Development of a dynamic headspace solid-phase microextraction procedure coupled to GC–qMSD for evaluation the chemical profile in alcoholic beverages

In the present study, a simple and sensitive methodology based on dynamic headspace solid-phase microextraction (HS-SPME) followed by thermal desorption gas chromatography with quadrupole mass detection (GC–qMSD), was developed and optimized for the determination of volatile (VOCs) and semi-volatile (SVOCs) compounds from different alcoholic beverages: wine, beer and whisky. Key experimental factors influencing the equilibrium of the VOCs and SVOCs between the sample and the SPME fibre, as the type of fibre coating, extraction time and temperature, sample stirring and ionic strength, were optimized. The performance of five commercially available SPME fibres was evaluated and compared, namely polydimethylsiloxane (PDMS, 100 μm); polyacrylate (PA, 85 μm); polydimethylsiloxane/divinylbenzene (PDMS/DVB, 65 μm); carboxen™/polydimethylsiloxane (CAR/PDMS, 75 μm) and the divinylbenzene/carboxen on polydimethylsiloxane (DVB/CAR/PDMS, 50/30 μm) (StableFlex). An objective comparison among different alcoholic beverages has been established in terms of qualitative and semi-quantitative differences on volatile and semi-volatile compounds. These compounds belong to several chemical families, including higher alcohols, ethyl esters, fatty acids, higher alcohol acetates, isoamyl esters, carbonyl compounds, furanic compounds, terpenoids, C13-norisoprenoids and volatile phenols. The optimized extraction conditions and GC–qMSD, lead to the successful identification of 44 compounds in white wines, 64 in beers and 104 in whiskys. Some of these compounds were found in all of the examined beverage samples. The main components of the HS-SPME found in white wines were ethyl octanoate (46.9%), ethyl decanoate (30.3%), ethyl 9-decenoate (10.7%), ethyl hexanoate (3.1%), and isoamyl octanoate (2.7%). As for beers, the major compounds were isoamyl alcohol (11.5%), ethyl octanoate (9.1%), isoamyl acetate (8.2%), 2-ethyl-1-hexanol (5.9%), and octanoic acid (5.5%). Ethyl decanoate (58.0%), ethyl octanoate (15.1%), ethyl dodecanoate (13.9%) followed by 3-methyl-1-butanol (1.8%) and isoamyl acetate (1.4%) were found to be the major VOCs in whisky samples.

Evolution of ethyl carbamate during Madeira wine ageing by GC-MS: a new methodology

Recently, ethyl carbamate (EC) was reclassified by the International Agency for Research on Cancer (IARC) as "probably carcinogenic to humans" and occurs mainly in fermented beverages. Nowadays many countries have set limit values for EC in alcoholic beverages. In this sense and taking into account the low concentrations found in alcoholic beverages, the scientific community has shown interest for the development of new analytical methods, whereby its simplification plays an important role in the EC control and prevention. Firstly, a simple, rapid and sensitive methodology was developed for the EC quantification in fortified wines by microextraction by packed sorbent (MEPS) with gas chromatography coupled with a mass spectrometer detector (GC-MS). This method showed good linearity (R2 = 0.999) and sensitivity (LOD = 1.5 μg/L). The accuracy of the method was assessed by means of repeatability and reproducibility (RSD < 7%). Moreover, a good recovery has been demonstrated (97 – 106%) as well as its applicability (16 fortified wines). Thus, the developed methodology has proven to be an excellent approach for routine quantification of EC in fortified wines. The EC evolution was also evaluated during a year and half of Madeira wine ageing submitted to two traditional ageing methods, estufagem and canteiro, in order to evaluate the formation kinetic. The results revealed that estufagem process increased the formation kinetic and promoted a linear increase of the EC concentration (R2 ≥ 0.977), proportionally to the ageing time (4 months). However, when the wines are firstly submitted to estufagem and then undergo canteiro ageing, the EC values remain almost constant during the following 14 months. The results suggest that estufagem does not seem to be the critical factor in the EC formation, but instead the amount of precursors in the medium.

Alasdair Gray`s 1982 Janine (1984): a postmodernist scottish novel

Alasdair Gray is now an established figure in the Scottish literary scene and has numerous claims to be considered an important voice writing in English. First Lanark: A Life in Four Books (1981) and then 1982 Janine (1984) contributed to the recognition of Gray as one of the founding fathers of the new Scottish writing and as a figure of importance in international contemporary fiction due to his innovative, experimental and postmodernist novels. As the title of this dissertation - “Alasdair Gray’s 1982 Janine (1984): A Postmodernist Scottish Novel” - suggests, it aims at analysing the author’s second novel, 1982 Janine (1984), in a thematic and formal perspective, in order to justify the choice of the terms - Postmodernist and Scottish - to classify this novel. 1982 Janine projects a world through Jock McLeish’s mind and is a powerful stream-of-consciousness narrative. Jock is an alcoholic who lives a personal crisis and, therefore, tries to escape from his depressing reality through sexual fantasies and political diatribes. During a single night in a Scottish hotel room, he drinks and dreams, and spends the whole night alone with his fantasies and fears, his memories and hopes. In Chapter 11, the most daring experimental section of the novel, Jock attempts to commit suicide by taking an overdose of tablets with alcohol but fails. Following this, he decides to review his life and make for a new beginning; the novel thus closing with an optimistic note. Also, the narrative is based on a constant interweaving of sex fantasy with political satire, that is, it is through his protagonist that Gray manages to convey the state of Scotland as well as the concerns and aspirations of the Scottish people and then, proceed to a political and social critique. This dissertation appears structured in three chapters. In Chapter I - “Alasdair Gray: A Postmodernist Scottish Writer” - I present Gray as a powerful postmodernist writer who also sees himself as a Scottish author, and more particularly as a Glaswegian, who concentrates on Scottish subject matter in his literary work. In a first section, I offer a brief survey of the Scottish literary scene from the fourteenth to the twentieth century, in order to understand Gray’s choice of setting and themes and to check his influence or indebtedness to previous Scottish authors. As 1982 Janine is also a good example of selfconscious experimental writing, in a second section, I present various seminal fictional works that introduced and developed experimentalism in British fiction, in order to evaluate the influence of modernist developments in form and technique on recent experimental writing. The third section consists of an introduction to Gray’s work for he is not only a novelist, but also an artist, a playwright, a poet, an activist and a scholar. Chapter II - “Postmodernist Features in 1982 Janine” - aims at listing and examining the postmodernist devices that the novel includes, in what content and form are concerned. On the one hand, the use of a developed type of the modernist stream of consciousness, the presence of a protagonist who feels entrapped in a specific system, the quest for freedom, the incoherence and fragmentation of time, the nonchronological order of the narrative, the blending of fantasy and “reality”, as well as the importance of the Scottish material are definitely current aspects within postmodernist literature that can be found in Gray’s novel. On the other hand, the handling of literary self-conscious devices, such as typographical experimentation, presence of metafiction and intertextuality, and inclusion of an Epilogue, are likewise among recurrent postmodernist features. As the title - “A Narratological Analysis of 1982 Janine” - evidences, Chapter III offers a description of the mechanics of the narrative and its functioning in order to better understand the narrative technique of postmodernist fiction. This study is based primarily on Gérard Genette’s theoretical framework and terminology, presented in Narrative Discourse: An Essay in Method, an analytical tool that allows me to provide a more objective and scientific analysis. Hence, I follow the Genettian division of narrative discourse in Time, Mood and Voice while examining the novel. Finally, I proceed to a description of the intertextual relationships 1982 Janine establishes with other texts.

Comparative study of the whisky aroma profile based on headspace solid phase microextraction using different fibre coatings

A dynamic headspace solid-phase microextraction (HS-SPME) and gas chromatography coupled to ion trap mass spectrometry (GC–ITMS) method was developed and applied for the qualitative determination of the volatile compounds present in commercial whisky samples which alcoholic content was previously adjusted to 13% (v/v). Headspace SPME experimental conditions, such as fibre coating, extraction temperature and extraction time, were optimized in order to improve the extraction process. Five different SPME fibres were used in this study, namely, poly(dimethylsiloxane)(PDMS),poly(acrylate)(PA),Carboxen-poly(dimethylsiloxane)(CAR/PDMS),Carbowax-divinylbenzene(CW/DVB)and Carboxen-poly(dimethylsiloxane)-divinylbenzene (CAR/PDMS/DVB). The best results were obtained using a 75 m CAR/PDMS fibre during headspace extraction at 40◦C with stirring at 750rpm for 60min, after saturating the samples with salt. The optimised methodology was then appliedtoinvestigatethevolatilecompositionprofileofthreeScotchwhiskysamples—BlackLabel,BallantinesandHighlandClan.Approximately seventy volatile compounds were identified in the these samples, pertaining at several chemical groups, mainly fatty acids ethyl esters, higher alcohols, fatty acids, carbonyl compounds, monoterpenols, C13 norisoprenoids and some volatile phenols. The ethyl esters form an essential group of aroma components in whisky, to which they confer a pleasant aroma, with “fruity” odours. Qualitatively, the isoamyl acetate, with “banana” aroma,wasthemostinteresting.Quantitatively,significantcomponentsareethylestersofcaprilic,capricandlauricacids.Thehighestconcentration of fatty acids, were observed for caprilic and capric acids. From the higher alcohols the fusel oils (3-methylbutan-1-ol and 2.phenyletanol) are the most important ones.

Changes in volatile composition of Madeira wines during their oxidative ageing

The influence of the age in the volatile composition of Madeira wines made with Boal, Malvazia, Sercial and Verdelho varieties and aged in oak barrel during 1, 11 and 25 years old was been studied. For this purpose, the evolution of volatile compounds: higher alcohols, ethyl esters, fatty acids, furan compounds, enolic compounds, γ-lactones, dioxanes and dioxolanes, of the four most utilised varieties were determined using liquid–liquid extraction with dichloromeihane. Octan-3-ol was used as internal standard. The wines made with these varieties showed great differences in sugar content and small variations on pH and alcoholic degree. The results show that during ageing, the concentration of fatty acids ethyl esters, acetates and fatty acids decrease significantly contrarily to the great increase of ethyl esters of diprotic acids. There is a strong correlation between sotolon, 2-furfural, 5-methyl-2-furfural, 5-hydroxymethyl-2-furfural and 5-ethoxymethyl-2-furfural with wine ageing. These findings indicate that these compounds can be used as ageing wine markers. Among the molecules studied, sotolon [3-hydroxy-4,5-dimethyl-2(5H)-furanone] was one of the few molecules present in concentrations above the perception threshold in Madeira wines. 5-Eihoxymethyl-2-furfural formed from 5-hydroxymethyl-2-furfural and 2-furfural, derived from sugars, are also involved in the aroma of sweet fortified white wines aged in oxidative conditions. The sensory properties change significantly after long periods of conservation.