Pasquale Agozzino

Analysis of furan in coffee of different provenance by head-space solid phase microextraction gas chromatography-mass spectrometry: effect of brewing procedures.

A simple, sensitive and accurate method for the analysis of furan in roasted coffee has been used based on headspace–solid-phase micro-extraction (HS–SPME) coupled to gas chromatography–mass spectrometry (GC–MS). The extraction was performed using 75-µm carboxen/polydimethylsiloxane fiber. Ionic strength, extraction time and temperature, and desorption time were assessed as the most important parameters affecting the HS–SPME procedure and d 4-furan was used as the internal standard. The linearity range was in the range 0.0075–0.486 ng g−1; the LOD and LOQ calculated using the signal-to-noise ratio approach were 0.002 and 0.006 ng g−1, respectively. The inter- and intra-day precision was 8 and 10%, respectively. The concentration of furan found in batches of roasted coffee powder different producing countries ranged from 57.3 to 587.3 ng g−1. The mean reduction in furan levels observed when brewing coffee by either infusion, using a moka pot or an expresso machine was 57, 67.5 and 63.3%, respectively.

Fruit physical, chemical and aromatic attributes of early, intermediate and late apricot cultivars

BACKGROUND In order to reach good fruit quality, apricots require a balance of sugars and acids as well as a strong apricot aroma. In this study, fruit quality of early, intermediate and late apricot cultivars was evaluated by measuring physical, chemical and olfactory attributes. Multivariate analysis of quality and aroma attributes was used to identify groups of similar cultivars and association with ripening season. RESULTS Physical, chemical and aromatic attributes showed great variation among cultivars but no relation to ripening season. Aromatic profiles (34 volatiles) of fruit tissues indicated qualitative and quantitative differences among cultivars. Ninfa and Mandorlon were richest in aroma, with a prevailing fruity component; Goldrich and Orange Red were also highly aromatic, with all odour components well represented; Pinkot, Alba and Pellecchiella were lowest in aroma, with a prevailing grassy component. Linear functions including five volatiles (concentrations) and fruit diameter or six aromatic compounds (odour units) and peel colour were found to discriminate cultivars by ripening season. Principal component analysis individuated three groups of cultivars: Ninfa and Mandorlon with sweet and fruity-flavoured fruits; Bulida, Alba, Goldrich, Ouardy and Silvercot with large, acidic and well-coloured fruits; and Fracasso, Pellecchiella, Palummella and Pinkot with small and floral/grassy-flavoured fruits. CONCLUSION In apricot, detailed analysis of the aromatic profile may represent an efficient tool for classification of genotypes by ripening season, and volatiles with relevant odour contribution may serve as quality markers for selecting towards an extended ripening season of best quality apricots.

Influence of roasting and different brewing processes on the ochratoxin A content in coffee determined by high-performance liquid chromatography-fluorescence detection (HPLC-FLD)

A rapid and reliable procedure has been developed for the determination of ochratoxin A (OTA) in green and roasted coffee. The method consists of extraction of the sample with methanol–5% aqueous sodium hydrogen carbonate/1% PEG8000 (20:80), followed by immunoaffinity column (IAC) clean-up and, finally, high-performance liquid chromatography (HPLC) determination with fluorimetric detection. Mean recoveries for green and roasted coffee spiked at different levels ranging from 94 and 105% were obtained. The limit of determination (S/N = 3) was 0.032 ng g−1 and the precision (within-laboratory relative standard deviation) was 6%. The method described has been used to assess the influence of roasting and different brewing processes on OTA content in commercial lots of green and roasted coffee. The results provided evidence that roasting led to a significant drop on OTA levels (65–100%). Also, the way coffee is prepared affects the OTA content: brewing using a Moka Express (Italian coffee) led to a significant reduction of OTA concentration (50–75%) since hot water stays in contact with coffee for a short time. On the contrary, Turkish coffee-making (infusion for about 10 min) cause poor reduction in OTA.

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

Abstract: 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.

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 discrimination between fresh oils and 1-year-old samples.

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.

Determination of terpene alcohols in Sicilian Muscat wines by HS-SPME-GC-MS

Muscat is a grape family used to obtain several sweet, aromatic white dessert wines common in the Mediterranean area. Currently, three Sicilian cultivars (all classified DOC) are known: ‘Moscato di Siracusa’ the oldest and very rare today; ‘Moscato di Noto’, a modern derivative of the first and finally ‘Moscato di Pantelleria’, now the most common. This study concerns the volatile profile of 15 different Sicilian Muscat wines produced in different years using HS-SPME-GC-MS. In particular, four fundamental terpene alcohols (linalool, geraniol, nerol and citronellol) were considered. The principal aim was to study the evolution of aromatic compounds in wine during aging, and the information obtained is useful for production and marketing. It was found that the amount of terpenes decreased with aging, thereby reducing the quality characteristic of these wines. An accurate analysis of chromatograms could characterise Muscat wines on the basis of geographic origin.

Some Mass Spectrometry Contributions in the Study of Cultural Heritage

In the last decades the application of various scientific methods and technologies to study materials and handicrafts of historical, artistic or archaeological interest have dramatically increased. These studies contribute to successfully solve various problems of identification, dating, utilization of artistically or historically important objects.

Addition reactions of acetylenic esters with monosubstituted thioureas

Monoalkyl-substituted thioureas react with dimethyl acetylenedicarboxylate to give, in a good yield, two different dihydrothiazinones, and not one compound only as has been claimed previously. The structures of the adducts were assigned on the basis of i.r. and 1H n.m.r. spectroscopy, and mass spectrometry.

Interaction water-polyethyleneglycols: Determination of hydration parameters from hydrodynamic data

Densities, viscosities and refractive indexes of diluted aqueous solutions of polyethylene glycols (Mw=200−6000) are determined at 25 °C. The non-linear increase of viscosity B and C coefficients with the number of ethylenoxide (EO) units are discussed. The solvation (hydration) becomes dominant when the number of ethylenoxide group increases. The hydration parameter, ω, the specific increment of density, dds/dc, and of refractive index, dnD/dc, for the various PEGs are the consequence of dimension and of conformation that assumes the polymer.