Mass spectrometric studies of 2-aryl-5-acetylthiazole derivatives

Electron ionisation mass spectrometry was usefully used to characterize structurally 2-aryl-5-acetylthiazole derivatives in the gas phase. The compounds show characteristic fragmentation pathways depending on the chemical nature of the substituent at position 2, consisting mainly in the cleavage of both the 1,2- and 3,4-bonds of the thiazole ring. Liquid secondary ion mass spectrometry was applied to study the effects of protonation on the gas-phase unimolecular reactions of this class of compound. Tandem mass spectrometric experiments, carried out on molecular and protonated molecular ions, and also on fragment ions produced in the source, allowed the elucidation of gas-phase decompositions of low-internal energy ions.     

Gas‐phase doubly charged complexes of cyclic peptides with copper in +1, +2 and +3 formal oxidation states: formation,structures and electron capture dissociation

Copper complexes with a cyclic D‐His‐β‐Ala‐L‐His‐L‐Lys and all‐L‐His‐β‐Ala‐His‐Lys peptides were generated by electrospray which were doubly charged ions that had different formal oxidation states of Cu(I), Cu(II) and Cu(III) and different protonation states of the peptide ligands. Electron capture dissociation showed no substantial differences between the D‐His and L‐His complexes. All complexes underwent peptide cross‐ring cleavages upon electron capture. The modes of ring cleavage depended on the formal oxidation state of the Cu ion and peptide protonation. Density functional theory (DFT) calculations, using the B3LYP with an effective core potential at Cu and M06‐2X functionals, identified several precursor ion structures in which the Cu ion was threecoordinated to pentacoordinated by the His and Lys side‐chain groups and the peptide amide or enolimine groups. The electronic structure of the formally Cu(III) complexes pointed to an effective Cu(I) oxidation state with the other charge residing in the peptide ligand. The relative energies of isomeric complexes of the [Cu(c‐HAHK + H)]²⁺ and [Cu(c‐HAHK ? H)]²⁺ type with closed electronic shells followed similar orders when treated by the B3LYP and M06‐2X functionals. Large differences between relative energies calculated by these methods were obtained for open‐shell complexes of the [Cu(c‐HAHK)]²⁺ type. Charge reduction resulted in lowering the coordination numbers for some Cu complexes that depended on the singlet or triplet spin state being formed. For [Cu(c‐HAHK ? H)]²⁺ complexes, solution H/D exchange involved only the N–H protons, resulting in the exchange of up to seven protons, as established by ultra‐high mass resolution measurements. Contrasting the experiments, DFT calculations found the lowest energy structures for the gas‐phase ions that were deprotonated at the peptide C_α positions. Copyright © 2012 John Wiley & Sons, Ltd.     

An Algorithm for the Modular Decomposition of Hypergraphs

We propose an O(n⁴) algorithm to build the modular decomposition tree of hypergraphs of dimension three and show how this algorithm can be generalized to compute in O(n^{3k − 5}) time the decomposition of hypergraphs of any fixed dimension k.     

A simple method for timing an XFEL source to high-power lasers

We propose a technique for timing an X-ray free-electron laser (XFEL) to a high-power conventional laser with femtosecond accuracy, yielding the relative jitter between pump and X-ray probe, and allowing sorting of experimental results over a certain time window. The same electron bunch is used to produce both an XFEL pulse and an ultrashort optical pulse by means of an optical radiator downstream of the X-ray undulator. Being produced by the same electron bunch, these pulses are perfectly synchronized. Cross-correlation techniques will allow to determine relative jitter between the optical pulse (and, thus, the XFEL pulse) and a pulse from an external pump-laser. Technical realization of the proposed timing scheme uses an optical-replica synthesizer setup to be installed after the final bunch-compression stage of the XFEL for electron bunch diagnostics purposes. A number of critical issues are quantitatively analyzed.     

Effective Dynamics for Bloch Electrons: Peierls Substitution and Beyond

We consider an electron moving in a periodic potential and subject to an additional slowly varying external electrostatic potential, (x), and vector potential A(x), with x ^d and 1. We prove that associated to an isolated family of Bloch bands there exists an almost invariant subspace of L ² ( ^d ) and an effective Hamiltonian governing the evolution inside this subspace to all orders in . To leading order the effective Hamiltonian is given through the Peierls substitution. We explicitly compute the first order correction. From a semiclassical analysis of this effective quantum Hamiltonian we establish the first order correction to the standard semiclassical model of solid state physics.     

Antibacterial and Chemical Characterization of Silica-Quercetin-PEG Hybrid Materials Synthesized by Sol–Gel Route

This paper aims to synthesize, via the sol–gel method, a biomaterial usable in the medical field. Here, the silica-PEG-quercetin system was evaluated in relation to the different concentrations of PEG (0, 6, 12, 24, 50 wt%) and quercetin (0, 5, 10, 15 wt%), respectively. In addition, Fourier Transform-Infrared spectroscopy (FT-IR), Scanning Electron Microscopy (SEM), and Kirby–Bauer analyses were performed. FT-IR was used to evaluate the hybrid formation and the influence of both PEG and Quercetin in the hybrid synthesized materials, SEM was used to evaluate the morphological properties, while the Kirby–Bauer test was used to understand the ability of the materials to inhibit the growth of the assayed bacterial strains (Escherichia coli, Pseudomonas aeruginosa, Enterococcus faecalis, and Staphylococcus aureus).     

Polynuclear metal complexes of ligands containing phenolic units

The coordination properties of a selected series of acyclic and macrocyclic ligands containing one or more phenolic groups are explored. The formation of polynuclear metal complexes was only considered highlighting the key role played by the phenoxide oxygen atom in binding two metal centres in a bridge disposition. This arrangement allows two metal ions to stay close each other and consequently these dinuclear centres are able to mimic many biological sites, especially those where the two metals can cooperate to form an active centre. Catalytic properties of these polynuclear complexes, when studied, have been reported. Also some of the numerous heterodinuclear metal complexes that have been synthesized are here reviewed, included several crystal structures.     

Potential of membrane distillation in seawater desalination: Thermal efficiency,sensitivity study and cost estimation

In this work, an extensive analysis on direct contact membrane distillation (DCMD) performance was developed to estimate the mass flux and the heat efficiency, considering transport phenomena, membrane structural properties and most sensitive process parameters, with the aim to provide optimization guidelines for materials and methods. The results showed that an increase of the temperature gradient resulted in the enhancement of both transmembrane flux and thermal efficiency. The investigation of the effects of membrane properties confirmed that better DCMD performance was achieved when using polymeric membranes characterized by low thermal conductivity (flux and thermal efficiency declined by 26% and 50%, respectively, when increasing thermal conductivity from 0.1 to 0.5 W/m K), and high porosity. An optimal thickness value (around 0.7 mm) was identified when operating at low temperature gradient (<5 °C). However, at higher temperature gradient (>10 °C), increasing the membrane thickness from 0.25 to 1.55 mm resulted in a flux decay of about 70% without a significant improvement in thermal efficiency.     

Analytic-non-integrability of an integrable analytic Hamiltonian system

We introduce the polynomial Hamiltonian and we prove that the associated Hamiltonian system is Liouville-C^∞-integrable, but fails to be real-analytically integrable in any neighbourhood of an equilibrium point. The proof only uses power series expansions, and is elementary.