HS-SPME-GC×GC-qMS volatile metabolite profiling of Chrysolina herbacea frass and Mentha spp. leaves

Headspace solid-phase microextraction (HS-SPME) comprehensive two-dimensional (2D) gas chromatography combined with quadrupole-mass spectrometry (GC×GC-qMS) with dedicated comparative data elaboration was applied to separate chemical patterns arising from the interaction between some Mentha species and the herbivore Chrysolina herbacea, also known as the mint bug. Upon feeding on different Mentha species (Mentha spicata L., Mentha × piperita L. and Mentha longifolia L.), C. herbacea produced frass (faeces) which were characterized by a typical volatile fraction. HS-SPME GC×GC-qMS analysis of the complex volatile fraction of both mint leaf and C. herbacea frass was submitted to advanced fingerprinting analysis of 2D chromatographic data. 1,8-Cineole, found in the leaves of all the Mentha species examined, was oxidized, and C. herbacea frass yielded high rates of several hydroxy-1,8-cineoles, including 2α-hydroxy-, 3α-hydroxy-, 3β-hydroxy- and 9-hydroxy-1,8-cineole. Upon insect feeding, several unknown oxidized monoterpenes, a p-menthane diol and three unknown phenylpropanoids were also detected in the frass volatiles. In M. longifolia, the occurrence of the monoterpene piperitenone oxide was found to be toxic and associated with insect death. The results of this work show that high throughput techniques such as HS-SPME and GC×GC-qMS fingerprint analysis are ideal tools to analyze complex volatile matrices, and provide a sensitive method for the direct comparison and chemical visualization of plant and insect emitted volatile components.     

Luminescence mechanochromism in cyclometallated Ir(III) complexes containing picolylamine

The synthesis, crystal structure and luminescence properties of three cyclometalated Ir(III) complexes of general formula [(ppy)(2)Ir(pam)]X, where X = Cl(-) (1), PF(6)(-) (2), ClO(4)(-)(3), and pam = 2-picolylamine, are described. While 2 and 3 crystallize in a unique form, two pseudo-polymorphs, a solvated (1a) and a non-solvated (1b) species, have been observed for compound 1. 1a crystallizes in the monoclinic centrosymmetric space group P2(1)/c. On the contrary, 1b, 2 and 3 crystallize in the non-centrosymmetric space group P2(1)2(1)2(1) (1b) and Pca2(1) (2 and 3), respectively. All the crystalline supramolecular materials have been fully photophysically characterized. While 1 shows a bright blue-green emission in both solution and solvated crystalline state 1a, crystals of 1b, 2 and 3 show a significantly red shifted emission with respect to solution. Unexpectedly, and differently from 1a, mechanical stimuli-responsive colour and luminescence changes have been observed for 1b, 2 and 3. Upon mechanical grinding the colour of the crystalline solids changes from orange to yellow while the emission energy is partially (2 and 3) or completely (1b) converted from orange to green. The grinding-triggered colour and luminescence changes have been attributed to a crystal-to-amorphous phase conversion for all crystalline solids.     

Gravitational instability of the primordial plasma: Anisotropic evolution of structure seeds

We study how the presence of a background magnetic field, of intensity compatible with current observation constraints, affects the linear evolution of cosmological density perturbations at scales below the Hubble radius. The magnetic field provides an additional pressure that can prevent the growth of a given perturbation; however, the magnetic pressure is confined only to the plane orthogonal the field. As a result, the “Jeans length” of the system not only depends on the wavelength of the fluctuation but also on its direction, and the perturbative evolution is anisotropic. We derive this result analytically and back it up with direct numerical integration of the relevant ideal magnetohydrodynamics equations during the matter-dominated era. Before recombination, the kinetic pressure dominates and the perturbations evolve in the standard way, whereas after that time magnetic pressure dominates and we observe the anisotropic evolution. We quantify this effect by estimating the eccentricity ?   of a Gaussian perturbation in the coordinate space that was spherically symmetric at recombination. For a perturbations at the sub-galactic scale, we find that ?=0.7$?=0.7$ at z=10$z=10$ taking the background magnetic field of order 10⁻⁹${10}^{-9}$ gauss.     

A Galactomannan-Driven Enhancement of the In Vitro Multiplication Rate for the Marubakaido Apple Rootstock (<Emphasis Type="Italic">Malus prunifolia</Emphasis> (Willd.) Borkh) is Not Related to the Degradation of the Exogenous Galactomannan

Agar is a complex mixture of gel-forming polysaccharides. Gelling agents are very often used to provide proper support for plants grown in semisolid culture media. And agar is the most frequently used gelling agent in plant tissue culture media. Galactomannans, another group of gel-forming polysaccharides, consists of a (1 → 4)-linked β-d-mannopyranosyl backbone partially substituted at O-6 with d-galactopyranosyl side groups. In this work, we demonstrate that a statistically significant 2.7-fold increase on the multiplication rate (MR) for in vitro-grown Marubakaido (Malus prunifolia) shoots was associated with a 12.5% replacement of agar in the semi-solid culture media for a galactomannan obtained from seeds of Schizolobium paraybae. This increase on MR was due mainly to a 1.9-fold increase in the number of main branches and an 8.6-fold increase in the number of primary lateral branches. Gas liquid chromatography and thin layer chromatography analyzes demonstrated that the galactomannan-driven enhancement of the in vitro multiplication rate of the Marubakaido apple rootstock was not related to the galactomannan degradation. To the best of our knowledge, this is the first report on the successful use of partial replacement of high quality agar by a galactomannan from S. paraybae in a micropropagation system for a tree species.     

Prediction of properties of biodiesel-diesel blends using spectrofluorimetry and multivariate calibration

Regressions based on fluorescence spectroscopy were developed to provide relatively inexpensive and rapid measurements of the concentration, viscosity, and specific gravity of biodiesel-diesel blends. The methods involved obtaining a mathematical model from spectrofluorimetric data and data from a given property (concentration, dynamic viscosity, or specific gravity) using partial least squares (PLS) regression, which was then applied as a model for predicting properties of interest. The predicted concentrations, dynamic viscosities, and specific gravities of the biodiesel-diesel blends were compared with actual values and agreed reasonably well with the obtained results. The models showed high correlation between real and predicted values. The R-square values near 1 indicated excellent model accuracy for predicting concentrations, specific gravities, and dynamic viscosities of biodiesel-diesel blends. The residual distribution did not follow a trend with respect to the predicted variables, indicating an excellent fit to the data.      

Synthetic approach toward cis-disubstituted γ- and δ-lactones through enantioselective dialkylzinc addition to aldehydes: application to the synthesis of optically active flavors and fragrances

A versatile and straightforward approach to optically active cis-4,5-disubstituted γ- and δ-lactones by catalytic enantioselective addition of dialkyzincs to cinnamic aldehydes and RCM ring closure has been reported. The synthetic importance of the enantioselective dialkylzinc alkylation of aldehydes has been thus widened. Such an approach has then been employed for the enantioselective synthesis of naturally occurring γ-lactone flavors like (S)-5-ethyl-butanolide (6a) and (4S,5S)-cis-whisky lactone (6b) and extended to the preparation of δ-lactones like (5S,6S)-5-methyl-6-ethylpentanolide (9a), precursor of the pheromone serricornin.     

Embeddings for Morrey–Lorentz Spaces

In this paper, new classes of functions are defined. These spaces generalize Lorentz spaces and give a refinement of Lebesgue spaces, weak-Lebesgue spaces, and Morrey spaces. Some embeddings between these new classes are also proved.     

Spirobifluorene bridged Ir(III) and Os(II) polypyridyl arrays: synthesis, photophysical characterization, and energy transfer dynamics

The synthesis, characterization, photophysics, and time-dependent density functional theory (TD-DFT) calculations of spirobifluorene-bipyridine based iridium(III), osmium(II), and mixed Ir/Os complexes are presented. The preparation of the reference and mixed complexes proceeded step-by-step and microwave irradiation facilitated the complexation of osmium. The absorption of the target heterobimetallic derivative, Ir-L-Os, is described by linear combination of half of the absorption spectra of the homobimetallic analogues, Ir-L-Ir and Os-L-Os, due to the occurrence of mixed ligand and metal based transitions when the spirobifluorene-(bpy)(2) bridging ligand L is linked to the metal, confirming a negligible interaction between the substituted metallic chromophores. TD-DFT calculations on monometallic, homo- and hetero-bimetallic complexes fully disentangled the origin of the absorption features. Noticeably, in the mixed Ir-L-Os complex an almost quantitative energy transfer from the (3)Ir to the (3)Os MLCT state is occurring, with a rate constant of 4.1 × 10(8) s(-1) and nearly exclusively via a Dexter-type mechanism mediated by the orbitals of the spiroconjugated ligand. This result, together with the outcomes of the TD-DFT calculations, supports the existence of spiroconjugation and evidences the interesting role of this kind of bridge in the energy transfer dynamics of the arrays. In all the complexes, moreover, the ligand fluorescence is heavily quenched by energy transfer processes toward the metallic appended units; the rate constant is estimated in the order of 10(10) s(-1) for Ir-L-Os and higher than 10(12) s(-1) for the other complexes. In the heterometallic array, both at room temperature and at 77 K, all photons are thus funneled to the emissive Os (3)MLCT state, which acts as energy trap for the antenna cascade.     

Potential energy surfaces for van der waals complexes of rare gases with H2S and H2S2: Extension to xenon interactions and hyperspherical harmonics representation

This article is an account and extension of a series of recent investigations, which using extensive quantum chemical methods provide analytical hyperspherical representations of the potential energy surfaces for the interactions of rare gases with H₂S as a rigid molecule, and H₂S₂, considered as a floppy molecule with respect to torsional mode. For the H₂S‐rare gas systems, the representation is based on a minimal model, here introduced and discussed. For H₂S₂, the study of the interaction with Xe, not considered previously, completes the series. The results are discussed with reference to the properties and trends expected for interactions of van der Waals type. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Detecting DNA mismatches with metallo-insertors: a molecular simulation study

Molecules that selectively recognize DNA mismatches (MMs) play a key role as nucleic acids probes and as chemotherapeutic agents. Metallo-insertors bind to the minor groove (mG) of double strand (ds) DNA, expelling the mismatched base pairs and acting as their π-stacking replacement. In contrast, metallo-intercalators bind to the major groove (MG) of ds DNA and π-stack to adjacent base pairs. In this study we focused on structural and energetic properties of Δ-[Rh(bpy)(2)(chrysi)](3+) (1), Δ-[Ru(bpy)(2)(ddpz)](2+) (2), and Δ-[Ru(bpy)(2)(eilatin)](2+) (3) as prototypical examples of metallo-insertors and intercalators. For all molecules we characterized both insertion and intercalation into a DNA dodecamer via force field based molecular dynamics (MD) and hybrid quantum-classical (QM/MM) MD simulations. A structural analysis of the 1-3/DNA noncovalent adducts reveals that the insertion provokes an untwist of the DNA, an opening of the mG and of the phosphate backbone in proximity of the mismatch, while the intercalation induces smaller changes of these structural parameters. This behavior appears to be correlated with the size of the inserting/intercalating ligand in proximity of the metal coordination site. Moreover, our simulations show that the different selectivity of 1 toward distinct MM types may be correlated with the thermodynamic stability of the MMs in the free DNA and with that of the corresponding insertion adduct. Understanding the factors which tune a specific insertion is of crucial importance for designing specific luminescent probes that selectively recognize MMs, as well as for developing more effective anticancer drugs active in MM repair of deficient cells lines.