Analytical characterization of wine and its precursors by capillary electrophoresis

The accurate determination of marker chemical species in grape, musts, and wines presents a unique analytical challenge with high impact on diverse areas of knowledge such as health, plant physiology, and economy. Capillary electromigration techniques have emerged as a powerful tool, allowing the separation and identification of highly polar compounds that cannot be easily separated by traditional HPLC methods, providing complementary information and permitting the simultaneous analysis of analytes with different nature in a single run. The main advantage of CE over traditional methods for wine analysis is that in most cases samples require no treatment other than filtration. The purpose of this article is to present a revision on capillary electromigration methods applied to the analysis of wine and its precursors over the last decade. The current state of the art of the topic is evaluated, with special emphasis on the natural compounds that have allowed wine to be considered as a functional food. The most representative revised compounds are phenolic compounds, amino acids, proteins, elemental species, mycotoxins, and organic acids. Finally, a discussion on future trends of the role of capillary electrophoresis in the field of analytical characterization of wines for routine analysis, wine classification, as well as multidisciplinary aspects of the so-called "from soil to glass" chain is presented.     

A 1,6-ring closure mechanism for (+)-δ-cadinene synthase?

Recombinant (+)-δ-cadinene synthase (DCS) from Gossypium arboreum catalyzes the metal-dependent cyclization of (E,E)-farnesyl diphosphate (FDP) to the cadinane sesquiterpene δ-cadinene, the parent hydrocarbon of cotton phytoalexins such as gossypol. In contrast to some other sesquiterpene cyclases, DCS carries out this transformation with >98% fidelity but, as a consequence, leaves no mechanistic traces of its mode of action. The formation of (+)-δ-cadinene has been shown to occur via the enzyme-bound intermediate (3R)-nerolidyl diphosphate (NDP), which in turn has been postulated to be converted to cis-germacradienyl cation after a 1,10-cyclization. A subsequent 1,3-hydride shift would then relocate the carbocation within the transient macrocycle to expedite a second cyclization that yields the cadinenyl cation with the correct cis stereochemistry found in (+)-δ-cadinene. An elegant 1,10-mechanistic pathway that avoids the formation of (3R)-NDP has also been suggested. In this alternative scenario, the final cadinenyl cation is proposed to be formed through the intermediacy of trans, trans-germacradienyl cation and germacrene D. In addition, an alternative 1,6-ring closure mechanism via the bisabolyl cation has previously been envisioned. We report here a detailed investigation of the catalytic mechanism of DCS using a variety of mechanistic probes including, among others, deuterated and fluorinated FDPs. Farnesyl diphosphate analogues with fluorine at C2 and C10 acted as inhibitors of DCS, but intriguingly, after prolonged overnight incubations, they yielded 2F-germacrene(s) and a 10F-humulene, respectively. The observed 1,10-, and to a lesser extent, 1,11-cyclization activity of DCS with these fluorinated substrates is consistent with the postulated macrocyclization mechanism(s) en route to (+)-δ-cadinene. On the other hand, mechanistic results from incubations of DCS with 6F-FPP, (2Z,6E)-FDP, neryl diphosphate, 6,7-dihydro-FDP, and NDP seem to be in better agreement with the potential involvement of the alternative biosynthetic 1,6-ring closure pathway. In particular, the strong inhibition of DCS by 6F-FDP, coupled to the exclusive bisabolyl- and terpinyl-derived product profiles observed for the DCS-catalyzed turnover of (2Z,6E)-farnesyl and neryl diphosphates, suggested the intermediacy of α-bisabolyl cation. DCS incubations with enantiomerically pure [1-(2)H(1)](1R)-FDP revealed that the putative bisabolyl-derived 1,6-pathway proceeds through (3R)-nerolidyl diphosphate (NDP), is consistent with previous deuterium-labeling studies, and accounts for the cis stereochemistry characteristic of cadinenyl-derived sesquiterpenes. While the results reported here do not unambiguously rule in favor of 1,6- or 1,10-cyclization, they demonstrate the mechanistic versatility inherent to DCS and highlight the possible existence of multiple mechanistic pathways.     

Associated production evidence against Higgs impostors and anomalous couplings

We analyze bicovariant differential calculus on κ-Minkowski spacetime. It is shown that corresponding Lorentz generators and noncommutative coordinates compatible with bicovariant calculus cannot be realized in terms of commutative coordinates and momenta. Furthermore, κ-Minkowski space and NC forms are constructed by twist related to a bicrossproduct basis. It is pointed out that the consistency condition is not satisfied. We present the construction of κ-deformed coordinates and forms (super-Heisenberg algebra) using extended twist. It is compatible with bicovariant differential calculus with κ-deformed $\mathfrak{igl}(4)$ -Hopf algebra. The extended twist leading to κ-Poincaré-Hopf algebra is also discussed.     

Lanthanide-Containing 2,2′-Bipyridine Bridged Urea Cross-Linked Polysilsesquioxanes

Urea-based bis-silylated 2,2′–Bipyridine (bpy) organic–inorganic hybrids incorporating different lanthanide (Ln³⁺) ions (Eu³⁺, Gd³⁺, Tb³⁺ or Eu³⁺/Tb³⁺) were obtained by the sol–gel process. The structure and the emission characteristics of the hybrids were ascertained using X-ray diffraction, nuclear magnetic resonance, Fourier transform infrared spectroscopy, photoluminescence, and quantum yield measurements. The hybrids feature both the emission of the host and the Eu³⁺ and/or Tb³⁺ transitions allowing a fine-tuning of the color from the blue to the red, orange, or green spectral regions. Bpy-to-Ln³⁺ and Tb³⁺-to-Eu³⁺ energy transfer mechanisms are demonstrated and the hybrids present slightly distinct Ln³⁺ coordination spheres due to the different bpy/Ln³⁺ ratios.     

Quantifying the sorting efficiency of self-propelled run-and-tumble swimmers by geometrical ratchets

Suitable asymmetric microstructures can be used to control the direction of motion in microorganism populations. This rectification process makes it possible to accumulate swimmers in a region of space or to sort different swimmers. Here we study numerically how the separation process depends on the specific motility strategies of the microorganisms involved. Crucial properties such as the separation efficiency and the separation time for two bacterial strains are precisely defined and evaluated. In particular, the sorting of two bacterial populations inoculated in a box consisting of a series of chambers separated by columns of asymmetric obstacles is investigated. We show how the sorting efficiency is enhanced by these obstacles and conclude that this kind of sorting can be efficiently used even when the involved populations differ only in one aspect of their swimming strategy.     

Coherent sequences of polynomial ideals on Banach spaces

This article deals with the relationship between an operator ideal and its natural polynomial extensions. We define the concept of coherent sequence of polynomial ideals and also the notion of compatibility between polynomial and operator ideals. We study the stability of these properties for maximal and minimal hulls, adjoint and composition ideals. We also relate these concepts with conditions on the underlying tensor norms (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Gold‐Catalyzed Reactions of 1,5‐ and 1,6‐Enynes with Carbonyl Compounds: Cycloaddition vs. Metathesis

Gold and rings : The gold(I)‐catalyzed addition of aldehydes to 1,6‐enynes gives 1,3‐dienes, by a cycloaddition/fragmentation process. 1,5‐Enynes react with aldehydes and ketones by the 5‐endo‐dig pathway to give the corresponding cycloadducts.

     

Formation of unusual iridabenzene and metallanaphthalene containing electron-withdrawing substituents

A new route to irida-aromatic derivatives which consists of the oxidation of bicyclic compounds has been disclosed. The iridanaphthalene 3 experiences hydrolytic cleavage of the Ir-carboxylate moiety regenerating the bicyclic structure 5, whereas treatment of 5 with ClC(O)CO2Me yields back the metalla-aromatic 3.     

A note on Halley's method

Summary We introduce the degree of logarithmic convexity which provides a measure of the convexity of a function at each point. Making use of this concept we obtain a new theorem of global convergence for Halley's method.