mass spectrometry

International descriptive and interventional survey for oxycholesterol determination by gas- and liquid-chromatographic methods

Increasing numbers of laboratories develop new methods based on gas-liquid and high-performance liquid chromatography to determine serum concentrations of oxygenated cholesterol metabolites such as 7α-, 24(S)-, and 27-hydroxycholesterol. We initiated a first international descriptive oxycholesterol (OCS) survey in 2013 and a second interventional survey 2014 in order to compare levels of OCS reported by different laboratories and to define possible sources of analytical errors.

High performance liquid chromatography coupled with mass spectrometry for/and nanomaterials: an overview

The story of mass spectrometry applied to the nanoparticles world is very young but actually it is expected to evolve as one of the most powerful tool for the characterization of the smaller-size nanoparticles in terms of composition, size, shape, surface chemistry, because of its versatility, sensitivity, reliability and the possibility to be coupled with high performance chromatographic separation techniques. A short overview on different fields where liquid chromatography coupled with mass spectrometry, nanomaterials and nanotechnology come together is herein given.

Green route for the isolation and purification of hyrdoxytyrosol, tyrosol, oleacein and oleocanthal from extra virgin olive oil

Extra virgin olive oil (EVOO) phenols represent a significant part of the intake of antioxidants and bioactive compounds in the Mediterranean diet. In particular, hydroxytyrosol (HTyr), tyrosol (Tyr), and the secoiridoids oleacein and oleocanthal play central roles as anti-inflammatory, neuro-protective and anti-cancer agents. These compounds cannot be easily obtained via chemical synthesis, and their isolation and purification from EVOO is cumbersome. Indeed, both processes involve the use of large volumes of organic solvents, hazardous reagents and several chromatographic steps.

Charge-tagged N-heterocyclic carbenes (NHCs): revealing the hidden side of NHC-catalysed reactions through electrospray ionization mass spectrometry

N‐heterocyclic carbenes (NHCs) are key intermediates in a variety of chemical reactions. Owing to their transient nature, the interception and characterization of these reactive species have always been challenging. Similarly, the study of reaction mechanisms in which carbenes act as catalysts is still an active research field. This Minireview describes the contribution of electrospray ionization mass spectrometry (ESI‐MS) to the detection of charge‐tagged NHCs resulting from the insertion of an ionic group into the molecular scaffold.

Insights into the phytochemistry of the cuban endemic medicinal plant phyllanthus orbicularis: fideloside, a novel bioactive 8-c-glycosyl 2,3-dihydroflavonol

Phyllanthus orbicularis (Phyllanthaceae) is an endemic evergreen tropical plant of Cuba that grows in the western part of the island and is used in traditional medicine as an infusion. The aqueous extract of this plant presents a wide range of pharmacological activitiessuch as antimutagenic, antioxidant and antiviral effects.

Can an elusive Pt(III) oxidation state be exposed in an isolated complex?

Platinum(IV) complexes are extensively studied for their activity against cancer cells as potential substitutes for the widely used platinum(II) drugs. Pt(IV) complexes are kinetically inert and need to be reduced to Pt(II) species to play their pharmacological action, thus acting as prodrugs. The mechanism of the reduction step inside the cell is however still largely unknown. Gas-phase activation of deprotonated platinum(IV) prodrugs was found to generate products in which platinum has a formal +3 oxidation state.

Mass spectrometry for evolved gas analysis: an update

Advances in evolved gas analysis (EGA) techniques are periodically reported by our group to provide useful examples of their applications in many different fields. It is actually recognized that anytime is requested a correct interpretation of the thermally induced reaction mechanism, involving the formation of gaseous species, it is strongly recommended the characterization of the evolved products.

Inner shell photofragmentation of 2Cl-pyrimidine studied by mass spectrometry and electron–ion coincidence experiments

Photoelectron spectroscopy, mass spectrometry and electron–ion coincidence experiments combined with tunable synchrotron radiation have been used to study the decay and fragmentation of 2Cl-pyrimidine after Cl(2p), C(1s) and N(1s) excitations. The goal is to investigate how the state- and site-selected excitation and the chemical environment affect the fragmentation paths of the molecule and to make a comparison with fragmentation induced by direct valence ionization.

Electrochemical oxidation of theophylline in organic solvents: HPLC‐PDA‐ESI‐MS/MS analysis of the oxidation products

The electrochemical oxidation of theophylline was investigated by controlled potential electrolysis in two different organic solvents and in water for comparison. The anodic oxidation was monitored by cyclic voltammetry in situ and UV‐Vis spectrophotometry ex situ and the final electrolyzed solutions were analyzed by tandem mass spectrometry after chromatographic separation with an HPLC‐PDA‐ESI‐MS/MS system.

From ascorbic acid to furan molecules: a theoretical and experimental study on the gas phase acid catalyzed degradation of Vitamin C

Degradation of L-ascorbic acid (L-AA) occurs into two types of reactions, named the non-oxidative and the oxidative. The main difference between these two pathways is that furfural is more easily produced through the former. It should be noted that the expression non-oxidative refers solely to the nature of the initial step, since subsequent transformations may involve various oxidation steps. Indeed, the oxidative pathway describes the reaction which involves as an initial step the oxidation of L-ascorbic acid to dehydro-L-ascorbic acid.

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