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Application of chromatography, spectroscopy and mass spectrometry techniques to coffee authentication
No full text[eng] Nowadays, the quality of food products is an issue of great interest in our society. Food products comprise intricate mixtures containing a diverse array of compounds (that originate from the nature of the product or the food chain processes). The extensive and complex nature of the food chain can lead to food fraud cases, which in recent years, has seen a significant increase. Food fraud is a dishonest practice aimed at obtaining economic benefits by deceiving consumers. It can occur by different forms including manipulation, adulteration or imitation, among other practices. Food fraud is illegal, and not only causes economic losses to consumers, but it can also lead to health risks, especially when harmful ingredients are added or important nutrients are removed from the food products. So, the assessment of food authenticity is a crucial issue in quality control and food safety. In this field, beverages are highly susceptible food products to adulteration and manipulation through practices like the addition of unspecified additives to increase volume, mislabeling or misrepresentation, and supplementation with flavors or aromas, among others. Beverages with elevated rates of adulteration encompass fruit juices, tea, coffee, wine and other alcoholic beverages. Thus, the study presented in this work focuses on preventing food fraud cases in one of the most popular beverages in the world: coffee. In this line, the development of analytical methodologies is proposed to classify, characterize, and authenticate different types of coffee. Non-targeted methodologies based on liquid chromatography coupled with spectroscopic detections: ultraviolet (LC-UV) and fluorescence (LC-FL) are employed. Additionally, liquid chromatography coupled with high-resolution mass spectrometry (LC-HRMS) is used for precise authentication through both targeted and non-targeted approaches. Furthermore, for the analysis of volatile compounds, which provide coffee characteristic aroma, a non-targeted method based on Headspace Solid-Phase Micro-Extraction (HS-SPME) and gas chromatography coupled to mass spectrometry (GC-MS) was employed. Moreover, the feasibility of rapid analysis methods is explored using direct flow injection analysis coupled with mass spectrometry (FIA-MS) and rapid near-infrared spectroscopy (NIR) non-targeted methods. All employed methodologies are complemented with the use of chemometric methods to achieve an effective data interpretation.[cat] La qualitat dels productes alimentaris, especialment dels productes naturals, és un tema de gran rellevància en la societat actual, ja que la demanda de productes segurs i autèntics no ha deixat de créixer en els darrers anys. Els aliments són barreges complexes que contenen una gran varietat de compostos, els quals poden provenir de la mateixa naturalesa del producte o dels processos de producció, transformació i distribució dins de la cadena alimentària. La naturalesa extensa i complexa d’aquesta cadena fa que els aliments siguin susceptibles a pràctiques deshonestes, conegudes com a frau alimentari, que han experimentat un augment significatiu en els darrers anys a nivell global. El frau alimentari es defineix com una acció il·legal destinada a obtenir un benefici econòmic enganyant als consumidors. Pot adoptar múltiples formes, com ara la manipulació del producte, la seva adulteració o imitació, l’ús d’ingredients no declarats o la retirada de nutrients essencials. Aquestes pràctiques no només generen pèrdues econòmiques considerables per als consumidors i les empreses, sinó que poden comportar riscos greus per a la salut, especialment quan s’afegeixen substàncies nocives o es modifica la composició natural dels aliments. Per aquest motiu, l’avaluació de l’autenticitat dels productes alimentaris és un element clau dins del control de la qualitat i la seguretat alimentària. En aquest context, les begudes constitueixen un grup de productes especialment vulnerables al frau alimentari. Entre les pràctiques més comunes hi ha l’addició d’additius no declarats per augmentar el volum o modificar el sabor, l’etiquetatge incorrecte o enganyós, la suplementació amb aromes artificials i la imitació de productes de qualitat superior amb alternatives més econòmiques. Els productes més afectats per aquestes pràctiques inclouen sucs de fruites, té, cafè, vi i altres begudes alcohòliques, que presenten taxes elevades d’adulteració a nivell mundial. El present estudi es centra en la prevenció del frau alimentari en una de les begudes més consumides i valorades del món: el cafè. L’objectiu principal és desenvolupar i aplicar metodologies analítiques avançades capaces de classificar, caracteritzar i autenticar diferents tipus de cafè, assegurant la seva qualitat i autenticitat. Per aconseguir-ho, s’empren tècniques de cromatografia líquida acoblada amb detecció espectroscòpica ultraviolada (LC-UV) i de fluorescència (LC-FL), així com cromatografia líquida acoblada a espectrometria de masses d’alta resolució (LC-HRMS), que permet realitzar una anàlisi precisa amb enfocaments tant dirigits com no dirigits. Per a l’estudi dels compostos volàtils responsables de l’aroma característic del cafè, s’utilitza una metodologia no dirigida basada en la microextracció en fase sòlida de l’espai de cap (HS-SPME) seguida de cromatografia de gasos acoblada a espectrometria de masses (GC-MS). A més, es valoren mètodes d’anàlisi ràpids mitjançant l’anàlisi per injecció en flux amb espectrometria de masses (FIA-MS) i l’espectrometria en l’infraroing proper (NIR), que permeten una caracterització no destructiva i eficient del producte. Totes aquestes metodologies analítiques es complementen amb l’aplicació de mètodes quimiomètrics, els quals faciliten la interpretació de grans volums de dades i permeten establir patrons fiables per a la identificació i autenticació del cafè. D’aquesta manera, es poden detectar adulteracions, classificar varietats i establir correlacions entre les propietats químiques i sensorials dels productes. En conclusió, aquest treball posa de relleu la importància de desenvolupar estratègies analítiques robustes i integrals per prevenir el frau alimentari, especialment en begudes de consum massiu com el cafè. La combinació de tècniques cromatogràfiques, espectromètriques i quimiomètriques proporciona una eina poderosa per garantir la seguretat, la qualitat i l’autenticitat dels aliments, beneficiant tant els consumidors com la indústria alimentària
Refranes meteorológicos del asturianoleonés en su contexto romance, según los datos de ParemioRom
Get PDFEven though the Project ParemioRom (Romance Paremiology: sayings and proverbs on meteorological issues and territory) finished some years ago (FFI2011- 1 Agradezco las valiosas observaciones de Maria-Reina Bastardas y Joan Fontana. 38 JOSÉ ENRIQUE GARGALLO GIL 123 (2020): 37-63 ISSN: 0212-0534 - eISSN: 2174-9612 DOI:10.17811/LLAA.123.2020.37-63 24032), it is still valid from a scientific point of view. Its data basis, which is inserted in a previous one (Database of calendar and meteorological sayings in the Romancespeaking areas: BADARE, 2005-2011), the functionality of its geolocalization brings together other four pre-existing search types: textual, according to language, thematic (chronology, meteorology and general) and according to bibliographical sources. The ParemioRom database allows us to have a simple of 726 files of meteorological sayings (paroemies with meteorological or atmospheric implications), organised according to the Astur-Leonese label, proverbs which are mostly located in Asturias, but which extend to Leon; and, likewise, the Romance confrontation between similar paroemies will be shown. Methodologically, all these proverbs will be presented from the abstract concept of what is paremiological. The sample is internally categorised according to thematic varieties such as sun height and projection, fixed dates or various atmospheric phenomena. It also shows similarities of different kind in the Romance-speaking context, specially with Western Galician and Portuguese, at times with the whole Iberian-Romance territory, from which Catalan is usually left apart. Besides, there are also some Asturian-Leonese cases which integrate into a Romance-speaking paremiological continuum, which extends along the diverse European territorial continuum (including the Mediterranean isles), and, in spite of this, far from Romanian, a different language not only in terms of aspect, but also in paremiological and folkloric aspects. The Atlas de ParemioRom (APR) also offers a paremiotype which replies to the formula: «[If/when] the Candlemas cries [rains] → Winter is out; [if/when] the Candlemas smiles [shines] → Winter still to come», with its corresponding Asturian representation in the Iberian-Romance context
Las actitudes lingüísticas del castellanohablante en la sociedad catalana
Get PDFA partir de un análisis cualitativo de algunas vidas lingüísticas de hablantes de entre 20 y 24 años de edad, nacidos en Cataluña, cuya lengua primera es el castellano, en este estudio descriptivo se expone la situación actual de lo que acontece en la comunidad lingüística catalana sobre la tendencia general ante la selección lingüística de la lengua española en la variedad funcional de la conversación
Guiding the starting dose of the once-daily formulation of tacrolimus in " de novo" adult renal transplant patients: a population approach
Get PDFAims: The once-daily extended-release tacrolimus formulation (ER-Tac) has demonstrated similar efficacy and safety to the twice-daily immediate-release formulation (IR-Tac), but few population-based pharmacokinetic models have been developed in de novo kidney transplant patients to optimize doses. Therefore, this study aimed i) at developing a population pharmacokinetic model for ER-Tac in de novo adult kidney transplant patients ii) and identifying genetic factors and time-varying covariates predictive of pharmacokinetic variability to guide tacrolimus dosage during the early post-transplant period.
Methods: A total of 1,067 blood tacrolimus concentrations from 138 kidney transplant patients were analyzed. A total of 29 out of 138 patients were intensively sampled for 24 h on the day 5 post-transplantation; meanwhile, for the remaining patients, concentrations were collected on days 5, 10, and 15 after transplantation. Tacrolimus daily doses and genetic and demographic characteristics were retrieved from the medical files. Biochemistry time-varying covariates were obtained on different days over the pharmacokinetic (PK) study. A simultaneous PK analysis of all concentrations was carried out using the non-linear mixed-effects approach with NONMEM 7.5.
Results: A two-compartment model with linear elimination and delayed absorption best described the tacrolimus pharmacokinetics. Between-patient variability was associated with oral blood clearance (CL/F) and the central compartment distribution volume (Vc/F). Tacrolimus concentrations standardized to a hematocrit value of 45% significantly improved the model (p < 0.001). This method outperformed the standard covariate modeling of the hematocrit–blood clearance relationship. The effect of the CYP3A5 genotype was statistically (p < 0.001) and clinically significant on CL/F. The CL/F of patients who were CYP3A5*1 carriers was 51% higher than that of CYP3A5*1 non-carriers. Age also influenced CL/F variability (p < 0.001). Specifically, CL/F declined by 0.0562 units per each increased year from the value estimated in patients who were 60 years and younger.
Conclusion: The 36% between-patient variability in CL/F was explained by CYP3A5 genotype, age, and hematocrit. Hematocrit standardization to 45% explained the variability of tacrolimus whole-blood concentrations, and this was of utmost importance in order to better interpret whole-blood tacrolimus concentrations during therapeutic drug monitoring. The dose requirements of CYP3A5*/1 carriers in patients aged 60 years or younger would be highest, while CYP3A5*/1 non-carriers older than 60 years would require the lowest doses
Care complexity factors and discharge destination in an emergency department: A retrospective cohort study
Get PDFIntroduction: Emergency department discharge destination is an important topic in both clinical practice and management.This study aimed to analyze the association of Care Complexity Individual Factors (CCIFs) with discharge destinations in patients who visit the emergency department (ED). Methods: This is a retrospective cohort study with consecutive sampling, including all patients who visited the ED of a tertiary hospital during 2021-2022. Data were collected from electronic health records. The main study outcomes were discharge destinations (mortality, intensive care unit admission, hospitalization, left without being seen/discharge against medical advice, and home discharge) and 26 CCIFs. Independent multinomial logistic regression was used for assessing the association of each factor and the discharge destinations, adjusted for age, sex, and triage level. All analyses were performed with R, version 4.3.2. Results: A total of 35,383 patients were included. Of these, 60.8% were home discharged, 34.1% were hospitalized, 2.6% were transferred to the intensive care unit, 2.1% were left without being seen, and 0.4% died. The presence of CCIFs was a risk factor of ED mortality (odds ratio (OR): 13.49 [95% confidence interval (CI): 4.99;36.46]), intensive care unit admission (OR:1.26 [95%CI:1.08;1.47]), and hospitalization (OR: 1.62 [95%CI:1.53;1.71]), whilst the presence of care complexity factors was a protective factor of discharge against medical advice (OR:0.64 [95%CI:0.55;0.74]). Conclusion: The discharge destinations from the ED showed strong associations with the patient’s complexity factors. Health professionals should consider these relationships for the design of early detection strategies and as an aid in decision-making, to ensure equity and quality of care
Understanding how servant leaders can influence employee playful work design: the role of meaningful work, positive affect and work engagement
Get PDFLeadership plays a pivotal role for employees’ proactive work behaviours. A recently researched concept is playful work design (PWD), a proactive process wherein employees redesign their work activities to infuse elements of fun and competition, has garnered significant attention for its positive outcomes, including for employee wellbeing. However, the underlying factors through which leaders can influence such proactive behavior over time remains relatively unexplored. Further, information on which leadership style enables PWD remains unclear. Bridging this gap and adopting a resource-based work-centric perspective, our study investigates the underlying psychological pathways through which servant leadership influences employee PWD. Using three-wave time-lagged data from 234 workers in Ghana, the study identifies four key psychological pathways. First, an affective pathway, where servant leaders boost PWD through positive affect. Second, a motivational pathway, where servant leaders enhance PWD by fostering meaningful work. Third, a complex motivational pathway, where meaningful work leads to work engagement, which in turn, promotes PWD. Finally, an affective-motivational pathway, where positive affect and work engagement sequentially mediate the relationship between servant leadership and PWD. These findings suggest that integrating servant leadership into leadership development programs can effectively encourage PWD, enhancing employee engagement and wellbeing
ICAM-1 Targeting of Nanocarriers in a Human Blood-Brain-Barrier-on-a-Chip Complements In Vivo Brain Delivery Observations
Get PDFTargeting therapeutic nanocarriers (NCs) to endothelial receptors favours transport across the blood-brain barrier (BBB), a main obstacle to access the brain. While these strategies compel validation in animals, quantitative sub-cellular resolution is non-viable in vivo. BBB-on-chip (BBB-oC) devices can help. Illustrating this, we used a BBB-oC comprising a lateral channel containing a human brain endothelial lining and a central chamber containing hydrogel-embedded pericytes and astrocytes. We studied NCs targeting intercellular adhesion molecule-1 (ICAM-1), a cell-surface protein overexpressed in pathology and involved in CAM-mediated transport. Brain access was validated in vivo after injection of NCs coated with anti-ICAM-1 vs. control IgG. ICAM-1 expression was verified in vitro using endothelial cells, pericytes, and astrocytes (756-, 511-, 690-fold over non-specific signal under TNFα). VE-cadherin presence and lack of dextran leakage demonstrated a restrictive BBB-oC barrier. Data showed endothelial targeting of anti-ICAM-1 NCs (428 NCs/cell at 1 h), uptake (60% of cell-interacting NCs), and transcytosis (90%; 24 h) downregulated by a CAM-pathway inhibitor (88% decay; 1 h). Non-transcyosed NCs trafficked to lysosomes, while transcytosed NCs interacted with pericytes and astrocytes (2643 NCs/cell; 24 h) and entered them (90% of transcytosed NCs). This BBB-oC represents a valuable model to evaluate ICAM-1-mediated transcytosis, complementing animal studies
Climate Litigation in Argentina: A Critical and Prospective Analysis
Get PDFThis article analyses the climate litigation scenario in Argentina. Based on the Sabin Center Database, we conducted an in-depth study of all the proceeding documents of the identified cases. We found that, in Argentina, a significant number of climate cases exists compared to other jurisdictions in the region and in the Global South as a whole. These cases show civil society actors suing public and corporate actors due to the deployment of ‘climate-disruptive’ projects or the failed protection of climate-relevant ecosystems. Plaintiffs use a variety of judicial avenues and grounds from different regulatory levels. That said, the case law study leads us to conclude that climate litigation is still incipient in Argentina. Climate change is a very novel legal issue for Argentinean litigants and courts, with lawsuits only developing actual climate argumentation very recently and with not even one judgment, let alone a landmark decision, addressing climate concerns. That is a notable difference from other jurisdictions in the region. Furthermore, we anticipate that climate litigation will continue to grow in Argentina, given weak political opportunities for climate action and stronger legal opportunities provided by broad judicial avenues, a multiplicity of grounds that can be used in climate arguments, and innovative environmental legal approaches developed by the Supreme Court
Coordinació i presentació del dossier "Vides paral·leles"
Get PDFPresentació del dossier "Vides paral·leles", coordinat per Helena Badell. "Els lectors d’aquest dossier hi trobarem moltes similituds i diferències entre uns autors i uns altres, però també serà una ocasió per emmirallar-nos-hi. En la comparació es va formant un reflex de com som ara: hi podem veure què ha ressaltat cada tradició dels seus autors del passat, hi podem veure quina importància donem al seu paper social, al seu compromís, a la seva funció més o menys vertebradora en la formació d’una literatura i alhora a les seves inquietuds poètiques i espirituals. Hi podem veure, en definitiva, com els llegim i com ens llegim.
The Translation of Advertising Texts in Culturally-Distant Languages: The Case of Spanish and Arabic
Get PDFTranslation problems can stem from the translator’s lack of familiarity with lexical, terminological, and textual correspondences between two languages. The roots of these problems are often deeply embedded in culture and context. Nord (1988) makes a distinction between translation problems and translation difficulties. She claims that problems are objective and are not related to the translator’s competence, whereas difficulties are subjective and depend on his/her working conditions. Translation problems can appear in the preliminary stages of translation as well as throughout the entire translation process. Initially, translators must deal with possible comprehension problems of the source text, and be able to foresee potential areas in the text where finding correspondences in the target language will be difficult. It goes without saying that translators must possess the necessary linguistic and extralinguistic knowledge to understand the text easily, extract its core meaning, and create a new text that will occupy a similar place in the target language text system and culture. Secondly, translators should know how and where to resolve their problems. This means being able to predict possible problem areas as well as being aware of which resources and search methods will provide them with precise information for text decoding and generation. Finally, translators must be sensitive to the vast array of contrasts and differences between languages and cultures since these can be the source of a wide range of translation problems. In fact, when source texts have a strong cultural component (which is often the case of advertising texts), translators are often obliged to seek creative solutions that involve adapting the translation so that its form and content will be fit into the target language culture. For all of these reasons, it is necessary for translators to be bicultural as well as bilingual. As an example of the translator’s need for cultural awareness, this article describes and analyzes problems that can arise in the translation of advertising texts from Spanish to Arabic. Our conclusions reflect the fact that translators should possess background knowledge and intercultural sensitivity, which will make them aware of potential translation problems that, can arise from differences in the two language-cultures