Biosynthèse de cellulose bactérienne à pertir de glycérol sélectivement deutérié en position 1, 2, ou 3: Etude par résonance magnétique nucléaire

Glycerol specifically deuterated at C-1, C-2, or C-3 was prepared and used for the biosynthesis of bacterial cellulose with Acetobacter xylinum.The material obtained were converted into glucitol hexaacetate and analyzed by 250-MHz nuclear magnetic resonance and mass spectrometry. The spectra indicated that the protons of the C-3 position of the starting glycerol were incorporated as substituents of the C-6 and C-1 positions of the cellulose. Similarly, protons of the C-2 and C-5 positions of the cellulose came essentially from water and the protons bonded at the C-3 and C-4 positions of the cellulose from protons bonded to C-1 of the starting glycerol.     

Étude des principaux facteurs influençant l‘émission d'attractifs sexuels synthétiques à partir de diffuseurs en caoutchouc et en plastique

Deux types de diffuseurs en caoutchouc (Michelin) et en plastique polystratifié (Hercon^®) sont testés en laboratoire pour étudier quelques aspects des phénomènes de diffusion. Trois composantes phéromonales, le Z9-12: Ac, le 12: Ac et le Z9-14: Ac imprégnées dans ces différents supports servent à détermineer le rôle joué par la longueur de la chaîne de la molécule et la présence de doubles liaisons sur la vitesse de diffusion. L'influence de la température, de la vitesse du vent et de l'humidité est déterminée en cellules climatisées.Parmi les facteurs relatifs à la structure chimique, l'influence de la longueur de la chaîne est prédominante par rapport à la présence d'une double liaison. Parmi les facteurs climatiques, le vent agit plus que la température sur la diffusion, alors que l'humidité paraît secondaire.     

Synthèse de nucléosides pyrimidiques non protégés en O-2′ à partir de sulfites cycliques en C-1—C-2

Treatment of 3,5,6-tri-O-benzoyl-- -glucofuranose 1,2-sulfite with an excess of bis(trimethylsil) uracil, in fusion processes without any catalyst, afforded an excellent yield of 1-(3,5,6-tri-O-benzoyl-2-O-trimethylsilyl-β- -glucofuranosyl)uracil, which was readily hydrolyzed in slightly acid conditions to give in almost quantitative yield 1-(3,5,6-tri-O-benzoyl-β- -glucofuranosyl)uracil. This new synthetic method for nucleosides unprotected at O-2′ was also tested in other sugar series. In some cases, only the 1′,2′-trans-nucleosides were obtained, but in others, small yields (3–10%) of 1′,2′-cis-nucleosides were detected. The -to-β ratio seems to be dependent on the reaction temperature. 2,4-Dimethoxypyrimidine also reacted with sugar 1,2-sulfites and 4-O-methyl-1-(3,5,6-tri-O-benzyl-β- -glucopyranosyl)-2-pyrimidinone was prepared in 85% yield from 3,5,6-tri-O-benzyl-- -glucopyranose 1,2-sulfite.     

Étude ultrastructurale du cycle nucléolaire de Physarum polycephalum après mise en évidence préférentielle des RNP par la réaction régressive à l''EDTA

Nucleolar cycle in Physarum polycephalum was studied using EDTA preferential stain for RNP. We have been able to establish the following.

1. 1. The nucleolar remnants that are observed during mitosis correspond to the fibrillar zones of the interphase nucleolus.

2. 2. In prometaphase and metaphase the nucleolar remnants lie peripherically around the chromosomal mass with which they are only superficially associated.

3. 3. Preribosomal granules appear 10–15 min after metaphase in the prenucleolar bodies.

The results shown that the interphase nucleolus is an assembly of multiple subunits. The relationship between the nucleolar remnants and chromosomes is discussed in the light of the recent understanding of the extrachromosomal nature of rDNA.Le cycle nucléolaire de Physarum polycephalum a été étudié en microscopie électronique après réaction régressive à l'EDTA qui met préférentiellement en évidence les RNP. Nous avons suivi ainsi la dispersion du nucléole en prophase, le devenir des restes nucléolaires au cours de la métaphase et de la télophase, puis l'apparition des corps prénucléolaires en début d'interphase.     

Interaction entre la cochenille du manioc Phenacoccus manihoti et ses différentes plantes-hôtes: étude de la teneur de la sève en acide aminé et en sucre

Résumé L'analyse (acides aminés et sucres) d'extrait de feuille, de 5 variétés de manioc (Manihot esculenta), du Faux caoutchouc (Hybride deM. esculenta x M.glaziovii), du Poinsettia (Euphorbia pulcherrina) et du Talinum (Talinum triangularae), caractérisés par différents degrés de résistance par antibiose à la cochenille du manioc (Phenacoccus manihoti (Mat. Ferr.)) (Homoptera: Pseudococcidae), a été réalisée sur des extraits obtenus par centrifugation du matériel foliaire. Les teneurs en acids aminés, très différentes d'une plante à l'autre, apparaissent aussi importantes entre les variétés de l'espèce manioc qu'entre les différentes espèces végétales avec respectivement un rapport de variation de 4,5 et 5,5. De même, les teneurs en sucres (exprimées en équivalent saccharose), sont très différentes d'une plante à l'autre avec un rapport de variation de 1 à 33 entre les deux extrêmes, si l'on ne considère que l'espèceM. esculenta, il n'est plus que de 3,5.Des différences dans les proportions relatives des acids aminés libres d'extrait de feuille sont observées aussi bien entre les variétés de manioc qu'entre les espèces végétales. Cependant pour toutes les plantes étudiées l'acide glutamique, la glutamine, l'ethanolamine, et l'alanine représentent près de 50% des acides aminés de l'extrait de feuille; l'acide aspertique, l'asparagine et la sérine près de 20% tandis que la tyrosine, la méthionine, l'isoleucine, la leucine et la lysine sont présents en très faibles pourcentages.Le degré de résistance à la cochenille du manioc des différentes plantes-hôtes n'a pu être relié, ni à la teneur de leur extrait de feuille en acides aminés et en sucres, ni à leur composition relative en acides aminés. Il n'a pu être non plus relié au rapport Sucres/Acides aminés Nos résultats suggèrent que des caractéristiques biochimiques autres que celles étudiées dans ce travail interviennent dans les mécanismes de résistance vis-à-vis de la cochenille du manioc.

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Summary The levels of sugars and amino acids were determined in leaf extracts from a number of plants showing different levels of resistance to the cassava mealybug,Phenacoccus manihoti (Homoptera: Pseudococcidae). There were five varieties of cassava (Manihot esculenta), as well as a hybrid obtained by crossingM. esculenta andM. glaziovii, poinsettia (Euphorbia pulcherrina) and talinum (Talinum triangularae). The variability in the total concentration of amino acid concentrations was as great between varieties of cassava as at the species level. In contrast, there was much less variability in the concentration of sugars at the intervarietal that at the interspecies level.While there were both intervarietal and interspecific differences in the amino acid composition, glutamic acid, glutamine, ethanolamine and alanine represented nearly 50% of the total in all plants examined. Aspartic acid, asparagine and serine accounted for approximately 20%, while tyrosine, methionine, isoleucine, leucine and lysine are present at low levels.The different levels of resistance noted in the different plants were not associated with the concentrations of either amino acids or sugars, the ratios of sugar/amino concentrations or the amino acid compositions obtained from leaf extracts. This suggests that other aspects of plant chemistry confer resistance to cassava mealybugs.

     

Changement de structure de la poly-L-proline à l'état solide par hydratation: Etude par spectrométrie infra-rouge

Films of poly-L -proline I and II have been hy drated by water vapor and their infrared spectra analysed between 1250 and 3500 cm^?1. Forms I and II behave differently. Water binds to the carbonyl of form II through hydrogen bridges and, when released by drying, leaves the polypeptide conformation unchanged. In form I, complex formation with water seems to proceed through a different mechanism involving more than the carbonyls. Hydration of form I yields a partial irreversible transition to form II. Successive hydration and drying of the film brings the transition to completion. This I → II transition in the solid state has a cooperative character; its mechanism is discussed. Poly-L -prolines I and II also absorb vapors of aliphatic alcohols but not change in conformation is observed.     

Mise en évidence d'une relation entre la longueur el la constante de sédimentation des molécules de DNA en solution

A comparative study on sonicated calf thymus DNA was made by using electron microscopy and sedimentation methods. The length distribution, established by electron microscopy by using Kleinschmidt's technique, is related to the sedimentation curve obtained with the same solution. The relation permits a determination of the sedimentation constant corresponding to a given length up to 8000 Å and vice versa.     

Interactions de la chloroquine avec la ferriprotoporphyrine IX: Étude par résonance magnétique nucléaire

Chloroquine is still the antimalarial drug which is the most utilized. Nevertheless the molecular mode of action of this drug is not very well understood. When mouse erythrocytes injected with Plasmodium berghei are exposed to chloroquine, the first biochemical event is rapid accumulation of the drug. This process is energy dependent, saturable and competively inhibited by drugs of the same therapeutic class (Quinine, Amodiaquine, Mefloquine). Receptors for chloroquine have been proposed for the process of accumulation. The nature of the chloroquine receptor is presently the subject of debates. The latest hypothesis proposed by Chou and coll. [12], is that ferriprotoporphyrin IX, formed by the degradation of hemoglobin by the parasite, binds to chloroquine with a dissociation constant of 3.5.10⁻⁹ M. We studied here the molecular interactions between these two species by Proton Nuclear Magnetic Resonance in order to elucidate the nature and the geometry of were undertaken.The perturbations of the NMR spectra of chloroquine (10⁻² M) induced by addition of hematin or hemin were measured. Two types of measures were indertaken.The first study carried out in organic solvent (DMSO) has shown that the interaction occured between the acidic functions of hemin and the sidechain nitrogen of chloroquine. The iron atom was not implicated in this process.The second study carried out in aqueous medium (phosphate buffer; 0.1 M; pH = 7) allowed us to demonstrate that chloroquine is able to intercalate into a polymer of hematin. The quinoleic nucleus of chloroquine was intercalated between two dimers of hematin as shown by the broadening of the signal of the quinoleic protons due to very large increase in the correlation time.Finally it was shown that chloroquine is associated as a dimer in aqueous medium by hydrophobic interactions. The association constant is 5.5 M⁻¹.     

Possibilitiés d'étude des variantes de la cholinestérase plasmatique humaine par électrophorèse d'affinitéPossibilities of study of the human plasma cholinesterase variants by affinity electrophoresis

Affinity electrophoresis has been applied to the study of the multiple molecular forms of three human plasma cholinesterase phenotypes (usual enzyme U, atypical enzyme A and intermediate UA). Electrophoreses were carried out in polyacrylamide gels containing a water-soluble macromolecular derivative of m-amino-(substituted)-phenyltrimethylammonium immobilized within the gel network.Apparent dissociation constants (K_{D app}) were estimated from the mobilities of the enzymes versus ligand concentration.The ratio of K_{D app} values of the molecular forms of phenotypes A and U which is approximately 2 is consistent with the hypothesis that the anionic site is altered in atypical enzyme.     

Contribution à l'étude de la structure de la chromatine: I - Etude physico-chimique de la stabilité de la chromatine

Physicochemical studies of calf thymus chromatin were performed on micromicellar suspensions by thermal denaturation. These diluted suspensions were obtained, by a controlled shearing method, from a compact gel chromatin. Sedimentation and free-flow electrophoresis determined the size distribution of these particles. The most important result is a new transition on the melting profiles corresponding to a sudden increase of solution turbidity. This chromatin solution transition occurs at a higher temperature than usual DNA transition. The degree of « turbidity transitiondiminishes with micelle size but disappears when they are very mildly degraded by DNAases and when F₁ histone fraction is removed.This transition is not only size dependent but also depends on the micellar structure. This phenomenon is interpreted as an excluded volume effect by contact between compact and native regions of nucleoprotein micelles and denatured coils of DNA. Our study tried to show that the degree of turbidity transition can be a criterion of chromatin native structure.     

Structure primaire de l'anhydrase carbonique érythrocytaire B humaine: II. Clivage par le bromure de cyanogène et séquence des résidus 1–148

The amino acid sequence of the IICNBr fragment of the human erythrocyte carbonic anhydrase B has been determined. This fragment contains the first 148 of the 260 residues of the N-acetylated single polypeptide chain of the protein. After tryptic hydrolysis of this fragment, eleven peptides have been isolated by gel filtration and chromatography on Dowex 50 W-X₂ or DEAE-Sephadex. Eight of them were identified with already sequenced peptides previously isolated from tryptic hydrolysate of the whole protein. The other three ones were obtained in pure form and sequenced. The combined amino acid content of these eleven peptides only account for 124 of the 148 amino acid residues in the IICNBr fragment. The tryptic attack of the maleylated IICNBr fragment gave three peptides as was expected from the number of arginine residues (2) in this fragment: two arginyl peptides (II₁, II₃) and one homoseryl peptide (II₂). They were purified by gel filtration. The unidentified 24 residue tryptic peptide has been isolated from the demaleylated II₂ tryptic hydrolysate and sequenced. The order of the twelve tryptic peptides of IICNBr fragment has been obtained by study of chymotrypsic peptides isolated from II₁ and IICNBr fragment.     

Étude expérimentale de l'auto-association des molécules modèles dipeptidiques. II. Association stéréosélective des molécules énantiomères

Modes of aggregation fo alanine-, norvaline- and valine-contaiing dpepetides with the general formula R₁? C₁O₁? N₂H₂? CHR₂? C₂O₂? N₃H₃? R₃ have been studied in CCl₄ solution by using infrared and nuclear magnetic resonance spectroscopies. Solutions of the pure L isomer and of the racemic mixture do not give identical data. At a given concentration, the racemic mixtrue is more aggregated than the pure enantiomer, and the difference, negligible in the case of alanine derivative, increases wiht the bulkiness of the side cahin R₂. The results show that a selective interaction takes place between enantiomeric molecules, resulting ina dimer associating tow inverse configurated C₅ conformers. The stabilizaion of this dimer proceeds from two symmetrical and intermolecular H₃ … O₁ hydrogen bondings.     

Étude thermodynamique de la transition hélice–pelote statistique en solvants mixtes de différents esters de l'acide poly(L-glutamique)

Helix–coil transition of poly(γ-methyl-L -glutamate), poly(γ-ethyl-L -glutamate), and poly(γ-benzyl-L -glutamate) has been studied in mixed solvents by calorimetry, polarimetry, and viscometry. The experimental data have allowed the evaluation of solvation enthalpy Δh_b, equilibrium constant K for hydrogen bond formation between the active solvent component and CO and NH groups, and the cooperativity parameter σ. The conformational transition of polypeptides in solution in a mixed solvent containing enough active solvent to maintain the coiled conformation has been produced by dilution with the helix-supporting solvent for the measurements of enthalpy of transition Δh_s. The average value for Δh_s is 3550 ± 300 J/mol and is practically independent of the nature of the side chain for the dichloroacetic acid-ethylene dichloride solvent pair at 25°C. A noticeable concentration effect exists in the case of poly(γ-benzyl-L -glutamate). The helical conformation is less stable for poly(γ-ethyl-L -glutamate), and this is explained by a steric effect hindering the access of dichloroacetic acid to side chains. Constant K has been calculated using polarimetric data and also from values of Δh_s obtained at different temperatures using the Bixon and Lifson theory on the one hand and that of Sayama and coworkers on the other hand. Values of σ for poly(γ-ethyl-L -glutamate) have been calculated according to both theories mentioned, and the results show that the two sets of values are quite similar. The constant σ depends on the nature of the active solvent, on temperature, and on the binary-solvent composition. These conclusions are confirmed by viscometric results. Values of Δh_b calculated from constant K are 5230 J/mol when Bixon and Lifson theory is used and 5569 J/mol when the theory at Sayama and coworkers is used. In both cases the value for Δh_b is much lower than that of an intramolecular hydrogen bond. Experimental results suggest that the solvation mechanism would proceed in a manner so that mechanisms described in both theories are involved.