Synthetic UDP-furanoses as potent inhibitors of mycobacterial galactan biogenesis

UDP-galactofuranose (UDP-Galf) is a substrate for two types of enzymes, UDP-galactopyranose mutase and galactofuranosyltransferases, which are present in many pathogenic organisms but absent from mammals. In particular, these enzymes are involved in the biosynthesis of cell wall galactan, a polymer essential for the survival of the causative agent of tuberculosis, Mycobacterium tuberculosis. We describe here the synthesis of derivatives of UDP-Galf modified at C-5 and C-6 using a chemoenzymatic route. In cell-free assays, these compounds prevented the formation of mycobacterial galactan, via the production of short "dead-end" intermediates resulting from their incorporation into the growing oligosaccharide chain. Modified UDP-furanoses thus constitute novel probes for the study of the two classes of enzymes involved in mycobacterial galactan assembly, and studies with these compounds may ultimately facilitate the future development of new therapeutic agents against tuberculosis.     

An accurate determination of the triple point temperature of pure 20Ne and 22Ne

The paper reports on new determinations at INRIM of the triple point temperature of pure neon isotopes ²⁰Ne and ²²Ne, obtained on samples sealed in cryogenic cells and measured with an uncertainty much lower than that of the previous determinations. The experimental technique is the same used at INRIM for recent studies on neon of natural-isotopic composition, showing an expanded uncertainty of ≈30 μK for a single cell and ≈50 μK for the comparison of sample pairs. The determinations were mainly intended to obtain a more accurate value of the temperature difference for the two pure isotopes, found to be 0.14660 K with an expanded uncertainty of 0.00007 K. The temperature values were found to be 24.5422 K for ²⁰Ne and 24.6888 K for ²²Ne on ITS-90, but each with a larger expanded uncertainty, 0.00032 K. This is mainly caused, contrarily to the difference, by each of these values being affected by the present ambiguity of the ITS-90 definition. This definition refers to neon generically to ‘natural’ composition, while its uncorrected variability heavily affects the uncertainty of the thermometer calibrations. These results for pure isotopes are compared with those recently obtained at INRIM on samples of commercial neon of natural composition and with literature data. The problems involved in the correction for the residual content of isotopic impurities and for chemical impurities are discussed.     

Ideals, idempotents and right cancelable elements in the uniform compactification

No abstract. November 6, 2000     

Theoretical and empirical differentiations of phases in the modelling process

The reconstruction of pupils modelling processes can be found in many empirical studies within the literature on modelling. The empirical differentiations of the phases, which includes putting statements and actions of the pupils in the right phase, has not been reconstructed from a cognitive psychological point of view on a micro level thus far: In this article different modelling cycles are discussed with attention to distinctions in the various phases. The «modelling cycle under cognitive psychological aspects» is specifically emphasized in contrast to the other cycles. On the basis of the results of the COM²-project (Cognitive psychological analysis of modelling processes in mathematics lessons, Borromeo Ferri) the phases of the modelling processare described empirically. Some difficulties in the process of distinguishing the various phases are also pointed out.     

Theoretical and spectroscopic study of the effect of ring substitution on the adsorption of anisole on platinum

The adsorption of anisole, 3,5-dimethylanisole, and 3,5-bis-(trifluoromethyl)-anisole on Pt(111) was studied theoretically and compared to the adsorption of benzene using relativistically corrected density functional theory. A cluster of 31 platinum atoms was used to simulate the surface. The three anisoles were found to be less strongly adsorbed than the parent molecule benzene, 3,5-bis-(trifluoromethyl)-anisole showing weakest adsorption, with an adsorption energy of only one-third that of benzene. The theoretical study was complemented by in situ ATR-IR spectroscopy of the adsorption of the anisole derivatives on a polycrystalline Pt film. The spectroscopic study indicated that the adsorption strength of the anisoles follows the same order as predicted by the calculations. In addition, catalytic hydrogenation tests showed that the propensity to aromatic ring hydrogenation can also be correlated to the mode and strength of adsorption of the anisoles. The degree of saturation followed the same order as the adsorption strength found by the calculations and indicated by spectroscopy. Although 3,5-dimethyl substitution on anisole resulted in only a partial loss of adsorption energy and reactivity toward ring hydrogenation as compared to anisole, the substitution by CF(3) groups led to a large loss of adsorption energy and complete loss of reactivity toward aromatic ring saturation. Along with the study of the substituent effect on the adsorption of aromatic molecules, the correlation between adsorption and propensity to saturation of aromatic substrates could be corroborated.     

A Bayesian Networks approach to Operational Risk

A system for Operational Risk management based on the computational paradigm of Bayesian Networks is presented. The algorithm allows the construction of a Bayesian Network targeted for each bank and takes into account in a simple and realistic way the correlations among different processes of the bank. The internal losses are averaged over a variable time horizon, so that the correlations at different times are removed, while the correlations at the same time are kept: the averaged losses are thus suitable to perform the learning of the network topology and parameters; since the main aim is to understand the role of the correlations among the losses, the assessments of domain experts are not used. The algorithm has been validated on synthetic time series. It should be stressed that the proposed algorithm has been thought for the practical implementation in a mid or small sized bank, since it has a small impact on the organizational structure of a bank and requires an investment in human resources which is limited to the computational area.     

Discrimination of active palladium sites in catalytic liquid-phase oxidation of benzyl alcohol

Knowledge of the structure of active sites is a prerequisite for the rational design of solid catalysts. Using site-selective blocking by CO and isotope labeling combined with in situ attenuated total reflection infrared (ATR-IR) spectroscopy, we were able to discriminate the different sites involved in the liquid-phase oxidation of benzyl alcohol on Pd/Al(2)O(3). The main reaction, that is, the oxidative dehydrogenation of the alcohol to the corresponding aldehyde, showed only little dependence on structure and occurred on all exposed Pd faces, whereas the undesired product decarbonylation occurred preferentially on hollow sites on (111) Pd faces. This explains why specific blocking of the latter sites, as realized in the industrially used Pd-Bi/Al(2)O(3) catalysts, leads to improved catalytic performance.