Structural characterizations of lipids A by MS/MS of doubly charged ions on a hybrid linear ion trap/orbitrap mass spectrometer

Here, a new 'one pot' and fast approach is described, based on electrospray ionization (ESI) of negative ions by using a hybrid linear ion trap/orbitrap mass spectrometer (LTQ/orbitrap) for MS and MS/MS analysis. By this method the distribution of the primary and secondary acyl residues of the intact lipid A is inferred by analysis of the ESI spectra measured in positive and negative mode. The analysis of these data allows an unequivocal assignment of the fatty acid distribution. This methodology was successfully tested on two different lipid A with known structures, deriving from the Agrobacterium tumefaciens and Escherichia coli lipopolysaccharides (LPS).     

Chemical Identification of Specialized Metabolites from Sulla (Hedysarum coronarium L.) Collected in Southern Italy

Sulla (Hedysarum coronarium L.) is a biennal forage legume originated from the Mediterranean basin and used for animal feeding due to its high forage quality and palatability. Several species of Hedysarum have been considered for their nutritional, pharmaceutical, and biological properties, and different applications have been reported, both for human consumption and animal nutrition. Although a systematic investigation of the chemical constituents of Hedysarum spp. has been performed in order to provide chemotaxonomic evidences for the genus and to support the pharmacological application of several species within the genus, few data are available on the chemical constituents of H. coronarium, and only the content of condensed tannins and flavonoids in leaves has been previously reported. In the present paper, results from a detailed chemical analysis of the extracts from the leaves and flowers of H. coronarium grown wild in southern Italy are presented. Identification of the main specialized metabolites within the chemical classes of flavonoids, proanthocyanidins and saponins, is described, including considerations on their content in the two plant organs. Information acquired from this study expands the knowledge on H. coronarium as a source of valuable phytochemicals for different applications in human and animal health and nutrition.     

SEM-EDS investigation on PM10 data collected in Central Italy: Principal Component Analysis and Hierarchical Cluster Analysis

Background

Principal Component Analysis (PCA) and Hierarchical Cluster Analysis (HCA) were applied on PM10 particle data in order to: identify particle clusters that can be differentiated on the bases of their chemical composition and morphology, investigate the relationship among the chemical and morphological parameters and evaluate differences among the sampling sites. PM10 was collected in 3 different sites in central Italy characterized by different conditions: yard, urban and rural sites. The concentration of 20 chemical parameters (C, O, Na, Mg, Al, Si, P, Cd, Cl, K, Ca, Sn, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn) were determined by Scanning Electron Microscopy – Energy Dispersive X-ray Spectroscopy (SEM-EDS) and the particle images were processed by an image analysis software in order to measure: Area, Aspect Ratio, Roundness, Fractal Dimension, Box Width, Box Height and Perimeter.

Result

Results revealed the presence of different clusters of particles, differentiated on the bases of chemical composition and morphological parameters (aluminosilicates, calcium particles, biological particles, soot, cenosphere, sodium chloride, sulphates, metallic particles, iron spherical particles). Aluminosilicates and Calcium particles of rural and urban sites showed a similar nature due to a mainly natural origin, while those of the yard site showed a more heterogeneous composition mainly related to human activity. Biological particles and soot can be differentiated on the bases of the higher loads of Fractal Dimension, which characterizes soot, and content of Na, Mg, Ca, Cl and K which characterize the biological ones. The soot of the urban site showed higher loadings of Roundness and Fractal Dimension than the soot belonging to the yard and rural sites, this was due to the different life time of the particles. The metal particles, characterized mainly by the higher loading of iron, were present in two morphological forms: spherical and angular particles. The first were generated by a fusion process at high temperature, while the second one had crustal origin (those characterized by typical terrigenous elements) and also human origin.

Conclusion

In this work a protocol for the morphological-chemical characterization of single particles has been developed. SEM analysis allows to classify particles in 10 different families and PCA and HCA have provided information about the sources of PM and similarities and differences among the sites.

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Study of Late Roman and Byzantine glass by the combined use of analytical techniques

In the present work, we report on a detailed characterization of Late Roman and Byzantine (from 2nd to 8th century A.D.) glass specimen found in Catania (Sicily, Southern Italy) by the employment of two complementary techniques, namely scanning electron microscopy coupled with energy-dispersive spectrometry (SEM–EDS) and Fourier transform infrared (FT-IR) absorbance spectroscopy. The glass fragments come from archaeological excavations in the courtyard of St. Agata la Vetere's church in Catania. In particular, compositional data were obtained by scanning SEM–EDS measurements and the investigation of the degradation on the surface of the glass specimen was made combining the SEM–EDS observations with those performed through FT-IR absorbance. The whole set of results contributed to define the provenance of the specimens. Furthermore, the data furnished new evidences of the technical development of glass production in Late Roman and Byzantine period in Catania.     

Measuring financial risk and portfolio optimization with a non-Gaussian multivariate model

In this paper, we propose a multivariate market model with returns assumed to follow a multivariate normal tempered stable distribution. This distribution, defined by a mixture of the multivariate normal distribution and the tempered stable subordinator, is consistent with two stylized facts that have been observed for asset distributions: fat-tails and an asymmetric dependence structure. Assuming infinitely divisible distributions, we derive closed-form solutions for two important measures used by portfolio managers in portfolio construction: the marginal VaR and the marginal AVaR. We illustrate the proposed model using stocks comprising the Dow Jones Industrial Average, first statistically validating the model based on goodness-of-fit tests and then demonstrating how the marginal VaR and marginal AVaR can be used for portfolio optimization using the model. Based on the empirical evidence presented in this paper, our framework offers more realistic portfolio risk measures and a more tractable method for portfolio optimization.     

Remarks on the total variation of the Jacobian

The total variation TV(u) of the Jacobian determinant of nonsmooth vector fields u has recently been studied in [2] [3]. We focus on the subclass u(x) = φ(x/|x|) of homogeneous extensions of smooth functions In the case n = 2, we explicitely compute TV(u) for some relevant examples exhibiting a gap with respect to the total variation |Det Du| of the distributional determinant. We then provide examples of functions with |DetDu| = 0 and TV(u) = + ∞. We finally show that this gap phenomenon doesn’t occur if n ≥ 3.     

Environment-mediated control of a quantum system

Recently, a new approach for the controllability of a two-dimensional quantum system S has been proposed, based on its interaction with an initially uncorrelated two-dimensional probe P whose initial state can be arbitrarily modified. Following this scheme and considering a particular model for the environment, we show that, in some specific cases, the environment-induced entanglement is rich enough to completely control the dynamics of S. Under suitable conditions on the interaction of S, P, and the environment, we prove that the state of S can be driven to an arbitrary target state by varying the initial state of P.     

Structures and electronic absorption spectra of a recently synthesised class of photodynamic therapy agents

A theoretical study was performed on a novel class of boron-containing molecules (various substituted tetraarylazadipyrromethenes), which show in vitro activity for application in photodynamic therapy. Geometric optimisation of the structures for the singlet and triplet electronic states was carried out on compounds in vacuo at the density functional level of theory, by employing the PBE0 hybrid functional and the split-valence plus polarisation basis set. The absorbance properties in the UV-visible region were examined by means of time-dependent density functional response theory, using the same functional as mentioned above. To evaluate the influence of the solvent on the excitation energies, the continuum polarisable model was applied. Calculated electronic excitations, such as those regarding the Q-like band, were found to be in good agreement (within 0.01-0.1 eV) with experimental values and experimental trends on changing both the substituents and solvent.     

Synthesis and antimicrobial activity of 2‐(acyl or carboxyalkyl)‐3‐(H or alkyl or aryl)‐5 (or ‐6 or ‐8)‐monochloro, 7‐fluoro‐substituted‐4H‐1,4‐benzothiazines

A series of 2‐(acyl or carboxyalkyl)‐3‐(H or alkyl or aryl)‐5 (or ‐6 or ‐8)‐monochloro, 7‐fluoro‐substituted‐4H‐1,4‐benzothiazines 3a‐x were prepared to investigate their potential biological activity. In this work the 3a‐w structures are supported with physical and analytical data and the results of their in vitro antimicrobial activity against some strains Gram positive, Gram negative, and Fungi are reported. It was found that compounds 3a, 3d displayed interesting antibacterial activity, whereas compound 3f displayed interesting antifungal activity.     

On the rearrangement in dioxane/water of (Z)-arylhydrazones of 5-amino-3-benzoyl-1,2,4-oxadiazole into (2-aryl-5-phenyl-2H-1,2,3-triazol-4-yl)ureas: substituent effects on the different reaction pathways

We have recently evidenced an interesting differential behavior in the reactivity in dioxane/water between the (Z)-2,4-dinitrophenylhydrazone (1a) and the (Z)-phenylhydrazone (1b) of 5-amino-3-benzoyl-1,2,4-oxadiazole. The former rearranges into the relevant triazole 2a only at pS+ > 4.5 while undergoing hydrolysis at high proton concentration (pS+ < 3.5); on the contrary, the latter rearranges into 2b in the whole pS+ range examined (0.1 < or = pS+ < or = 14.9). Thus, for a deeper understanding of these differences we have now collected kinetic data on the rearrangement in dioxane/water of a series of 3- or 4-substituted (Z)-phenylhydrazones (1c-l) of 5-amino-3-benzoyl-1,2,4-oxadiazole in a wide range of proton concentrations (pS+ 0.1-12.3) with the aim of gaining information about the effect of the substituent on the course of the reaction. All of the (Z)-arylhydrazones studied rearrange via three different reaction routes (specific-acid-catalyzed, uncatalyzed, and general-base-catalyzed), and the relevant results have been examined by means of free energy relationships.