STUDIES ON ALKALY METAL HALIDES AGGREGATES IN GAS PHASE

Dimethoxy Aromatic Compounds. VIII. Degenerate Dealkylation-Realkylation Reaction of 1-Bis(2,4-dimethoxyphenyl)-2-methylpropane.

The condensation reaction under acid condition of the benzylic alcohols 1, 2 and 3 with the hexadeutero dimethoxybenzenes 4, 5 and 6 leads to the expected hexadeutero bis(dimethoxyphenyl)-2-methylpropanes 7, 8 and 9, respectively. However, the presence of both dodecadeutero and unlabelled 1-bis(2, 4-dimethoxyphenyl)-2-methylpropanes 10 and 11 indicates that 9 undergoes a rapid degenerate dealkylation-alkylation reaction.

A Novel HPLC-MS Method for Analysis of Plasma Sterols

Dimethoxy aromatic compounds. IV.—determination of stereochemistry of 2,3,6,7-tetraalkoxy-9,10-dihalomethyl-9,10-dihydroanthracenes by13C NMR chemical shifts

The analysis of the 13C NMR spectra of several 2,3,6,7-tetraalkoxy-9,10-dihalomethyl-9,10-dihydroanthracenes showed a strong dependence of the chemical shift values on the orientation of the halomethyl groups. On this basis it was possible to determine both the configuration (cis or trans) and conformation of the isomers, even if only one isomer was available.

Self-assembly and intra-cluster reactions of erbium and ytterbium bis(2-ethylhexyl)sulfosuccinates in the gas phase

RATIONALE The study of surfactant organization in vacuum allows surfactant–surfactant interaction to be unveiled in the absence of surrounding solvent molecules. Knowledge on their chemical-physical properties may also lead to the definition of more efficient gas-phase carriers, air-cleaning agents and nanoreactors. In addition, the presence of lanthanide-group ions adds unique photochemical properties to surfactants. METHODS The structural features, stability and fragmentation patterns of charged aggregates formed by lanthanide-functionalized surfactants, ytterbium and erbium bis(2-ethylhexyl)sulfosuccinate ((AOT)3Yb and (AOT)3Er), have been investigated by electrospray ionization mass spe…

ChemInform Abstract: Mass Spectrometry of 3,4-Dihydroquinazolin-4-ones of Pharmaceutical Interest. Part 3. Electron Ionization Mass Spectra of 2-Substituted-3-( 5′-pyrazolyl)-4(3H)-quinazolinones.

The fragmentation reactions induced by electron impact of eighteen title compounds has been investigated with the aid of low beam energy spectra (14 eV, nom. value), metastable ion detection, high resolution measurements and labelling experiments. The loss of the 4-carbonyl oxygen together with the 3-substituent, which constitutes a characteristic fragmentation route of 3-aryl and 3-heteroaromatic substituted-4(3H)-quinazolinones, is again observed, but the presence of a carboxyethyl group at the 4′-position of the pyrazole ring is responsible of an anomalous loss of 47 daltons from the molecular ion. Lastly, a comparison with the previously described behaviour of 3-(5′-isoxazolyl) derivati…

AN HPLC/APCI METHOD, USING PARTLY MISCIBLE SOLVENTS, FOR A SIMPLE SEPARATION AND DETERMINATION OF STEROLS IN BLOOD

Benzyl ions from 1,1-(2,2′-dimethoxyphenyl)-substituted 2-methylpropanes under electron ionization

The electron ionization (EI)-induced fragmentations of a series of 1,1-(2,2'-dimethoxyphenyl)-substituted 2-methylpropanes (1-20) in both 70 eV and mass-analyzed ion kinetic energy (MIKE) spectra have been investigated. The EI-MS spectra of these compounds are characterized by the presence of abundant benzyl ions. These ions result from competitive hydrogen migration from the 2- and 2'-methoxy groups on the carbenium center of the diphenylmethyl cations formed by benzylic cleavage of the molecular ions. The relative abundances of the benzyl ions arising from such competitive processes are discussed and rationalized. The steric effect of the 3- or 3'-substituents is the main discriminating f…

A molecular dynamics study of structure, stability and fragmentation patterns of sodium bis(2-ethylhexyl)sulfosuccinate positively charged aggregates in vacuo

Positively charged supramolecular aggregates formed in vacuo by n AOTNa (sodium bis(2-ethylhexyl)sulfosuccinate) molecules and n(c) additional sodium ions, i.e. [AOT(n)Na(n+n(c))](n(c)), have been investigated by molecular dynamics (MD) simulations for n = 1-20 and n(c) = 0-5. Statistical analysis of physical quantities like gyration radii, atomic B-factors and moment of inertia tensors provides detailed information on their structural and dynamical properties. Even for n(c) = 5, all stable aggregates show a reverse micelle-like structure with an internal solid-like core including sodium counterions and surfactant polar heads surrounded by an external layer consisting of the surfactant alky…

Positively and negatively singly charged aggregates of sodium bis-(ethylhexyl)sulfosuccinate by ESI-mass spectrometry. The first evidence of the formation of reversed micelles in gas phase?

IRMPD-MS ( Infrared Multiphoton Dissociation-Mass Spectrometry) di aggregati supremolecolari carichi positivamente di Bis (2-etilesil) solfosuccinato di sodio (AOTNa) in fase gas”

Micelles of the chiral biocompatible surfactant (1R,2S)-dodecyl(2-hydroxy-1-methyl-2-phenylethyl)dimethylammonium bromide (DMEB): molecular dynamics and fragmentation patterns in the gas phase.

RATIONALE: The study of self-assembly processes of surfactant molecules in the gas phase is of great interest for several theoretical and technological reasons related to their possible exploitation as drug carriers, protein shields and cleaning agents in the gas phase. METHODS: The stability and fragmentation patterns of singly and multiply charged (either positively or negatively) aggregates of the surfactant (1R,2S)-dodecyl(2-hydroxy-1-methyl-2-phenylethyl)dimethyl ammonium bromide (DMEB) in the gas phase have been studied by ion mobility mass spectrometry and tandem mass spectrometry. Molecular dynamics (MD) simulations of positively and negatively singly and multiply charged DMEB aggre…

Urinary metabolites and antioxidant products of exogenous melatonin in the mouse

Exogenous melatonin is widely used for sleep disorders and has potential value in neuroprotection, cardioprotection and as an antioxidant. Here, a novel method is described for the determination of melatonin and six metabolites in mouse urine by use of LC-MS/MS and GC-MS. LC-MS/MS is used for the measurement of melatonin, N-1-acetyl-5-methoxykynuramine (AMK), N-1-acetyl-N-2-formyl-5-methoxykynuramine (AFMK) and 6-hydroxymelatonin (6-HMEL), while GC/MS is used for the determination of N-[2-(5-methoxy-2-oxo-2,3-dihydro-1H-indol-3-yl)-ethyl]-acetamide (2-OMEL) and cyclic 3-hydroxymelatonin (3-HMEL) with detection limits on column of 0.02-0.5 pmol, depending on the metabolite. Following oral ad…

Physicochemical Investigation of the Solubilization of Ytterbium Nitrate in AOT Reverse Micelles and Liquid Crystals

A wide investigation of the solubilization of the water-soluble salt Yb(NO3)(3) in sodium bis(2-ethylhexyl)sulfosuccinate (AOT) reverse micelles and AOT liquid crystals has been carried out. After saturation of water/AOT/organic solvent w/o microemulsions with pure Yb(NO3)(3), the Yb(NO3)(3)/AOT composites were prepared by complete evaporation under vacuum of the volatile components (water and organic solvent) of the salt-containing microemulsions. It was observed that these composites can be totally dissolved in pure n-heptane or CCl4, allowing the solubilization of a noticeable amount of Yb(NO3)(3) in quite dry apolar media. By UV-vis-NIR, FT-IR, and H-1 NMR spectroscopies, some informati…

Ceremonial customs of Greek age (5th Century, bC) in Sicily: a study by GC-MS of some fictile unguentaria from two necropolises

Electron Ionization Induced Fragmentation of some 3-Aroylamino-5-Methyl-1,2,4- Oxadiazoles and 3-Acetylamino-5-Aryl-1,2,4-Oxadiazoles

: Background and objectives. 1,2,4-Oxadiazoles show a high reactivity and represent starting compounds for the synthesis of several other heterocycles. Some their derivatives can give the so called Boulton-Katritzky Reactions (BKR) which opens the way to the synthesis of several azoles. For this reason we have registered the mass spectra of several 3-aroylamino-5-methyl-1,2,4-oxadiazoles and 3-acetylamino-5-aryl-1,2,4-oxadiazoles. Methods and results. Thus, studying the mass spectra of the isomeric couple 3-benzoylamino-5-methyl-1,2,4-oxadiazole (1A) and 3-acetylamino-5-phenyl-1,2,4-oxadiazoles (1B) we have observed that MIKE and CID MIKE spectra of their molecular ions and of the [M – CH2C…

Analysis of sterols by high-performance liquid chromatography/mass spectrometry combined with chemometrics

A newly developed high-performance liquid chromatography/mass spectrometry (HPLC/MS) method has been successfully used to analyze plasma concentrations of various phytosterols (cholestanol and beta-sitosterol) and cholesterol metabolites (desmosterol and lathosterol). This was based on an unusual solvent combination of water/methanol vs. methanol/acetone/n-hexane applied on a Purospher Star RP-18e (125 x 2 mm, 3 microm) column, which proved excellent for the separation, identification and quantification of plasma sterols. Simple solid-phase extraction preparation of plasma samples was performed, followed by the developed fast and robust HPLC separation. Results on four groups of people were…

Evaluation of Biological Effects and Heterogeneous Photodegradation of Terpenes Present in Wastewater From a Citrus Fruit Transformation Factory

Electrospray ion mobility mass spectrometry of positively and negatively charged (1R,2S)-dodecyl(2-hydroxy-1-methyl-2-phenylethyl)dimethylammonium bromide aggregates

Rationale Self-assembling processes of surfactants in the gas phase constitute a developing research field of interest since they allow information to be gained on the peculiar structural organization of these aggregates, on their ability to incorporate from small molecules up to proteins and on their possible use as carriers of drugs in the gas phase or as cleaning agents and exotic reaction media. Methods The mass spectra of charged aggregates of the chiral surfactant (1R,2S)-dodecyl(2-hydroxy-1-methyl-2-phenylethyl)dimethylammonium bromide (DMEB) in the gas phase have been recorded using a Synapt G2-Si mass spectrometer in the positive and negative ion mode. For comparison purposes, the …

Gas Phase Charged Aggregates of Bis(2-ethylhexyl)sulfo-succinate (AOT) and Divalent Metal Ions. First evidence of AOT solvated aggregates

Assembling and chelating properties of sodium bis(2-ethylhexyl)sulfosuccinate (AOTNa) towards divalent metal ions have been investigated in the gas phase by electrospray ionization mass spectrometry. A variety of positively charged monometallated and mixed metal aggregates are formed. Interestingly, several ions contain solvent (MeOH, H2O) molecules and constitute the most abundant AOT cationic aggregates not containing sodium. These species are the first example of solvated AOT-metal ion aggregates in the gas phase. By increasing the surfactant aggregation number, the abundance of solvated species becomes lower than that of unsolvated ones. Decompositions of ionic species have been studied…

Mass spectrometry of surfactant aggregates.

In contrast with the enormous amount of literature produced during many decades in the field of surfactant aggregation in liquid, liquid crystalline and solid phases, only a few investigations concerning surfactant self-assembling in the gas phase as charged aggregates have been carried out until now. This lack of interest is disappointing in view of the remarkable theoretical and practical importance of the inherent knowledge. The absence of surfactant–solvent interactions makes it easier to study the role of surfactant–surfactant forces in determining their peculiar self-assembling features as well as the ability of these assemblies to incorporate selected solubilizate molecules. Thus, t…

STUDY OF VOLATILE COMPONENTS OF TEN VARIETIES OF SALVIA BY SPME-GC/MS AND GENERAL DISCRIMINANT ANALYSIS

Orientation and molecular contacts of melatonin confined into AOT and lecithin reversed micellar systems

Abstract The state of increasing amounts of melatonin (MLT) confined in dry AOT or lecithin reversed micelles dispersed in CCl 4 has been investigated by UV–vis and 1 H NMR spectroscopies. The experimental results are consistent with MLT totally entrapped in reversed micelles, as a consequence of specific melatonin/surfactant interaction; the main driving force of the MLT solubilization in the core of reversed micelles is the establishment of H-bonding between the MLT NH groups (both indolic and amidic) and the head group of surfactants. The short contacts deduced from intermolecular NOEs are accounted for by favourable interactions between the surfactant's polar head and the H7–NH–H2 fragm…

Temporal trends of heavy metals in sediment core from the gulf of Palermo (Sicily, Italy)

The evaluation of long–term heavy metal concentrations in the Gulf of Palermo was carried out in this study. Measurements of Cr, Cu, Hg, Pb and Zn concentrations were performed by atomic absorption spectrophotometry (AAS) on dated fractions of a sediment core, dated by the 210Pbex method. They are found to cover a time period from 1951 to 2004. The constant sedimentation rate model was used for dating. Specific activities of 137Cs have also been measured in the sediment core sections as a check of the time scale derived by the 210Pbex method. A time-series analysis based on temporal decomposition was used in order to investigate the presence of heavy metal pollution trend. The additive comp…

Characterization of isomeric 1,2,4-oxadiazolyl-N-methylpyridinium salts by electrospray ionization tandem mass spectrometry.

The mass spectrometric behavior of 1,2,4-oxadiazolyl- N-methylpyridinium salts has been investigated. These substances are of current interest as perspective ionic liquids, compounds used as green solvents for synthesis, and for their catalytic properties. The studies have been developed through electrospray ionization tandem mass spectrometry (ESI-MS/MS) experiments. The obtained results demonstrate a ready distinction between the two isomeric classes, 3- N-methylpyridinium- and 5- N-methylpyridinium-1,2,4-oxadiazoles, is possible through ESI-MS/MS experiments. A deeper investigation on the principal fragmentation pathways of characteristic ions has been also developed.

Characterization of isomeric organic cations by Esi/MS: 3-alkyl-5-(4-N-methylpyridinium)-1,2,4-oxadiazole cations, 5-alkyl-3-(4-N-methylpyridinium)-1,2,4-oxadiazole cations and 3-perfluoroakyl-5-(4-N-methylpyridinium)-1,2,4-oxadiazole cations, 5-perfluoroakyl-3-(4-N-methylpyridinium)-1,2,4-oxadiazole cations

Hydrogen-carbon, carbon-carbon double rearrangement induced by proximity effects. 1-formation of methoxybenzyl ions in the electron impact mass spectra of substituted 1,1-bis(dimethoxyphenyl)methanes

The 75 eV electron impact mass spectra of 1,1-bis(dimethoxyphenyl)methanes bearing o-methoxy groups are dominated by intense peaks corresponding, at least formally, to benzyl ions [(CH3O)2C6H3CH2]+(b). They arise from ions [((CH3O)2C6H3)2CH]+(a), which are in turn formed from molecular ions by loss of an alkyl radical through benzylic cleavage. The analysis of compounds labelled with 2H or 13C at methoxy groups led to the determination of the mechanism. Hydrogen migration, as hydride, followed by electrophilic substitution by the methylene carbon of the phenyl methylene ether cation through a six-centred transition state is responsible for the formation of benzylic ions b.

Mass spectrometry of 3,4-dihydroquinazol-4-ones of pharmaceutical interest. Part 2: Common structure of the C8H4N2R+ ions from 3-isoxazolyl-3-pyrazolyl-, and 3-o-tolyl-2-R-substituted derivatives.

Beta agonist determination in bovine liver using liquid cromatography tandem mass spectrometry

Sodium bis(2-ethylhexyl)sulfosuccinate self-aggregation in vacuo: molecular dynamics simulation.

Molecular dynamics (MD) simulations were conducted for systems in vacuo consisting of n AOT(-) anions (bis(2-ethylhexyl)sulfosuccinate ions) and n+/- 1 or n Na(+) ions up to n = 20. For n = 15, positively charged systems with Li(+), K(+), and Cs(+) cations were also considered. All systems were observed to form reverse micelle-like aggregates whose centre is occupied by cations and polar heads in a very compact solid-like way, while globally the aggregate has the form of an elongated and rather flat ellipsoid. Various types of statistical analyses were carried out on the systems to enlighten structural and dynamical properties including gyration radius, atomic pair correlation functions, at…

COUPLING ELECTROCHEMISTRY TO ELECTROSPRAY: A NOVEL PREPARATION OF GOLD NANOSTRUCTURES

nanoparticles on ITO (Indium tin oxide) coated glass using the electrospray (ESI) method Method:The starting point of this study is that the ESI/MS spectrum (Figure 1) of an ethanolic solution of HAuCl 4 shows a reduction process of Au (III) strongly dependent on the Cone Voltage (CV) values (20, 80, 150 V), affording to the ion at m/z 197 (Au+). Further, the decrease of the abundance of this ion at the highest cone voltage suggests the subsequent its reduction with the formation of Au 0 . Figure 1: ESI/MS spectra of an ethanolic solution of HAuCl4 at various cone voltages: Conclusion: Such experimental evidence leads us to use electrospray technique as a preparative tool to obtain the form…

GC/SIM-MS per la determinazione quali-quantitativa di idrocarburi in gas naturali

Mass Spectrometry of Simple Indoles. Part 2: Fourier Transform Mass spectrometry, Fast Atom Bombardment, Laser Desorption and Electrospray Ionisation. TARGETS IN HETEROCYCLIC SYSTEMS: CHEMISTRY AND PROPERTIES

Micelles, Rods, Liposomes, and Other Supramolecular Surfactant Aggregates: Computational Approaches

Surfactants are an interesting class of compounds characterized by the segregation of polar and apolar domains in the same molecule. This peculiarity makes possible a whole series of microscopic and macroscopic effects. Among their features, their ability to segregate particles (fluids or entire domains) and to reduce the surface/interfacial tension is the utmost important. The interest in the chemistry of surfactants never weakened; instead, waves of increasing interest have occurred every time a new field of application of these molecules has been discovered. All these special characteristics depend largely on the ability of surfactants to self-assemble and constitute supramolecular struc…

Gas-phase ion chemistry of protonated melatonin

The gas-phase ion chemistry of protonated melatonin has been investigated by mass spectrometric (MS) techniques involving chemical ionisation, fast atom bombardment and electrospray ionisation. Either naturally- occurring or collision-induced decomposition e-D derivatives obtained by exchange with D(2)O. The analysis of experimental results allows definite pathways for the formation of the ion at m/z 174 to be assigned and sheds some more light on the overall fragmentation pathways. Experiments on labelled derivatives evidenced H-D scrambling processes during fragmentation

VOCS DETERMINATION IN GROUND WATERS BY SPME/GC-MS

Studies in organic mass spectrometry. Part 23. Role of the aroyl group on the competitive fragmentation reactions of the molecular ion of aroylanilides

The 70 eV and mass-analysed ion kinetic energy (MIKE) spectra of some thiophenecarboxanilides and benzoylanilides (1–10) have been compared in order to investigate the role of the aroyl (or heteroaroyl) moiety on the abundance of the competitive fragmentation reactions occurring in their molecular ions (amide–bond cleavage and phenol radical ion formation). It has been shown that the electron ionisation induced decompositions with high (70 eV) and low (MIKE) internal energy excess are qualitatively similar, but remarkable quantitative differences have been observed that can be accounted for in terms of the different effectiveness in the transmission of electronic effects of substituents in …

Localization and interactions of melatonin in dry cholesterol/lecithin mixed reversed micelles used as cell membrane models

The state of melatonin confined in dry cholesterol/lecithin mixed reversed micelles dispersed in CCl4 was investigated using 1H-NMR and FT-IR spectroscopies as a function of the melatonin to lecithin molar ratio (R(MLT)) and of the cholesterol to lecithin molar ratio (R(CHL)). An analysis of experimental results leads to the hypothesis that, independent of R(MLT) and as a consequence of anisotropic melatonin/lecithin, melatonin/cholesterol and cholesterol/lecithin interactions, melatonin is totally solubilized in reversed micelles. Melatonin is mainly located in and oriented in the nanodomain constituted by the hydrophilic groups of cholesterol and lecithin. A competition of melatonin and c…

Recent Approaches for Chemical Speciation and Analysis by Electrospray Ionization (ESI) Mass Spectrometry

In these latest years, the chemical speciation of several species has been increasingly monitored and investigated by means of electrospray ionization mass spectrometry (ES-MS). This soft ionization technique is capable to gently take into the gas phase metal-ligand complexes and gather a wealth of information on their energetics, shape, and fragmentation pathways. For this reason, this technique is frequently chosen in a synergistic approach to investigate competitive ligand exchange-adsorptive other ways analyzed by cathodic stripping voltammetry (CLE-ACSV). ESI-MS analyses require a careful experimental design as they may be impacted by instrumental artifacts such as ESI adduct formation…

Detection and localisation of disulphide bonds in a synthetic peptide reproducing the sequence 1-30 ofPar j1.0101 by electrospray ionisation mass spectrometry

The structural characterisation of a synthetic peptide reproducingthe 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, usingthe combined p…

Inclusion complexes of cyclomaltooligosaccharides (cyclodextrins) with melatonin in solid phase

Fourier transform infrared spectrometry (FT-IR) and X-Ray diffraction (XRD) investigations were carried out on MLT plus α-, β- and γ-CD physical mixtures and lyophilized or crystalline MLT/α-, β-, γ-CD complexes. Inclusion complexes formation between MLT and cyclodextrins in solid phase has been emphasized by the significant differences between IR and XRD spectra of physical mixtures with respect to those of the complexes. The structure of MLT CDs complexes in the solid state as well as the biochemical and pharmaceutical implications are discussed.

A Novel Liquid Chromatography/Mass Spectrometry Method for Analysis of Plasma Sterol Concentrations

Charged supramolecular assemblies of surfactant molecules in gas phase

The aim of this review is to critically analyze recent literature on charged supramolecular assemblies formed by surfactant molecules in gas phase. Apart our specific interest on this research area, the stimuli to undertake the task arise from the widespread theoretical and applicative benefits emerging from a comprehensive view of this topic. In fact, the study of the formation, stability, and physicochemical peculiarities of non-covalent assemblies of surfactant molecules in gas phase allows to unveil interesting aspects such as the role of attractive, repulsive, and steric intermolecular interactions as driving force of supramolecular organization in absence of interactions with surround…

DRY LECITHIN REVERSED MICELLES AS BIOMEMBRANE MODELS:INTERACTION WITH VITAMIN E

Studies in organic mass spectrometry. Part 20: a hidden ortho effect in the electron ionisation mass spectra of some 2′-alkyl substituted 2-and 3-thiophenecarboxanilides

The electron-ionisation-induced amide-bond cleavage of some 2′-methyl- and 2′-ethyl-substituted 2- and 3-thiophenecarboxanilides, which yields formally anilylium ions having relative intensities apparently in contrast with the Stevenson‐Audier rule, has been investigated by mass-analysed ion kinetic energy (MIKE) spectrometry and compared to that of the 3 ′- and 4′-isomers. It has been shown that, in the case of the 2 ′-methyl and 2′-ethyl derivatives, the amide-bond cleavage is anchimerically assisted through the hidden migration of a benzyl hydrogen to the nitrogen. Analysis of the MIKE and collision-induced decomposition (CID) MIKE spectra of model compounds indicates that this cryptic o…

Do electrospray mass spectra of surfactants mirror their aggregation state in solution?

One important feature in the gas phase chemistry of surfactants is to ascertain whether their aggregates produced by electrospray ionization reflect those formed in the starting solution. With this aim, we have performed ESI-MS, ESI-MS/MS and ER-MS spectra of bis(2-ethylhexyl)sulfosuccinate (AOTNa) solutions in different solvents, i.e. water, water/methanol, methanol and n-hexane. The results clearly indicate that, notwithstanding the strongly different aggregation state in solution (direct micelles in water and in water/methanol, molecular dispersion in methanol and reverse micelles in n-hexane) and marked effects of the solvent polarity on the total ionic current, the surfactant aggregate…

Hydrogen–carbon, carbon–carbon double rearrangement induced by proximity effect in alkyldiaryl- and triarylmethyl cations

Gas-phase ion chemistry of protonated melatonin

The gas-phase ion chemistry of protonated melatonin has been investigated by mass spectrometric (MS) techniques involving chemical ionisation, fast atom bombardment and electrospray ionisation. Either naturally-occurring or collision-induced decomposition experiments have been carried out using side chain tetra-deuterium-labelled derivatives, as well as the corresponding N–D derivatives obtained by exchange with D2O. The analysis of experimental results allows definite pathways for the formation of the ion at m/z 174 to be assigned and sheds some more light on the overall fragmentation pathways. Experiments on labelled derivatives evidenced H–D scrambling processes during fragmentation.

Guest-to-host proton transfer in melatonin-beta-cyclodextrin inclusion complex by ionspray, fast atom bombardment and tandem mass spectrometry.

Ionspray (IS) and fast atom bombardment (FAB) positive ionization mass spectrometry (MS) of 1:1 β-cyclodextrin (β-CD)-melatonin (MLT) host-guest complex allowed the detection of gaseous protonated 1:1 β-CD-MLT. Tandem MS collision-induced dissociation (CID) of such protonated 1:1 β-CD-MLT species showed the proton (charge) to be retained to a significant extent by the host and by its cage fragmentation products, in spite of the higher proton affinity of MLT with respect to that of β-CD. This requires an endothermic guest-to-host proton transfer to occur within the gaseous association. Collisional activation could be accounted for by the promotion of such an endothermic process; however…

ESI/MS study of singly charged clusters formed by bis-(ethylhexyl)sulfosuccinate (AOT-) and Fe 3+

Self Assembling di tensioattivi in fase gassosa: ESI/MS di aggregati a sigola carica di Yb(AOT)3

Mapping of volatile organic compounds in Sicilian groundwater determined by HS-SPME/GC-MS

Analisi ambientale: determinazione di IPA, pesticidi e acrilammide in bacini idrogeologici della regione sicilia

Surfactant self-assembling in the gas phase: bis(2-ethylhexyl)- sulfosuccinate divalent metal ion anionic aggregates

RATIONALE: Investigation of fundamental aspects driving surfactant self-assembling and of the capability of including guest molecules or ions in their micellar aggregates is an exciting research field for theoretical and technological reasons. In this light, assembling and chelating properties of sodium bis(2-ethylhexyl)sulfosuccinate (AOTNa) towards divalent metal ion chlorides have been investigated in the gas phase by electrospray ionization mass spectrometry in negative ion mode, tandem mass spectrometry and energy-resolved mass spectrometry. METHODS:Water/methanol solutions of AOTNa and chloride salts of nickel, magnesium, calcium and manganese, with different AOTNa/metal salt ratios, …

Surfactant self-assembly in the gas phase: Bis(2-ethylhexyl)sulfosuccinate- alkaline metal ion aggregates

Molecular dynamics (MD) simulations were conducted for systems in vacuo consisting of n AOT anions (bis(2-ethylhexyl)sulfosuccinate ions) and n 1 or n Na+ ions up to n = 20. For n = 15, positively charged systems with Li+, K+, and Cs+ cations were also considered. All systems were observed to form reverse micelle-like aggregates whose centre is occupied by cations and polar heads in a very compact solid-like way, while globally the aggregate has the form of an elongated and rather flat ellipsoid. Various types of statistical analyses were carried out on the systems to enlighten structural and dynamical properties including gyration radius, atomic pair correlation functions, atomic B-factor …

Studies in organic mass spectrometry.VIII. The electron impact mass spectra of 2,4-substituted-3-diazo-5-phenylpyrroles

The electron impact mass spectra (75 eV) of the β-diazopyrroles always show the molecular ions and undergo as the main fragmentation process the elimination of nitrogen followed by ring opening reactions leading to benzonitrile either as neutral or charged species. The peaks at 26 amu below the molecular ions, which are a general feature of these spectra, are due to the presence of the corresponding pyrroles which are formed by reductive reactions during the vaporization process of the samples.

Aroma compounds in sicilian olive oils from three cultivars at different ripening stages

Interactions of α-tocopherol with biomembrane models: Binding to dry lecithin reversed micelles

Abstract The state of α-tocopherol (Vitamin E) in solutions of dry lecithin reversed micelles dispersed in an apolar medium has been investigated as a function of the Vitamin E to surfactant molar ratio (RVE) at fixed surfactant concentration by FT-IR, 1H NMR and SAXS with the aim to emphasize the role played by anisotropic intermolecular interactions and confinement effects as driving forces of its partitioning between apolar bulk solvent and polar nanodomains and of mutual Vitamin E/reversed micelle effects. It has been found that its binding strength to reversed micelles, triggered by steric and orientational constrains, is mainly regulated by specific interactions between the hydrophili…

Review: Mass spectrometry of surfactant aggregates

In contrast with the enormous amount of literature produced during many decades in the field of surfactant aggregation in liquid, liquid crystalline and solid phases, only a few investigations concerning surfactant self-assembling in the gas phase as charged aggregates have been carried out until now. This lack of interest is disappointing in view of the remarkable theoretical and practical importance of the inherent knowledge. The absence of surfactant–solvent interactions makes it easier to study the role of surfactant–surfactant forces in determining their peculiar self-assembling features as well as the ability of these assemblies to incorporate selected solubilizate molecules. Thus, th…

The fragmentation of 5- and 3-substituted thiophene-2-carboxamides under electron impact

The 70 eV electron impact mass spectra of twelve 5- and 3-substituted thiophene-2-carboxamides are discussed with the aid of exact mass measurements and labelling experiments. All mass spectra exhibit pronounced molecular ions. Some isomeric 5- and 3-substituted title compounds can be differentiated by mass spectrometry. The fragmentation is influenced by a strong ‘ortho-effect’ which activates the NH3 elimination. In the other cases the most important fragmentation is NH2˙ loss, followed by CO elimination.

Electrospray Ion Mobility Mass Spectrometry of positively and negatively charged (1R,2S)-Dodecyl(2-hydroxy-1-methyl-2-phenyl-ethyl)dimethylammonium bromide aggregates

RATIONALE: Self-assembling processes of surfactants in the gas phase constitute a developing research field of interest since they allow information to be gained on the peculiar structural organization of these aggregates, on their ability to incorporate from small molecules up to proteins and on their possible use as carriers of drugs in the gas phase or as cleaning agents and exotic reaction media. METHODS: The mass spectra of charged aggregates of the chiral surfactant (1R,2S)-dodecyl(2-hydroxy-1-methyl-2- phenylethyl)dimethylammonium bromide (DMEB) in the gas phase have been recorded using a Synapt G2-Si mass spectrometer in the positive and negative ion mode. For comparison purposes, t…

Gas phase infrared multiple photon dissociation spectra of positively charged sodium bis(2-ethylhexyl)sulfosuccinate reverse micelle-like aggregates

The capability of infrared multiple photon dissociation (IRMPD) spectroscopy to gain structural information on surfactant-based supramolecular aggregates has been exploited to elucidate intermolecular interactions and local organization of positively charged sodium bis(2-ethylhexyl)sulfosuccinate (AOTNa) aggregates in the gas phase. A detailed analysis of the stretching modes of the AOTNa CO and SO(3)(-) head groups allows one to directly probe their interactions with sodium counterions and to gain insight in their organization within the aggregate. Similarities and differences of the IRMPD spectra as compared to the infrared absorption spectrum of micellized AOTNa in CCl(4) have been analy…

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 non-covalent 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 b…

Supramolecular Aggregates in Vacuum: Positively Mono-Charged Sodium Alkanesulfonate Clusters

The formation and structural features of positively mono-charged aggregates of sodium bis(2-ethylhexyl) sulfosuccinate (AOT) and sodium methane—(MetS), butane—(ButS) and octane—(OctS) sulfonate molecules in the gas phase have been investigated by electrospray ionization mass spectrometry, energy-resolved mass spectrometry and density functional theory (DFT) calculations. The experimental results show that the center-of-mass collision energy required to dissociate 50% of these mono-charged aggregates scantly depends on the length of the alkyl chain as well as on the aggregation number. This, together with the large predominance of mono-charged species in the mass spectra, was rationalized i…

Interaction and location of melatonin in cellular membrane models constituted by lecithin and cholesterol anhidrous reversed micellar systems

Studies in organic mass spectrometry. Part 24† Electron ionization mass spectra of some aryl(2-nitrobenzo[b]thiophen-3-yl)amines

The main fragmentation routes of eighteen title compounds and of three 5-chloro derivatives have been investigated with the aid of linked scan (B/E = constant) spectrometry, accurate mass measurements and deuterium labelling. Copyright © 1999 John Wiley & Sons, Ltd.

Studio comparativo quali-quantitativo sul profilo aromatico di vini D.O.C. Marsala “Fine”

Applicazioni di spettrometria di massa in campo alimentare: analisi di olii di oliva tramite HPLC-Ms e HS-SPME-GC-MS

Distribution of volatile organic compounds in Sicilian groundwaters analysed by head space-solid phase micro extraction coupled with gas chromatography mass spectrometry (SPME/GC/MS).

This work presents the results of an assessment of the existence and concentration of 13 volatile organic compounds (VOCs) in groundwaters from 14 hydrological basins in Sicily (25,710km (2)). On the basis of hydrological, hydrogeochemical and geological studies, 324 sampling points were selected. All groundwater sampled were collected twice, from October to December 2004 and from February to May 2005, and were analysed to determine the concentration and spatial distribution of the VOCs in the aquifers. The need to analyze a large number of samples in a short space of time so as to obtain quantitative analyses in trace concentration levels spurred us to create a new analytical method, both …

Localization and Interactions of Melatonin in Cell Membrane Models

A new general fragmentation reaction in mass spectrometry: The hydrogen-carbon, carbon-carbon double rearrangement of 2 heteroalkyl substituted diphenylmethyl cations

Diphenylmethyl cations formed by benzylic cleavage of the molecular ions of ortho heteroalkyl substituted 1,1-diphenylalkanes undergo the double rearrangement process (H to C followed by C to C) previously reported for ortho-methoxy derivatives. Hence the formation of substituted benzyl (or tropylium) ions allowing this double rearrangement process constitutes an interesting type of fragmentation reaction characteristic for 1,1-diphenylalkanes bearing ortho substituents (OMe, OEt, OiPr, SMe, NHMe, NMe2) which are able to transfer a hydride to the charged benzyl carbon of diphenylmethyl cations formed by benzylic cleavage of the molecular ion.

LC- MS/MS method for determination of clenbuterol and clenbuterol-like anabolic drugs in meat and liver –Po-05 pag 47

Determination of Monoterpens in Citrus Processing Factory’s Wastewater Using SPME/FAST-GC/MS

Distribution of Volatile Organic Compounds in Sicilian groundwaters analysed by Head Space Solid Phase Micro Extraction coupled with Gas Chromatography Mass Spectrometry (SPME/GC/MS)

This work presents the results of an assessment of the existence and concentration of 13 volatile organic compounds (VOCs) in groundwaters from 14 hydrological basins in Sicily (25,710 km2). On the basis of hydrological, hydrogeochemical and geological studies, 324 sampling points were selected. All groundwater sampled were collected twice, from October to December 2004 and from February to May 2005, and were analysed to determine the concentration and spatial distribution of the VOCs in the aquifers. The need to analyze a large number of samples in a short space of time so as to obtain quantitative analyses in trace concentration levels spurred us to create a new analytical method, both si…

Idrocarburi policiclici aromatici: studi di ripartizione tra acqua e sistemi complessi per la ricerca di nuove metodiche analitiche

orthoeffect on the nitrosation of the 2,3-diphenyl-5(2-methoxyphenyl)pyrrole

A comparison of the behaviour on the nitrosation of the isomers 5-(2-methoxyphenyl)- (1a) 5-(3-methoxyphenyl)- (1b) and 5-(4-methoxyphenyl)2,3-diphenylpyrroles (1c) carried out in the usual way with iso-amyl nitrite in a solution of sodium ethoxide in ethanol evidences that 1a is dramatically less reactive with respect to 1b and 1c. The different reactivity was ascribed to the occurrence of a strong hydrogen bond involving pyrrole NH and the ortho-methoxy group.

Melatonin: Structural characterization of its non-enzymatic mono-oxygenate metabolite

Oxidation of melatonin by Fenton reagents as well as with hypochlorous acid or oxoferryl hemoglobin has been investigated. Analysis of products by low resolution/mass spectra (MS), high resolution/MS, 1H-nuclear magnetic resonance (NMR), 13C-NMR, correlated spectroscopy (COSY) and heterocorrelated spectroscopy (HETCOR) 2D NMR reveals the formation of a single mono-oxygenated product under all conditions and unequivocally assigns the N-[2-(5-methoxy-2-oxo-2,3-dihydro-1H-indol-3-yl)-ethyl]-acetamide structure, which had not been previously considered.

Mass spectrometry coupled to chromatography systems and cultural heritage: a case study on the content of an ancient jar

In this chapter an introduction to mass spectrometry will be given, with particular reference to mass spectrometry coupled to chromatography systems. Further some mass spectrometry applications in the field of cultural heritage will be briefly reported and discussed. Finally a experimental investigation on the content of an ancient jar will be reported. Together with experimental details a description of the techniques adopted, results obtained and forthcoming experiments will be also given.

Characterization of gas phase aggregates of bis(2-ethylhexyl)sulfosuccinate (AOT) and divalent metal ions. Elimination of radical species in the decomposition pathways of even-electron [AOTMIICl2]– anions

Structure and properties of even-electron anionic species formed by bis(2-ethylhexyl)sulfosuccinate (AOT) and divalent metal ions (MII) with stoichiometry [AOTMIICl2]– have been investigated by using electrospray ionization and different mass spectrometry techniques, such as high resolution, accurate mass measurements, collision-induced dissociation (CID) multiple-stage mass spectrometry. Owing to CID, eliminations of neutrals, mainly consisting in hydrochloric acid, 2-ethyl-1-hexene and 2-ethylhexanol, and an unexpected loss of an alkyl radical have been observed. The radical anions [C4HO6SMIICl]–• so produced have been characterized by MS3 experiments. Density functional theory calculatio…

Some Observations on Recent Studies Concerning the Electron Ionization Mass Spectrometry of 4(3H)-Quinazolinones

Studies in organic mass spectrometry. IV. Electron impact induced fragmentation of 2-substituted 3-(5-isoxazolyl)-4(3H)-quinazolinones of pharmaceutical interest

The fragmentation under electron impact of thirteen 2-substituted-3-(5-isoxazolyl)-4(3H)-quinazolinones has been investigated with the aid of metastable ion detection and high resolution measurements. Molecular ions are always abundant and the main primary fragmentation route involves acetonitrile elimination through isoxazole ring opening. The other common processes, particularly those leading to the abundant [R-C8H4N2]+ ion (b or b'), as well as those due to the nature of the 2-substituent are reported and discussed.

Evidences for the Formation of Inclusion Complexes of Cyclomaltooligosaccharides (Cyclodextrins) with Melatonin in solid Phase

Micelle in fase gas: una nuova frontiera della spettroMetria di Massa

Spectrophotometric investigation of the binding of vitamin E to water-containing reversed micelles.

The distribution constants of vitamin E partitioned between apolar organic phase and water-containing reversed micelles of sodium bis (2-ethylhexyl) sulfosuccinate (AOT), didodecyldimethylammonium bromide (DDAB), soybean phosphatidylcholine (lecithin) and tetraethylene glycol monododecyl ether (C12E4) have been evaluated by a spectrophotometric method. The results suggest that in the presence of domains from apolar organic solvent to surfactant and to water, vitamin E is partitioned between the micellar palisade layer and the organic solvent and also that its binding strength to reversed micelles depends mainly by specific interactions between the head group of vitamin E and that of the sur…

Groundwater of Sicily (Italy) Close to Landfill Sites: Quality and Human Health Risk Assessment

Groundwater close to three municipal solid waste landfill sites in Sicily (southern Italy) was sampled to determine the presence of contaminants and the risk associated with its possible use as drinking and sanitary water. Polycyclic aromatic hydrocarbons, polychlorinated biphenyls, polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and metals were investigated. These target compounds are the most common pollutants present in leachates. Risk Assessment Guidance for Superfund (RAGS, US EPA) was used to assess human health risk. Ingestion, dermal, and total exposure to these xenobiotic contaminants in groundwater were evaluated, and the cancer and non-cancer risk indexes were c…

Characterization of glyceridic components of Sicilian extra virgin olive oils using LC/MS and L.D.A.

Micelles of the chiral biocompatible surfactant (1R,2S)-dodecyl(2-hydroxy-1-methyl-2-phenylethyl)dimethylammonium bromide (DMEB): molecular dynamics and fragmentation patterns in the gas phase

Rationale The study of self-assembly process of surfactant molecules in gas phase is of actually interest for several theoretical and technological reasons related to their possible exploitation as drug carriers, protein shields and cleaning agents in gas phase. Methods Stability and fragmentation patterns of singly and multiply charged (either positively or negatively) aggregates of the surfactant (1R,2S)-dodecyl(2-hydroxy-1-methyl-2-phenylethyl) dimethyl ammonium bromide (DMEB) in gas phase have been studied by ion mobility mass spectrometry and tandem mass spectrometry. Molecular dynamics (MD) simulations of positively and negatively singly and multiply charged DMEB aggregates have been …

self-assembly and intra-cluster reaction of erbium and ytterbium bis(2-ethylhexyl)sulfosuccinate reverse micelle in gas phase

Gas-phase ion chemistry of protonated melatonin: naturally occurring and collision induced fragmentation

Beta-agonist Determination in Bovine Liver Using Liquid Chromatography- Tandem Mass Spectrometry

Interaction and location of melatonin in cellular membrane models constituted by lecithin and cholesterol anhydrous reversed micelles

Analysis of melatonin interaction with receptioral models of biological interest: alfa, beta and gamma-cyclodextrins

Charged supramolecular assemblies of surfactant molecules in gas phase

The aim of this review is to critically analyze recent literature on charged supramolecular assemblies formed by surfactant molecules in gas phase. Apart our specific interest on this research area, the stimuli to undertake the task arise from the widespread theoretical and applicative benefits emerging from a comprehensive view of this topic. In fact, the study of the formation, stability, and physicochemical peculiarities of non-covalent assemblies of surfactant molecules in gas phase allows to unveil interesting aspects such as the role of attractive, repulsive, and steric intermolecular interactions as driving force of supramolecular organization in absence of interactions with surround…

Halogenated Anesthetics Determination in Urine by SPME/GC/MS and Urine Levels Relationship Evaluation with Surgical Theatres Contamination

In this work, a new sensitive analytical method has been developed and evaluated for the determination of the most commonly used gaseous anesthetics, desflurane, sevoflurane, and this latter’s hepatic metabolite hexafluoroisopropanol (HFIP) in the urine. In addition, an evaluation of anesthetics exposition on the urine levels of a small population of surgical operators has been performed and results are briefly discussed.

LC-MS/MS method for the determination of clenbuterol and clembuterol-like anabolic drugs in meat and liver.

High Performance Liquid Chromatografy-Mass Spectrometry based chemometric characterization of olive oils

In this study the effective discrimination of extra virgin olive oils is described using HPLC-MS, combined with chemometric evaluation. The presented method is simple since the diluted oil sample is directly injected into the system, without any preliminary chemical derivatization or purification step. Separation of diacylglycerols, triacylglycerols and sterols occurs within 20 min and is achieved using an octadecyl-silica column. Detection is performed by positive APCI mass spectrometry which provided sensitivity to detect over 50 compounds in the sample. After extraction of data, stepwise discriminant function analysis is used to select the variables with the highest discriminative power.…

FT-IR and nuclear overhauser enhancement study of the state of urea confined in AOT-reversed micelles

Abstract The system urea/sodium-bis(2-ethylhexyl)sulfosuccinate (AOT) dispersed in CCl 4 and benzene-d6 was investigated by viscosimetry, FT-IR and high-resolution 1 H NMR spectroscopy, as a function of urea/AOT molar ratio ( R urea ) at fixed AOT molal concentration (0.3467 mol kg −1 ) and as a function of AOT concentration at fixed R urea (0.5) at 25 °C. The experimental data are consistent with the hypothesis that urea is encapsulated as small-size hydrogen-bonded cluster in the hydrophilic micellar core of the AOT-reversed micelles and that this structure is maintained well above the volume fraction of the dispersed phase, where a percolative transition occurs. Intermolecular nuclear ov…

ION MOBILITY STUDIES ON SODIUM-BIS (2- ETHYLHEXIL)SULFOSUCCINATE (AOTNa) AGGREGATES

The supramolecular charged aggregates formed during ESI ionization of AOTNa solutions under critical micelle concentration have been studied thorough ion mobility experiments. In particular, positively charged clusters with several charge states, ranging from +1 to +4, have been investigated. It has been found that, despite to previous investigations (Siuzdak et al. 1995, Nohara et al. 1998), specific ionic aggregates with a peculiar cross section are observed. Indeed a single drift time is observed for each charged aggregate. Using both calculated cross section and experimental calibration curves the experimental cross section of the observed cation has been determined. It is worth noting …

Spatially ordered surfactant assemblies in the gas phase: negatively charged bis(2-ethylhexyl)sulfosuccinate-alkaline metal ion aggregates

The formation and structural features of negatively charged aggregates of sodium bis(2-ethylhexyl)sulfosuccinate (AOTNa) surfactant molecules in the gas phase have been investigated by electrospray ionization mass spectrometry (ESI-MS) and density functional theory calculations. Mainly driven by the interactions of alkali metal ions both with the oxygen atoms of the sulfonate group and with the succinate moiety of the AOT− anion, spatially ordered supramolecular assemblies, characterized by an internal core composed of surfactant counterions and hydrophilic head groups surrounded by the surfactant alkyl chains pointing outwards, are formed. Calculations have shown that surfactant self-organ…

A fatal case of a paint thinner ingestion: Comparison between toxicological and histological findings

Toluene and xylene are aromatic hydrocarbons commonly used as an industrial solvent for the manufacturing of pharmaceuticals, paints, and chemicals. The Occupational Safety and Health Administration has determined that toluene levels of 2000 parts per million (ppm) are considered dangerous to life and health. Several studies have examined the absorption of toluene and xylene following inhalation and oral ingestion in humans. Volatile organic compounds that are absorbed into the blood are distributed throughout the body; in particular, distribution of absorbed toluene and xylene in humans and rodents is characterized by preferential uptake in well-perfused and lipophil tissues such as the br…

One-Pot Analysis: a New Integrated Methodology for Determination of TAG and FA Determination through LC/MS and in-silico Saponification

Vegetable oils differ significantly for their lipid profile and are mainly constituted by triacylglycerols (TAGs). These are esters formed bonding glycerol to three fatty acids (FAs). To the best of our knowledge, FA and TAG profiles in oils and fats are obtained using at least two different experimental techniques. In particular, FA determination requires elaborated procedures for sample preparation and analyte derivatization. In this work, we propose a one-pot analysis able to determine both TAG and FA contents of edible oils, using experimental data obtained from a simple liquid chromatography/mass spectrometry determination of TAGs. This experimental procedure is followed by an in silic…

HS-SPME-GC/MS analysis in a fatal case of a paint thinner ingestion

Total petroleum hydrocarbons (TPH) determination in surfactant stabilized marine water emulsions

Bilge waters are wastewaters produced on boats during navigation and usually contain hydrocarbons and oils. They cannot be released into the sea if not below certain hydrocarbon concentration limits set by current legislation. Surfactants are often used to improve the solubility of petroleum hydrocarbons in water and in this work, the analytical approach proposed is suitable to determine accurately the concentration of hydrocarbons in surfactant-rich waters, as found in bilge water or similar wastewater. The method relies on the surfactant precipitation by addition of potassium and calcium salts, which also promote TPH extraction through a “salting out” effect. This allows for an accurate d…

Multivariate analysis of historical data (2004-2013) in assessing the possible environmental impact of the Bellolampo landfill (Palermo).

Multivariate analysis was performed on a large data set of groundwater and leachate samples collected during 9 years of operation of the Bellolampo municipal solid waste landfill (located above Palermo, Italy). The aim was to obtain the most likely correlations among the data. The analysis results are presented. Groundwater samples were collected in the period 2004–2013, whereas the leachate analysis refers to the period 2006–2013. For groundwater, statistical data evaluation revealed notable differences among the samples taken from the numerous wells located around the landfill. Characteristic parameters revealed by principal component analysis (PCA) were more deeply investigated, and corr…

NEW INSIGHTS ON SUPRAMOLECULAR AGGREGATES OF SODIUM DOCUSATE (AOTNa) BY ION MOBILITY MASS SPECTROMETRY

Backgorund: The ability of some surfactants to form charged aggregates in gas phase has been proven experimentally by electrospray ionization (ESI) spectrometry [1- 5]. However, in the early investigations, interesting questions concerning the structural organization of these aggregates in gas phase and if they reflect their typical self-assembling in the starting liquid solutions were not addressed. Subsequently, independently of their aggregation motive in liquid phase and of the charge state in the gas phase, some hints suggesting that surfactant molecules are organized in gas phase as reverse micelle-like aggregates have been reported Objective: The supramolecular charged aggregates for…

Self-assembly and intra-cluster reactions of erbium and ytterbium bis(2-ethylhexyl)sulfosuccinates in the gas phase.

RATIONALE: The study of surfactant organization in vacuum allows surfactant–surfactant interaction to be unveiled in the absence of surrounding solvent molecules. Knowledge on their chemical-physical properties may also lead to the definition of more efficient gas-phase carriers, air-cleaning agents and nanoreactors. In addition, the presence of lanthanide-group ions adds unique photochemical properties to surfactants. METHODS: The structural features, stability and fragmentation patterns of charged aggregates formed by lanthanide- functionalized surfactants, ytterbium and erbium bis(2-ethylhexyl)sulfosuccinate ((AOT) 3 Yb and (AOT) 3 Er), have been investigated by electrospray ionization m…

Studies in organic mass spectrometry. Part 25. Benzyl ion formation in chemical ionisation (methane or isobutane) of someortho-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 © 2000 John Wiley & Sons, Ltd.

Partitioning study of polycyclic aromatic hydrocarbons between water and some selected water-insoluble phases

An investigation on the partitioning of naphthalene and phenanthrene between water and some water-insoluble phases has been carried out by Uv-vis-NIR spectrophotometry. The analysis of the experimental results emphasized the role of intermolecular interactions and structural features of the hosting phases as driving forces of the partitioning of these polycyclic aromatic hydrocarbons. The critical comparison of the resulting distribution constants allowed to evaluate the potentials of some extracting phases to set up sensitive analytical methods and/or effective environment remediation technologies.

A simple High Performance Liquid Chromatography-Mass spectrometry approach combined with Linear Discriminant Analysis for the characterization of top quality olive oils

Gas phase charged aggregates of bis(2-ethylhexyl)sulfosuccinate (AOT) and divalent metal ions: first evidence of AOT solvated aggregates

Assembling and chelating properties of sodium bis(2-ethylhexyl)sulfosuccinate (AOTNa) towards divalent metal ions have been investigated in the gas phase by electrospray ionization mass spectrometry. A variety of positively charged monometallated and mixed metal aggregates are formed. Interestingly, several ions contain solvent (MeOH, H2O) molecules and constitute the most abundant AOT cationic aggregates not containing sodium. These species are the first example of solvated AOT-metal ion aggregates in the gas phase. By increasing the surfactant aggregation number, the abundance of solvated species becomes lower than that of unsolvated ones. Decompositions of ionic species have been studied…

Entrapment of amino acids in gas phase surfactant assemblies: The case of tryptophan confined in positively charged (1R,2S)-dodecyl (2-hydroxy-1-methyl-2-phenylethyl) dimethylammonium bromide aggregates.

The ability of positively charged aggregates of the surfactant (1R,2S)‐dodecyl (2‐hydroxy‐1‐methyl‐2‐phenylethyl))dimethylammonium bromide (DMEB) to incorporate D-tryptophan or L-tryptophan in the gas phase has been investigated by electrospray ion mobility mass spectrometry (ESI‐IM‐MS). Strongly impacted by the pH of the electrosprayed solutions, both protonated (T+) and deprotonated (T-) tryptophan are effectively included into the aggregates, whereas, tryptophan in zwitterionic (T0) form is practically absent in singly charged DMEB aggregates but can be found in multiply charged ones. The ability to incorporate tryptophan increases with the aggregation number and charge state of aggr…

aggregati micellari in fase gas una nuova frontiera per la spettrometria di massa

Electrospray ion mobility mass spectrometry of positively charged sodium bis[2-ethythexyl)sulfosuccinate aggregates.

Collision cross-sections (CCS) of positively singly and multiply charged aggregates of the surfactant sodium bis(2-ethylhexyl)sulfosuccinate (AOTNa) in the gas phase have been measured by quadrupole ion mobility time-of-flight mass spectrometry. Calibration of the observed drift times to the CCS of the AOTNa non-covalent aggregates was achieved by collecting, under the same experimental conditions, the drift times of a range of singly and multiply charged polyalanine peptides whose CCS had been obtained by conventional ion mobility spectrometry. Together with an obvious increase of the aggregate cross-section with the aggregation number, it was found that the aggregate cross-section increa…

Oxidation of melatonin by oxoferryl hemoglobin: A mechanistic study

Reaction of melatonin with the hypervalent iron centre of oxoferryl hemoglobin, produced in aqueous solution from methemoglobin and H2O2, has been investigated at 37 degrees C and pH 7.4, by absorption spectroscopy. The reaction results in reduction of the oxoferryl moiety with formation of a heme-ferric containing hemoprotein. Stopped-flow spectrophotometric measurements provide evidence that the reduction of oxoferryl-Hb by melatonin is first-order in oxoferryl-Hb and first-order in melatonin. The bimolecular reaction constant at pH 7.4 and 37 degrees C is 112 +/- 1.0 M(-1) s(-1). Two major oxidation products from melatonin have been found by gas chromatography-mass spectroscopy: the cycl…

Surfactant Self-Assembling in the Gas Phase:bis(2-ethylhexyl)sulfosuccinate-Metal Ion Aggregates

A fast liquid chromatography-mass spectrometry method combined with linear discriminant analysis for the characterization of extra virgin sicilian olive oils”

The Structure and the Stereochemistry of Atractyliretin

The nor-kaurane diterpene Atractyliretin was obtained by acid hydrolysis of Atractyloside, a toxic substance isolated from ATRACTYLIS GUMMIFERA L (Compositae). On the basis of spectral (IR, (1)H-NMR, (13)C-NMR and MS) analysis and chemical degradation its structure and stereochemistry was identified as 4.

Effect of solid waste landfill organic pollutants on groundwater in three areas of Sicily (Italy) characterized by different vulnerability

The aim of this study was to obtain information on the presence and levels of hazardous organic pollutants in groundwater located close to solid waste landfills. Eighty-two environmental contaminants, including 16 polycyclic aromatic hydrocarbons (PAHs), 20 volatile organic compounds (VOCs), 29 polychlorinated biphenyls (PCBs), 7 dioxins (polychlorinated dibenzo-p-dioxins, PCDDs) and 10 furans (polychlorinated dibenzofurans, PCDFs) were monitored in areas characterised by different geological environments surrounding three municipal solid waste landfills (Palermo, Siculiana and Ragusa) in Sicily (Italy) in three sampling campaigns. The total concentrations of the 16 PAHs were always below t…

Effects of the net charge on abundance and stability of supramolecular surfactant aggregates in gas phase

Self-assembling of amphiphilic molecules under electrospray ionization (ESI) conditions is characterized by quite unexpected phenomenology. The noticeable differences with respect to the condensed phase are attributable to the absence of the surfactant-solvent interactions, the presence of net charge in the aggregates, and the strong deviation from equilibrium conditions. Aiming to investigate the effects of the net charge on abundance and stability of supramolecular surfactant aggregates, positively and negatively charged aggregates of sodium bis(2-ethylhexyl)sulfosuccinate (AOT) and sodium methane sulfonate (MetS), butane sulfonate (ButS) and octane sulfonate (OctS) have been studied by E…

Surfactant self-assembling in the gas phase: bis(2-ethylhexyl)-sulfosuccinate divalent metal ion anionic aggregates

RATIONALE Investigation of fundamental aspects driving surfactant self-assembling and of the capability of including guest molecules or ions in their micellar aggregates is an exciting research field for theoretical and technological reasons. In this light, assembling and chelating properties of sodium bis(2-ethylhexyl)sulfosuccinate (AOTNa) towards divalent metal ion chlorides have been investigated in the gas phase by electrospray ionization mass spectrometry in negative ion mode, tandem mass spectrometry and energy-resolved mass spectrometry. METHODS Water/methanol solutions of AOTNa and chloride salts of nickel, magnesium, calcium and manganese, with different AOTNa/metal salt ratios, w…

Structure, stability, and fragmentation of sodium bis(2-ethylhexyl)sulfosuccinate negatively charged aggregates in vacuo by MD simulations.

Negatively charged supramolecular aggregates formed in vacuo by n bis(2-ethylhexyl)sulfosuccinate (AOT(-)) anions and n + n(c) sodium counterions (i.e., [AOT(n) Na(n+nc)](nc)) have been investigated by molecular dynamics (MD) simulations for n = 1 to 20 and n(c) = -1 to -5. By comparing the maximum excess charge values of negatively and positively charged AOTNa aggregates, it is found that the charge storage capability is higher for the latter systems, the difference decreasing as the aggregation number increases. Statistical analysis of physical properties like gyration radii and moment of inertia tensors of aggregates provides detailed information on their structural properties. Even for …

Electronic ionization mass spectra of 3-(5'-(3'-methylisoxazol))- and 3-(3'-(5'-methylisoxazol)-2-styryl-4(3H)quinazolinones of pharmaceutical interest:an useful tool to distinguish the two isomeric series

FT-IR investigation of the state of iron (III) chloride clusters confined in AOT reverse micelles dispersed in carbon tetrachloride

The state of the water-soluble salt iron(III) chloride in AOT reverse micelles dispersed in carbon tetrachloride has been investigated by FT-IR spectroscopy. Interestingly, while the entrapment of a lot of water-soluble inorganic salts in AOT reverse micelles requires preliminarily the presence of significant amounts of water within the micellar core, solubilization of FeCl3 occurs without the need to add water in the micellar solution reaching the very high solubility value, expressed as the maximum salt-to-surfactant molar ratio, of 1.30. The analysis of the spectral features of the investigated samples leads to hypothesize that iron(III) chloride is confined within the reverse micellar c…

Bio-phenols determination in olive oils: Recent mass spectrometry approaches

Extra virgin olive oil (EVOO) is largely used in Mediterranean diet, and it is also worldwide apprised not only for its organoleptic properties but also for its healthy effects mainly attributed to the presence of several naturally occurring phenolic and polyphenolic compounds (bio-phenols). These compounds are characterized by the presence of multiple phenolic groups in more or less complex structures. Their content is fundamental in defining the healthy qualities of EVOO and consequently the analytical methods for their characterization and quantification are of current interest. Traditionally their determination has been conducted using a colorimetric assay based on the reaction of Folin…

Collision induced decomposition of AOT5YB2+: an unespected intracluster rearrangment

Surfactant self-assembling in gas phase: positively monocharged sodium alkanesulfonate clusters

ChemInform Abstract: ortho Effect on the Nitrosation of the 2,3-Diphenyl-5-(2-methoxyphenyl)pyrrole.

A comparison of the behaviour on the nitrosation of the isomers 5-(2-methoxyphenyl)- (1a) 5-(3-methoxyphenyl)- (1b) and 5-(4-methoxyphenyl)2,3-diphenylpyrroles (1c) carried out in the usual way with iso-amyl nitrite in a solution of sodium ethoxide in ethanol evidences that 1a is dramatically less reactive with respect to 1b and 1c. The different reactivity was ascribed to the occurrence of a strong hydrogen bond involving pyrrole NH and the ortho-methoxy group.

Determination of the cultivar and aging of Sicilian olive oils using HPLC-MS and linear discriminant analysis

A large number of certified samples (84) of Sicilian olive oils arising from the eight cultivars most represented in Sicily (Biancolilla, Cerasuola, Moresca, Nocellara del Belice, Nocellara Etnea, Oglialora Messinese, Brandofino and Tonda Iblea) have been collected and analyzed by HPLC/MS using an atmospheric pressure chemical ionization (APCI) source. The sample preparation is very simple; in fact, the oil samples are diluted without any chemical derivatization. A following statistical data treatment by general discriminant analysis (GDA) allows the determination of the olive oil cultivar. Furthermore, changes in the composition of glyceridic components of the olive oils lead to easy discr…

Studi di macroaggregati a singola carica in fase gassosa: AOT in presenza di ioni sodio e itterbio

Spatially ordered surfactant assemblies in the gas phase: negatively charged bis(2-ethylhexyl)sulfosuccinate- alkaline metal ion aggregates

The formation and structural features of negatively charged aggregates of sodium bis(2-ethylhexyl)sulfosuccinate (AOTNa) surfactant molecules in the gas phase have been investigated by electrospray ionization mass spectrometry (ESI-MS) and density functional theory calculations. Mainly driven by the interactions of alkali metal ions both with the oxygen atoms of the sulfonate group and with the succinate moiety of the AOT(-) anion, spatially ordered supramolecular assemblies, characterized by an internal core composed of surfactant counterions and hydrophilic head groups surrounded by the surfactant alkyl chains pointing outwards, are formed. Calculations have shown that surfactant self-org…

Studies in organic mass spectrometry. Part 9—mass spectra of 9,10-disubstituted 2,3,6,7-tetraalkoxy-9,10-dihydroanthracenes: A remarkable loss of radicals from even-electron ions

The electron impact-induced fragmentations of 23 9,10-disubstituted 2,3,6,7-tetraalkoxy-9,10-dihydroanthracenes, including six stereoisomeric pairs, were studied. The loss of the 9-(or 10-)substituent constitutes the main fragmentation route. The resulting ions give rise to a remarkable violation of the so-called even-electron rule as they eject the second substituent at the 10-(or 9-)position as a radical. The latter aspect was particularly investigated with the aid of low-energy (nominal value 15 eV) and mass-analysed ion kinetic energy spectra

Structural and physicochemical characterization of the inclusion complexes of cyclomaltooligosaccharides (cyclodextrins) with melatonin

The stoichiometry, geometry, stability, and solubility of the inclusion complexes of melatonin (MLT) with native cyclomaltooligosaccharides (α-, β- or γ-cyclodextrins, CDs) are determined experimentally by high-resolution NMR spectroscopy, calorimetric and solubility measurements, and mass spectrometry. The observed differences are discussed in terms of molecular recognition expression of the host-guest (h-g) interactions within the hydrophobic CDs cavities of different size. The 1:1 h-g stoichiometry in water solution prevails at low CD concentrations; the trend to form higher order associations is observed at increasing CD concentrations. The stability order β-CD>γ-CD>α-CD for the c…

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 …

H-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-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 a…

Surfactant self-assembling in gas phase: electrospray ionization- and matrix-assisted laser desorption/ionization-mass spectrometry of singly charged AOT clusters.

The self-assembling of sodium bis (2-ethylhexyl) sulfosuccinate (AOT) in gas phase has been investigated by electrospray ionization- and matrix-assisted laser desorption/ionization mass spectrometry. Large surfactant clusters with an aggregation number close to that found in apolar media have been observed either as positive or negative ions. Moreover, the marked predominance of singly charged species as well as preliminary theoretical calculations strongly suggest an aggregate structure characterized by an internal hydrophilic core hosting the extra charge surrounded by an apolar shell constituted by the surfactant alkyl chains. This structure is similar to that of the more familiar revers…

Supramolecular surfactant aggregates in gas-phase:monocharged sodium alkanesulfonate clusters

Dry lecithin reversed micelles as biomebrane models: interaction with vitamin E

Analysis of Melatonin interaction with receptorial models of biological interest: "alpha - beta - and gamma - cyclodextrins"

Mass spectrometry of 3,4-dihydroquinazolin-4-ones of pharmaceutical interest. Part3. Electron ionization mass spectra of 2-substituted-3-(5′-pyrazolyl)-4(3H)-quinazolinones

The fragmentation reactions induced by electron impact of eighteen title compounds has been investigated with the aid of low beam energy spectra (14 eV, nom. value), metastable ion detection, high resolution measurements and labelling experiments. The loss of the 4-carbonyl oxygen together with the 3-substituent, which constitutes a characteristic fragmentation route of 3-aryl and 3-heteroaromatic substituted-4(3H)-quinazolinones, is again observed, but the presence of a carboxyethyl group at the 4′-position of the pyrazole ring is responsible of an anomalous loss of 47 daltons from the molecular ion. Lastly, a comparison with the previously described behaviour of 3-(5′-isoxazolyl) derivati…