Unbiased sex-specific survival in Alpine chamois

Many polygynous ungulates show higher mortality of males than of females, because of the intense male–male competition during the rut and the costs associated with the development of sexual-size dimorphism. In the weakly dimorphic Alpine chamois Rupicapra rupicapra the occurrence of differential sex-specific survival strategies is controversial. To date, only two studies investigated the survivorship of males and females in this species, producing conflicting results: these works, based on the use of life tables, require confirmation from researches carried out on living populations. We assessed the survival pattern of a protected Alpine chamois population in the Swiss National Park, where 116 individuals were marked and monitored over 13 years (1996–2008). We tested for sex-, age- and year-dependence of survival by means of capture-mark-resight models. Resighting probabilities were sex-dependent, and survival rates were time-dependent. Females had higher resighting probabilities (0.84) than males (0.74). All over the time periods, sex had a weak influence on survival probability (males = 0.91; females = 0.92) and survival rates remained surprisingly high until late age (1 year = 0.90; 2–7 years = 0.91; 8+ years = 0.92). The growing evidence for a high adult survival and a weak differential mortality of the two sexes, together with the highly seasonal sexual-size dimorphism observed for Alpine chamois, might indicate the occurrence of a unique conservative survival strategy in both sexes and a low-risk mating strategy by males.     

Analogs of oxytocin containing a pseudopeptide Leu-Gly bond of cis and trans configuration

Analogs of deamino-oxytocin wherein the Leu-Gly peptide bond has been replaced by a tetrazole moiety or by a double bond of trans configuration were synthesized and their biological activities evaluated. Trans double bond was found to be the most appropriate substitution for the amide bond (uterotonic activity 24% of the deamino-oxytocin). In the case of all three analogs low but prolonged galactogogic activity was found and the ratio of uterotonic in vitro and in vivo activity was surprisingly high (ranging from 4.5 to 20).     

Proton n.m.r. spectroscopic evidence for sulfur-aromatic interactions in peptides

The downfield shift of the tyrosyl proton resonances and an increased chemical shift difference between the resonances for the 2',6' and 3',5' hydrogens in a series of deamino-oxytocin analogs modified in the disulfide bridge provide evidence for aromatic-sulfur interactions in d6-dimethylsulfoxide solutions.     

Conformationally restricted analogs of oxytocin; stabilization of inhibitory conformation

Analogs of oxytocin containing tetrahydroisoquinoline carboxylic acid (Tic) of L or D configuration in position 2 were synthesized and their biological activities were tested. Both analogs showed negligible agonist activity in uterotonic, galactogogic, and pressor assays, but they are in vitro uterotonic inhibitors. In comparison with oxytocin analogs containing L- or D-phenylalanine in position 2, the analog with the D-configuration of the conformationally fixed aromatic residue has significantly increased inhibitory activity which suggests that the proper conformation for the interaction with the receptor, but not for its activation, was stabilized. 1H NMR and CD studies, supported by theoretical calculations, suggest that the conformational properties of the analog containing D-tetrahydroisoquinoline carboxylic acid are similar to those of [2-D-phenylalanine]oxytocin.     

Analogs of oxytocin containing a modified peptide bond

Analogs of deamino-oxytocin and deamino-oxypressin containing a CH2-NH group instead of an amide bond between positions 8 and 9 were synthesized. All tested compounds exhibit significantly lowered biological activities.     

Cyclic melanotropins. Part VII: Modified ring structures--synthesis and biological activity

The highly potent cyclic analogue of alpha-MSH, Ac-[Cys4,Cys10]-alpha-MSH4-13-NH2, was structurally modified in position 4. Four analogues were prepared and their biological activities in the in vitro frog and lizard skin bioassays were determined. It was shown that removing the terminal acetylamino group to give [Mpa4,Cys10]-alpha-MSH4-13-NH2 resulted in little change in the biological activity, but a change in the stereochemistry of cysteine in position 4 to give Ac-[D-Cys4,Cys10[-alpha-MSH4-a3-NH2 led to a small decrease of activity in both bioassays. Decreasing the size of the intramolecular ring by removing one methylene group to give [Maa2,Cys10]-alpha-MSH4-13-NH2, resulted in an analogue with lower activities in both assays (about 3 times in the lizard and 500 times in the frog), and increasing the size of the righ by methylene group to give Ac-[Hcy4,Cys10]-alpha-MSH4-13-NH2 led to much lower activities in the lizard system and similar effects were seen upon decreasing the ring size in the frog skin assay.     

Search for optimal coupling reagent in multiple peptide synthesizer

Ten different coupling reagents and their combinations were tested in parallel in the synthesis of four model peptide sequences. Significant differences were found between uronium and phosphonium salt-based reagents and carbodiimide. Diisopropylcarbodiimide was identified as an optimal reagent based on the purity of the product, stability of the reagent, and convenience of handling on plate-based multiple parallel centrifugation synthesizer.     

Solid-phase peptide synthesis by fragment condensation: Coupling in swelling volume

The condensation of short peptides to resin-bound fragments was examined with respect to high coupling yields with only a small molar excess of a peptide in the reaction solution. The best results were achieved by the addition of reactants (C-unprotected peptide, DIC, and HOBt) dissolved in a so-called swelling volume of an appropriate solvent to a dry resin with an attached N-deprotected peptide chain. Each coupling step was followed by the end-capping of unreacted resin-bound peptide with 2,4-dinitrofluorobenzene. The substituted dinitroaniline chromophore formed in this reaction made the detection and separation of deletion peptides easy. Both conventional and swelling volume methods were compared on parallel syntheses of the HIV-1 protease C-terminal 78–99 fragment. The yields of the isolated heneicosapeptide were 21 and 81% in favor of the swelling volume procedure.     

Inclusion volume solid-phase synthesis

Solid-phase synthesis of peptides was carried out using only the volume of the solvent included in the swollen solid-phase resin beads [inclusion volume synthesis]. This approach enables (i) the use of higher concentrations of activated amino acids, resulting in increased coupling rates, (ii) drastically decreased consumption of solvents, and (iii) the construction of multiple peptide synthesizers having virtually no reaction vessels.