New examples of template catalysis based processes: glycerol-like units as efficient promoters for dehydrative nucleophilic substitutions of ferrocenylmethanol

The direct high-yield synthesis without solvent and catalyst, under mild conditions, of eleven novel mono substituted ferrocenylmethyl ethers and amine derivatives from ferrocenemethanol and vicinal oxygenated alcohols and amines is here reported. The peculiar ability of these classes of non acidic compounds to favor the dehydrative nucleophilic substitution is attributed to the presence of vicinal oxygen atoms to the reactive group able to build a hydrogen bonding network with the reactant. The role of carbon dioxide and hexafluoroisopropanol was investigated to support the hypothesis that a template catalysis effect is occurring. The in vitro anti-fungal activity of some of these derivatives was tested on two plant fungi, Botrytis cinerea and Penicillium species, with moderate activity.     

Quantitative measurements in thermo-fluid dynamics based on colour processing

Colour can be expressed as a weighted combination of three attributes: hue, intensity, and saturation. Non-coherent light reflected by thermo-sensitive liquid crystals holds a variable hue, moving in a generally narrow temperature interval and also depending on its inclination with respect to the plane of the crystals and on the characteristics of the impinging light. In experimental practice it is not feasible to ensure uniform lighting over an extensive area and its entire view under the same angle. Thus, the acquired hue field is non-uniform even if the liquid crystal sheet is isothermal. However, by means of proper filtering and calibration of the colour attribute, this optical technique, besides being non-intrusive and inexpensive, is capable of mapping the temperature with an accuracy better than 5% of its measuring-range amplitude. A similar method can be applied for measuring the thickness of a thin liquid film. In this case, the colour attribute to be processed is its intensity. In fact, the light transmitted through a dyed liquid decreases with an increasing thickness of the layer. Again, a perfectly uniform light source is unattainable and the recorded intensity field is non-homogeneous even if the liquid free surface is flat. Nevertheless, the film thickness can be determined by this colour-processing procedure with an accuracy better than 8% of the measuring-range amplitude, which is dictated by the utilised dyestuff concentration. Further thermo-fluid dynamic measurements performed over extensive areas could be handled with analogous methodologies. Surface temperature by emitted infrared waves and void fraction in ducts by light absorption are particular examples.     

Radio Geminid meteor shower of 1994

Summary The geminid meteor shower observed by a radio forward-scatter system on the baseline Bologna-Lecce (Italy) in 1994 is discussed. The 1994 Geminid shower exhibited a distinct maximum for overdense echoes of duration >1 s, with the peak rate on December 13, 21–22 UT at solar longitude 261.0° (equinox 1950.0). The maxima of echoes of longer duration (>8 s and >32 s) are shifted to solar longitude 261.3°.     

Quark matter equation of state with Hartree-Fock approximation

Both the MIT bag model and potential models are able to reproduce with reasonable accuracy static hadron properties. However while extending the MIT bag model to compute the quark matter equation of state is straightforward, this is not so for potential models. Here this is attempted, starting from a Dirac equation in the Hartree-Fock approximation.     

Absolute and relative quantification of sheep brain prion protein (PrP) allelic variants by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry

Transmissible spongiform encephalopathies (TSEs) are characterised by the accumulation in the tissues of affected individuals of an abnormal form (PrP(Sc)) of a protein naturally produced by the host, the cellular prion protein (PrP(C)). In sheep, susceptibility to TSEs is tightly controlled by polymorphism at positions 136 (A or V), 154 (R or H) and 171 (R or Q) of the Prnp gene encoding the prion protein (PrP). Quantification of PrP variants at positions 136, 154 and 171 can be achieved by matrix-assisted laser desorption/ionisation time-of-flight (MALDI-TOF) mass spectrometric analysis of the respective peptides 114-139, 152-159 and 160-171 obtained after tryptic digestion of the PrP protein. In this study we quantified the tryptic peptide 114-139 containing the first polymorphic site. Quantification was either relative, between variants of this peptide, or absolute with respect to the C-terminally (18)O-labelled peptide obtained by hydrolysing known amounts of recombinant protein with trypsin in H(2) (18)O. After purification of PrP(C) and PrP(Sc) from the brain of two heterozygous sheep carrying either the ARQ/VRQ or ARR/VRQ genotypes, the proportion of each variant was measured. In the ARQ/VRQ animal, while both variants were equally represented in the normal isoform, the VRQ variant was predominantly found in the abnormal PrP protein, suggesting dissimilar behaviour of the two variants in the pathological process. The situation was even more contrasted in the ARR/VRQ animal where PrP(Sc) was solely composed of the VRQ variant. These two examples clearly illustrate the value of MALDI-TOF analysis, combined with appropriate immunopurification techniques, in seeking a precise understanding of the influence of PrP polymorphisms on TSE pathogenesis.     

Cannabioxepane, a novel tetracyclic cannabinoid from hemp, Cannabis sativa L.

Apart from large amounts of cannabidiol, the known stilbenoids 1-4 and the oxylipins 7 and 8, a fibre cultivar of Cannabis sativa derived from the historical Carmagnola variety gave the novel spiranic stilbenoid isocannabispiradienone (5) and the biphenyl-type cannabinoid cannabioxepane (CBX, 6), a tetracyclic compound characterized by an unprecedented C-5/C-8′ oxygen bridge and devoid of cannabinoid activity. Structures were established by analysis of MS and NMR data, and the biogenetic derivation of the new compounds is discussed.     

Gold nanoparticles incarcerated in nanoporous syndiotactic polystyrene matrices as new and efficient catalysts for alcohol oxidations

The controlled synthesis of gold nanoparticles (AuNPs), incarcerated in a semicrystalline nanoporous polymer matrix that consisted of a syndiotactic polystyrene-co-cis-1,4-polybutadiene multi-block copolymer is described. This catalyst was successfully tested in the oxidation of primary and secondary alcohols, in which we used dioxygen as the oxidant under mild conditions. Accordingly, (±)-1-phenylethanol was oxidised to acetophenone in high yields (96%) in 1 h, at 35 °C, whereas benzyl alcohol was quantitatively oxidised to benzaldehyde with a selectivity of 96% in 6 h. The specific rate constants calculated from the corresponding kinetic plots were among the highest found for polymer-incarcerated AuNPs. Similar values in terms of reactivity and selectivity were found in the oxidation of primary alcohols, such as cinnamyl alcohol and 2-thiophenemethanol, and secondary alcohols, such as indanol and α-tetralol. The remarkable catalytic properties of this system were attributed to the formation, under these reaction conditions, of the nanoporous ε crystalline form of syndiotactic polystyrene, which ensures facile and selective accessibility for the substrates to the gold catalyst incarcerated in the polymer matrix. Moreover, the polymeric crystalline domains produced reversible physical cross-links that resulted in reduced gold leaching and also allowed the recovery and reuse of the catalyst. A comparison of catalytic performance between AuNPs and annealed AuNPs suggested that multiple twinned defective nanoparticles of about 9 nm in diameter constituted the active catalyst in these oxidation reactions.     

Chemoenzymatic synthesis of O-mannosylpeptides in solution and on solid phase

O-mannosyl glycans are known to play an important role in regulating the function of α-dystroglycan (α-DG), as defective glycosylation is associated with various phenotypes of congenital muscular dystrophy. Despite the well-established biological significance of these glycans, questions regarding their precise molecular function remain unanswered. Further biological investigation will require synthetic methods for the generation of pure samples of homogeneous glycopeptides with diverse sequences. Here we describe the first total syntheses of glycopeptides containing the tetrasaccharide NeuNAcα2-3Galβ1-4GlcNAcβ1-2Manα, which is reported to be the most abundant O-mannosyl glycan on α-DG. Our approach is based on biomimetic stepwise assembly from the reducing end and also gives access to the naturally occurring mono-, di-, and trisaccharide substructures. In addition to the total synthesis, we have developed a "one-pot" enzymatic cascade leading to the rapid synthesis of the target tetrasaccharide. Finally, solid-phase synthesis of the desired glycopeptides directly on a gold microarray platform is described.