Identification by LC-ESI-MS of flavonoids responsible for the antioxidant properties of Mallotus species from Vietnam

Several Mallotus species (Euphorbiaceae) are used in Vietnam as edible plants or as traditional medicines for different indications, some related to the treatment of inflammatory diseases. This study investigated the antioxidant activities of 33 samples from 17 Vietnamese Mallotus species. We also evaluated potential cytotoxic activity against human cervix carcinoma HeLa and human lung fibroblast WI-38 cells. Our aim is to develop safe dietary supplements with a protective effect against various diseases caused by tissue damage and the acceleration of the aging process linked to reactive oxygen species. These tests allowed the identification of non-cytotoxic plant species exhibiting significant antiradical properties. These antioxidant properties may be explained by their polyphenol composition. The antioxidant activity of the most active Mallotus species was further analyzed with and without tannins removal. We also identified by LC-ESI-MS some flavonoids responsible for a part of this activity.     

A bidirectional approach to the synthesis of polypropionates: synthesis of C1-C13 fragment of zincophorin and related isomers

The structure-activity study of a bioactive natural product containing polypropionate subunits requires that its stereoisomers also be evaluated. Therefore, a general approach to synthesize these motifs is necessary. We describe herein the synthesis of the C1-C13 polypropionate subunit of zincophorin and isomers thereof using a two-reaction sequence: an aldol reaction using a mixture of tetrasubstituted enoxysilanes and a hydrogen-transfer reaction, both under Lewis acid control. Selection of the appropriate Lewis acid dictates the stereochemical outcome of these reactions. From a tactical standpoint, this study shows how a polypropionate sequence can be read and constructed in two directions, either the east-west or the west-east approaches. The choice of the optimal route is influenced by the number of complexation sites that can interfere in the aldol step under bidentate Lewis acid control.     

Tactics for the asymmetric preparation of 2-azabicyclo[3.1.0]hexane and 2-azabicyclo[4.1.0]heptane scaffolds

In this contribution, two methods are presented for the removal of benzyl-type protecting groups attached to the nitrogen atom of 2-azabicyclo[3.1.0]hexane and 2-azabicyclo[4.1.0]heptane systems. The first, based on the Polonovski reaction, is suitable for [3.1.0] systems. The second relies on an elimination process, starting from derivatives of O-methyl phenylglycinol, and is more general in terms of the substrates tolerated. Secondary bicyclic cyclopropylamines, including enantiomerically pure molecules, can thus be accessed. These compounds are then ready for further functionalisation.     

Optimization of organic electrochemical transistors for sensor applications

Despite the recent interest in organic electrochemical transistors (OECTs) as chemical and biological sensors, little is known about the role that device architecture and materials parameters play in determining sensor performance. We use numerical modeling to establish design rules in two regimes of operation: We find that for operation as an ion‐to‐electron converter, the response of OECTs is maximized through the use of a gate electrode that is much larger than the channel or through the use of a nonpolarizable gate electrode. Improving the conductivity of the polymer and using a channel geometry that maximizes channel width and thickness, and minimizes channel length helps increase the response. For operation as an electrochemical sensor, the sensitivity is maximized in OECTs with gate electrodes that are smaller than their channels. The sensitivity can be improved by increasing the charge carrier mobility and the capacitance per unit area of the conducting polymer, and also its ability to be penetrated by ions from the electrolyte. A channel geometry that maximizes channel width and minimizes channel length also improves sensitivity. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

A finite-volume version of Aizenman–Higuchi theorem for the 2d Ising model

In the late 1970s, in two celebrated papers, Aizenman and Higuchi independently established that all infinite-volume Gibbs measures of the two-dimensional ferromagnetic nearest-neighbor Ising model at inverse temperature ${\beta\geq 0}$ are of the form ${\alpha\mu^{+}_\beta + (1-\alpha)\mu^{-}_\beta}$ , where ${\mu^{+}_\beta}$ and ${\mu^{-}_\beta}$ are the two pure phases and ${0\leq\alpha\leq 1}$ . We present here a new approach to this result, with a number of advantages: (a) We obtain an optimal finite-volume, quantitative analogue (implying the classical claim); (b) the scheme of our proof seems more natural and provides a better picture of the underlying phenomenon; (c) this new approach might be applicable to systems for which the classical method fails.     

Preparation and characterisation of silica monoliths using a triblock copolymer (F68) as porogen

Silica-based monoliths with co-continuous structure were successfully prepared through a sol–gel process in the presence of a poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (F68). The triblock copolymer was compared to the classical PEG, in the formation of silica monoliths and was demonstrated to lead to co-continuous structures in a wider composition range, presenting smaller through pores. Moreover, mesoporous structures templated at the sol–gel transition were assumed to occur at the surface of the silica skeleton while PEG exhibited no mesopore templating.     

3D tracking of foraging belugas from their clicks: Experiment from a coastal hydrophone array

A simple passive acoustic monitoring (PAM) setup was used to localize and track beluga whales underwater in three dimensions (3D) in a fjord. In June 2009, beluga clicks were recorded from a cabled hydrophone array in a regularly frequented habitat in Eastern Canada. Beluga click energy was concentrated in the 30-50 kHz frequency band. The click trains detected on several hydrophones were localized from their time difference of arrivals. Cluster analysis linked localizations into tracks based on criteria of spatial and temporal proximity. At close ranges from the array, the localized click-train series allowed three-dimensional tracking of a beluga during its dive. Clicks within a train spanned a large range of durations, inter-click intervals, source levels and bandwidths. Buzzes sometimes terminated the trains. Repeated click packets were frequent. All click characteristics are consistent with oblique observations from the beam axis, and ordered variation of the source pattern during a train, likely resulting from a scan of angles from the beam axis, was observed before click trains indicated focusing of the echolocation clicks in one direction. The click-train series is interpreted as echolocation chasing for preys during a foraging dive. Results show that a simple PAM system can be configured to passively and effectively 3D track wild belugas and small odontocetes in their regularly frequented habitat.     

Gas Chromatographic Fingerprint Analysis for the Comparison of Seized Cannabis Samples

Cannabis sativa L. is widely used as recreational illegal drugs. Illicit Cannabis profiling, comparing seized samples, is challenging due to natural Cannabis heterogeneity. The aim of this study was to use GC–FID and GC–MS herbal fingerprints for intra (within)- and inter (between)-location variability evaluation. This study focused on finding an acceptable threshold to link seized samples. Through Pearson correlation-coefficient calculations between intra-location samples, ‘linked’ thresholds were derived using 95% and 99% confidence limits. False negative (FN) and false positive (FP) error rate calculations, aiming at obtaining the lowest possible FP value, were performed for different data pre-treatments. Fingerprint-alignment parameters were optimized using Automated Correlation-Optimized Warping (ACOW) or Design of Experiments (DoE), which presented similar results. Hence, ACOW data, as reference, showed 54% and 65% FP values (95 and 99% confidence, respectively). An additional fourth root normalization pre-treatment provided the best results for both the GC–FID and GC–MS datasets. For GC–FID, which showed the best improved FP error rate, 54 and 65% FP for the reference data decreased to 24 and 32%, respectively, after fourth root transformation. Cross-validation showed FP values similar as the entire calibration set, indicating the representativeness of the thresholds. A noteworthy improvement in discrimination between seized Cannabis samples could be concluded.     

1‐Methoxyhexane‐3‐thiol,a Powerful Odorant of Clary Sage (Salvia sclarea L.)

The peculiar and highly diffusive odor signal of flowering clary‐sage plants (Salvia sclarea L.) was identified to derive from trace amounts of 1‐methoxyhexane‐3‐thiol ( 1 ) by mass‐spectrometry analysis and confirmed by comparison with synthetic racemic thiol (±)‐ 1 . The enantiomers (S)‐ and (R)‐ 1 were prepared by enantioselective synthesis, and the absolute configuration of (S)‐ 1 was fully corroborated by X‐ray‐diffraction analysis of the crystalline thioester (1′S,1S)‐ 2 . Compound (S)‐ 1 is one of the most powerful odorants known, with a detection threshold of 0.04⋅10⁻³ ng/l air, and is, with its herbaceous‐green, alliaceous, and perspiration profile, key to the fragrance of clary‐sage flowers and of the freshly distilled essential oil. As a consequence of its unique odor, 1 was also suspected to be part of the volatiles of a Ruta species where it was subsequently identified together with its homologue, 1‐methoxyheptane‐3‐thiol ( 3 ), 1‐methoxy‐4‐methylpentane‐3‐thiol ( 4 ), and the known 4‐methoxy‐2‐methylbutane‐2‐thiol ( 5 ). The syntheses of (±)‐ 3 and (±)‐ 4 as well as of the enantiomer (R)‐ 4 are described. In both natural fractions, the ratio (S)‐ 1 /(R)‐ 1 was slightly in favor of the (S)‐enantiomer. Natural 4 has (R)‐configuration.