STUDIES ON ALKALY METAL HALIDES AGGREGATES IN GAS PHASE

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…

Automated untargeted stable isotope assisted lipidomics of liver cells on high glucose shows alteration of sphingolipid kinetics

Abstract Untargeted lipidomics is a powerful tool to discover new biomarkers and to understand the physiology and pathology of lipids. The use of stable isotopes as tracers to investigate the kinetics of lipids is another tool able to supply dynamic information on lipid synthesis and catabolism. Coupling the two methodology is then very appealing in the study of lipid metabolism. The main issue to face is to perform thousands of calculations in order to obtain kinetic parameters starting from the MS raw data. An automated computerized routine able to do accomplish such task is presented in this paper. We analyzed the lipid kinetics of palmitic acid (PA) in hepatoma liver cells cultured in v…

Fatty Acids and Triacylglycerols Profiles from Sicilian (Cold Pressed vs. Soxhlet) Grape Seed Oils

Among the Sicilian economic productive sectors, that of wine production has today a considerable economic value. However, with the growth of this sector, notable was the increase in the production of waste, which to date is not only an economic damage for companies, but also a threat to the environment. It is known that waste from wine production has properties (e.g., antioxidants) which have potential reuse at cosmetic, pharmaceutical and nutritional levels to obtain economically sustainable applications. A new goal is given by the recovery of added value compounds from agri-food wastes and by-products. Grape seed oil is a promising vegetable fat and cold pressing does not involve the use …

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…

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…

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 …

Co-inertia multivariate approach for the evaluation of anthropogenic impact on two commercial fish along Tyrrhenian coasts

Abstract Aliphatic hydrocarbon levels were determined by the GC/MS technique in fish livers of Engraulis encrasicolus (Ee) and Trachurus trachurus (Tt), collected from a particular area of the Mediterranean Sea, called GSA 10, which is located exactly in Tyrrhenian Sea between Campania coast and North Sicily coast. The aim was to evaluate their potential use as specific bioindicators towards this class of contaminants. Both Tt and Ee are considered to be pollution monitoring bioindicators, due to their dominance in marine communities and economic fishing interest. Ee showed a higher tendency to bioaccumulate TAHs, due to the lower quantity of fatty acids in liver tissues with respect to Tt.…

Molecular and physiological characterization of in vivo Sulfamethoxazole response in Procambarus clarkii

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

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.

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

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…

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…

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…

Freeze dried pomegranate juices of Moroccan fruits: main representative phenolic compounds.

The pomegranate (Punica granatum) is an ancient perennial plant species of the Punicaceae family. Its seeds are consumed as food or as juice. Previous studies have noted that pomegranate juice encompasses many active compounds with beneficial effects. The main goals of this work were to study the phenolic components of freeze-dried and reconstituted pomegranate juices obtained from 13 pomegranate genotypes growing in Morocco.We analyzed several pomegranate juices using high-performance liquid chromatography and high-resolution mass spectrometry to determine phenolic compounds. Twenty-seven bio-phenols, belonging to four different classes (phenolic acids, hydrolyzable tannins, anthocyanins, …

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

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…

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.

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

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

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…

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…

Effect of a co-substrate supply in a MBR treating shipboard slop: Analysis of hydrocarbon removal, biomass activity and membrane fouling tendency

The paper reports the main results of an experiment carried out on a membrane bioreactor (MBR) plant designed for the treatment of shipboard slops. With a view of a co-treatment process of the slop with other wastewaters, sodium acetate, as external co-substrate, was supplied (high dosage – Period 1, low dosage – Period 2) to evaluate its effects on hydrocarbons removal. The MBR pilot plant enabled approximately 99% of total petroleum hydrocarbon (TPH) removal during the entire experiment, confirming the robustness of the MBR technology for the treatment of slops. The chromatography/mass spectrometry analysis showed that the removal efficiency for each alkane was close to the value observed…

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…

HPLC/HRMS and GC/MS for Triacylglycerols Characterization of Tuna Fish Oils Obtained from Green Extraction

Background: Fish oil is one of the most common lipidic substances that is consumed as a dietary supplement. The high omega-3 fatty acid content in fish oil is responsible for its numerous health benefits. Fish species such as mackerel, herring, tuna, and salmon are particularly rich in these lipids, which contain two essential omega-3 fatty acids, known as eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA). Objectives: Due to the scarcity of information in the literature, this study aimed to conduct a qualitative and quantitative characterization of triglycerides (TAGs) in crude tuna fish oil using HPLC/HRMS. Fatty acid (FA) determination was also performed using GC/MS. The tuna fis…

Polyphenol Characterization and Antioxidant Activity of Grape Seeds and Skins from Sicily: A Preliminary Study

The interest in the consumption of health-promoting foods has led to identifying derivatives of the wine industry as products to increase the functional properties of different foods or to design new functional foods. The main goal of this study is to characterize and valorize byproducts and wastes of Sicilian grapes as new sources of bioactive components, from the perspective of a circular economy and a biorefinery approach. In particular, this research investigated: 1. the total phenolic content and antioxidant activities and 2. the phenolic profiles of free and bound fractions of defatted grape seeds and red grape skins from Sicily. Defatted grape seeds (DGS) and red grape skins (RGSK) a…

Profiling the physiological and molecular response to sulfonamidic drag in Procambarus clarkii

Sulfamethoxazole (SMZ) is one of the most widely employed sulfonamides. Because of the widespread use of SMZ, a considerable amount is indeed expected to be introduced into the environment. The cytotoxicity of SMZ relies mainly on arylhydroxylamine metabolites (S-NOH) of SMZ and it is associated with the production of reactive oxygen species (ROS). There is limited information about the toxic potential of SMZ at the cellular and molecular levels, especially in aquatic and/or non-target organisms. In the present study, the red swamp crayfish (Procambarus clarkii), being tolerant to extreme environmental conditions and resistant to disease, was used as a model organism to profile the molecula…

Developing Antibiofilm Fibrillar Scaffold with Intrinsic Capacity to Produce Silver Nanoparticles

The development of biomedical systems with antimicrobial and antibiofilm properties is a difficult medical task for preventing bacterial adhesion and growth on implanted devices. In this work, a fibrillar scaffold was produced by electrospinning a polymeric organic dispersion of polylactic acid (PLA) and poly(α,β-(N-(3,4-dihydroxyphenethyl)-L-aspartamide-co-α,β-N-(2-hydroxyethyl)-L-aspartamide) (PDAEA). The pendant catechol groups of PDAEA were used to reduce silver ions in situ and produce silver nanoparticles onto the surface of the electrospun fibers through a simple and reproducible procedure. The morphological and physicochemical characterization of the obtained s…

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

Monitoraggio ambientale e biologico dei gas anestetici: studio condotto in 20 sale operatorie di ospedali palermitani

Rapid assay of resveratrol in red wine by paper spray tandem mass spectrometry and isotope dilution.

A rapid analytical approach for the assay of resveratrol in red wines, based on Paper Spray Mass Spectrometry (PS-MS) and Multiple Reaction Monitoring (MRM) is described. The assay involves the use of the stable isotope dilution method. The analytical parameters calculated analyzing fortified samples confirm the reliability of the proposed approach, with accuracy values about 100%, and LOD and LOQ values calculated at 0.5 and 0.8 μg/mL, respectively. Furthermore, both the recovery, which was quantitative for the analyte, and the reproducibility (RSD%), checked on different days on the same wine, always below 7%, highlighted the consistency of the methodology.

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

Edible Insects an Alternative Nutritional Source of Bioactive Compounds: A Review

Edible insects have the potential to become one of the major future foods. In fact, they can be considered cheap, highly nutritious, and healthy food sources. International agencies, such as the Food and Agriculture Organization (FAO), have focused their attention on the consumption of edible insects, in particular, regarding their nutritional value and possible biological, toxicological, and allergenic risks, wishing the development of analytical methods to verify the authenticity, quality, and safety of insect-based products. Edible insects are rich in proteins, fats, fiber, vitamins, and minerals but also seem to contain large amounts of polyphenols able to have a key role in specific bi…

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 …

Improvement of a rapid direct blood culture microbial identification protocol using MALDI-TOF MS and performance comparison with SepsiTyper kit

Fast diagnosis of pathogens is critical to guarantee the most adequate therapy for infections; bacterial culture methods, which constitute the actual gold standard, are precise and sensitive but rather slow. Today, new methods have been made available to enable faster diagnosis, with the Matrix-Assisted Laser Desorption Ionization-Time Of Flight Mass Spectrometry (MALDI-TOF MS) technique being the most promising. Even if simpler and faster than traditional bacterial culture methods, analysis of positive blood cultures via MALDI-TOF MS requires a preliminary extraction process of samples. In this study, we compared two extraction protocols for bacterial identification directly from positive …

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

Erratum: FragClust and TestClust, two informatics tools for chemical structure hierarchical clustering analysis applied to lipidomics. The example of Alzheimer's disease (Analytical and Bioanalytical Chemistry DOI: 10.1007/s00216-015-9229-6)

Erratum to: FragClust and TestClust, two informatics tools for chemical structure hierarchical clustering analysis applied to lipidomics. The example of Alzheimer’s disease

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.

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 …

Antioxidant activity and phenolic composition in pomegranate (Punica granatumL.) genotypes from south Italy by UHPLC-Orbitrap-MS approach

Background: Pomegranate fruits are a rich source of polyphenols with numerous health-promoting effects. Pomegranate juices of five genotypes ('Mollar', 'Kingdom', 'Dente di Cavallo', and two old populations 'Francofonte' and 'Santa Tecla') were evaluated regarding anthocyanin and non-anthocyanin phenolic contents using ultrahigh performance liquid chromatography (UHPLC)-Orbitrap-mass spectrometry (MS). Moreover, total antioxidant activity (TAA) was evaluated using a 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS) assay.; Results: Twenty-three phenolic compounds were identified. Cyanidin-3,5-O-diglucoside and pelargonidin-3,5-O-diglucoside were the most represent…

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…

Multiple points of view of heteronuclear NOE: long range vs short range contacts in pyrrolidinium based ionic liquids in the presence of Li salts.

The nuclear Overhauser enhancement (NOE) is a powerful tool of NMR spectroscopy extensively used to gain structural information in ionic liquids (ILs). A general model for the distance dependence of intermolecular NOE in ILs was recently proposed showing that NOE spots beyond the first solvation shell and accounts for long-range effects. This conclusion prompted for a deep rethinking of the NOE data interpretation in ILs. In this paper we present an extensive and quantitative study of N-propyl-N-methyl pyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR13TFSI), the homologue with bis(fluorosulfonyl)imide (PYR13FSI), and their mixtures with LiTFSI based on 1H-19F and 1H-7LiNOE correlation …

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…

MODELLING BIOGAS GENERATION AND RELEASE FROM MUNICIPAL SOLID WASTE LANDFILLS

MSW sanitary landfills represent nowadays one of the most important issue related to the waste management cycle. In particular, knowledge about biogas production is a key aspect for a proper exploitation of this energy source, even in the after-care phase. In the present study, a simple mathematical model was proposed for the simulation of biogas production. The model is based on 1st order biodegradation kinetic and takes also into account the temperature variation in time and depth and the landfill settlement. The model was applied to a real landfill located in Sicily (ITALY) and its simulation result was compared with experimental data (volumes of biogas collected by the recovery system a…

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…

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…

Triacylglycerols in edible oils: Determination, characterization, quantitation, chemometric approach and evaluation of adulterations

Vegetable oils are a dietary source of lipids that constitute an essential component of a healthy diet. The commonly used vegetable oils differ significantly for their triacylglycerol (TAG) profile. TAGs represent the principal components of oils and may contain different fatty acids (FA) esterified with glycerol leading to several positional isomers. To differentiate individual TAGs species in edible oils, advanced analysis systems and innovative methods are therefore required. TAGs can be considered as good fingerprints for quality control and many studies have been performed to develop rapid and low cost analytical methods to determinate the authenticity, origin and eventually evidence f…

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

Clinical and hormonal characteristics in heterozygote carriers of congenital adrenal hyperplasia

Abstract Non-classical congenital adrenal hyperplasia (NC-CAH) includes a group of genetic disorders due to a broad class of CYP21A2 variants identifying a disease-causing ‘C’ genotype. The heterozygous carriers of CYP21 mutations are at increased risk of developing clinically evident hyperandrogenism, even though clinical and laboratory characteristics are still underestimated. With the aim of obtaining a more accurate delineation of the phenotype of heterozygous carrier of CAH, we analyzed clinical, biochemical and molecular characteristics in a cohort of Sicilian subjects. Fifty-seven females with biallelic and monoallelic CYP21A2 variants classifying NC-CAH (24) and heterozygous carrier…

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…

Quantitative evaluation of the phenolic profile in fruits of six avocado (Persea americana) cultivars by ultra-high-performance liquid chromatography-heated electrospray-mass spectrometry

The phenolic profiles of six varieties of avocado (Persea americana) grown in Sicily were investigated. The ultra-high-performance liquid chromatography-heated electrospray-mass spectrometry method was developed to determine qualitative and quantitative changes in fruits at two different ripening stage. Nineteen individual phenolic compounds were detected in avocado pulp extracts. Gallic acid, sinapinic acid, vanillin, p-coumaric acid, and gentisic acid were present only in ripe fruits. On the contrary, epicatechin decreased with fruit ripening, whereas protocatechuic acid, 4-hydroxybenzoic acid, chlorogenic acid, and benzoic acid were relatively stable or exhibited erratic changes with fru…

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…

Untreated Opuntia ficus indica for the Efficient Adsorption of Ni(II), Pb(II), Cu(II) and Cd(II) Ions from Water

The raw cladode of Opuntia ficus indica (OFI) was evaluated as a sustainable biosorbent for the removal of heavy metals (Ni, Pb, Cu, and Cd) from aqueous solutions. The functional groups of OFI were identified by employing DRIFT-FTIR and CP-MAS-NMR techniques before and after contact with the ions in an aqueous media, showing a rearrangement of the biomass structure due to the complexation between the metal and the functional groups. The adsorption process was studied in both single- and multi-component systems under batch conditions at different pHs (4.0, 5.0, and 6.0), different metal concentrations, and different biomass amounts. The results show that the raw OFI had a removal capacity a…

Collision induced decomposition of AOT5YB2+: an unespected intracluster rearrangment

FragClust and TestClust, two informatics tools for chemical structure hierarchical clustering analysis applied to lipidomics. The example of Alzheimer's disease

Lipidomic analysis is able to measure simultaneously thousands of compounds belonging to a few lipid classes. In each lipid class, compounds differ only by the acyl radical, ranging between C10:0 (capric acid) and C24:0 (lignoceric acid). Although some metabolites have a peculiar pathological role, more often compounds belonging to a single lipid class exert the same biological effect. Here, we present a lipidomics workflow that extracts the tandem mass spectrometry data from individual files and uses them to group compounds into structurally homogeneous clusters by chemical structure hierarchical clustering analysis (CHCA). The case-to-control peak area ratios of the metabolites are then a…

Dietary Supplements as Surrogate of Mediterranean Diet in Healthy Smoking Subjects

The interventions to slow aging, favoring active life expectancy, represent the new perspectives in ageing investigation. Some mechanisms that delay or prevent the onset of aging pathologies have been identified. Between them, a healthy lifestyle seems to reduce many risk factors. In particular, eating habits represent the most concrete, low-cost way to act on aging process. Mediterranean diet has received much attention since its antioxidant and anti-inflammatory effects have been consistently demonstrated. Unfortunately, many people follow a Western diet, poor in phytochemicals that represent the main source of beneficial effects of this dietary pattern. So, supplements administration sho…

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

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

Molecular and physiological characterization of in vivo Sulfamethoxazole response in Procambarus clark

Determination of ketosteroid hormones in meat by liquid chromatography tandem mass spectrometry and derivatization chemistry.

A method for the determination and quantification of ketosteroid hormones in meat by mass spectrometry, based on the derivatization of the carbonyl moiety of steroids by O-methylhydroxylamine, is presented. The quantitative assay is performed by means of multiple-reaction-monitoring (MRM) scan mode and using the corresponding labelled species, obtained by reaction with d 3-methoxylamine, as internal standard. The accuracy of the method was established by evaluating artificially spiked samples, obtaining values in the range 90-110%. Recovery tests were performed on blank matrix samples spiked with non-natural steroids including trenbolone and melengestrol acetate. The latter experiment revea…

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

Bioplastics: A new analytical challenge

Even though petroleum-based plastics are advantageous in complying with the performance requirements in many applications, these are related, throughout their life cycle, to several environmental problems, including greenhouse gas emissions and persistence in marine and terrestrial environments. Therefore, the preservation of natural resources and climate change is considered worldwide, the main reason for which is necessary to reduce consumption and dependence on fossil-based materials. Biopolymers (PLA, PHAs, etc.) are examples of plastics whose use is grown exponentially over the years because of the improvements of their physical and mechanical properties using additives of various natu…

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

The ascidian Styela plicata hemocytes as a potential biomarker of marine pollution: In vitro effects of seawater and organic mercury.

Toxic metals, such as mercury, contribute substantially to anthropogenic pollution in many estuarine environments. Animals living in those environments, particularly invertebrate filter feeders like tunicates, can be used as bioindicators. In an attempt to identify cellular markers for revealing pollution, this study examined in vitro the effects of different concentrations of methyl mercury on Styela plicata hemocytes. The harvested hemocytes from S. plicata that were exposed to the metal had a significant mortality, cellular count and morphometric alterations. These findings provided evidence of MeHg immunotoxic effects on S. plicata, resulting in hemocyte death and morphological changes …

The young hard active Sun: soft X-ray irradiation of tryptophan in water solutions

AbstractThe X-ray emission of the young Sun was much harder and intense than today and might have played a significant role in the evolution of complex organics in protoplanetary environments. We investigate the effects of soft X-rays on tryptophan molecules in aqueous solutions at room temperature. As results of the irradiation experiments we detect several light species indicative of fragmentation, together with large molecular structures such as tryptophan dipeptide and tripeptide. Complexification is more evident in H2O solution than in D2O, probably due to isotopic effects. The abundances of peptides depend on the irradiation dose and decrease with increasing energy deposition. Radical…