Simultaneous separation by reversed-phase high-performance liquid chromatography and mass spectral identification of anthocyanins and flavonols in Shiraz grape skin

A limitation of large-scale viticultural trials is the time and cost of comprehensive compositional analysis of the fruit by high-performance liquid chromatography (HPLC). In addition, separate methods have generally been required to identify and quantify different classes of metabolites. To address these shortcomings a reversed-phase HPLC method was developed to simultaneously separate the anthocyanins and flavonols present in grape skins. The method employs a methanol and water gradient acidified with 10% formic acid with a run-time of 48 min including re-equilibration. Identity of anthocyanins and flavonols in Shiraz (Vitis vinifera L.) skin was confirmed by mass spectral analysis.     

One-pot enol silane formation-Mukaiyama aldol-type addition to dimethyl acetals mediated by TMSOTf

Various ketones, esters, amides, and thioesters add in high yield to dimethyl acetals in the presence of silyl trifluoromethanesulfonates and an amine base. Acetals derived from aryl, unsaturated, and aliphatic aldehydes are all effective substrates. The reaction proceeds in a single reaction flask, with no purification of the intermediate enol silane necessary.     

Generic muchnik reducibility and presentations of fields

We prove that the subgroup zeta function and the normal zeta function of a finitely generated virtually nilpotent group are finite sums of Euler products of cone integrals over Q and we deduce from this that they have rational abscissa of convergence and some meromorphic continuation. We also define Mal’cev completions of a finitely generated virtually nilpotent group and we prove that the subgroup growth and the normal subgroup growth of the latter are invariants of its Q-Mal’cev completion.     

Dynamics of water molecules in the active-site cavity of human cytochromes P450

We have studied the dynamics of water molecules in six crystal structures of four human cytochromes P450, 2A6, 2C8, 2C9, and 3A4, with molecular dynamics simulations. In the crystal structures, only a few water molecules are seen and the reported sizes of the active-site cavity vary a lot. In the simulations, the cavities are completely filled with water molecules, although with approximately 20% lower density than in bulk water. The 2A6 protein differs from the other three in that it has a very small cavity with only two water molecules and no exchange with the surroundings. The other three proteins have quite big cavities, with 41 water molecules on average in 2C8 and 54-58 in 2C9 and 3A4, giving a water volume of 1500-2100 A3. The two crystal structures of 2C9 differ quite appreciably, whereas those of 3A4 are quite similar. The active-site cavity is connected to the surroundings by three to six channels, through which there is a quite frequent exchange of water molecules (one molecule is exchanged every 30-200 ps), except in 2A6. Most of the channels are observed also in the crystal structures, but two to three channels in each protein open only during the simulations. There are no water molecules close to the heme iron ion in these simulations of the high-spin ferric state (the average distance to the closest water molecule is 3.3-5 A), and there are few ordered water molecules in the active sites, none of which is conserved in all proteins.     

The ratio of the extreme to the sum in a random sequence

For X ₁ , X ₂ , ..., X _n a sequence of non-negative independent random variables with common distribution function F(t), X _(n) denotes the maximum and S _n denotes the sum. The ratio variate R _n  = X _(n) / S _n is a quantity arising in the analysis of process speedup and the performance of scheduling. O’Brien (J. Appl. Prob. 17:539–545, 1980) showed that as n → ∞, R _n →0 almost surely iff is finite. Here we show that, provided either (1) is finite, or (2) 1 − F (t) is a regularly varying function with index ρ < − 1, then . An integral representation for the expected ratio is derived, and lower and upper asymptotic bounds are developed to obtain the result. Since is often known or estimated asymptotically, this result quantifies the rate of convergence of the ratio’s expected value. The result is applied to the performance of multiprocessor scheduling.      

On Genericity and Ershov's Hierarchy

It is natural to wish to study miniaturisations of Cohen forcing suitable to sets of low arithmetic complexity. We consider extensions of the work of Schaeffer [9] and Jockusch and Posner [6] by looking at genericity notions within the Δ₂ sets. Different equivalent characterisations of 1‐genericity suggest different ways in which the definition might be generalised. There are two natural ways of casting the notion of 1‐genericity: in terms of sets of strings and in terms of density functions, as we will see here. While these definitions coincide at the first level of the difference hierarchy, they turn out to differ at other levels. Furthermore, these differences remain when the remainder of the Δ⁰₂ sets are considered. While the string characterization of 1‐genericity collapses at the second level of the difference hierarchy to 2‐genericity, the density function definition gives a very interesting hierarchy at level w and above. Both of these results point towards the deep similarities exhibited by the n‐c.e. degrees for n ≥ 2.     

APN permutations on and Costas arrays

We study PN and APN functions over the integers modulo n. We give some construction techniques based on Costas arrays, which allow us to construct APN permutations on where p is a prime. Although PN permutations do not exist, one set of our functions is very close to being a set of PN permutations.     

Density functional analysis of group 10 organometallic diphosphinito complexes for catalytic formation of C‐P bonds

New group 10 metalloorganic complexes are proposed as the basis of new catalysts for the formation of carbon‐phosphorous bonds. Density functional theory (DFT) is applied, using multiple DFT functionals, to model molecular geometry as well as electron density distribution in the highest occupied molecular orbitals (HOMOs) expected to carry out a reductive catalytic cycle. DFT/M06 analysis predicts a robust planar geometry, regardless of alteration of major components. Precursors for rapid catalyst generation should begin with an electron‐withdrawing monodentate ligand. Palladium and platinum catalysts have lower chemical hardness, but the electron distribution in the HOMO of the nickel‐based catalyst is preferred for reductive catalytic mechanisms. Both electron density and chemical hardness, however, are affected by the choice of metal ion and the composition of the monodentate ligand bound to it. Group 10 metalloorganic complexes are modeled as precursors for generating new catalysts for a minimally wasteful method of forming bonds commonly found in biochemically active compounds. Suitable precursors have an accessible metal center, as well as significant the HOMO/LUMO involvement at the metal center. All complexes studied offer similar geometries, but precursor transformation into catalyst depends on the electron‐withdrawing ligand being exchanged. Catalyst turn over number is predicted to depend primarily on the central metal. © 2016 Wiley Periodicals, Inc.     

Use of CT scans and treatment planning software for validation of the dose component of food irradiation protocols

The challenging problem of estimating the dose delivered to heterogeneous products by radiation modalities of limited penetration can be readily handled by using technologies developed for, and widely used in, radiation therapy applications. In particular, combining CT scanning with radiation treatment planning programs can simulate radiation processing with either photons or electrons, and can provide detailed, high resolution and accurate dose maps for any arbitrary product and package configuration. Such dose maps are an essential part of process validation. Comparison of the simulated dose distributions with measured dose maps verifies the soundness of this approach. The present communication presents results obtained with the simulation technique for a variety of common food items which are likely candidates for radiation processing.