Development of a method based on on-line reversed phase liquid chromatography and gas chromatography coupled by means of an adsorption–desorption interface for the analysis of selected chiral volatile compounds in methyl jasmonate treated strawberries

A method based on the use of the through oven transfer adsorption–desorption (TOTAD) interface in on-line coupling between reversed phase liquid chromatography and gas chromatography (RPLC–GC) for the determination of chiral volatile compounds was developed. In particular, the method was applied to the study of the influence of methyl jasmonate (MJ) treatment on the production and enantiomeric composition of selected aroma compounds in strawberry. The compounds studied were ethyl 2-methylbutanoate, linalool and 4-hydroxy-2,5-dimethyl-3(2H)-furanone (i.e. furaneol), which were examined on days 3, 6 and 9 after treatment. The method developed resulted in relative standard deviations (RSDs) of 21.6%, 8.1% and 9.8% and limits of detection (LD) of 0.04, 0.07 and 0.02 mg/l for ethyl 2-methylbutanoate, linalool and furaneol, respectively. The application of the RPLC–TOTAD–GC method allowed higher levels of ethyl 2-methylbutanoate, linalool and furaneol to be detected, particularly after 9 days of treatment. Besides, MJ demonstrated to affect the enantiomeric distribution of ethyl 2-methylbutanoate. On the contrary, the enantiomeric composition of linalool and furaneol kept constant in both control and MJ-treated strawberries throughout the study. These results are discussed.     

Fast and accurate algorithm for the simulation of NMR spectra of large spin systems

The computational cost for the simulation of NMR spectra grows exponentially with the number of nuclei. Today, the memory available to store the Hamiltonian limits the size of the system that can be studied. Modern computers enable to tackle systems containing up to 13 spins [1], which obviously does not allow to study most molecules of interest in research. This issue can be addressed by identifying groups of spins or fragments that are not or only weakly interacting together, i.e., that only share weakly coupled spin pairs. Such a fragmentation is only permitted in the weak coupling regime, i.e., when the coupling interaction is weak compared to the difference in chemical shift of the coupled spins. Here, we propose a procedure that removes weak coupling interactions in order to split the spin system efficiently and to correct a posteriori for the effect of the neglected couplings. This approach yields accurate spectra when the adequate interactions are removed, i.e., between spins only involved in weak coupling interactions, but fails otherwise. As a result, the computational time for the simulation of 1D spectra grows linearly with the size of the spin system.     

Gold aggregates on silica templates and decorated silica arrays for SERS applications

In this work, we report the fabrication and characterization of size controllable gold nanoparticles (NPs) aggregates for their application in surface enhanced Raman scattering (SERS). Aggregates were prepared using two methodologies: (i) by using silica particles arrays as a template to agglomerate gold NPs between the inter-particle interstices, and (ii) by functionalizing silica particles to be used as support to graft gold nanoparticles and thus to form decorated silica particle arrays. These substrates were used in the detection of Rhodamine 6G producing an enhancement factor (EF) from 10⁴ to 10⁶ that is associated to the increment of hot spot (HS) sites, and the fact that plasmon resonance from aggregates and absorption wavelength of test molecules are closely in resonance with excitation wavelength. The EF was also reduced when the plasmon resonance was red-shifted as a result of the increment of aggregate size. In spite of this, the EF is high enough to make these SERS substrates excellent candidates for sensing applications.     

Stereoselective enzymatic synthesis of monoglucosyl-myo-inositols with in vivo anti-inflammatory activity

The monoglucosyl-inositols α-d-glucopyranosyl-(1→4)-4d-myo-inositol 3 and α-d-glucopyranosyl-(1→1)-1d-myo-inositol 4 were synthesized by a combined enzymatic transglucosylation and hydrolysis strategy, using cyclodextrin glucosyl transferase (CGTase) from Thermoanaerobacter sp., followed by hydrolysis with Aspergillus niger glucoamylase. The glucosides were separated by preparative HPLC and fully characterized by extensive 1D and 2D NMR studies. The structure of the regioisomer 4 was confirmed by X-ray crystallography of its perbenzoylated derivative 4a. Both isomers demonstrated in vivo anti-inflammatory activity at comparative levels to corticosterone on mouse ear oedema induced by 12-O-tetradecanoylphorbol-13-acetate (TPA) and in rat hind paw oedema induced by carrageenan.     

Statistical testing of optimality conditions in multiresponse simulation-based optimization

This article studies simulation-based optimization with multiple outputs. It assumes that the simulation model has one random objective function and must satisfy given constraints on the other random outputs. It presents a statistical procedure for testing whether a specific input combination (proposed by some optimization heuristic) satisfies the Karush–Kuhn–Tucker (KKT) first-order optimality conditions. The article focuses on “expensive” simulations, which have small sample sizes. The article applies the classic t test to check whether the specific input combination is feasible, and whether any constraints are binding; next, it applies bootstrapping (resampling) to test the estimated gradients in the KKT conditions. The new methodology is applied to three examples, which gives encouraging empirical results.     

On higher order Stickelberger-type theorems

We discuss an explicit refinement of Rubin?s integral version of Stark?s conjecture. We prove that this refinement is a consequence of the relevant case of the Equivariant Tamagawa Number Conjecture of Burns and Flach, hence obtaining a full proof in several important cases. We also derive several explicit consequences of this refinement concerning the annihilation as Galois modules of ideal class groups by explicit elements constructed from the values of higher order derivatives of Dirichlet L-functions. We finally describe the relation between our approach and those found in recent work of Emmons and Popescu and of Buckingham.     

A nonlinear programming algorithm based on non-coercive penalty functions

 We consider first the differentiable nonlinear programming problem and study the asymptotic behavior of methods based on a family of penalty functions that approximate asymptotically the usual exact penalty function. We associate two parameters to these functions: one is used to control the slope and the other controls the deviation from the exact penalty. We propose a method that does not change the slope for feasible iterates and show that for problems satisfying the Mangasarian-Fromovitz constraint qualification all iterates will remain feasible after a finite number of iterations. The same results are obtained for non-smooth convex problems under a Slater qualification condition. Received: September 2000 / Accepted: June 2002 Published online: March 21, 2003 Research partially supported by CAPES, Brazil Research partially supported by CNPq, Brazil, and CONICIT, Venezuela. Mathematics Subject Classification (1991): 20E28, 20G40, 20C20     

Speciation of Cr(VI)/Cr(III) by electrothermal atomisation AAS after electrodeposition on a L'vov platform

Summary The pyrolysed graphite L'vov platform of a tube furnace is considered as an electrode for the electrodeposition and speciation of chromium by electrothermal atomisation atomic absorption spectrometry (ETA-AAS). Firstly, a preliminary study of the Cr(VI)/Cr(III) voltammetric behavior at pH 4.70 on a glassy-carbon electrode is carried out. Secondly, the L'vov platform is used as a cathodic macro-electrode for the selective preconcentration of Cr(VI)/Cr(III) on a mercury film. Speciation of Cr(VI)/Cr(III) is carried out on the basis of the electrolysis potential (E_e): at pH 4.70 and E_e=–0.30 V, only Cr(VI) is reduced to Cr(III) and accumulated as Cr(OH)₃ by adsorption on a mercury film; at E_e=–1.80 V both Cr(VI) and Cr(III) are accumulated forming an amalgam with added mercury(II) ions. Once the film has been formed, the platform is transferred to a graphite tube to atomise the element. The reliability of the method was tested for the speciation of chromium in natural waters and it proves to be highly sensitive thanks to the electroanalytical step. In all samples, the Cr(VI) concentration was less than the detection limit (0.15 ng ml^–1), and the concentration of Cr(III) agrees with those of total chromium. The analytical recovery of Cr(VI) added to water samples [3.50 ng ml^–1 of Cr(VI)] was 105±6.2%.     

A package for symbolic solution of real functional equations of real variables

Summary This paper discusses the problems associated with the symbolic treatment of functional equations and presents a Mathematica package for the solution of real functional equations of real variables. The package includes a minimal basic database which contains a reduced set of functional equations with its four components: equation, domain, class and the corresponding solution. The word minimal is used in the sense that any equation that is solvable by the system using non-searching methods is excluded from the database. The package incorporates a searching algorithm which can solve functional equations independently of their notation and their algebraic representation. Not only general solutions but particular and candidate solutions are dealt with. This implies a careful analysis of domains and classes. The package includes some methods for solving functional equations, which are used when the input functional equations are not found in the database. Some methods have been implemented internally and some are in an external package. Finally, some examples illustrate the use of the package.