Thorough evaluation of the validity of conventional enantio-gas chromatography in the analysis of volatile chiral compounds in mandarin essential oil: A comparative investigation with multidimensional gas chromatography

The present research is focused on the determination of the enantiomeric distribution of chiral compounds, contained in mandarin essential oils, by means of conventional chiral gas chromatography with flame ionization detection (enantio-GC-FID); the results attained were compared with those derived from heart-cutting multidimensional GC-mass spectrometry (MDGC/MS), to evaluate the reliability of the monodimensional technique as a tool for quality control. The Deans-switch MDGC system was equipped with two GC ovens, which were connected via a heated transfer line, a flame ionization detector (FID1) in the first dimension and a quadrupole MS as second-dimension detector. The a priori knowledge of potential co-elutions concerning target compounds (an enantiomer and an interfering compound), when using enantio-GC-FID, could enable the use of corrected enantiomer excess values. Correction factors could be calculated through a preliminary GC-FID analysis (using an apolar column), considering the peak areas of the known interferences. The method used for the calculation of a so-called “coelution correction factor” is described, along with some examples.     

First hyperpolarizability of polymethineimine with long-range corrected functionals

Using the long-range corrected (LC) density functional theory (DFT) scheme introduced by Iikura et al. [J. Chem. Phys. 115, 3540 (2001)] and the Coulomb-attenuating model (CAM-B3LYP) of Yanai et al. [Chem. Phys. Lett. 393, 51 (2004)], we have calculated the longitudinal dipole moments and static electronic first hyperpolarizabilities of increasingly long polymehtineimine oligomers. For comparison purposes Hartree-Fock (HF), Moller-Plesset perturbation theory (MP2), and conventional pure and hybrid functionals have been considered as well. HF, generalized gradient approximation (GGA), and conventional hybrids provide too large dipole moments for long oligomers, while LC-DFT allows to reduce the discrepancy with respect to MP2 by a factor of 3. For the first hyperpolarizability, the incorrect evolution with the chain length predicted by HF is strongly worsened by BLYP, Perdew-Burke-Ernzerhof (PBE), and also by B3LYP and PBE0. On the reverse, LC-BLYP and LC-PBE hyperpolarizabilities are correctly predicted to be positive (but for the two smallest chains). Indeed, for medium and long oligomers LC hyperpolarizabilities are slightly smaller than MP2 hyperpolarizabilities, as it should be. CAM-B3LYP also strongly improves the B3LYP results, though a bit less impressively for small chain lengths. The present study demonstrates the efficiency of long-range DFT, even in very pathological cases.     

Self-Assembling of cytosine nucleoside into triply-bound dimers in acid Media. A comprehensive evaluation of proton-bound pyrimidine nucleosides by electrospray tandem mass spectrometry,X-rays diffractometry,and theoretical calculations

Electrospray tandem mass spectrometry (ESI-MS/MS) is used to evaluate the assembling of cytosine and thymine nucleosides in the gas phase, through the formation of hydrogen bonded supermolecules. Mixtures of cytidine analogues and homologues deliver in the gas phase proton-bound heterodimers stabilized by multiple interactions, as proven by the kinetics of their dissociation into the corresponding protonated monomers. Theoretical calculations, performed on initial structures of methylcytosine homodimers available in the literature, converged to a minimized structure whereby the two pyrimidine rings interact through the formation of three hydrogen bonds of similar energy. The crystallographic data here reported show the equivalency of the two interacting pyrimidines which is attributable to the presence of an inversion center. Thymine and uracil pyrimidyl nucleosides form, by ESI, gaseous proton-bound dimers. The kinetic of their dissociation into the related protonated monomers shows that the nucleobases are weekly interacting through a single hydrogen bond. The minimized structure of the protonated heterodimer formed by thymine and N-1-methylthymine confirmed the existence of mainly one hydrogen bond which links the two nucleobases through the O4 oxygens. No crystallographic data exists on thymine proton-bound species, nor have we been able to obtain these aggregates in the solid phase. The gaseous phase, under high vacuum conditions, seems therefore a suitable environment where vanishing structures produced by ESI can be studied with a good degree of approximation.     

A computational study of [2.2]cyclophanes

A computational study of isomeric [2.2]cyclophanes, namely [2.2]paracyclophane 1, [2.2]metacyclophane 2, and [2.2]metaparacyclophane 3, has been carried out. For 1, geometry optimizations performed by various methods at different basis sets showed that MP2/6-31+G(d,p) and B3PW91/6-31+G(d,p) provide the best results in comparison to the X-ray data. Compound 1 has D(2) symmetry with distorted bridges. A conformational search was performed for [2.2]cyclophanes 2 and 3. Each cyclophane exists in two conformations which have different energies in the case of 3 but are degenerate in the case of 2. Relative energies and strain energies at the bridges follow the same order, indicating that the relief of bridge tension and repulsion between pi clouds are determining factors for the stability of [2.2]cyclophanes. Through a decomposition of strain energy, it can be concluded that both the rings or the bridges can absorb strain, but it depends on the conformer of butane that is considered in the calculation of SE(br). Changes in aromaticity of these compounds were evaluated by NICS and HOMA and were compared with benzene and xylenes dimers as models. Despite distortions from planarity and shortening and lengthening of the C-C bonds relative to the mean, the phenyl rings are aromatic. NICS suggests a concentration of electronic density between the rings as a result of bridging process. Computed MK, NPA, and GAPT charges were compared for the isomeric cyclophanes. The GIAO chemical shifts were calculated and indicate that 1 has a larger diamagnetic anisotropy than the other isomers.     

Structure-based approach for identification of novel phenylboronic acids as serine-β-lactamase inhibitors

β-Lactamases are bacterial enzymes conferring resistance to β-lactam antibiotics in clinically-relevant pathogens, and represent relevant drug targets. Recently, the identification of new boronic acids (i.e. RPX7009) paved the way to the clinical application of these molecules as potential drugs. Here, we screened in silico a library of ~1400 boronic acids as potential AmpC β-lactamase inhibitors. Six of the most promising candidates were evaluated in biochemical assays leading to the identification of potent inhibitors of clinically-relevant β-lactamases like AmpC, KPC-2 and CTX-M-15. One of the selected compounds showed nanomolar K _i value with the clinically-relevant KPC-2 carbapenemase, while another one exhibited broad spectrum inhibition, being also active on Enterobacter AmpC and the OXA-48 class D carbapenemase.     

Enantioselective cycloadditions of 2-alkenoylpyridine-N-oxides catalysed by a bis(oxazoline)/Cu(II) complex: structure of the reactive intermediate

Diels–Alder and 1,3‐dipolar cycloadditions involving (E)‐3‐aryl‐1‐(pyridin‐2‐yl‐N‐oxide)prop‐2‐en‐1‐ones as the 2π components are efficiently catalysed by bis(oxazoline)–Cu^II complexes. The cycloadducts are obtained in quantitative yields with up to 98 % ee; absolute configurations were determined by X‐ray analysis. The structure of the reactive complex, determined by X‐ray analysis, is fully consistent with the stereochemical outcome of the catalysed process (approach of the diene or nitrone to the less hindered face of the coordinated pyridine‐N‐oxide derivative).     

Redox processes of ruthenium (II) polypyridine complexes induced by fast-atom bombardment mass spectrometry

Fast-atom bombardment (FAB) mass spectrometry in the negative ionization mode enables the sputtering into the gas phase of the ruthenium complexes [Ru(2,2′-bipyridine[bpy])₂(2,5-bis) (pyrydil)pyrazine[dpp])](PF₆)₂; [Ru(bpy)₂,(2,3dpp)](PF₆)₂;[Ru(bpy)₂,(2,3-dpp-Me)]( PF₆)₃; and [Ru(bpy)₂(?-2,3-dpp)]₂ RuCl₂(PF₆)₄ as intact radical anions. These data, combined with those avaiiable from the positive FAB spectra allow a full characterization of the analytes.     

Unimolecular reaction sequence in the electron impact induced fragmentation of some methylenoxazolidinones

The unimolecular processes of some methylenoxazolidinones bombarded in the gas phase by electrons have been investigated by MIKE analysis, precise mass measurements and isotopic labelling studies. The overall delocalisation effect of the substitution on the nitrogen contained has been ascertained through the study of the reaction mechanism and of the possible reacting ionic structures.     

Recent advances with π-conjugated salen systems

Schiff base ligands have long been successfully employed as ligands in combination with various metals to give catalysts capable of realizing a variety of synthetic transformations. One of the most widely used Schiff base ligands, the "salen" ligand, has been extensively researched. Recently, there has been increased interest in π-conjugated salen systems, known as "salphen" ligands, as a result of the differences in reactivity of the complexes in catalytic applications compared with the salen analogues. Complexes of salphen ligands display interesting photophysical and supramolecular properties which are not always observed with salen systems as a result of their π-conjugation. This tutorial review therefore describes the most significant advances recently made with salphen and related π-conjugated ligand systems.     

Electronic structure of uracil-like nucleobases adsorbed on Si(001): uracil,thymine and 5-fluorouracil

We study the electronic properties of the Si(001):Uracil, Si(001):Thymine, andSi(001):5-Fluorouracil systems, focusing on the Si dimer-bridging configuration withadsorption governed by carbonyl groups. While the overall structural and electronicproperties are similar, with small differences due to chemical substitutions, much largereffects on the surface band dispersion and bandgap show up as a function of the molecularorientation with respect to the surface. An off-normal orientation of the molecular planesis favored, showing larger bandgap and lower total energy than the upright position. Wealso analyze the localization of gap-edge occupied and unoccupied surface states.