0000000000099332
AUTHOR
L. Ceraulo
Studies in organic mass spectrometry. Part 25. Benzyl ion formation in chemical ionisation (methane or isobutane) of some ortho-alkylhetero-substituted diphenylcarbinols
The behaviour of some ortho-alkylhetero-substituted diphenylcarbinols, including deuterium labelled derivatives, under chemical ionisation (methane or isobutane) conditions has been investigated. It has been determined that ortho-alkylhetero diphenylmethyl cations formed by water elimination from the protonated molecule undergo consecutive rearrangements which afford benzyl (or tropylium) ions previously observed for ortho- substituted diphenylcarbenium ions generated by electron ionisation. This reaction also occurs under low-energy collision conditions. Copyright (C) 2000 John Wiley and Sons, Ltd.
Molecular dynamics of electrosprayed water nanodroplets containing sodium bis(2-ethylhexyl)sulfosuccinate
The behavior of aqueous solutions of sodium bis(2-ethylhexyl)sulfosuccinate (AOTNa) subject to electrospray ionization (ESI) has been investigated by molecular dynamics (MD) simulations at three temperatures (350, 500 and 800 K). We consider several types of water nanodroplets containing AOTNa molecules and composed of a fixed number of water molecules (1000), N(AOT)(0) AOT(-) anions (N(AOT)(0) = 0, 5, 10) and N(Na)(0) sodium ions (N(Na)(0) = 0, 5, 10, 15, 20): in a short time scale (less than 1 ns), the AOTNa molecules, initially forming direct micelles in the interior of the water nanodroplets, are observed in all cases to diffuse nearby the nanodroplet surface, so that the hydrophilic …
Detection and localisation of disulphide bonds in a synthetic peptide reproducing the sequence 1-30 of Par j 1.0101 by electrospray ionisation mass spectrometry
The structural characterisation of a synthetic peptide reproducing the sequence 1–30 of Par j 1.0101, a major allergenic protein present in the pollen of Parietaria judaica, by combined use of chemical and enzymatic cleavage, reversed-phase high-performance liquid chromatography (RP-HPLC) and electrospray ionisation mass spectrometry (ESI-MS), is described. Direct ESI-MS of the synthetic peptide after reaction with methyl iodide showed that the product is a mixture of two peptides: one form in which two out of the four cysteine residues present in the sequence are oxidised and a minor amount of another form in which all the cysteines are fully reduced. It was ascertained, using the combined…
Crystal and molecular structure of 2,3,6,7-tetramethoxy-9-trichloromethyl-10-carboxymethyl-9,10-dihydroanthracene
Cl3O6C21H21,Mr=475.75, orthorhombic,P212121,a=21.895(3),b=12.101(2), andc=8.237(2) A,V=2182.4(7) A3,Dx=1.45 g cm−3 forZ=4, λ(MoKα)=0.71069 Aμ=3.99 cm−1,F(000) 984, room temperature,R=0.035 for 1877 observed reflections. The molecule exhibits a folded conformation: the dihedral angle between the benzene rings is 28.3(1)°. The central ring is characterized by acis diaxal configuration of hydrogen atoms in the 9, 10 positions, confirming the 13-C NMR results.
Degrees of freedom effect on fragmentation in tandem mass spectrometry of singly charged supramolecular aggregates of sodium sulfonates
The characteristic collision energy (CCE) to obtain 50% fragmentation of positively and negatively single charged noncovalent clusters has been measured. CCE was found to increase linearly with the degrees of freedom (DoF) of the precursor ion, analogously to that observed for synthetic polymers. This suggests that fragmentation behavior (e.g. energy randomization) in covalent molecules and clusters are similar. Analysis of the slope of CCE with molecular size (DoF) indicates that activation energy of fragmentation of these clusters (loss of a monomer unit) is similar to that of the lowest energy fragmentation of protonated leucine-enkephalin. Positively and negatively charged aggregates be…
Atractyligenin chemistry. Part 4: Synthesis of the 15β-ol epimer of atractyligenin
The oxidation with PCC of atractyligenin 3, the aglicone of the toxic glycoside 1 isolated from Atractylis gummifera L., led to the 15-oxo-derivative 6, together with a small amount of 2,15-dioxoderivative 5, with a selective oxidation of the allylic 15-OH group of the molecule. Further reduction with NaBH4 and KOH hydrolysis gave stereoselectively the 15β-ol epimer of atractiligenin 9.
Collision induced fragmentations of multiply charged sodium bis(2-ethylhexyl)-sulfosuccinate aggregates in gas phase: neutral loss versus charge separation
Abstract Stability and fragmentation patterns of multicharged aggregates of sodium bis(2-ethylhexyl)-sulfosuccinate (NaAOT) in gas phase have been investigated by ion mobility mass spectrometry (IM-MS) and tandem mass spectrometry (MS-MS). Positively doubly charged NaAOT aggregates show at low collision energy a preference for the loss of NaAOT molecules, whereas fragmentation through charge separation process is favored at higher collision energy. By increasing the charge state of the aggregates, the fragmentation through charge separation tends to predominate especially at low aggregation number and only charge separation fragmentation is observed for positively quadruply charged species.…
Volatile profiles of Sicilian prickly pear (Opuntia ficus indica) by SPME-GC/MS analysis
The aroma compounds present in the headspace of homogenized slurries of fresh prickly pears (Opuntia ficus-indica) from Sicilian cultivars were determined. Solid Phase Microextraction (SPME) followed by Gas-chromatography/Mass Spectrometry (GC/MS) analysis was used to characterize the volatile compounds. The volatile flavour profiles of the three cultivars investigated (red, white and yellow) showed significant differences. The aromatic profile of peeled prickly pears stored for one day was different from the one of the fresh samples, mainly due to the occurrence of some oxidative and hydrolytic reactions
Interactions of tryptophan and serotonin with biomembrane models: Binding to reversed micellar systems of ionic and non ionic surfactants
The interactions of Tryptophan (TRP) and Serotonin (5-HT), with water-containing sodium bis (2-ethylhexyl) sulfosuccinate (AOT), didodecyldimethylammonium bromide (DDAB) and tetraethylene glycol monododecyl ether (C12E4) reversed micelles have been investigated by UV absorption spectroscopy. Our results suggest that independently of the nature of the surfactant and the amount of the water encapsulated into the micellar core, TRP and 5-HT are solubilized in the micellar phase, preferring to be located in a shallow region constituted by the hydrated surfactant head groups. This is due to the amphiphilic nature of TRP and 5-HT and the biological implications are discussed.
1H-NMR and FT-IR study of the state of melatonin confined in membrane models: location and interactions of melatonin in water free lecithin and AOT reversed micelles
The state of melatonin confined either in dry lecithin or bis(2-ethylhexyl) sulfosuccinate sodium salt (AOT) reversed micelles has been investigated by H-1-NMR and FT-IR spectroscopies as a function of the melatonin to surfactant molar ratio (R). The analysis of experimental results leads to hypothesize that, independently of R and the surfactant nature and as a consequence of anisotropic melatonin/surfactant interactions, melatonin is totally solubilized in reversed micelles and mainly located by opportune orientation in the nanodomain constituted by the surfactant head groups. The absence of significant spectral changes related to the protons linked to the first carbon atoms of surfactant…