Formal orthogonal polynomials revisited. Applications

From some results concerning the formal orthogonal polynomials, already proved in [5], we develop new properties of generalized adjacent polynomials which correspond to a change in the weight function. A new structure of the singular blocks is given. These results have a direct application to Lanczos methods, theG and -algorithms.     

Binding evaluation of isoform 1 fromCratylia mollis lectin to human mammary tissues

The phenomenon of altered carbohydrates in transformed cell surfaces has been studied through histochemical techniques using lectins. Specific binding patterns to normal and transformed mammary tissues were evaluated by Isoform 1 fromCratylia mollis lectin (Cra Iso 1). Protocols using a direct method, incubation of Cra Iso I conjugated to peroxidase (Cra Iso 1-Per) with mammary tissues, followed by diaminobenzidine and hydrogen peroxidase interaction, were performed. Neoplastic tissues, marked by Cra Iso 1, showed a higher intensity of staining than normal ones, in comparison withCanavalia ensiformis lectin, Concanavalin A (Con A), conjugated to peroxidase (Con A-Per). The assay with Cra Iso 1 also indicated a possible utilization of this lectin to characterize normal and transformed mammary cells.     

Synthesis, Structural Characterization, and Oxidation-Reduction Behavior of the gamma-Isomer of the Dodecatungstosilicate Anion

The reaction of tungstate ions with the gamma-10-tungstosilicate in mixed water-ethanol (v/v) yields the corresponding isomer of the 12-tungstosilicate isolated as its tetrabutylammonium salt. It was characterized by means of (183)W NMR, infrared, Raman, and UV spectroscopies and was identified with the isomer resulting from the Keggin structure (alpha-isomer) by rotation of two tritungstic groups by pi/3. Cyclic voltammetry shows that the reducibility increases in the sequence alpha-beta-gamma as the number of rotated tritungstic groups. Whereas the gamma-12-tungstosilicate anion is unstable in pure aqueous solution whatever the pH value, it is stable in mixed aqueous-organic or pure organic solvents, even at boiling temperatures. In contrast, the two- and four-electron-reduced blue species are stable in aqueous media but not the one-electron-reduced blue. Study of the (183)W NMR spectrum of the two-electron-reduced species showed that the two spin-paired electrons are delocalized on all the W atoms on the NMR time scale but have a larger residency time on one group of four atoms.     

Novel Cleavage of Propargylamines by Reaction with Organolithium Compounds

Treatment of secondary aliphatic 2-bromoallylamines with an excess of an organolithium compound led to saturated amines in which the organic group of the organolithium compound is incorporated at the alpha carbon. On the other hand, the successive reaction of the former amines with BuLi and t-BuLi between -80 degrees C and rt gave 1,3-diamines or hexahydropyrimidines depending on the reaction time. The formation of these unexpected products involves initial generation of lithium propargylamides, which subsequently undergo cleavage of the C propargylic-C acetylenic bond induced by the organolithium present in each case in the reaction medium. A mechanism which takes into account all the different reaction products has been proposed and additionally supported by successful trapping of dilithium acetylide.     

Asymmetric Pauson-Khand Reaction. Cobalt-Mediated Cycloisomerization of 1,6-Enynes in Carbohydrate Templates: Synthesis of Bis-Heteroannulated Pyranosides

The Pauson-Khand reaction on the carbohydrate derived precursors 1-6 is reported. We have described for the first time the cobalt-mediated cyclization of some O-branched chain 1,6-enynes in carbohydrate templates. The resulting bis-heteroannulated pyranosides 17-22 have been obtained in diastereomerically pure form, in moderate to good yield, and in one, simple synthetic operation. These enantiomerically pure, densely functionalized carbocycles are attractive advanced intermediates for the synthesis of complex natural products.     

Thermodynamics of alpha-Cyclodextrin-p-Nitrophenyl Glycoside Complexes. A Simple System To Understand the Energetics of Carbohydrate Interactions in Water

Thermodynamic studies of the binding of a series of p-nitrophenyl glycosides (PNPGly) of varying stereochemistry to alpha-cyclodextrin (alpha-CD) were performed at three different temperatures (25, 35, and 42 degrees C) using a microcalorimetric technique. The system p-nitrophenol (PNP) at pH = 3 and alpha-CD was also studied for the sake of comparison. All these complexes were found to be enthalpy driven with a favorable enthalpic term clearly dominant over an unfavorable entropic term. A clear enthalpy-entropy compensation effect was observed at all the temperatures, with a slope close to unity (alpha = 1.02) and an intercept TDeltaS degrees (o) = 2.91 kcal mol(-)(1). This thermodynamic pattern is in agreement with those usually found for lectin-carbohydrate associations and for the binding processes of several host-guest systems. This pattern is explained in terms of the contribution of primarily two driving forces: the van der Waals interactions between the host and the guest, and the solvation/desolvation processes which accompany the association reaction. The presence of the carbohydrate molecule in the PNP ring causes a slight destabilization of the complex at 25 degrees C with respect to the alpha-CD-PNP (pH = 3) complex, although a different behavior has been observed depending on the axial/equatorial configuration of the glycoside and the temperature. This behavior is modulated by the stereochemistry of the glycoside. Differences were observed between the deoxy-derivatives (LAra and LFuc) and those derivatives with a hydroxymethyl group (Glc, Gal, Man). DeltaC(p) degrees values were obtained from the dependency of DeltaH degrees on temperature (=( partial differentialDeltaH degrees / partial differentialT)(p)). These values are small and negative except for alphaMan complex. For the latter complex, discrepancy between the calorimetric and the calculated van't Hoff enthalpies was observed. Parallels are drawn between the thermodynamics of our model and those proposed for carbohydrate-protein associations.     

Effects of Aqueous and Organic Solvents on the Conformational Properties of the Helix-Forming alpha-Methyl-beta-L-aspartamyl Residue

The conformational preferences of N-acetyl-N'-methyl-alpha-methyl-beta-L-aspartamide, which is the model compound for helical poly(beta-L-aspartate)s, have been determined by ab initio SCF-MO computations. Two driving patterns have been found for the existing 13 minimum energy conformations: (i) intramolecular hydrogen bonding interactions of both amide-amide and amide-ester type; and (ii) repulsive interactions between the four oxygen atoms contained in the molecule. Self-consistent reaction-field (SCRF) calculations based on the method proposed by Miertus, Scrocco, and Tomasi have been performed in order to evaluate the effect of the solvent on the conformational preferences of the compound subject of study. Water and carbon tetrachloride were the solvents chosen for this purpose, and results have been discussed and interpreted on the basis of their electronic structures. The conclusions drawn from this study are of assistance to understand some features of the conformational transitions experimentally found in poly(beta-L-aspartate)s.