References of "Stefanuto, Pierre-Hugues"
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See detailMedical Application: Breath Volatile Compounds in Asthma Patients
Stefanuto, Pierre-Hugues ULiege; Zanella, Delphine ULiege; dejong, Thibaut et al

Scientific conference (2019, June)

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See detailOptimizing of TD-GC×GC-HRTOFMS for the profiling of cannabis blends
Dubois, Lena ULiege; Ledent, Maxime ULiege; Franchina, Flavio ULiege et al

Poster (2019, May 13)

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See detailComprehensive Approach for Monitoring Human Tissue Degradation
Dubois, Lena ULiege; Stefanuto, Pierre-Hugues ULiege; Perrault, Katelynn ULiege et al

in Chromatographia (2019)

In recent years, comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC × GC–TOFMS) has been reported as a suitable tool for the determination of volatile organic ... [more ▼]

In recent years, comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC × GC–TOFMS) has been reported as a suitable tool for the determination of volatile organic compounds (VOCs) emitted during the process of cadaveric decomposition. The main aim of the present study was to investigate temporal changes in VOC patterns during the decomposition process of various human tissues. The focus of previous research was mainly on the analysis of VOCs produced by whole cadavers. However, this study aimed to identify whether the VOCs produced during decomposition differ between specific organs, and further, to determine the extent of the variation between cadavers. The sampling process developed for this project allowed inter- and intra-cadaveric comparison. The headspace of heart, lung, liver, kidney and blood was monitored during the decomposition process. Tissue samples from five different cadavers were sampled regularly by dynamic pumping onto sorbent tubes that were further thermally desorbed onto a GC × GC–TOFMS system. A large amount of data (n = 774) was obtained, leading to challenges in the integration, interpretation and representation of the results. Eventually, multivariate statistical methods, such as principal components analysis (PCA) and hierarchical cluster analysis (HCA) were applied to the dataset to evaluate trends and differences in subgroups. It was demonstrated that there were subtle differences between the sets of compounds produced from each organ due to the different functions they carry out within the body. However, VOC profiles were more similar among organs from the same cadaver than when comparing samples from different cadavers. Various reasons may cause the differences between the analyzed cadavers, ranging from the individual diet and lifestyle to the time since death. © 2019, Springer-Verlag GmbH Germany, part of Springer Nature. [less ▲]

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See detailMolecular characterization of petroleum mixtures using multiple ionization modes and GC×GC-HRTOFMS
Stefanuto, Pierre-Hugues ULiege; Giri, Anupam; Courtiade, Marion et al

Poster (2019, May)

Introduction: Comprehensive two-dimensional gas chromatography (GC×GC) has become a method of choice for complex mixture characterization, especially in the petroleum industry. Indeed, the high resolving ... [more ▼]

Introduction: Comprehensive two-dimensional gas chromatography (GC×GC) has become a method of choice for complex mixture characterization, especially in the petroleum industry. Indeed, the high resolving power of the 2D separations offers structured separation allowing pattern recognition and group type classification of sample composition. For years, the technique was relying on electron ionization (EI) fragmentogram and chromatographic-based identification due to practical limitations on the detector side, mainly the high acquisition frequency required. The development of high-speed high-resolution time-of-flight mass spectrometers (TOFMS) offers opportunities to go deeper in the sample characterization. To obtain the most of the HRMS dimension, there is a growing interest to combine EI with softer ionization techniques, which preserve the molecular ion. Method: In this study, different base oil samples and standard mixtures were analyzed by GC×GC-HRTOMS. Three different soft-ionization techniques including photo ionization (PI), chemical ionization (CI), and field ionization (FI) were compared against EI to elucidate their relative capabilities to reveal different base oil hydrocarbon classes. Deeper investigations were also conducted on the PI fragmentation process for different chemical families. All the experiments were performed on a single system, a JEOL AccuTOF GCv 4G with modular ionization technologies. A low-polar (ZB-XLB-HT Inferno, 15.0 m, 0.25 mm ID, 0.1 μm, Phenomenex ) and polar (ZB-50HT, 2.0 m, 0.1 mm ID, 0.1 μm, Phenomenex) columns were used for base oil analysis for first and second dimension separation respectively. Preliminary Data: Compared to EI (70 eV), capabilities and limitations of PI were tested using an authentic mixture of compounds of several chemical classes. Ionization energy exhibited by PI, equivalent to 10.8 eV, resulted in significant retention of molecular ion information; [M]+• for alkanes, ketones, FAMEs, aromatics, [M−H]+• for chloroalkanes, and [M−H2O]+• for alcohols. In addition, considering the potential of PI for hydrocarbons, base oils, complex mixtures of saturated and unsaturated hydrocarbons blended for finished lubricant formulations, were extensively evaluated. PI retained significant molecular ion (M+‧) information for a large number of isomeric species including branched-alkanes and saturated mono-cyclic hydrocarbons along with unique fragmentation patterns. However, for bi-/poly cyclic naphthenic and aromatic compounds, EI played upper hand by retaining molecular as well as fragment ions to identify the species, whereas PI exhibited mainly molecular ion signals. CI revealed selectivity towards different base oil groups, particularly for steranes, sulfur-containing thiophenes, and esters; yielding protonated molecular ions (M+H) + for unsaturated and hydride abstracted ions (M-H+) for saturated hydrocarbons. FI, as expected, generated intact molecular ions (M+‧) irrespective to the base oil chemical classes. It allowed elemental composition by TOFMS with a mass resolving power up to 8,000 (FWHM) and a mass accuracy of 1 mDa, leading to the calculation of heteroatomic content, and carbon number of the compounds. The qualitative and quantitative results presented herein offer a unique perspective into the detailed comparison of different ionization techniques corresponding to several chemical classes. Novel aspect: The GC×GC field is ongoing a paradigm shift in which the MS dimension is even further contributing than before. [less ▲]

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See detailPhenotypage de l'asthme par volatilomique de l'haleine
Zanella, Delphine ULiege; Stefanuto, Pierre-Hugues ULiege; SCHLEICH, FLorence ULiege et al

Conference (2019, March 26)

L’asthme est l’une des maladies inflammatoires chroniques les plus répandues dans le monde, touchant 235 millions de personnes. Cela représente un problème majeur de santé publique dû aux coûts élevés ... [more ▼]

L’asthme est l’une des maladies inflammatoires chroniques les plus répandues dans le monde, touchant 235 millions de personnes. Cela représente un problème majeur de santé publique dû aux coûts élevés, estimés à 19,3 milliards d’euros par an, liés au traitement et au diagnostic. L’asthme est caractérisé par différents mécanismes inflammatoires des voies respiratoires. En fonction du profil inflammatoire, le traitement le plus adapté sera différent. C’est pourquoi, les traitements actuels ne sont pas efficaces pour une majorité des patients. Le développement de méthode pouvant caractériser efficacement les différents types d’asthme (éosinophilique, neutrophilque, paucigranulocytique, mixte-granulocytique) permettrait l’établissement de traitement personnalisé. L’utilisation de l’haleine comme outils de diagnostic permettrait l’établissement d’une procédure non-invasive pour le suivi de l’asthme. Dans cette étude, nous avons analysé les composés organiques volatils provenant de l’haleine de 521 patients. Les échantillons ont été collectés dans des sacs Tedlar®. Cette étude a été réalisée en deux phases cliniques. La chromatographie gazeuse couplée à la spectrométrie de masse (GC-MS) a été utilisée lors de la première phase. Sept composés ont été identifiés comme marqueurs potentiels de l’asthme par utilisation d’algorithmes d’apprentissage automatique. La phase de validation a été réalisée en analysant l’haleine de 245 patients par chromatographie gazeuse bidimensionnelle exhaustive couplée à la spectrométrie de masse à haute résolution (GC×GC-HRTOFMS). Cette phase de validation a confirmé l’efficacité de cinq composés. L’utilisation des indices de rétention, de la haute résolution et de l’injection de standards internes ont permis l’identification robuste des composés cibles. Dans les deux phases cliniques, les courbes ROC (receiver operating characteristic) ont été construites pour évaluer la performance de la classification dans un scénario de classification binaire. Chaque cohorte de patients a été divisée en un deux sets : un set d’apprentissage servant à la construction du modèle statistique et un set de validation. La phase clinique de validation a confirmé l’efficacité de cinq composés pour la classification des patients sur base de leur phénotype avec une précision de 70%, 60% et 64%. Ces molécules cibles fonctionnent mieux que les méthodes classiques de diagnostiques basées sur l’analyse sanguine ou du NO. La combinaison des analyses sanguines, de mesure du NO et des molécules volatiles cibles fournit la meilleure performance de classification avec une précision de 76%. Cette étude représente la première étude clinique à grande échelle dans le domaine des méthodes de diagnostic basée sur l’haleine. Elle a permis l’identification de marqueurs permettant le phénotypage des patients asthmatiques. Cette étude démontre le potentiel de l’analyse d’haleine pour le diagnostic clinique. [less ▲]

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See detailMultidimensional Chromatography, what is the synergy with untargeted metabolomics profiling?
Stefanuto, Pierre-Hugues ULiege

Conference (2019, March)

Pierre-Hugues Stefanuto Multidimensional Chromatography, what is the synergy with untargeted metabolomics profiling? In this webinar, I will discuss the new development of multidimensional chromatography ... [more ▼]

Pierre-Hugues Stefanuto Multidimensional Chromatography, what is the synergy with untargeted metabolomics profiling? In this webinar, I will discuss the new development of multidimensional chromatography and the synergy with metabolomics. This presentation will be broadcasted in the context of the Multidimensional Chromatography Workshop held in Liège last January (http://multidimensionalchromatography.com). During this event, four focus group discussions were organized: 1) data processing for untargeted screening, 2) minimum reporting information for QC and compound validation, 3) hyphenation of MDGC with high-resolution MS, 4) and the general acceptance of MDC techniques. I will illustrate these topics through some ongoing medical research articulated around volatile organic compound (VOC) measurements in human breath and in vitro in metabolomic applications. Pierre-Hugues Stefanuto obtained is PhD in analytical chemistry in 2016 from Liège University, Belgium. He conducted his research in the group of Prof. Jef Focant on the development of analytical strategies for the characterization of complex volatile mixtures from life sciences. He worked on the development of analytical approaches for different type of samples including clinical, forensic, and food matrices. Following his PhD, he spent one year in the group of Prof. J. Hill at Dartmouth College, USA. During this period, he focused his research on small molecules metabolomics for clinical applications. Since 2018, he has been lecturer and research scientist at Liège University, where he is developing multimodal analytical strategies for the characterization of clinical samples. In his research, he is developing full analytical workflow mostly based on multidimensional chromatographic approaches coupled with mass spectrometry. His main interest is the implementation of robust analytical protocols based on QA/QC and identification validation. He is then combining information from different types of sample through advanced data processing to obtain a clearer picture of their composition. [less ▲]

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See detailImportance du type d'absorbant pour l'échantillonnage des volatils : application sur les cultures bactériennes et l'haleine
Zanella, Delphine ULiege; Franchina, Flavio ULiege; Stefanuto, Pierre-Hugues ULiege et al

Poster (2019, March)

Les composés organiques volatils bactériens (VOC) sont considérés comme des biomarqueurs sensibles et spécifiques pour le phénotypage bactérien dans les biofluides humains (haleine, sang, urine, etc.) et ... [more ▼]

Les composés organiques volatils bactériens (VOC) sont considérés comme des biomarqueurs sensibles et spécifiques pour le phénotypage bactérien dans les biofluides humains (haleine, sang, urine, etc.) et dans les milieux de culture. La possibilité d'utiliser les VOCs pour l'identification bactérienne ouvre de nouvelles possibilités pour la mise au point de techniques de diagnostiques plus efficaces. Outre les différences biologiques des environnements in-vivo et in-vitro, il est essentiel d'utiliser la même technique d’échantillonnage pour la caractérisation et la validation de biomarqueurs. Dans cette étude, la chromatographie gazeuse bidimensionnelle couplée à la spectrométrie de masse (GC×GC-MS) a été utilisée pour comparer et évaluer différents adsorbants de tubes de désorption thermique pour l’échantillonnage des VOCs. Plus précisément, les paramètres suivants ont été évalués pour chaque adsorbant: sensibilité, sélectivité, reproductibilité et linéarité. Cinq adsorbants différents (Carbopack Y, X, B, Carboxen 1000 et Tenax), utilisés individuellement ou en combinaison, ont été testés sur un mélange de standards (15 composés). Les meilleures sensibilité et reproductibilité ont été obtenues pour les tubes conditionnés avec du Tenax. Les deux tubes de désorption thermique les plus performants, Tenax et Carbopack Y + X + Carboxen 1000, ont également été évalués sur des cultures de E. coli, S. aureus et P. aeruginosa. Ces deux types de tubes ont pu distinguer les 3 types de culture bactérienne, mais une amélioration de la sensibilité et de la reproductibilité a été obtenue avec les tubes Tenax. Une comparaison similaire sur les performances des tubes a été effectuée sur des échantillons d'haleine. [less ▲]

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See detailDéveloppement et validation d'une méthode de diganostique non-ciblée pour la caractérisation des fluides pulmonaires
Zanella, Delphine ULiege; Stefanuto, Pierre-Hugues ULiege; Dubois, Lena ULiege et al

Poster (2019, March)

L’amélioration constante de l’instrumentation analytique génère un intérêt croissant dans les études métabolomiques. Dans ce contexte de caractérisation de mélanges complexes, la chromatographie gazeuse ... [more ▼]

L’amélioration constante de l’instrumentation analytique génère un intérêt croissant dans les études métabolomiques. Dans ce contexte de caractérisation de mélanges complexes, la chromatographie gazeuse bidimensionnelle (GC×GC) constitue une solution efficace pour obtenir un aperçu complet de la composition des échantillons. Cependant, l’augmentation de la résolution analytique s'accompagne d'une augmentation de la complexité des données générées [1,2]. Pour garantir l'utilisation correcte de l'instrumentation analytique, l’optimisation de la méthode et l’établissement d’un protocole de contrôle qualité (QC) adéquats et clairement définis sont nécessaires. Malheureusement, peu d'études GC×GC non ciblées présentent ces aspects importants et une utilisation abusive des termes validation et semi-quantification est florissante dans les publications. Ces biais conduisent au problème général du manque de reproductibilité des études en science, souligné dans les publications récentes de Nature [3,4]. Pour résoudre ce problème, plusieurs initiatives, telles que l'initiative de normalisation en métabolomique (MSI), ont établi des directives générales pour éviter ce manque de robustesse analytique [5,6].Cette étude présente l'application et l'adaptation des directives MSI pour l'analyse de mélanges volatils à l'aide de la GC×GC-TOFMS. Pour illustrer cette approche, les profils volatils de fluide de lavage bronchoalvéolaire (BALF) ont été analysés. Cette procédure médicale est largement répandue et fournit des informations importantes sur les processus immunologiques, inflammatoires et infectieux des voies respiratoires. Tout d'abord, une solution de QC a été créée en regroupant des échantillons de BALF provenant de différents patients. Cette solution a ensuite été utilisée pour l’optimisation de la méthode, c’est-à-dire l’échantillonnage ainsi que les conditions chromatographiques. Sur base des conditions optimales, la validation a été effectuée. La solution QC a également été utilisée comme base pour la mise en œuvre d'un protocole de contrôle de qualité pour l'analyse de volatils dans les matrices biologiques. Cette étude a pour objectif de fournir des conseils pour l’établissement d’une stratégie analytique robuste pour les analyses non ciblées. References 2. Stefanuto, P. H. et al. Advanced method optimization for volatile aroma profiling of beer using two-dimensional gas chromatography time-of-flight mass spectrometry. J. Chromatogr. A 1507, 45–52 (2017). 3. Monya Baker. Seek out stronger science. Nature 537, 703–704 (2016). 5. Sumner, L. W. et al. Proposed minimum reporting standards for chemical analysis: Chemical Analysis Working Group (CAWG) Metabolomics Standards Initiative (MSI). Metabolomics 3, 211–221 (2007). [less ▲]

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See detailUse of Blood Volatiles as Trace Evidence
Dubois, Lena ULiege; Perrault, Katelynn ULiege; Stefanuto, Pierre-Hugues ULiege et al

Poster (2019, February 20)

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See detailMultimodal chemometric approach for the analysis of human exhaled breath in lung cancer patients by TD-GC ×GC-TOFMS
Pesesse, Romain ULiege; Stefanuto, Pierre-Hugues ULiege; SCHLEICH, FLorence ULiege et al

in Journal of Chromatography. B, Biomedical Applications (2019)

Lung cancer is the deadliest cancer in developed countries. To reduce its mortality rate, it is important to enhance our capability to detect it at earlier stages by developing early diagnostic methods ... [more ▼]

Lung cancer is the deadliest cancer in developed countries. To reduce its mortality rate, it is important to enhance our capability to detect it at earlier stages by developing early diagnostic methods. In that context, the analysis of exhaled breath is an interesting approach because of the simplicity of the medical act and its non-invasiveness. Thermal desorption comprehensive two-dimensional gas chromatography time of flight mass spectrometry (TD-GC×GCTOFMS) has been used to characterize and compare the volatile content of human breath of lung cancer patients and healthy volunteers. On the sampling side, the contaminations induced by the bags membrane and further environmental migration of VOCs during and after the sampling have also been investigated. Over a realistic period of 6 h, the concentration of contaminants inside the bag can increase from 2 to 3 folds based on simulated breath samples. On the data processing side, Fisher ratio (FR) and random forest (RF) approaches were applied and compared in regards to their ability to reduce the data dimensionality and to extract the significant information. Both approaches allow to efficiently smooth the background signal and extract significant features (27 for FR and 17 for RF). Principal component analysis (PCA) was used to evaluate the clustering capacity of the different models. For both approaches, a separation along PC-1 was obtained with a variance score around 35%. The combined model provides a partial separation with a PC-1 score of 52%. This proof-of-concept study further confirms the potential of breath analysis for cancer detection but also underlines the importance of quality control over the full analytical procedure, including the processing of the data. [less ▲]

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See detailCompositional elucidation of heavy petroleum base oil by GC×GC-EI/PI/CI/FI-TOFMS
Giri, Anupam; Coutriade, Marion; Racaud, Amandine et al

in Journal of Mass Spectrometry (2019)

Comprehensive two‐dimensional gas chromatography (GC×GC) coupled to time‐of‐flight mass spectrometry is a powerful separation tool for complex petroleum product analysis. However, the most commonly used ... [more ▼]

Comprehensive two‐dimensional gas chromatography (GC×GC) coupled to time‐of‐flight mass spectrometry is a powerful separation tool for complex petroleum product analysis. However, the most commonly used electron ionization (EI) technique often makes the identification of the majority of hydrocarbons impossible due to the exhaustive fragmentation and lack of molecular ion preservation, prompting the need of soft‐ionization energies. In this study, three different soft‐ionization techniques including photo ionization (PI), chemical ionization (CI), and field ionization (FI) were compared against EI to elucidate their relative capabilities to reveal different base oil hydrocarbon classes. Compared to EI (70 eV), PI (10.8 eV) retained significant molecular ion (M+‧) information for a large number of isomeric species including branched‐alkanes and saturated mono‐cyclic hydrocarbons along with unique fragmentation patterns. However, for bi‐/poly cyclic naphthenic and aromatic compounds, EI played upper hand by retaining molecular as well as fragment ions to identify the species, whereas PI exhibited mainly molecular ion signals. On the other hand, CI revealed selectivity towards different base oil groups, particularly for steranes, sulfur‐containing thiophenes, and esters; yielding protonated molecular ions (M+H) + for unsaturated and hydride abstracted ions (M‐H+) for saturated hydrocarbons. FI, as expected, generated intact molecular ions (M+‧) irrespective to the base oil chemical classes. It allowed elemental composition by TOFMS with a mass resolving power up to 8,000 (FWHM) and a mass accuracy of 1 mDa, leading to the calculation of heteroatomic content, double bond equivalency, and carbon number of the compounds. The qualitative and quantitative results presented herein offer a unique perspective into the detailed comparison of different ionization techniques corresponding to several hydrocarbon classes. [less ▲]

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See detailGC×GC-(MR)TOFMS in Food and Feed Control: Going Beyond Dioxin Measurements
Stefanuto, Pierre-Hugues ULiege; Scholl, Georges ULiege; Miklasova, Z et al

Scientific conference (2018, December)

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See detailFingerprinting glues using HS-SPME GC×GC-HRTOFMS: a new powerful method allows tracking glues back in time
Cnuts, Dries ULiege; Perrault, Katelynn ULiege; Stefanuto, Pierre-Hugues ULiege et al

in Archaeometry (2018), 60(6), 1361-1376

The use of glues for stone tool hafting is an important innovation in human evolution. Compared to other organic remains, glues are preserved more frequently, though mainly in small spots. Reliable ... [more ▼]

The use of glues for stone tool hafting is an important innovation in human evolution. Compared to other organic remains, glues are preserved more frequently, though mainly in small spots. Reliable identification requires chemical molecular characterization, which is traditionally performed by gas chromatography-mass spectrometry (GC-MS). Current methods of extraction and derivatization prior to GC-MS are destructive and require relatively large samples, which is problematic for prehistoric glue residues. In this paper, we discuss the results of an experimental study using a new method (HS-SPME-GC×GC-HRTOFMS) that proves effective for identifying small quantities of compound glues. The method is non-destructive with an improved sensitivity in comparison to traditional GC-MS, and it has a high potential for prehistoric samples. [less ▲]

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See detailImportance of sorbent material selection for VOCs sampling: application on bacterial cultures and breath
Franchina, Flavio ULiege; Zanella, Delphine ULiege; Stefanuto, Pierre-Hugues ULiege et al

Scientific conference (2018, November 08)

Bacterial volatile organic compounds (VOCs) have been considered as sensitive and specific biomarkers for bacterial phenotyping in both human biofluids (breath, blood, urine, etc.) and culture media. The ... [more ▼]

Bacterial volatile organic compounds (VOCs) have been considered as sensitive and specific biomarkers for bacterial phenotyping in both human biofluids (breath, blood, urine, etc.) and culture media. The possibility of using VOCs markers for bacterial identification would open a new frontier for developing more efficient diagnostic techniques of infections. Besides the biological differences in in vivo/in vitro environments, the importance of using the same sampling technique and sorbent phase is crucial for the translation and validation of biomarker discovery. In the present contribution, GC×GC-MS was exploited to compare and evaluate different adsorption materials for thermal desorption tubes for VOCs sampling. Specifically, the following parameters were evaluated: sensitivity, selectivity, reproducibility and linear range. Five different adsorbent materials (Carbopack Y, X, B, Carboxen 1000 and Tenax), packed singularly or in combination, were tested on a standard mixture (15 compounds). The tubes packed with Tenax showed the best reproducibility (max 14% RSD) and sensitivity, with ~24 average fold increase compared to Carbopack Y+X+Carboxen 1000, which was second in terms of sensitivity. The two better performing thermal desorption tubes, Tenax and Carbopack Y+X+Carboxen 1000, was also evaluated on E. coli, S. aureus, and P. aeruginosa cultures. Both tubes were able to discriminate between the 3 culture types, but improved sensitivity and reproducibility were obtained with Tenax tubes. A similar comparison on tube performances was carried out on breath samples. [less ▲]

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