Hémisynthèse d'antibiotiques aminoglycosidiques: I. - Mise au point d'un réacteur enzymatique à cofacteur

In order to produce specifically N-monoalkylated derivatives of aminoglycoside antibiotics of potential therapeutic values, we have developed an enzymatic reactor. This system uses the aminoglycoside acetyltransferase as catalyst and acetylcoenzyme A as acetyl donor.The immobilization of one aminoglycoside acetyltransferase on different resins has been studied. The coreticulation of this enzyme on DEAE cellulose in the presence of glutaraldehyde gives rise to an enzymatic resin of high efficiency. On the other hand, we have also studied the acetylation of coenzyme A in a simple manner. Acetylation occurs in a quantitative yield when the reaction is performed in the presence of polyvinyl-4 pyridine/divinylbenzene 2 per cent.These conclusions enabled to develop two types of acetylating reactors which give rise without purification to 3-acetyl gentamicin.     

Utilisation préhistorique de la technique minière d’abattage au feu dans le district cuprifère de Cabrières (Hérault)Prehistoric use of the fire-setting method in the copper-mining district of Cabrières (Hérault, France).

Fire-setting to open up mines has been used on hard rock since prehistoric times. In the copper-mining district of Cabrières, the existence of metre-sized spherical or sub-spherical cavities, sometimes spaced along the same vertical in an ore seam, has usually been ascribed to this method 12; 13 and 20. Two AMS ¹⁴C dating of micro-charcoal found in dolomite and of burnt ore breccias related to extraction in these cavities give the ages 3830 ± 40 BP, cal BC 2340–2130 and 3900 ± 40 BP, cal BC 2480–2280, which is the first evidence in France of the use of fire-setting in prehistoric mines.

Résumé

L’abattage, ou l’ouverture des mines, par le feu, a été pratiqué dans le cas de roches dures depuis la Préhistoire. Dans le district minier cuprifère de Cabrières, l’existence de cavités sphériques ou sub-sphériques métriques, parfois échelonnées sur une même verticale le long des filons minéralisés, a été classiquement attribuée à cette technique 12; 13 and 20. Deux datations ¹⁴C par AMS des micro-charbons de bois récoltés dans les brèches de dolomie et de minerais brûlés liés au dépilage minier de ces cavités ont donné les âges de 3830 ± 40 BP, cal BC 2340–2130 et de 3900 ± 40 BP, cal BC 2480–2280, confirmant, pour la première fois en France, l’utilisation dans les mines préhistoriques de l’abattage au feu.     

Etude par Spectroscopie Infrarouge de la Transformation Hélice—Chaine Statistique des Polypeptides. I. Etude Comparée de l'Interaction de la Poly-L-alanine et d'un Amide Modèle avec l'Acide Trifluoroacétique

Infrared spectra of poly-L -alanine in trifluoroacetic acid-chloroform mixtures have been investigated and compared with those of a model amide (N-methylacetamide). The purpose of this work is to determine the nature of peptide-acid specific interactions responsible for the helix-random coil transition of polymer chains. Analysis is made in using amide (A, I, II, III) and acid (νC?O, νOH) vibrations which are specially sensitive to molecular interactions. We examined a model compound to determine the spectral characteristics of the different complexes or species formed between amide and acid. At a low acid concentration, hydrogen-bonded complexes: ? (NH) C?O…?HOOCCF₃ (1) are evidenced but no association between amide NH and acid CO groups (complexes A) is observed. For higher acid concentrations complexes (I) are progressively changed into ions pairs and free ions, which result from amide protonation by acid, according to the exothermic equilibrium (I)?? (NH)COH⁺, ^?OOCCF₃(II). Amidium and carboxylate bands are localized between 1680–1705 cm^?1 and 1620–1625 cm^?1, respectively. If the cation band is always clearly seen, the anion band is only observed for the most acidic solutions. For the polymer, a gradual complexation of type (I) is observed for all acid concentrations. From our results, the assumption of an (A) type interaction seems very unlikely but cannot be excluded. Moreover, proton transfer—similar to that observed with a model amide—is never evidenced since, in particular, the amidium band characteristic of protonation is never seen. In contrast to previous investigations, we conclude that the helix-random coil transition of polypeptides is not due to the protonation of the peptide functions. This transition does suggest a strong interaction by hydrogen bonds between polymer and acid molecules.     

Zahlenverhältnisse von Häufigkeiten

In evaluating data, one acknowledges as a scientist the superiority of the K-procedure on account of the versatility of its application, e.g. in answering the question not only as to its causal context, in proving two features to be contemporaneous and equally strong effects of a material third factor, or in accordance with a “criterion of parallel problems”, but also in demonstrating the mutual matching of two frequency-ratios and the matching of one frequency-ratio with a given proportion, e.g. 3: 1, and the matching of a continuing proportion collected from observed frequencies with a given continuing proportion, e.g. 9:3:3: 1. This is demonstrated in the examples in the literature, which hitherto have been treated only according to the classical procedure.