Protection of the Hydroxyphosphinyl Function of Phosphinic Dipeptides by Adamantyl. Application to the Solid-Phase Synthesis of Phosphinic Peptides

To develop solid-phase synthesis of phosphinic peptides, different FmocXaaPsi{PO(OAd)CH(2)}XaaOH building blocks have been prepared, where Fmoc is (fluorenylmethoxy)carbonyl. In this respect, the protection of the hydroxyphosphinyl function in these phosphinic dipeptides by the adamantyl group turns out to be convenient. The phosphinic adamantyl esters are completely stable in basic conditions and can be removed under relatively mild acidic conditions. Using these building blocks, despite the bulkiness of the adamantyl group, no particular problem of coupling was observed during the solid-phase synthesis of phosphinic peptides by the Fmoc strategy. The developed methodology is of particular interest to facilitate the development of potent inhibitors of zinc-metalloproteases.     

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.     

Positron lifetime study of several chiral materials in aqueous solution

The most obvious symmetry breaking in Nature is the left-right asymmetry of living beings: sugars and amino acids are almost exclusively represented by one of their stereoisomers (D-isomer for sugars and L-isomer for amino acids) at the expense of other possible isomers. In our experiment we studied the aqueous solutions of tartaric acid, alanine, and cysteine in the function of temperature by positron lifetime spectroscopy. The results were compared with those obtained in pure water under similar conditions. We always observed a sharp minimum of the positron lifetime at around 41 °C in water and in the solutions of the natural stereo-isomers. On the other hand, the same minimum occurred at considerably lower temperatures in the solutions of the unnatural isomers.     

Experimental determination of the flame expansion factor

The flame expansion factor (ratio of volumes of flame gases before and after burning) has been determined by mercury vapour introduction. The method is based on the determination of atomic concentration ratio in the flame and the flameless gas jet using the same sample introduction rate. A good agreement has been found between the expansion factors determined by the proposed method and those calculated by the gas law.     

Properties study of anhydrite(II) prepared from waste gypsums

Anhydrites(II)- CaSO₄ were prepared from two waste gypsums (PRECHEZA Perov, FOSFA Potorná). The samples of anhydrites(II) with sulphate activators were tested on spillage, beginning and the end of setting time, bending and pressure strength. Both sodium and potassium sulphates accelerated setting of anhydrite, more impressively that prepared from Potorná gypsum. The addition of Na₂SO₄ influenced the strength of this anhydrite very favourably. On the contrary K₂SO₄ influenced favourably the strength of Perov anhydrite. Results confirm the necessity to evaluate properties of such materials with respect to their origin.