An approach to branched-chain amino sugars,particularly derivatives of l-vancosamine (3-amino-2,3,6-trideoxy-3-C-methyl-l-lyxo-hexose) and its d enantiomer,via the cyanohydrin route

Methyl 4,6-O-benzylidene-2-deoxy-α-d-erythro-hexopyranosid-3-ulose reacted with potassium cyanide under equilibrating conditions to give, initially, methyl 4,6-O-benzylidene-3-C-cyano-2-deoxy-α-d-ribo-hexopyranoside (7), which, because it reverted slowly to the thermodynamically stable d-arabino isomer, could be crystallised directly from the reaction mixture. The mesylate derived from the kinetic product 7 could be converted by published procedures into methyl 3-acetamido-2,3,6-trideoxy-3-C-methyl-α-d-arabino-hexopyranoside, which was transformed into methyl N-acetyl-α-d-vancosaminide on inversion of the configuration at C-4. A related approach employing methyl 2,6-dideoxy-4-O-methoxymethyl-α-l-erythro-hexopyranosid-3-ulose gave the kinetic cyanohydrin and thence, via the spiro-aziridine 27, methyl 3-acetamido-2,3,6-trideoxy-3-C-methyl-α-l-arabino-hexopyranoside, a known precursor of methyl N-acetyl-α-l-vancosaminide.     

Synthesis of new branched-chain aminodeoxyhexoses related to daunosamine (3-amino-2,3,6-trideoxy-l-lyxo-hexose)

Addition of methylmagnesium iodide to methyl 2,3,6-trideoxy-3-trifluoro-acetamido-α-l-threo-hexopyranosid-4-ulose (3) gave methyl 2,3,6-trideoxy-4-C-methyl-3-trifluoroacetamido-α-l-lyxo-hexopyranoside (4) and its l-arabino analogue, depending upon the reaction temperature and the solvent. The corresponding 4-O-methyl derivatives were obtained by treatment of 4 and 5 with diazomethane in the presence of boron trifluoride etherate. Treatment of 4 with thionyl chloride, followed by an alkaline work-up, gave methyl, 2,3,4,6-tetradeoxy-4-C-methylene-3-trifluoro-acetamido-α-l-threo-hexopyranoside (8), which was stereoselectively reduced to methyl 2,3,4,6-tetradeoxy-4-C-methyl-3-trifluoroacetamido-α-l-arabino-hexopyranoside. Epoxidation of 8 with 3-chloroperoxybenzoic acid gave the corresponding 4,4₁-anhydro-4-C-hydroxymethyl-l-lyxo derivative (10), which was also prepared by treatment of 3 with diazomethane. Azidolysis of 10, followed by catalytic hydrogenation and N-trifluoroacetylation, gave methyl 2,3,6-trideoxy-3-trifuloroacetamido-4-C-trifluoroacetamidomethyl-α-l-lyxo-hexopyranoside.     

An approach to the synthesis of branched-chain amino sugars from c-methylene sugars

The reaction of 1,2:5,6-di-O-isopropylidene-3-C-methylene-α-D-ribo-hexofuranose (4) with mercuric azide in hot 50% aqueous tetrahydrofuran yielded, after reductive demercuration, 3-azido-3-deoxy-1,2:5,6-di-O-isopropylidene-3-C-methyl-α-D-glucofuranose (5). Partial, acid hydrolysis of5 afforded the diol7, which gave 3-azido-3-deoxy-1,2-O-isopropylidene-5,6-di-O-methanesulphonyl-3-C-methyl-α-D-glucofuranose (8) on sulphonylation. On hydrogenation over a platinum catalyst and N-acetylation, the dimethanesulphonate 8 furnished 3,6-acetylepimino-3,6-dideoxy-1,2-O-isopropylidene-5-O-methanesulphonyl-3-C-methyl-α-D-glucofuranose (9), which was also prepared by an analogous sequence of reactions on 3-azido-3-deoxy-1,2-O-isopropylidene-5-O-methanesulphonyl-3-C-methyl-6-O-toluene-p-sulphonyl-α-D-glucofuranose (13). The formation of the N-acetylepimine 9 establishes the D-gluco configuration for 5.1,2-O-Isopropylidene-3-C-methylene-α-D-ribo-hexofuranose (20) reacted with mercuric azide in aqueous tetrahydrofuran at ≈85° to give 3,6-anhydro-1,2-O-isopropylidene-3-C-methyl-α-D-glucofuranose (22) as a result of intramolecular participation by the C-6 hydroxyl group in the initial intermediate.     

Synthesis of new branched-chain aminodeoxyhexoses related to daunosamine (3-amino-2,3,6-trideoxy-l-lyxo-hexose)

Addition of methylmagnesium iodide to methyl 2,3,6-trideoxy-3-trifluoro-acetamido-α-l-threo-hexopyranosid-4-ulose (3) gave methyl 2,3,6-trideoxy-4-C-methyl-3-trifluoroacetamido-α-l-lyxo-hexopyranoside (4) and its l-arabino analogue, depending upon the reaction temperature and the solvent. The corresponding 4-O-methyl derivatives were obtained by treatment of 4 and 5 with diazomethane in the presence of boron trifluoride etherate. Treatment of 4 with thionyl chloride, followed by an alkaline work-up, gave methyl, 2,3,4,6-tetradeoxy-4-C-methylene-3-trifluoro-acetamido-α-l-threo-hexopyranoside (8), which was stereoselectively reduced to methyl 2,3,4,6-tetradeoxy-4-C-methyl-3-trifluoroacetamido-α-l-arabino-hexopyranoside. Epoxidation of 8 with 3-chloroperoxybenzoic acid gave the corresponding 4,4₁-anhydro-4-C-hydroxymethyl-l-lyxo derivative (10), which was also prepared by treatment of 3 with diazomethane. Azidolysis of 10, followed by catalytic hydrogenation and N-trifluoroacetylation, gave methyl 2,3,6-trideoxy-3-trifuloroacetamido-4-C-trifluoroacetamidomethyl-α-l-lyxo-hexopyranoside.     

Synthesis of derivatives of 3-amino-2,3-dideoxy-l-hexoses related to daunosamine (3-amino-2,3,6-trideoxy-l-lyxo-hexose)

The synthesis is described of 3-amino-2,3-dideoxy-l-arabino-hexose (10), methyl 2,3-dideoxy-3-trifluoroacetamido-α-l-lyxo-hexopyranoside (17), methyl 3-amino-2,3-dideoxy-α-l-ribo-hexopyranoside (21), methyl 2,3-dideoxy-3-trifluoroacetamido-α-l-xylo-hexopyranoside (26), and certain derivatives from methyl 4,6-O-benzylidene-2-deoxy-α-l-arabino-hexopyranoside (3). Conversion of 2-deoxy-l-arabino-hexose into 3 by modified, standard procedures, and on a large scale, gave a 75% yield.     

Gustation of sugars, amino acids and lipids by larvae of the scarabaeid, Sericesthis geminata (Coleoptera)

Third-instar larvae of the scarabaeid Sericesthis geminata were stimulated to bite and feed on filter paper by a number of sugars, amino acids and lipids. The degree of stimulation generally increased with increasing concentration, but high concentrations of fructose and amino acid had inhibitory effects. Sterols were non-stimulating at low concentrations and acted as feeding deterrents at high ones.

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Zusammenfassung In einer Reihe von einfachen Wahlkammerversuchen wurde das Verhalten der bodenbewohnenden Larven des Scarabaeiden Sericesthis geminata (Boisduval) gegenüber Zuckern, Aminosäuren und Lipiden geprüft. Die Versuchschemikalien wurden in verschiedenen Konzentrationen auf Filtrierpapier aufgetragen und die gefressenen Stellen ausgemessen.Jeder der drei Zucker Saccharose, Maltose und Glucose erhöhte die Nahrungsaufnahme. Die Disaccharide Saccharose und Maltose hatten einen größeren Effekt als Glucose. Bei diesen drei Zuckern war im allgemeinen bis zu einer Konzentration von 1.0 M ein zunehmender Effekt festzustellen. Fructose erhöhte die Nahrungsaufnahme nicht und hatte bei höheren Konzentrationen einen hemmenden Effekt. Die einzelnen Aminosäuren L-Isoleucin, L-Leucin und L-Alanin sowie eine Gruppe von sechs Aminosäuren erhöhten die Nahrungsaufnahme in einem begrenzten Konzentrationsbereich, hemmten aber die Nahrungsaufnahme bei hohen Konzentrationen. Die Wirkung der Gruppe von Aminosäuren zeigte, daß dabei der Effekt der verschiedenen Aminosäuren komplementär war. Freie Fettsäuren, Triglyceride und Phospholipoide erhöhten die Nahrungsaufnahme. Steroide hatten bis zu hohen Konzentrationen keinen wesentlichen Einfluß; bei hohen Konzentrationen wurde die Nahrungsaufnahme verringert.

     

The synthesis of 2,5-dideoxy-4,6-di-O-(2,3-dideoxy-α-D- erythro-hexopyranosyl)streptamine and 4,6-di-O(6-amino-2,3,6-trideoxy-α-D- erythro-hexopyranosyl)-2,5-dideoxystreptamine

The title pseudotrisaccharides, derived from 2,5-dideoxystreptamine, have been synthesized, in order to ascertain structure-activity relationships in aminoglycoside antibiotics. High yields of α-D-glycosides, virtually free of β anomers, were achieved by the BF₃-catalyzed addition of alcohols to glycals.     

Nucleotide sequence of genes hrdA, hrdC, and hrdD from Streptomyces coelicolor A3(2) having similarity to rpoD genes

Summary The complete nucleotide sequences were determined of hrdA, hrdC, and hrdD from Streptomyces coelicolor A3(2). They indicate the presence of a single open reading frame in each gene coding for polypeptides of 396 (43747 daltons), 339 (38173 daltons), and 332 amino acid residues (37190 daltons), respectively. These amino acid sequences revealed extensive similarities with the principal sigma factors of Bacillus subtilis, Escherichia coli, Mxyococcus xanthus, Pseudomonas aeruginosa, and also the katF gene product of E. coli. Besides the highly conserved amino acid residues in the rpoD box region, alignment of hrd gene products and the known principal sigma factors and sigma-related factors allowed us to postulate a common basic structure for the principal sigma type factors as distinct from the alternative sigma factors.     

Molecular structures and some properties of tris(2-aminoethyl) amine cobalt(III) complexes with thiocarboxylato-O,S such as 3-mercaptopropionato, 2-mercaptoacetato and their derivatives

Cobalt(III) complexes with a thiolate or thioether ligand, t-[Co(mp)(tren)]⁺ (2), t-[Co(mtp)(tren)]²⁺ (1Me) and t-[Co(mta)(tren)]²⁺ (2Me), (mp = 3-mercaptopropionate, MA = 3-(methylthio)propionate and MTA = 2-(methylthio)acetate) have been prepared in aqueous solutions. The crystal structures of 1, 2, 1Me and 2Me were determined by X-ray diffraction methods. The crystal data are as follows, t-[Co(mp)(tren)]ClO₄ (1CIO₄): monoclinic, P2₁/n, A = 10.877(8), B = 11.570(4), c = 12.173(7) Å, β = 92.20(5)°, V = 1531(1) ų, Z = 4 and R = 0.060; t-[Co(ma)(tren)]Cl·3H₂O (2Cl·3H₂O): monoclinic, P2₁/n, a = 7.7688(8), B = 27.128(2), C = 7.858(1) Å, β = 100.63(1)°, V = 1627.7(3) ų, Z = 4 and R = 0.066; (+)₄₆₅^CD-t-[Co(mtp)(tren)](ClO₄)₂ ((+)₄₆₅^CD-1Me(ClO₄)₂): orthorhombic, P2₁2₁2₁, A = 10.6610(7), B = 11.746(1), C = 15.555(1) Å, V = 1947.9(3) ų, Z = 4 and R = 0.068; (+)₄₆₅^CD-t-[Co(mta)(tren)](ClO₄)₂ ((+)₄₆₅^CD-2Me(ClO₄)₂): orthorhombic, P2₁2₁2₁, a = 10.564(1), B = 11.375(1), C = 15.434(2) Å, V = 1854.7(4) ų, Z = 4 and R = 0.047. All central Co(III) atoms have approximately octahedral geometry, coordinated by four N, one O, and one S atoms. All of the complexes are only isomer, of which the sulfur atom in the didentate-O,S ligands are located at the trans position to the tertiary amine nitrogen atom of tren. 1 and 1Me contain six-membered chelate ring, and 2 and 2Me do five-membered chelate ring in the didentate ligand. The chirality of the asymmetric sulfur donor atom in (+)₄₆₅^CD-1Me is the S configuration and that in (+)₄₆₅^CD-2Me is the R one. The ¹H NMR, ¹³C NMR and electronic absorption spectral behaviors and electrochemical properties of the present complexes are discussed in relation to their stereochemistries.     

(Z)-3-nonenol, (Z,Z)-3,6-nonadienol and (S,S)-(-)-epianastrephin: male produced pheromones of the Mexican fruit fly

(Z)-3-nonenol, (Z,Z)-3,6-nonadienol and (S,S)-(-)-epianastrephin proved active as male-produced pheromones which elicited behavioral responses from virgin female Mexican fruit flies (Anastrepha ludens) (Diptera: Tephritidae) in laboratory bioassays. All three chemicals elicited attraction and/or locomotor arrest when tested individually. When tested together, (Z)-3-nonenol inhibited the behavioral effect of (Z,Z)-3,6-nonadienol but either of the alcohols synergized the effect of (S,S)-(-)-epianastrephin. Quantities of the pheromones per male abdomen were: (Z)-3-nonenol-100 ng; (Z,Z)-3,6-nonadienol-40 ng; and total epianastrephin (R,R and S,S enantiomers)-700 ng. Relative to the quantities in abdominal extract, males released these chemicals during sexual display in a blend containing a higher proportion of the alcohols.

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Résumé Le (Z)-3-nonènol, le (Z,Z)-3,6-nonadiènol et le (S,S)-(-)-épianastréphine produits par les mâles de la mouche mexicaine du fruit (Anastrepha ludens) (Diptera: Tephritidae) ont attirés les femelles lors de tests conduits en laboratoire. Le pouvoir attractif du (Z)-3-nonènol est faible comparé à celui des deux autres phéromones. Evalués ensemble, le (Z)-3-nonènol inhibe l'attractivité du (Z,Z)-3,6-nonadiènol mais chacun des deux alcools synergise l'effet attractif de la (S,S)-(-)-épianastréphine. Les quantités recouvrées par mâle dans un extrait abdominal étaient respectivement de 100, 40 et 700 ng pour le (Z)-3-nonènol, le (Z,Z)-3,6-nonadiènol, et l'épianastréphine totale (R,R et S,S) énantiomères. Comparées à ces valeurs, le mélange élange émis par les mâles lors de leur cour sexuelle est plus riche in alcools. Le rapport (Z)-3-nonènol (Z,Z)-3,6-nonadiènol est cependant identique dans l'extrait abdominal et dans le mélange émis par les mâles.

     

A new locus (leuK) affecting the regulation of branched-chain amino acid, histidine, and tryptophan biosynthetic enzymes.

A locus (leuK) affecting regulation of the leucine operon was selected by isolating a spontaneous Ara+ derivative of an Escherichia coli B/r strain carrying an ara-leu fusion in which the arabinose operon is under leucine control. Genetic analyses by P1 transduction demonstrated that the lesion is located to the right of the galactose operon. Regulation of the biosynthetic enzymes for leucine, isoleucine-valine, histidine, and tryptophan was altered in a strain carrying leuK16. High-level gene expression in the heterozygous merodiploid strain F' leuK+/leuK16) demonstrated the dominance of the mutant allele to the wild-type allele. No apparent effect was observed in the mutant on N-acetylornithinase, a biosynthetic enzyme in the arginine pathway, nor on any of the 18 aminoacyl-tRNA synthetases examined. However, compared with that of the parent strain, the extent of the charging of leucyl-, isoleucyl-, valyl-, histidyl-, and arginyl-tRNA was decreased in the mutant.     

Diet and physiological responses of Spondyliosoma cantharus (Linnaeus, 1758) to the Caulerpa racemosa var. cylindracea invasion

Marine invasions are a worldwide problem that involves changes in communities and the acclimation of organisms to them. The invasive Chlorophyte Caulerpa racemosa var. cylindracea is widespread in the Mediterranean and colonises large areas from 0 to 70 m in depth. The omnivorous fish Spondyliosoma cantharus presents a high frequency of occurrence of C. racemosa in the stomach contents at invaded areas (76.3%) while no presence of C. racemosa was detected in control areas. The isotopic composition of muscle differed significantly between invaded and non-invaded sites for δ¹³C (− 16.67‰ ± 0.09 and − 17.67‰ ± 0.08, respectively), δ¹⁵N (10.22‰ ± 0.22 and 9.32‰ ± 0.18, respectively) and the C:N ratio (2.01 ± 0.0002 and 1.96 ± 0.009, respectively). Despite the high frequency of occurrence of C. racemosa in the stomach contents of S. cantharus and its important contribution to the δ¹³C source (20.7% ± 16.2), the contribution of C. racemosa to the δ¹⁵N in S. cantharus food sources was very low (6.6% ± 5.8). Other invertebrate prey such as decapods and polychaetes were more important contributors to the δ¹⁵N source at both invaded and non-invaded sites. Activation of enzymatic pathways (catalase, superoxide dismutase, glutathione-s-tranferase, 7-ethoxy resorufin O-de-ethylase) but not a significant increase in lipid peroxidation MDA (0.49 ± 0.01 nmol/mg prot at non-invaded and 0.53 ± 0.01 nmol/mg prot at invaded sites) was observed in S. cantharus individuals living in C. racemosa-invaded sites compared with control specimens. The low δ¹⁵N contribution values of C. racemosa by S. cantharus together with the toxicity demonstrated by the activation of the antioxidant defences and the important contribution of invertebrate prey to the δ¹⁵N could mean that the ingestion of C. racemosa by S. cantharus might be unintentional during the predation of invertebrate preys living underneath the entanglement of the C. racemosa fronds and stolons mats.     

An integrated approach to produce biodiesel and monoglycerides by enzymatic interestification of babassu oil (Orbinya sp)

Two screenings of commercial lipases were performed to find a lipase with superior performance for the integrated production of biodiesel and monoglycerides. The first screening was carried out under alcoholysis conditions using ethanol as acyl acceptor to convert triglycerides to their corresponding ethyl esters (biodiesel). The second screening was performed under glycerolysis conditions to yield monoglycerides (MG). All lipases were immobilized on silica–PVA composite by covalent immobilization. The assays were performed using babassu oil and alcohols (ethanol or glycerol) in solvent free systems. For both substrates, lipase from Burkholderia cepacia (lipase PS) was found to be the most suitable enzyme to attain satisfactory yields. To further improve the process, the Response Surface Methodology (RSM) was used to determine the optima operating conditions for each biotransformation. For biodiesel production, the highest transesterification yield (>98%) was achieved within 48 h reaction at 39 °C using an oil-to-ethanol molar ratio of 1:7. For MG production, optima conditions corresponded to oil-to-glycerol molar ratio of 1:15 at 55 °C, yielding 25 wt.% MG in 6 h reaction. These results show the potential of B. cepacia lipase to catalyze both reactions and the feasibility to consider an integrated approach for biodiesel and MG production.     

Interactions between the Parasitoid Rhopus nigroclavatus (Ashmead) (Hymenoptera: Encyrtidae) and its Mealybug Hosts Tridiscus sporoboli (Cockerell) and Trionymus sp. (Homoptera: Pseudococcidae)

This research investigated age-class-specific parasitism rates of the buffalograss mealybugs Tridiscus sporoboli (Cockerell) and Trionymus sp. by Rhopus nigroclavatus (Ashmead) (Hymenoptera; Encyrtidae), size class preference of this parasitoid, and mealybug–parasitoid interactions through choice and no-choice studies. In the no-choice studies, the mean rates of parasitism by R. nigroclavatus were 45, 20, 0, and 0%, respectively, for mealybugs adult female, third and fourth instars, first and second instars, and eggs. Choice studies indicated that rate of parasitism increased with host size. The mean rates of parasitism on mealybugs in the choice studies were 100% for adult females, 24% for third and fourth instars, 0% for first and second instars, and 0% for eggs. A second set of choice studies investigating mealybug/parasitoid behavior revealed that R. nigroclavatus oviposits in all post-egg mealybug age classes, but first and second instars were less often parasitized than older mealybugs.