Utjecaj udjela botritiziranih bobica grožđa na aromu vina Amarone

The aim of this study is to evaluate the impact of Botrytis cinerea, a noble rot, on the aroma components of Amarone, a dry red wine produced from withered grapes. A comparative analysis of wines obtained from manually selected healthy and botrytized grapes was done. Aroma analysis revealed that most compounds varied significantly according to the percentage of botrytized berries utilized. Botrytized wines contained less fatty acids and more fruity acetates than healthy wines. A positive correlation between the content of N-(3-methylbutyl)acetamide, sherry lactone and an unidentified compound and the level of fungal infection was also observed. The results indicate that noble rot can significantly modify important aroma components of Amarone wine.Svrha je ovoga rada bila procijeniti utjecaj plemenite plijesni Botrytis cinerea na sastojke arome suhoga crvenog vina Amarone, proizvedenog iz prosušenoga grožđa. Uspoređen je sastav vina dobivenog od ručno probranih zdravih i botritiziranih bobica grožđa, pa je utvrđeno da većina sastojaka arome bitno ovisi o udjelu navedenih bobica. Botritizirana vina sadrže manje masnih kiselina i više voćnih acetata od vina dobivenih od zdravoga grožđa. Opažena je pozitivna korelacija udjela N-(3-metilbutil)acetamida, laktona iz sherryja i neidentificiranog spoja te jačine gljivične infekcije. Rezultati pokazuju da plemenita plijesan bitno utječe na udjel glavnih sastojaka arome vina Amarone

Integration and holistic analysis of multiple multidimensional soil data sets

Complex matrices such as soil have a range of measurable characteristics, and thus data to describe them can be considered multidimensional. These characteristics can be strongly influenced by factors that introduce confounding effects that hinder analyses. Traditional statistical approaches lack the flexibility and granularity required to adequately evaluate such matrices, particularly those with large dataset of varying data types (i.e. quantitative non-compositional, quantitative compositional). We present a statistical workflow designed to effectively analyse complex, multidimensional systems, even in the presence of confounding variables. The developed methodology involves exploratory analysis to identify the presence of confounding variables, followed by data decomposition (including strategies for both compositional and non-compositional quantitative data) to minimise the influence of these confounding factors such as sampling site/location. These data processing methods then allow for common patterns to be highlighted in the data, including the identification of biomarkers and determination of non-trivial associations between variables. We demonstrate the utility of this statistical workflow by jointly analysing the chemical composition and fungal biodiversity of New Zealand vineyard soils that have been managed with either organic low-input or conventional input approaches. By applying this pipeline, we were able to identify biomarkers that distinguish viticultural soil from both approaches and also unearth links and associations between the chemical and metagenomic profiles. While soil is an example of a system that can require this type of statistical methodology, there are a range of biological and ecological systems that are challenging to analyse due to the complex interplay of global and local effects. Utilising our developed pipeline will greatly enhance the way that these systems can be studied and the quality and impact of insight gained from their analysi

Optimized experimental settings for the best detection of quantum nonlocality

Nonlocality lies at the core of quantum mechanics from both a fundamental and applicative point of view. It is typically revealed by a Bell test, that is by violation of a Bell inequality, whose success depends both on the state of the system and on parameters linked to experimental settings. This leads to find, given the state, optimized parameters for a successful test. Here we provide, for a quite general class of quantum states, the explicit expressions of these optimized parameters and point out that, for a continuous change of the state, the corresponding suitable experimental settings may unexpectedly vary discontinuously. We finally show in a paradigmatic open quantum system that this abrupt "jump" of the experimental settings may even occur during the time evolution of the system. These jumps must be taken into account in order not to compromise the correct detection of nonlocality in the system.Comment: 5 pages, 2 figure

Simultaneous extraction, derivatisation and analysis of varietal thiols and their non-volatile precursors from beer

Varietal thiols are important contributors to the aroma profile of a wide range of beverages including beer. A methodology for the simultaneous extraction and subsequent analysis of the varietal thiols 3-sulfanylhexan-1-ol (3SH), 3-sulfanylhexylacetate (3SHA) and 4-methyl-4-sulfanylpentan-2-one (4MSP), and the non-volatile precursors 3-S-cysteinylhexan-1-ol (Cys-3SH) and 3-S-glutathionylhexan-1-ol (GSH-3SH) in beer was developed and validated for the first time. The method, which utilises LC-MS/MS, was successfully tested on nine commercial beers, showing it to be widely applicable to this matrix. The syntheses of the novel internal standards d8-3SH and d8-3SHA, which allow a robust and accurate quantification of the hydronated congeners, are also reported. The simplicity of the QuEChERS-based (Quick, Easy, Cheap, Effective, Rugged and Safe) extraction allows for rapid, high throughput analyses suitable for both research and industry application

O cassinismo como fator de desenvolvimento turístico: uma análise comparativa entre Brasil e Portugal. Tramitação processual (2014-2021).

The practice of sports betting games (chance), or casino, in Brazil is an activity that has been prohibited since 1946 (Decree-Law 9.215 / 1946), and which has gone through phases of legalization and prohibition. Since gambling is an integral part of human culture, the objective was to address its possible recovery in a lawful and organized manner, which, according to the literature review, is in evidence, focusing on this research on tourism and economic development. to destinations (cities). The importance of discussing the issue is also due to the fact that Brazil is one of the few countries where it is still considered an illegal act, whose stance leads to a significant loss of tax collection for the government. In order to discuss the possible scenarios that approval would entail for the country, a literature review was carried out both of the history of gambling as well as of the current situation of legalized practice, in addition to an exploratory-comparative research based on the Brazilian law PL 530/2019 authored by the federal deputy, His Excellency Mr. Paulo Vellozo Dantas Azi and is currently being processed and awaits a plenary resolution in parallel with Decree Law No. 422/87 of Portugal, which is a reference among casino destinations , the market is expanding. The choice was based on the common language between the two countries, the characterization of this well-segmented market, and its wide expansion in Portugal. Due to the extension and complexity of the investigated legislative objects, three parts were selected for document analysis, namely: a) implementation process, b) access terminology, and c) economic resources. In this sense, the legislative texts were extracted and interpreted. The results indicate that the authorization of casino in Brazil would have much to add to the financial income (foreign exchange) and the emergence of new jobs, but above all it would result in the intensification of tourism activity due to its high power of attractiveness and entertainment.A prática de jogos de apostas esportivas (azar), ou cassinismo, é uma atividade proibida no Brasil desde 1946 (decreto-lei 9.215/1946), tendo passado por fases de legalização e proibição. Sendo os jogos de apostas parte integrante da cultura humana, objetivou-se tratar sobre a sua possível retomada de forma lícita e organizada que, segundo a revisão da literatura, encontra-se em evidência, tendo como foco para essa pesquisa o desenvolvimento turístico e econômico para os destinos (cidades).  A importância da discussão do tema também se dá  pelo fato de o Brasil ser um dos poucos países onde ainda é considerado um ato ilegal, cuja postura acarreta a uma perda significante de recolhimento de impostos para o poder público. A fim de debater sobre os possíveis cenários que a aprovação acarretaria ao país, realizou-se uma  revisão de literatura tanto do histórico dos jogos de azar como também da situação atual da prática legalizada, além de uma pesquisa de caráter exploratório-comparativo tendo como base  a legislação brasileira PL 530/2019 de autoria do deputado federal,  Excelentíssimo Senhor Paulo Vellozo Dantas Azi e atualmente está em tramitação e aguarda deliberação do plenário em paralelo com o Decreto Lei n° 422/87 de Portugal, que é referência entre destinos de cassinismo. .A escolha pautou-se na língua em comum entre os dois países, a caracterização desse mercado bem segmentado, e sua ampla expansão em Portugal. Devido à extensão e complexidade dos objetos legislativos investigados. Foram selecionadas três partes para análise documental, sendo: a) processo de implantação, b) terminologia de acesso, e c) recursos econômicos. Nesse sentido, os textos legislativos foram extraídos e interpretados. Os resultados indicam que a autorização do cassinismo no Brasil teria muito a agregar no rendimento financeiro (divisas) e surgimento de novos postos de trabalho,  mas acima de tudo acarretaria na intensificação da atividade turística devido ao seu alto poder de atração e entretenimento

O cassinismo como fator de desenvolvimento turístico: uma análise comparativa entre Brasil e Portugal. Tramitação processual (2014-2021).

The practice of sports betting games (chance), or casino, in Brazil is an activity that has been prohibited since 1946 (Decree-Law 9.215 / 1946), and which has gone through phases of legalization and prohibition. Since gambling is an integral part of human culture, the objective was to address its possible recovery in a lawful and organized manner, which, according to the literature review, is in evidence, focusing on this research on tourism and economic development. to destinations (cities). The importance of discussing the issue is also due to the fact that Brazil is one of the few countries where it is still considered an illegal act, whose stance leads to a significant loss of tax collection for the government. In order to discuss the possible scenarios that approval would entail for the country, a literature review was carried out both of the history of gambling as well as of the current situation of legalized practice, in addition to an exploratory-comparative research based on the Brazilian law PL 530/2019 authored by the federal deputy, His Excellency Mr. Paulo Vellozo Dantas Azi and is currently being processed and awaits a plenary resolution in parallel with Decree Law No. 422/87 of Portugal, which is a reference among casino destinations , the market is expanding. The choice was based on the common language between the two countries, the characterization of this well-segmented market, and its wide expansion in Portugal. Due to the extension and complexity of the investigated legislative objects, three parts were selected for document analysis, namely: a) implementation process, b) access terminology, and c) economic resources. In this sense, the legislative texts were extracted and interpreted. The results indicate that the authorization of casino in Brazil would have much to add to the financial income (foreign exchange) and the emergence of new jobs, but above all it would result in the intensification of tourism activity due to its high power of attractiveness and entertainment.A prática de jogos de apostas esportivas (azar), ou cassinismo, é uma atividade proibida no Brasil desde 1946 (decreto-lei 9.215/1946), tendo passado por fases de legalização e proibição. Sendo os jogos de apostas parte integrante da cultura humana, objetivou-se tratar sobre a sua possível retomada de forma lícita e organizada que, segundo a revisão da literatura, encontra-se em evidência, tendo como foco para essa pesquisa o desenvolvimento turístico e econômico para os destinos (cidades).  A importância da discussão do tema também se dá  pelo fato de o Brasil ser um dos poucos países onde ainda é considerado um ato ilegal, cuja postura acarreta a uma perda significante de recolhimento de impostos para o poder público. A fim de debater sobre os possíveis cenários que a aprovação acarretaria ao país, realizou-se uma  revisão de literatura tanto do histórico dos jogos de azar como também da situação atual da prática legalizada, além de uma pesquisa de caráter exploratório-comparativo tendo como base  a legislação brasileira PL 530/2019 de autoria do deputado federal,  Excelentíssimo Senhor Paulo Vellozo Dantas Azi e atualmente está em tramitação e aguarda deliberação do plenário em paralelo com o Decreto Lei n° 422/87 de Portugal, que é referência entre destinos de cassinismo. .A escolha pautou-se na língua em comum entre os dois países, a caracterização desse mercado bem segmentado, e sua ampla expansão em Portugal. Devido à extensão e complexidade dos objetos legislativos investigados. Foram selecionadas três partes para análise documental, sendo: a) processo de implantação, b) terminologia de acesso, e c) recursos econômicos. Nesse sentido, os textos legislativos foram extraídos e interpretados. Os resultados indicam que a autorização do cassinismo no Brasil teria muito a agregar no rendimento financeiro (divisas) e surgimento de novos postos de trabalho,  mas acima de tudo acarretaria na intensificação da atividade turística devido ao seu alto poder de atração e entretenimento

Mixed yeast communities contribute to regionally distinct wine attributes

There is evidence that vineyard yeast communities are regionally differentiated, but the extent to which this contributes to wine regional distinctiveness is not yet clear. This study represents the first experimental test of the hypothesis that mixed yeast communities—comprising multiple, region-specific, isolates and species—contribute to regional wine attributes. Yeast isolates were sourced from uninoculated Pinot Noir fermentations from 17 vineyards across Martinborough, Marlborough and Central Otago in New Zealand. New methodologies for preparing representative, mixed species inoculum from these significantly differentiated regional yeast communities in a controlled, replicable manner were developed and used to inoculate Pinot Noir ferments. Twenty-eight yeast-derived aroma compounds were measured in the resulting wines via Headspace Solid-Phase Microextraction coupled with Gas Chromatography-Mass Spectrometry. Yeast community region of origin had a significant impact on wine aroma, explaining ∼10% of the observed variation, which is in line with previous reports of the effects of region-specific S. cerevisiae isolates on Sauvignon Blanc ferments. This study shows that regionally distinct, mixed yeast communities can modulate wine aroma compounds in a regionally distinct manner and are in line with the hypothesis that there is a microbial component to regional distinctiveness, or terroir, for New Zealand Pinot Noir

Identification, quantitation and origin of sulfur compounds in grape products. An approach via hyphenated mass spectrometry techniques.

The contribute of the Analytical Chemistry in the study of complex matrices, as for instance foodstuff, is crucial. In particular the development of chromatographic methods allows to quantify important technological, microbiological and physiological markers. The ensemble of all these information furthers a deeper and higher knowledge. This Ph.D. project was designed to define the tools and evaluate the contribution of an important class of molecule on wine aroma. Grape products are really important in the cultural and dietary Italian traditions; moreover Italy is both the first producer and the first consumer around the world. Oenological products have been largely studied since the early ’70, even if the lack of biochemical and microbiological knowledge and the poor sensitivity of the analytical techniques did not allow to carry an deep study on sulfur compounds. This project, planned to bid analytical and oenological chemistry, focussed its attention on the study of sulfur compounds. Dealing with complex matrices, the first problem we had to face was the matrix effects. The overcoming of such issue or the attempts in reducing it, costs to chemical laboratory, wasting of time and money to prepare suitable internal standards. In this thesis we proposed a statistical approach based on the variance component model able to handle matrix effects. The benefits obtained by this approach definitely outweigh both the slightly worse sensitivity and uncertainty. Another topic discussed in the thesis is the definition of analytical methods to quantify sulfur compounds. This subject has been studied distinguishing sulfur compounds into two sub-groups: o fermentative sulfur compounds: molecules produced by yeast metabolisms from amino acidic precursors. o varietal sulfur compounds: molecules present in specific variety, as conjugated with cysteine and glutathione. The free forms, which are sensorially active, are released during fermentation by means of a specific enzymatic activity. This further classification was kept in the development of the analytical methods because the two classes required different sensitivity as well as metabolomics study were separated. Concerning fermentative sulfur compounds a HS-SPME/GC-MS method was optimised and validated. With this method a wide range of sulfur compounds were quantified. Such tool was applied to metabolomic studies, concerning the influence of variety, ageing, yeast strain and other technological practice on the level of 13 fermentative sulfur compounds. The results obtained from the development of the analytical method permitted to highlight the potentiality of the HS-SPME technique in sampling volatile compounds in complex matrices. This approach allows an easier and safer lab conditions, avoiding the use of organic solvents. The metabolomic studies furnished important suggestion on the influence of important oenological variables on the level of important sulfur compounds. The last topic discussed in this thesis concerns the study of varietal sulfur compounds. The lack of suitable analytical technique, sufficiently rapid and avoiding the use of mercuro-organic compounds stimulated our research in verifying the performance of headspace technique in extracting these analytes. We optimised and validated HS-SPME and purge and trap methods and finally we defined a non-parametric robust approach to compare performances from different analytical methods. Owing to the recent interest of the scientific research in trying to understand the formation and evolution of varietal sulfur compounds, we focussed our attention on their precursors. The first step was the synthesis of the putative precursors, followed by the optimisation of LC-MS/MS methods to quantify them. It was possible to identify a new precursor by LC-MS/MS experiments. Finally, by the isolation of the enzyme potentially responsible of the biosynthesis of the varietal thiols precursors, we gave a preliminary explanation of the formation of these glutathionylated precursors during grape ripening. By this project it has been possible to study and apply the newest analytical techniques available and it has been possible to define statistical procedures to overcome the most common issues in studying complex matrices. Furthermore it was clarified the contribution of an important class of molecules, such as sullfur compounds, on oenological matrices.Il contributo della Chimica Analitica nello studio delle matrici complesse, quali ad esempio quelle alimentari, è cruciale. In particolare lo sviluppo di metodi cromatografici avanzati può permettere di dosare importanti marker tecnologici, microbiologici e fisiologici e quindi consentire un approfondimento delle attuali conoscenze. Questo lavoro è stato concepito allo scopo di definire gli strumenti per valutare il contributo di un’importante classe di molecole all’aroma dei vini. Il vino riveste un ruolo di primaria importanza nelle tradizioni culturali ed alimentari Italiane, inoltre l’Italia risulta primo produttore e primo consumatore mondiale di vino. I prodotti enologici sono stati largamente studiati fin dai primi anni ’70, anche se l’assenza di conoscenze biochimiche e microbiologiche e la mancanza di tecniche analitiche sufficientemente sensibili non ha consentito lo studio esaustivo della classe dei composti solforati. Questa tesi, nata da esigenze legate alla chimica analitica e alla chimica enologica, ha avuto come punto centrale lo studio dei composti solforati nei vini. Il primo problema che si è dovuto affrontare nello studio di matrici complesse come quelle enologiche è stato quello relativo agli effetti matrice. Il superamento o il contenimento di questo problema crea ogni giorno costi in termini di tempo e di preparazione di opportuni standard interni. In questa tesi si è proposto un metodo statistico basato sul modello a componente di varianza in grado di gestire questo problema. I vantaggi sono notevoli, a fronte di una incertezza leggermente maggiore e di una sensibilità di poco peggiorata. Altro argomento trattato è stata la definizione dei metodi analitici in grado di quantificare e quindi di studiare i composti solforati. Questa materia è stata affrontata riconoscendo una prima distinzione all’interno del gruppo degli analiti indagati: o composti solforati fermentativi: molecole derivanti dal metabolismo del lievito a partire da precursori amminoacidici o composti solforati varietali: molecole presenti in specifiche varietà come coniugati della cisteina e del glutatione e rilasciati durante la fermentazione alcolica ad opera di specifiche attività enzimatiche. Questa suddivisione è stata mantenuta anche nello sviluppo dei metodi analitici, in quanto sensibilità richieste e conseguenze metabolomiche erano anch’esse distinte. Per quanto riguarda i composti solforati fermentativi, durante il dottorato di ricerca è stato ottimizzato e validato un metodo HS-SPME/GC-MS per l’analisi di un’ampia gamma di molecole tipicamente derivanti dal metabolismo del lievito. Tale approccio è poi stato la base per studi di natura più squisitamente metabolomica in cui è stato verificato come il cultivar (i.e. la varietà), l’invecchiamento, il ceppo di lievito e altre pratiche tecnologiche potessero influenze il livello e l’evoluzione degli analiti indagati. I risultati ottenuti per quanto attiene lo sviluppo del metodo in spettrometria di massa hanno potuto confermare con la tecnica SPME con campionamento in spazio di testa sia una tecnica di elezione per l’analisi di molecole volatili. Inoltre questo approccio consente una gestione semplice ed enviromental friendly in confronto con i più obsoleti metodi di estrazione con solvente. Gli studi metabolomici hanno consentito di trarre importanti considerazioni su aspetti molto importanti nella definizione della qualità del prodotto finale. Tali risultati consentono anche una trasferibilità nei settori della ricerca applicata e dell’enologia. Come ultima classe di analiti indagati si sono studiati i composti solforati varietali. L’assenza di metodi sensibili e sufficientemente rapidi da essere applicati per studi su un numero significativo di campioni ha spinto la nostra attenzione alla verifica delle potenzialità delle tecniche in spazio di testa nel dosare queste molecole. Si sono ottimizzati e validati metodi HS-SPME e purge and trap ed è stata definita una procedura non parametrica robusta per il confronto delle performance delle diverse procedure. Visto il recente interesse della ricerca scientifica operante nel settore al controllo della formazione ed evoluzione di queste molecole, abbiamo focalizzato la nostra attenzione sui precursori dei composti solforati varietali. Il primo stadio è stata la sintesi di queste molecole, seguito poi dall’ottimizzazione di metodi LC-MS/MS per il dosaggio di queste molecole. In questo contesto è stato possibile identificare per la prima volta un nuovo potenziale precursore di aroma, tramite esperimenti LC-MS/MS. Da ultimo, attraverso l’isolamento dell’enzima responsabile della biosintesi dei precursori d’aroma è stato possibile proporre una preliminare spiegazione alla formazione di tali molecole durante la maturazione della materia prima. In conclusione, grazie a questa tesi di dottorato, è stato possibile approfondire ed applicare alcune delle più moderne tecniche analitiche a disposizione, è stato possibile definire procedure statistiche per superare i più comuni ostacoli nello studio di matrici complesse, ed è stato possibile chiarire il contributo di una classe importante di molecole come i composti solforati nelle matrici enologiche

Syntheses of mono-acylated luteolin derivatives, evaluation of their antiproliferative and radical scavenging activities and implications on their oral bioavailability

Abstract Luteolin is a flavonoid found in a wide range of plant materials, including commonly eaten fruits and vegetables. It displays a wide range of biological activities but is known to have poor bioavailability. In this study, ten different mono-acyl (nine 5-O-acyl and one 7-O-acyl) derivatives of luteolin were synthesised for the purpose of improving bioactivity and bioavailability, and therefore enhance their therapeutic potential. The antiproliferative activity of these derivatives was assessed against the HCT116 colon cancer and MDA-MB-231 breast cancer cell lines using a 3[H] thymidine incorporation assay. The radical scavenging activity of these derivatives against 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) radical cation and 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical using Trolox as a standard, was also assessed. Some of these derivatives were found to have improved antiproliferative activity with comparable radical scavenging activity compared to luteolin. Increased lipophilicity has been shown to increase the bioavailability of flavonoids implying these analogues will also have increased bioavailability