New γ-pyrone propionates from the Indian Ocean sacoglossan Placobranchus ocellatus

A new γ-pyrone propionate, compound 9, and its peroxy derivative 10 have been isolated from the sacoglossan Placobranchus ocellatus. The structure and the relative stereochemistry of the new molecules, which displayed an unprecedented carbon skeleton characterised by a bicyclo [4.2.0] octane, have been determined by both spectroscopic methods and comparison with model compounds. By analogy with photodeoxytridachione (2), a sunscreen protective role could be also suggested for compound 9 in living P. ocellatus.     

Occipital-parietal interactions during shifts of exogenous visuospatial attention: trial-dependent changes of effective connectivity

We studied neural interactions between brain areas involved in exogenous (stimulus-driven) control of visuospatial attention. With event-related functional magnetic resonance imaging (fMRI), we investigated changes of connectivity during shifts of spatial attention from an attended location to a previously unattended target location. Using a 3-T scanner, fMRI data were acquired from three healthy volunteers. According to a central visual cue, participants directed endogenous spatial attention to the left or the right visual hemifield for blocks of 56 s. Peripheral visual targets were presented unpredictably in either the attended hemifield (valid trials, 80%) or in the unattended hemifield (invalid trials, 20%) and participants performed a two-alternative forced-choice discrimination task with the target, irrespective of cue validity. In accordance with previous results, we found that the temporal–parietal junction (TPJ) mediates the shift of spatial attention toward stimuli presented at the unattended side (i.e., invalid trials). We critically studied the interaction between occipital areas responding to the visual stimuli and other brain regions in order to find regions functionally coupled with the occipital cortex during invalid trials. We found that the coupling between occipital areas processing visual stimuli and the TPJ selectively increased during invalid trials. Our results highlight how changes of connectivity between brain areas can describe attentional processes such as stimulus-driven shifts of spatial attention.     

High-order stimulated Raman scattering in a highly transient regime driven by a pair of ultrashort pulses

We demonstrate efficient generation of high-order anti-Stokes Raman sidebands in a highly transient regime, using a pair of approximately 100-fs laser pulses tuned to Raman resonance with vibrational transitions in methane or hydrogen. The use of this technique looks promising for efficient subfemtosecond pulse generation.     

Structure-dependent modulation of a pathogen response in plants by synthetic O-antigen polysaccharides

Many phytopathogenic bacteria display lipopolysaccharides (LPS) with the O-chain repeating unit [alpha-l-Rha-(1-->3)-alpha-l-Rha-(1-->3)-alpha-l-Rha-(1-->2)](n)(). This trisaccharide unit was synthesized and oligomerized to obtain hexa- and nonasaccharides. The deprotected rhamnans were effective in suppressing the hypersensitive response (HR) and in inducing PR-1 gene expression in Arabidopsis thaliana. Conformational analysis of the oligorhamnans by NMR spectroscopy and molecular dynamics calculations revealed that a coiled structure develops with increasing chain length of the oligosaccharide. This is associated with increasing efficacy in HR suppression and PR-1 gene expression. We therefore infer that the coiled structure of phytopathogenic bacteria is a plant-recognizable pathogen-associated molecular pattern (PAMP).     

Cladonia verticillaris (lichen) can exhibit defense mechanisms against Rn-222 under controlled conditions

Journal of Radioanalytical and Nuclear Chemistry - This study aimed to evaluate the effects of the Rn-222 progeny on the lichen Cladonia verticillaris under controlled conditions. The results...     

Spatial and temporal distribution of environmental markers from Coastal to Plateau areas in Antarctica by firn core chemical analysis

The chemical analysis of shallow firn cores sampled in coastal and plateau areas in Northern Victoria Land and along a transect from Talos Dome to Dome C (East Antarctica, Pacific Ocean sector) allowed a global view of spatial and temporal changes in chemical composition of snow depositions over the last 100 years. Variations in concentration of primary (sea spray) and secondary (biogenic emission, atmospheric inputs) source markers were observed and discussed as a function of distance from the sea and altitude.

In the stations characterized by relatively high snow accumulation rates, the sub-sampling resolution was sufficient to obtain a stratigraphic dating by using the periodical variations of seasonal markers. In these stations, a subdivision in “summer” and “winter” samples was carried out in order to study the seasonal changes of the contributions of the measured compounds to the snow composition as elevation and distance from the sea increase.

Some evidence of post-depositional effects which are able to change the original deposition of chloride and nitrate, was observed at stations with low accumulation rates. The reliability of the depth/concentration profile of these substances for reconstructing past deposition was also discussed.     

A Semisynthetic Approach to New Immunoadjuvant Candidates: Site‐Selective Chemical Manipulation of Escherichia coli Monophosphoryl Lipid A

A semisynthetic approach to novel lipid A derivatives from Escherichia coli (E. coli) lipid A is reported. This methodology stands as an alternative to common approaches based exclusively on either total synthesis or extraction from bacterial sources. It relies upon the purification of the lipid A fraction from fed‐batch fermentation of E. coli, followed by its structural modification through tailored, site‐selective chemical reactions. In particular, modification of the lipid pattern and functionalization of the phosphate group as well as of the sole primary hydroxyl group were accomplished, highlighting the unusual reactivity of the molecule. Preliminary investigations of the immunostimulating activity of the new semisynthetic lipid A derivatives show that some of them stand out as promising, new immunoadjuvant candidates.     

Palladium‐Catalyzed Heteroaromatic Couplings Mediated by Microwave Irradiation

Nitrogen‐containing heterocycles bearing a halogen substituent have been converted to the corresponding amines by a synthetic protocol based on Buchwald methodology assisted by microwaves.