Bioactive clerodane diterpenes from roots of Carex distachya

Two new clerodane diterpenes were isolated from roots of Carex distachya Desf., a perennial plant widely distributed in the coastal area of the Mediterranean basin. Chemical characterization of the metabolites was carried out mainly by 1D and 2D NMR spectroscopy. The isolated compounds influenced either positively or negatively the plant growth (root and shoot elongation) of three coexisting herbaceous species.     

Investigation of Dienophile-TiCl(4) Complexation by Means of X-ray Absorption and (13)C-NMR Spectroscopies

Extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES) techniques, in combination with (13)C-NMR spectroscopy, have been used to study the complexation of methyl acrylate (1), N-acryloylbenzylamine (2), O-acryloyl-(R)-pantolactone (3), methyl N-acryloyl-(S)-prolinate (4), and methyl N-acryloyl-(S)-phenylalaninate (5) with excess TiCl(4) in solution. The results obtained show that TiCl(4) has a great tendency to coordinate with two ester ligands, but this tendency is not so marked with amides, which is related to the greater basicity of the latter. Complexation increases the Ti-Cl bond distance, in comparison with TiCl(4), which is clearly shown by the EXAFS spectra. Chelate complexes are formed with bidentate ligands, but comparison between the EXAFS spectra, obtained with different TiCl(4)/dienophile ratios, shows that chelation is more difficult with methyl N-acryloyl-(S)-phenylalaninate (5).     

Anion reaction of 1,3-benzoxathiole-3-oxide with several electrophilic compounds

The reaction of benzoxathiole-3-oxide with LDA in THF or THF/hexane or THF/HMPA gave a carbanion which was reacted with methyl iodide, aromatic aldehydes or carbon dioxide. The conformational stability (-diastereoselectivity) of the carbanion and the asymmetric induction due to the prochiral electrophiles (β-diastereoselectivity) was studied. The temperature and the solvent effects on the - and β-diastereoselectivity are discussed.     

Visible and near-infrared absorption spectroscopy by an integrating sphere and optical fibers for quantifying and discriminating the adulteration of extra virgin olive oil from Tuscany

Because of its high price, extra virgin olive oil is frequently targeted for adulteration with lower quality oils. This paper presents an innovative optical technique capable of quantifying and discriminating the adulteration of extra virgin olive oil caused by lower-grade olive oils. An original set-up for diffuse-light absorption spectroscopy in the wide 400–1,700 nm spectral range was experimented. It made use of an integrating sphere containing the oil sample and of optical fibers for illumination and detection; it provided intrinsically scattering-free absorption spectroscopy measurements. This set-up was used to collect spectroscopic fingerprints of authentic extra virgin olive oils from the Italian Tuscany region, adulterated by different concentrations of olive-pomace oil, refined olive oil, deodorized olive oil, and refined olive-pomace oil. Then, a straightforward multivariate processing of spectroscopic data based on principal component analysis and linear discriminant analysis was applied which was successfully capable of predicting the fraction of adulterant in the mixture, and of discriminating its type. The results achieved by means of optical spectroscopy were compared with the analysis of fatty acids, which was carried out by standard gas chromatography.     

Polynomial auction algorithms for shortest paths

In this paper we consider strongly polynomial variations of the auction algorithm for the single origin/many destinations shortest path problem. These variations are based on the idea of graph reduction, that is, deleting unnecessary arcs of the graph by using certain bounds naturally obtained in the course of the algorithm. We study the structure of the reduced graph and we exploit this structure to obtain algorithms withO (n min{m, n logn}) andO(n ²) running time. Our computational experiments show that these algorithms outperform their closest competitors on randomly generated dense all destinations problems, and on a broad variety of few destination problems.Research supported by NSF under Grant No. DDM-8903385, by the ARO under Grant DAAL03-86-K-0171, by a CNR-GNIM grant, and by a Fullbright grant     

Estimation of the effective and functional human cortical connectivity with structural equation modeling and directed transfer function applied to high-resolution EEG

Different brain imaging devices are presently available to provide images of the human functional cortical activity, based on hemodynamic, metabolic or electromagnetic measurements. However, static images of brain regions activated during particular tasks do not convey the information of how these regions are interconnected. The concept of brain connectivity plays a central role in the neuroscience, and different definitions of connectivity, functional and effective, have been adopted in literature. While the functional connectivity is defined as the temporal coherence among the activities of different brain areas, the effective connectivity is defined as the simplest brain circuit that would produce the same temporal relationship as observed experimentally among cortical sites. The structural equation modeling (SEM) is the most used method to estimate effective connectivity in neuroscience, and its typical application is on data related to brain hemodynamic behavior tested by functional magnetic resonance imaging (fMRI), whereas the directed transfer function (DTF) method is a frequency-domain approach based on both a multivariate autoregressive (MVAR) modeling of time series and on the concept of Granger causality.

This study presents advanced methods for the estimation of cortical connectivity by applying SEM and DTF on the cortical signals estimated from high-resolution electroencephalography (EEG) recordings, since these signals exhibit a higher spatial resolution than conventional cerebral electromagnetic measures. To estimate correctly the cortical signals, we used a subject's multicompartment head model (scalp, skull, dura mater, cortex) constructed from individual MRI, a distributed source model and a regularized linear inverse source estimates of cortical current density. Before the application of SEM and DTF methodology to the cortical waveforms estimated from high-resolution EEG data, we performed a simulation study, in which different main factors (signal-to-noise ratio, SNR, and simulated cortical activity duration, LENGTH) were systematically manipulated in the generation of test signals, and the errors in the estimated connectivity were evaluated by the analysis of variance (ANOVA). The statistical analysis returned that during simulations, both SEM and DTF estimators were able to correctly estimate the imposed connectivity patterns under reasonable operative conditions, that is, when data exhibit an SNR of at least 3 and a LENGTH of at least 75 s of nonconsecutive EEG recordings at 64 Hz of sampling rate.

Hence, effective and functional connectivity patterns of cortical activity can be effectively estimated under general conditions met in any practical EEG recordings, by combining high-resolution EEG techniques and linear inverse estimation with SEM or DTF methods. We conclude that the estimation of cortical connectivity can be performed not only with hemodynamic measurements, but also with EEG signals treated with advanced computational techniques.     

Detection of multiple sclerosis lesions using EPI-FLAIR images

Fast fluid-attenuated inversion recovery (fast-FLAIR) sequences are very sensitive for detecting lesions of patients with multiple sclerosis (MS). Echo planar imaging allows to obtain FLAIR images (EPI-FLAIR) with significantly shorter scanning times. EPI-FLAIR images obtained with 10 measurements are as sensitive as fast-FLAIR for the detection of large MS lesions. Aim of this study was to compare the numbers of MS lesions seen on EPI-FLAIR images with fewer measurements (and, as a consequence, very short scanning times) with those seen on EPI-FLAIR images with 10 measurements. EPI-FLAIR scans with 2 (EPI-2), 4 (EPI-4), 6 (EPI-6), 8 (EPI-8) and 10 (EPI-10) measurements were obtained from 29 MS patients. Lesions seen using each of the five approaches were counted by agreement by two observers. EPI-10 images were used as the "gold standard" for pairwise comparisons. EPI-FLAIR scans with fewer measurements (EPI-2, -4, -6, -8) were all significantly less sensitive than EPI-10 for the detection of small, intermediate and large MS lesions. All the EPI-FLAIR scans, however, fulfilled MR diagnostic criteria for definite MS. When rapid MR scanning of uncooperative MS patients is needed, EPI-FLAIR images covering the entire brain in less than one minute may be considered.