Fatty Acids Profile of Wild and Cultivar Tunisian Peanut Oilseeds (A. hypogaea L.) at Different Developmental Stages.

Eleven fatty acids were identified during maturity in the wild (AraA) and varieties peanut kernels (AraC and AraT). These fatty acids included C (palmitic acid), C (stearic acid), C (oleic acid), C (linoleic acid), C (nonadecanoic acid), C (gadoleic acid), C (arachidic acid), C (erucic acid), C (behenic acid), C (tricosanoic acid) and C (linoceric acid). Two fatty acids C and C were not previously detected from peanut kernels.

Electronic effects of 11β substituted 17β-estradiol derivatives and instrumental effects on the relative gas phase acidity.

Numerous studies have highlighted the role of the proton donor characteristics of the phenol group of 17β-estradiol (E(2)) in its association with the estrogen receptor alpha (ERα). Since the substitutions at position C((11)) have been reported to modulate this association, we hypothesized that such substitutions may modify the phenol acidity. Hence, phenol gas-phase acidity of nine C((11))-substituted E(2)-derivatives were evaluated using the extended Cooks' kinetic method, which is a method widely used to determine thermochemical properties by mass spectrometry.

Changes in phospholipid composition, protein content and chemical properties of flaxseed oil during development.

The aim of the present research is to investigate the effect of harvest date on the composition of flaxseed. Samples were collected at regular intervals from 7 to 56 days after flowering (DAF) and analyzed for phospholipid composition, storage protein content and chemical properties. Phospholipid (PL) percentage of the total lipid decreased from 32.

Characteristics and pathways of bioactive 4-desmethylsterols, triterpene alcohols and 4α-monomethylsterols, from developing Tunisian cultivars and wild peanut (Arachis hypogaea L.).

Seven 4-desmethylsterols, five triterpene alcohols and three 4α-monomethylsterols were identified by GC-MS during the development of wild peanut, which is Arbi (AraA), and cultivars peanut, which are Trabelsia (AraT) and Chounfakhi (AraC). Our results showed that the maximum level of 4-desmethylsterols (881.07 mg/100 g of oil) was reached at 12 days after flowering (DAF) date of peanut plant in AraA, as well as the highest level of triterpene alcohols (31.

Non-thermal internal energy distribution of ions observed in an electrospray source interfaced with a sector mass spectrometer.

The internal energy distribution P(E(int)) of ions emitted in an electrospray (ESI) source interfaced with a sector mass spectrometer is evaluated by using the experimental survival yield (SY) method including the kinetic shift. This method is based on the relationship between the degree of fragmentation of an ion and its amount of internal energy and uses benzylpyridinium cations due to their simple fragmentation scheme. Quantum chemical calculations are performed, namely at G3(MP2)//B3LYP and QCISD/MP2 levels of theory.

Comparison of the concentrations of long-chain alcohols (policosanol) in three Tunisian peanut varieties (Arachis hypogaea L.).

Policosanol (PC) is a mixture of high molecular weight aliphatic primary alcohols. Literature about the contents and compositions of PC derived from peanut varieties is scarce. Total PC composition and content in whole peanut grain samples from three varieties of peanut (two cultivars, AraC and AraT, and a wild one, AraA) were identified using a gas chromatograph system coupled with a mass spectrophotometer.

Energy-dependent dissociation of benzylpyridinium ions in an ion-trap mass spectrometer.

Benzylpyridinium ions, generated via electrospray ionization of dilute solutions of their salts in acetonitrile/water, are probed by collisional activation in an ion-trap mass spectrometer. From the breakdown diagrams obtained, phenomenological appearance energies of the fragment ions are derived. Comparison of the appearance energies with calculated reaction endothermicities shows a reasonably good correlation for this particular class of compounds.

Gas chromatography-mass spectrometry screening for phytochemical 4-desmethylsterols accumulated during development of Tunisian peanut kernels (Arachis hypogaea L.).

4-Desmethylsterols, the main component of the phytosterol fraction, have been analyzed during the development of Tunisian peanut kernels ( Arachis hypogaea L.), Trabelsia (AraT) and Chounfakhi (AraC), which are monocultivar species, and Arbi (AraA), which is a wild species, by gas chromatography-mass spectrometry. Immature wild peanut (AraA) showed the highest contents of beta-sitosterol (554.

Decameric uracil complexes around Li+.

Electrospray ionization (ESI) in combination with mass spectrometry (MS) experiments were carried out to study decameric uracil complexes cationized with Li(+) ion. A previous study has shown that, under specific experimental conditions, a particularly intense peak of the decamer U(10)Li(+) is formed, which was referred to as an indication for so-called 'magic number' cluster. In order to gain more insight on the structure of this decameric complex, here, we report experimental studies concerning the kinetics of the fragmentation.

Investigations of the fragmentation pathways of benzylpyridinium ions under ESI/MS conditions.

Benzylpyridinium ions are often used as 'thermometer ions' in order to evaluate the internal energy distribution of the ions formed in sources of mass spectrometers. However, the detailed fragmentation pathways of these parent ions were not well established. In particular, fragmentation involving a rearrangement (RR) process may be influencing the simulated distribution curves.

Stereochemical effects during [M-H]- dissociations of epimeric 11-OH-17beta-estradiols and distant electronic effects of substituents at C(11) position on gas phase acidity.

The affinity of estradiol derivatives for the estrogen receptor (ER) depends strongly on nature and stereochemistry of substituents in C(11) position of the 17beta-estradiol (I). In this work, the stereochemistry effects of the 11alpha-OH-17beta-estradiol (III(alpha)) and 11beta-OH-17beta-estradiol (III(beta)) were investigated using CID experiments and gas-phase acidity (DeltaH degrees (acid)) determination. The CID experiments showed that the steroids decompose via different pathways involving competitive dissociations with rate constants depending upon the alpha/beta C(11) stereochemistry.

Phytosterols accumulation in the seeds of Linum usitatissimum L.

A comparative study was performed to determine the free sterols content and composition during the development of three varieties of linseed (H52, O116 and P129). Seed samples were collected at regular intervals from 7 to 60 days after flowering (DAF). Ten compounds were identified: cholesterol, campesterol, brassicasterol, stigmasterol, beta-sitosterol, Delta5-avenasterol, cycloartenol; 24-methylene cycloartanol, obtusifoliol, citrostadienol.

Characterization and quantification of the aliphatic hydrocarbon fraction during linseed development ( Linum usitatissimum L.).

Changes in hydrocarbon composition were investigated during maturation of three varieties of linseed (H52, O116, and P129) cultivated in Tunisia. The hydrocarbon fraction of the three linseed oil samples was found to contain mainly n-alkanes and squalene. The greatest decrease of these components occurred between 7 and 21 days after flowering (DAF); thereafter, the changes were slight.

Formation of complexes between uracil and calcium ions: an ESI/MS/MS study in combination with theoretical calculations.

Cationized uracil clusters around calcium metal ions were generated in the gas phase by electrospray ionization (ESI). A previous study showed that with particular experimental conditions, hexamer, octamer, decamer, dodecamer and tetradecamer uracil clusters are present in high quantities. New experiments were carried out to understand the reasons for the particular stability of these complexes.

Theoretical and experimental studies of cationized uracil complexes in the gas phase.

Cationized uracil clusters were generated in the gas phase by electrospray ionization (ESI). Mass spectrometry experiments showed that with particular experimental conditions, decameric uracil clusters are magic number clusters. MS/MS experiments demonstrated that the structure of these decameric uracil clusters depends substantially on the size and the charge of the cation.

Theoretical and experimental study of tropylium formation from substituted benzylpyridinium species.

Fragmentation pathways of unsubstituted and substituted benzylpyridinium compounds were investigated using mass-analysed kinetic energy (MIKE) technique in combination with high level of quantum chemical calculations in the gas phase. Fast atom bombardment (FAB) source was used for ionisation of the studied compounds. The formation of both benzylium and tropylium species were investigated.

Theoretical and gas-phase studies of specific cationized purine base quartet.

Guanine tetraplexes are biological non-covalent systems stabilized by alkali cations. Thus, self-clustering of guanine, xanthine and hypoxanthine with alkali cations (Na(+), K(+) and Li(+)) is investigated by electrospray ionization mass spectrometry (ESI-MS) in order to provide new insights into G-quartets, hydrogen-bonded complexes. ESI assays displayed magic numbers of tetramer adducts with Na(+), Li(+) and K(+), not only for guanine, but also for xanthine bases.

Anionic copper complex fragmentations from enkephalins under low-energy collision-induced dissociation in an ion trap mass spectrometer.

Peptide metallation with Cu2+ was explored in the negative ESI mode using an ion trap mass spectrometer. Under these conditions, the [(M-3H) + CuII]- species formed were investigated under low-energy collision-induced dissociation conditions. MS2 experiments indicate a very different behavior of CuII metallated complexes compared with [M-H]- species.