) = 34 +/- 3 kJ mol(-1), DeltaS(#) = -32 +/- 11 J K(-1) mol(-1), at pH 8.0. The proposed mechanism involves the formation of a precursor associative complex between SNP and MeHA, followed by an OH(-)-assisted reversible formation of a deprotonated adduct, [Fe(CN)(5)(N(O)NMeOH)](3-), and rapid dissociation of MeN(NO)OH. In excess SNP, the precursor complex reacts through a competitive one-electron-transfer path, forming the [Fe(CN)(5)NO](3-) ion with slow production of small quantities of N(2)O. The stoichiometry and mechanism of the main adduct-formation path are similar to those previously reported for hydroxylamine (HA) and related nucleophiles. The nitrosated product, MeN(NO)OH, decomposes thermally at physiological temperatures, slowly yielding NO.