Austrodoral and austrodoric acid: nor-sesquiterpenes with a new carbon skeleton from the Antarctic nudibranch Austrodoris kerguelenensis

Two unprecedented nor-sesquiterpenes, austrodoral (4) and its oxidised derivative austrodoric acid (5), have been isolated from the skin of the marine dorid Austrodoris kerguelenensis, collected in Antarctica. The structures and the relative stereochemistry were elucidated on the basis of spectroscopic data. A role of stress-metabolites could be suggested for these compounds.     

Cellulose beads: a new versatile solid support for microwave- assisted synthesis. Preparation of pyrazole and isoxazole libraries

The synthesis of libraries of substituted pyrazoles and isoxazoles has been developed via in situ generation of polymer-bound enaminones. The synthetic protocol makes use of commercially available aniline cellulose, a low-cost and versatile biopolymer, under very mild conditions. This new support allowed us to carry out reactions in polar solvents under both conventional heating and MW irradiation without degradation of the polymer. The reaction between cellulose-bound enaminone and hydroxylamine or hydrazines to afford the target heterocycles in high yields directly in solution is the key step. The support can be conveniently recycled.     

Structural and stereochemical revision of isocyanide and isothiocyanate amphilectenes from the Caribbean marine sponge Cribochalina sp.

The absolute stereochemistry of amphilectene metabolites from Cribochalina sp. has been revised by a detailed NMR spectroscopic study of the Mosher ester derivatives of a related alcohol. The relative stereochemistry of the previously described amphilectenes has been reinvestigated and reassigned on the basis of the X-ray structural analysis carried out on one of them. The structure of a new amphilectene metabolite, which is an isothiocyanato analogue is also presented.     

Spatial and temporal variations of the inherent and apparent optical properties in a shallow coastal lake

Apparent and inherent optical properties in the coastal lagoon of Fogliano were measured in three seasonal surveys in 2002. Irradiance data from in situ measurements of ultraviolet and visible wavebands permitted to estimate the related attenuation coefficients. Laboratory extinction measurements on filtered (0.22 microm) and unfiltered water samples were also performed. The integrated approach between in situ and laboratory measurements allowed the determination of the role of the suspended and dissolved matter in the attenuation and extinction of ultraviolet and visible radiation within the water column. As noted, the impact of the suspended and dissolved matter on the lake optical quality was influenced by wind resuspension of particulate matter: the relative role of dissolved matter in the absorption of UV and visible radiation was prevailing at low wind velocity conditions (less than 2.2 m s(-1)), while at high wind velocities (3.9 m s(-1)), particulate matter resuspension strongly influenced the attenuation and the extinction measurements. The extinction in the analyzed wavelengths of filtered and unfiltered water samples and the in situ irradiance measurements allowed us to define new optical parameters and important correlations with limnological and classical optical measurements. By sampling at high spatial resolution (18 stations in 4 km2), it was possible to evidence a spatial gradient of the optical and limnological properties, these distributions showed a consistent pattern in all three surveys, and were important for the characterization of the chromophoric dissolved organic matter that was estimated with the spectral slope of the extinction curve spectra. A relatively higher spectral slope was found in the southern basin with respect to the northern, where the maximum values of the attenuation coefficients and limnological parameters were found. These results suggest different sources of dissolved organic matter and/or a different level of photobleaching.     

Olefin metathesis: what have we learned about homogeneous and heterogeneous catalysts from surface organometallic chemistry?

Since its early days, olefin metathesis has been in the focus of scientific discussions and technology development. While heterogeneous olefin metathesis catalysts based on supported group 6 metal oxides have been used for decades in the petrochemical industry, detailed mechanistic studies and the development of molecular organometallic chemistry have led to the development of robust and widely used homogeneous catalysts based on well-defined alkylidenes that have found applications for the synthesis of fine and bulk chemicals and are also used in the polymer industry. The development of the chemistry of high-oxidation group 5–7 alkylidenes and the use of surface organometallic chemistry (SOMC) principles unlocked the preparation of so-called well-defined supported olefin metathesis catalysts. The high activity and stability (often superior to their molecular analogues) and molecular-level characterisation of these systems, that were first reported in 2001, opened the possibility for the first direct structure–activity relationships for supported metathesis catalysts. This review describes first the history of SOMC in the field of olefin metathesis, and then focuses on what has happened since 2007, the date of our last comprehensive reviews in this field.

Surface organometallic chemistry bridges the gap between homogeneous and heterogeneous olefin metathesis catalysts.     

Modeling sequence evolution with kernel methods

We model the evolution of biological and linguistic sequences by comparing their statistical properties. This comparison is performed by means of efficiently computable kernel functions, that take two sequences as an input and return a measure of statistical similarity between them. We show how the use of such kernels allows to reconstruct the phylogenetic trees of primates based on the mitochondrial DNA (mtDNA) of existing animals, and the phylogenetic tree of Indo-European and other languages based on sample documents from existing languages. Kernel methods provide a convenient framework for many pattern analysis tasks, and recent advances have been focused on efficient methods for sequence comparison and analysis. While a large toolbox of algorithms has been developed to analyze data by using kernels, in this paper we demonstrate their use in combination with standard phylogenetic reconstruction algorithms and visualization methods.     

Complete charge pooling is prevented in viologen-based dendrimers by self-protection

We have investigated the electrochemical behavior, and chemical and photosensitized reduction of two dendrimers based on a 1,3,5-trisubstituted benzenoid core, which contain 9 and 21 4,4'-bipyridinium (usually called viologen) units, respectively, in their branches and are terminated with tetraarylmethane groups. For comparison purposes, the behavior of reference compounds that contain a single viologen unit have also been investigated. We have found that only part of the viologen units can be reduced in the dendrimer species. For the larger dendrimer, the number of reducible viologens (out of the 21 present) is 14 in electrochemical experiments (in MeCN), 9 on reduction with bis(benzene)chromium (in MeCN), and 13 by photoinduced electron transfer with 9-methylanthracene as a photosensitizer and triethanolamine as a sacrificial reductant in CH2Cl2. The reduced viologen units undergo partial dimerization. The photochemical experiments have shown that only monomeric, one-electron-reduced viologen units are formed at the beginning of the irradiation, followed by dimer formation, until a photostationary state is reached that contains 40 % nonreduced, 33 % monomeric reduced, and 27 % reduced units associated in the dimeric form. The results suggest that, upon reduction of a fraction of the viologen units, the dendrimer structure shrinks, with the result that the bulky terminal groups protect other viologen units from being reduced.     

Stability of a NDIR analyser for CO2 at atmospheric concentration

Carbon dioxide monitoring is significant in the environmental field since this gas plays an important role in the greenhouse effect. In order to determine CO2 concentration and to develop simulation models, it is necessary to carry out measurements which are accurate and comparable in time and space, i.e. SI-traceable. Non-dispersive infrared (NDIR) analysers are employed for CO2 measurements, as they are precise and stable. In order to achieve traceability, such instruments have to be characterized and calibrated. At the Istituto di Metrologia "G. Colonnetti"--CNR, a procedure for calibrating NDIR analysers for CO2 at atmospheric level was developed, which enables to calculate a correction for the analyser output. In addition, a complete uncertainty analysis was carried out and a correct traceability chain was established. The goal of the present work is the study of the stability of a NDIR analyser by repeating calibrations during three years and comparing the correction curves obtained to identify a proper re-calibration interval for such analysers. The investigated instrument has good repeatability and reproducibility, hence satisfactory stability during time, as shown by the short-term and long-term compatibility of calibration curves.