Integrating analytical resolutions in non-targeted wine metabolomics

Direct injection Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS), and ultra-high performance liquid chromatography coupled to mass spectrometry (UPLC/MS) were combined for the non-targeted analysis of wine metabolites. The unrivalled resolution on mass measurement allowed by the former and the separation ability of isomeric and isobaric substances by the latter, clearly increases the scope of detectable unknown metabolites in wines. Such methodology is illustrated through the comparison of chemical spaces of a young and an older Pinot noir wine. RP and HILIC chromatography could reveal up to five isomers for a given mass, throughout the explored mass range. CHO, CHOS …

Wine microbiome : A dynamic world of microbial interactions

International audience; Most fermented products are generated by a mixture of microbes. These microbial consortia perform various biological activities responsible for the nutritional, hygienic, and aromatic qualities of the product. Wine is no exception. Substantial yeast and bacterial biodiversity is observed on grapes, and in both must and wine. The diverse microorganisms present interact throughout the winemaking process. The interactions modulate the hygienic and sensorial properties of the wine. Many studies have been conducted to elucidate the nature of these interactions, with the aim of establishing better control of the two fermentations occurring during wine processing. However, …

Natural oxygenation of Champagne wine during ageing on lees: A metabolomics picture of hormesis

International audience; The oxygenation of Champagne wine after 4 and 6 years of aging on lees in bottle was investigated by FTICR-MS and UPLC-Q-TOF-MS. Three levels of permeability were considered for the stoppers, ranging from 0.2 to 1.8 mg/L/year of oxygen transfer rate. Our results confirmed a good repeatability of ultrahigh resolution FTICR-MS, both in terms of m/z and coefficient of variation of peak intensities among biological replicates. Vintages appeared to be the most discriminated features, and metabolite annotations suggested that the oldest wines (2006) were characterized by a higher sensitivity towards oxygenation. Within each vintage, the oxygenation mechanisms appeared to b…

Dry vs soaked wood: Modulating the volatile extractible fraction of oak wood by heat treatments

The aim of this study was to analyze the impact of the water content of wood on the concentrations of volatile compounds which can be extracted after heat treatments. Head Space-Solid Phase Micro Extraction Gas Chromatography coupled to Mass Spectrometry (HS-SPME GC-MS) has been used to compare the concentrations of six aroma compounds (vanillin, furfural, eugenol, guaiacol and cis- and trans-whisky lactones) in hydroalcoholic extracts of heated oak wood samples either previously soaked in hot water or not. Except for eugenol, concentrations of extracted aromas appeared to be lower in soaked woods than in dry woods for temperatures up to 200 °C. If a delaying effect of water could explain s…

Heat transfer inside wood treated by infrared radiation (IR): application to the process of barrel making. Experimental result

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A grape and wine chemodiversity comparison of different appellations in Burgundy: vintage vs terroir effects.

Abstract This study aimed at assessing the ability of high resolution Fourier Transform Ion Cyclotron Resonance – Mass Spectrometry (FTICR–MS) to differentiate grapes and corresponding wines from distinct vineyards managed by a same producer, according to complex chemical fingerprints. Grape extracts (at harvest) and corresponding wines from four different vineyards, sampled immediately after the alcoholic fermentation over three successive vintages, were analysed by FTICR–MS. Thousands of metabolites that are specific to a given vintage, or a given class (wine, skin or must) could be revealed, thus emphasising a strong vintage effect. The same wines were reanalyzed after a few years in bot…

Molecular Characterization of White Wines Antioxidant Metabolome by Ultra High Performance Liquid Chromatography High-Resolution Mass Spectrometry

International audience; The knowledge about the molecular fraction contributing to white wines oxidative stability is still poorly understood. However, the role of S- and N-containing compounds, like glutathione and other peptides, as a source of reductant in many oxidation reactions, and acting against heavy metals toxicity, or lipid and polyphenol oxidation as ROS-scavenger is today very well established. In that respect, the aim of the present study is to introduce an original analytical tool for the direct determination of the available nucleophilic compounds in white wine under acidic pH conditions. One step derivatization of nucleophiles has been realized directly in wines using 4-met…

Diffusion of Oxygen through Cork Stopper: Is It a Knudsen or a Fickian Mechanism?

International audience; The aim of this work is to identify which law governs oxygen transfer through cork: Knudsen or Fickian mechanism. This is important to better understand wine oxidation during post-bottling aging. Oxygen transfer through cork wafers is measured at 298 K using a manometric permeation technique. Depending on the mechanism, we can extract the transport coefficients. Increasing the initial pressure of oxygen from 50 to 800 hPa leads to a change in the values of the transport coefficients. This implies that oxygen transport through cork does not obey the Knudsen law. From these results, we conclude that the limiting step of oxygen transport through cork occurs in the cell …

Chemical messages in 170-year-old champagne bottles from the Baltic Sea: Revealing tastes from the past

International audience; Archaeochemistry as the application of the most recent analytical techniques to ancient samples now provides an unprecedented understanding of human culture throughout history. In this paper, we report on a multiplatform analytical investigation of 170-y-old champagne bottles found in a shipwreck at the bottom of the Baltic Sea, which provides insight into winemaking practices used at the time. Organic spectroscopy-based nontargeted metabolomics and metallomics give access to the detailed composition of these wines, revealing, for instance, unexpected chemical characteristics in terms of small ion, sugar, and acid contents as well as markers of barrel aging and Maill…

Transfer of volatile phenols at oak wood/wine interface in a model system

Abstract In order to assess the influence of wood on the concentration of aroma compounds during ageing of wine, the transfer of volatile phenols including 4-ethylphenol, eugenol and a homologous series of guaiacols from wine to oak wood were studied in a model system at 10°C. At equilibrium most of the volatile phenols adsorbed in the wood. The results display that the amounts adsorbed depend on the nature of the volatile phenols and the botanical origin of oak wood.

Adsorption equilibria of water vapor on cork.

International audience; We report here for the first time a complete thermodynamic study of water vapor adsorption on crude cork powder and plate. Adsorption−desorption isotherms were accurately measured by thermogravimetry at 283, 298, and 313 K in a large range of relative pressure. Adsorption enthalpies were determined by calorimetry as a function of loading. Adsorption−desorption isotherms exhibit a hysteresis due to the swelling of the material. The influence of the presence of lenticels on the adsorption properties of cork is found to be negligible. A detailed analysis and interpretation of adsorption data allow proposal of an adsorption mechanism in two steps. (i) First, water adsorb…

Water sorption isotherms of molecularly imprinted polymers. Relation between water binding and iprodione binding capacity

International audience; Molecularly imprinted polymers are often used in aqueous medium in order to recognize specifically a target molecule. The molecular recognition is usually based on hydrogen bonding. In this case, water molecule presents a serious competition towards the target molecule. In this study, the water sorption by molecularly imprinted polymers was studied in aqueous medium. The molecularly imprinted polymers were specific for iprodione fungicide and were prepared using a 24 full factorial experimental design. They were synthesized using EGDMA or TRIM as crosslinker, methacrylamide or styrene as functional monomer and using bulk or precipitation polymerization. The water sor…

High precision mass measurements for wine metabolomics

An overview of the critical steps for the non-targeted Ultra-High Performance Liquid Chromatography coupled with Quadrupole Time-of-Flight Mass Spectrometry (UPLC-Q-ToF-MS) analysis of wine chemistry is given, ranging from the study design, data preprocessing and statistical analyses, to markers identification. UPLC-Q-ToF-MS data was enhanced by the alignment of exact mass data from FTICR-MS, and marker peaks were identified using UPLC-Q-ToF-MS(2). In combination with multivariate statistical tools and the annotation of peaks with metabolites from relevant databases, this analytical process provides a fine description of the chemical complexity of wines, as exemplified in the case of red (P…

How subtle is the "terroir" effect? Chemistry-related signatures of two "climats de Bourgogne".

The chemical composition of grape berries is influenced by various environmental conditions often considered to be representative of a "terroir". If grapes from a given terroir are assumed to reflect this origin in their chemical compositions, the corresponding wine should also reflect it. The aim of this work was therefore to reveal the "terroir" expression within the chemodiversity of grapes and related wines, using ultrahigh-resolution mass spectrometry. Grapes and corresponding wines, from two distinct - though very proximate - terroirs of Burgundy were analyzed over three vintages (2010, 2011 and 2012). Ultrahigh-resolution mass spectrometry and ultra-high performan…

Influence of regionality and maturation time on the chemical fingerprint of whisky.

International audience; Understanding the chemical composition of whisky and the impact of each step in the manufacturing process provides a basis for responding to the challenges of producing high quality spirits. In this study, the objective was to discriminate whiskies according to their geographical origin and authenticate the maturation time in cask based on the non-volatile profiles. The combination of FT-ICR-MS and chemometrics allowed the distinction of whiskies from four geographical origins in Scotland (Highlands, Lowlands, Speyside and Islay). Statistical modeling was also used to discriminate whiskies according to the maturation time in cask and reveal chemical markers associate…

Chemical messages from an ancient buried bottle: Metabolomics for wine archeochemistry.

Restoration works in the old Clunisian Saint-Vivant monastery in Burgundy revealed an unidentified wine bottle (SV1) dating between 1772 and 1860. Chemical evidence for SV1 origin and nature are presented here using non-targeted Fourier Transform Ion Cyclotron Resonance Mass Spectrometry and Nuclear Magnetic Resonance analyses. The SV1 chemical diversity was compared to red wines (Pinot Noir) from the Romanée Saint Vivant appellation and from six different vintages spanning from 1915 to 2009. The close metabolomic signature between SV1 and Romanée Saint Vivant wines spoke in favor of a filiation between these wines, in particular considering the Pinot noir grape variety. A further statistic…

Diffusion of small molecules in edible films: Effect of water and interactions between diffusant and biopolymer

Mass transfers of various molecules in multiphasic food products lead to quality modification and thus require the use of edible films or coatings in-between the foodstuff. Consequently, it is important to assess the barrier properties and efficiencies of edible films as well as to determine the diffusivities of the migrants. Translational diffusion of a reference molecule such as fluorescein, determined by the fluorescence recovery after photobleaching (FRAP) method, displays a threshold of a critical water content inducing an increase of the molecular mobility, and demonstrates that multiple populations of a single molecular specie can be involved in different diffusion kinetics. Further …

Combined Nontargeted Analytical Methodologies for the Characterization of the Chemical Evolution of Bottled Wines

An Off-On-Off Fluorescent Sensor for pH Windows Based on the 13aneN4-Zn 2+ System

International audience; The new ligand L was prepared and features a 13-membered tetraaza macrocyclic ring with a 1,8-naphthalimide fluorophore appended to a C atom of its backbone. The protonation constants of L as well as its complexation constants with Zn2+ ions were determined in 1:1 water/methanol solutions by potentiometric titrations. Fluorimetric pH titrations were performed with L alone and L in the presence of Zn2+ ions (1:1), and the species distributions (%) versus pH were compared. A window-shaped fluorescence trend was observed with pH for the L/Zn2+ system, which behaves as an off-on-off pH sensor. The on window is centred in the 6.5-7.5 pH range, in correspondence with the f…

A HS-SPME-GC-MS analysis of IR heated wood: Impact of the water content on the depth profile of oak wood aromas extractability

http://www.sciencedirect.com/science/article/pii/S0963996913003736; International audience; Controlled and reproducible IR heat treatments were applied to oak wood surfaces in order to establish a depth-profiled picture of the extractability of volatile compounds, with particular emphasis on the impact of the initial water content. Headspace-solid phase microextraction-gas chromatography coupled to mass spectrometry (HS-SPME-GC-MS) has been used to compare the concentrations of six aroma compounds (vanillin, furfural, eugenol; guaiacol and cis- and trans-whisky lactones) in hydroalcoholic extracts of series of slices representative of the first 8 mm of the wood facing the IR source. Results…

Capillary electrokinetic fractionation mass spectrometry (CEkF/MS): Technology setup and application to metabolite fractionation from complex samples coupled at-line with ultrahigh-resolution mass spectrometry

Capillary electrokinetic fractionation (CEkF) is investigated as a new, simple, and robust approach for semipreparative and analytical sample analysis based on pKa -dependant pH-driven electrophoretic mobility. CEkF was optimized with contactless conductivity detection and conducted with 10 kV reverse voltage for 10 min, then coupled on/at-line to ESI/MS. We propose a semi-empirical model with 14 representative compounds based on the correlation between sample/medium pH regulating the partial charge, the electrokinetic loading of the capillary and intensity (I) of analytes. According to the model, an empirical function (I = f (pH)) could be derived to calculate the acid dissociation constan…

Fluorescence fingerprinting of bottled white wines can reveal memories related to sulfur dioxide treatments of the must.

For the first time, Excitation Emission Matrix (EEM) fluorescence spectroscopy was combined with parallel factor statistical analysis (PARAFAC) and applied to a set of 320 dry white wines of the Chardonnay grape variety. A four component PARAFAC model (C1, C2, C3 and C4) best explained the variability of fluorescence signatures of white wines. Subtle changes were observed in EEMs of white wines from two different vintages (2006 and 2007), where different concentrations of sulfur dioxide (0, 4, and 8 g·hL(-1)) were added to the grape must at pressing. PARAFAC results clearly indicated that sulfur dioxide added to the must subsequently influenced white wine chemistry into three distinct sulfu…

The cork viewed from the inside

International audience; Cork is the natural material stripped from the outer bark of cork oak. It is still the most used stopper to seal wine bottles and to preserve wine during storage. Cork stoppers are sorted in different classes according to apparent defects, named lenticels, which can be related to the cork macroporosity. The more lenticels there are, the worst cork quality is. The present work aims at investigating defects analysis of cork stoppers from two classes by comparing images recorded by digital photography and neutron imaging. Surface analysis of defects obtained from photography leads to more surface defects in class 4 (6.7%) than in class 0 (4.1%). Neutron radiography and …

Transfer of Water and Active Molecules at the Interfaces in Complex Food Systems: Theoretical and Practical Aspects

Abstract During processing, storage and consumption, mass transfer of various molecules (water, gases, flavour compounds or other solutes) occur between the different phases in complex food products, and/or also between the complex food and its surroundings. These mass transfers can lead to physical and/or chemical changes and thus induce food quality modifications. The objective of this presentation is to better understand the behaviour of small molecules at the interfaces, especially in model heterogeneous food systems. Different techniques have been developed to characterize their properties and their impact on the mass transfers. Particularly, techniques such as rotative diffusion cell …

Different Sorption Behaviors for Wine Polyphenols in Contact with Oak Wood

The evolution of polyphenols of enological interest- monomeric anthocyanins, (+)-catechin, (-)-epicatechin, gallic acid, and trans-resveratrol-in the presence of oak wood was investigated in aging-model conditions. Disappearance kinetics showed that, except for gallic acid, all of the wine polyphenols tend to disappear from the model wine in presence of oak wood, to reach an equilibrium after 20 days of contact. At equilibrium, the higher disappearance rates were obtained for monomeric anthocyanins and trans-resveratrol with values of 20 and 50%, respectively. For monomeric anthocyanins, the rate of disappearance seemed to be independent of their nature. In order to evaluate the contributio…

Water-induced local ordering of chitosan polymer chains in thin layer films

International audience; Carbon-13 NMR (CP-MAS and FSLG 1H–13C HETCOR) have been applied to chitosan salt films synthesized in acetic acid and exposed to different relative humidity environments (32% or 75%) at 20 °C for 1 month. It gives insight in the relationship between structure and functional properties according to the hydration level of this biomaterial as a film. The acetate ions trapped in the chitosan act as structuring agents between chitosan chains for the low hydration state. But, increasing the moisture content induces spontaneous removal of acetic acid and a subsequent modification in the film structure, with an increase in local ordering. HETCOR experiments also showed a mul…

The Antioxidant Potential of White Wines Relies on the Chemistry of Sulfur-Containing Compounds: An Optimized DPPH Assay

The DPPH (2,2-Diphenyl-1-picrylhydrazyl) assay is an easy and efficient method commonly used to determine the antioxidant capacity of many food matrices and beverages. In contrast with red wines, white wines are poorer in antioxidant polyphenolics, and the more hydrophilic sulfur-containing compounds in them may contribute significantly to their antioxidant capacity. The modification of the classical DPPH method, with a methanol-buffer and the measure of EC20 (quantity of sample needed to decrease the initial DPPH concentration by 20%) has shown that sulfur-containing compounds such as cysteine (0.037 &plusmn

Chemical Transfers Occurring Through Oenococcus oeni Biofilm in Different Enological Conditions

International audience; Chardonnay wine malolactic fermentations were carried out to evaluate the chemical transfers occurring at the wood/wine interface in the presence of two different bacterial lifestyles. To do this, Oenococcus oeni was inoculated into must and wine in its planktonic and biofilm lifestyles, whether adhering or not to oak chips, leading to three distinct enological conditions: (i) post-alcoholic fermentation inoculation in wine in the absence of oak chips, (ii) post-alcoholic fermentation inoculation in wine in the presence of oak chips, and (iii) co-inoculation of both Saccharomyces cerevisiae and O. oeni directly in Chardonnay musts in the presence of oak chips. Classi…

Cultivar- and Wood Area-Dependent Metabolomic Fingerprints of Grapevine Infected by Botryosphaeria Dieback

International audience; Botryosphaeria dieback is one of the most significant grapevine trunk diseases that affects the sustainability of the vineyards and provokes economic losses. The causal agents, Botryosphaeriaceae species, live in and colonize the wood of the perennial organs causing wood necrosis. Diseased vines show foliar symptoms, chlorosis, or apoplexy, associated to a characteristic brown stripe under the bark. According to the susceptibility of the cultivars, specific proteins such as PR-proteins and other defense-related proteins are accumulated in the brown stripe compared with the healthy woody tissues. In this study, we enhanced the characterization of the brown stripe and …

Structural studies of adsorbed protein (betalactoglobulin) on natural clay (montmorillonite)

International audience; In this work, the adsorption of a small globular protein (betalactoglobulin, BLG), on a natural montmorillonite clay (Mt) was investigated in acidic buffer (pH = 3). The combination of different characterization techniques such as zetametry, X-ray diffraction, transmission electronic microscopy, fluorescence and solid state nuclear magnetic resonance spectroscopies shed light on the interaction mechanism between the clay mineral and the proteins. For low BLG concentration, a slight increase of the interlayer spacing of the clay mineral was noticed as well as structural changes of the protein. In contrast, as the concentration of BLG increased, the adsorption led to a…

Capillary Electrophoresis in Wine Science

International audience; Capillary electrophoresis appeared to be a powerful and reliable technique to analyze the diversity of wine compounds. Wine presents a great variety of natural chemicals coming from the grape berry extraction and the fermentation processes. The first and more abundant after water, ethanol has been quantified in wines via capillary electrophoresis. Other families like organic acids, neutral and acid sugars, polyphenols, amines, thiols, vitamins, and soluble proteins are electrophoretically separated from the complex matrix.Here, we will focus on the different methodologies that have been employed to conduct properly capillary electrophoresis in wine analysis.Two examp…

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Attachment of chloride anion to sugars: mechanistic investigation and discovery of a new dopant for efficient sugar ionization/detection in mass spectrometers.

International audience; A new method for efficient ionization of sugars in the negative-ion mode of electrospray mass spectrometry is presented. Instead of using strongly hydrophobic dopants such as dichloromethane or chloroform, efficient ionization of sugars has been achieved by using aqueous HCl solution for the first time. This methodology makes it possible to use hydrophilic dopants, which are more appropriate for chromatographic separation techniques with efficient sugar ionization and detection in mass spectrometry. The interaction between chloride anions and monosaccharides (glucose and galactose) was studied by DFT in the gas phase and by implementing the polarizable continuum mode…

The chemodiversity of wines can reveal a metabologeography expression of cooperage oak wood

Wine chemical compositions, which result from a complex interplay between environmental factors, genetic factors, and viticultural practices, have mostly been studied using targeted analyses of selected families of metabolites. Detailed studies have particularly concerned volatile and polyphenolic compounds because of their acknowledged roles in the organoleptic and therapeutic properties. However, we show that an unprecedented chemical diversity of wine composition can be unraveled through a nontargeted approach by ultrahigh-resolution mass spectrometry, which provides an instantaneous image of complex interacting processes, not easily or possibly resolvable into their unambiguous individu…

Impact of Oak Wood Barrel Tannin Potential and Toasting on White Wine Antioxidant Stability

International audience; Wines aged in oak wood barrels with various uniform tannin contents (which were classified according to their total ellagitannins contents as predicted by Near Infrared Spectroscopy on the untoasted wood) and different toasting levels (high precision toasting by radiation) were distinguished according to their overall abilities to resist against oxidation. Wine trials were carried out on two different vintages (2015, 2016) and three grape varieties (Sauvignon blanc, Sémillon, Chardonnay). Regardless of the vintage and the wine matrix, a relationship was established between wine oxidative stability (based on EPR spin trapping methodology) and oak barrel tannin potenti…

Sorption behavior of volatile phenols at the oak wood/wine interface in a model system.

The sorption in a model system of aroma compounds of enological interest (mixture of the eight derivatives from guaiacol, 4-ethylphenol, and whiskylactone) onto wood was investigated to assess the influence of wood on the concentration of these volatiles during the aging of wine. To evaluate the influence of the solubility of aroma compounds in sorption phenomena, this parameter was determined for each volatile compound in model wine at 10 and 25 degrees C. The solubility is significantly higher in the model wine than in water and remains constant in the range of temperatures studied, except for guaiacol and vanillin. Kinetic and equilibrium sorptions were investigated. Sorption kinetics sh…

Foodomics assessed by Fourier transform mass spectrometry

Abstract With its ultrahigh resolution power and excellent mass accuracy, Fourier transform ion cyclotron resonance mass spectrometry is the perfct tool to analyze the “foodome” as the set of all polar small molecular compounds present in an investigated food sample. We present here selected applications of this technique in unraveling the metabolome in complex foods (thermally affected, fermentation products, distillates) such exemplified with Maillard reaction products or with wines and spirits. Technical considerations for high resolution mass analyzers are provided from a practical point of view. Moreover, aspects of food safety and nutritional quality are covered by presenting applicat…

Role of Wood Macromolecules on Selective Sorption of Phenolic Compounds by Wood

Wood is a complex structure of various macromolecules, mainly cellulose, hemicellulose, and lignin. Although the sorption process of some organic compounds by wood has been elucidated, the relative contribution of its different fractions in the sorption mechanism is not clearly determined. Certain works predict the amount of organic compounds sorbed on wood as a direct relationship to its lignin fraction. All wood macromolecules, however, seem to have the capacity to sorb organic compounds. Sorption of phenolic compounds on individual wood macromolecules has been studied and compared to that on wood. Wood-water partition coefficients ( K wood) for phenolic volatiles and their sorption rates…

(−)Geosmin sorption by enological yeasts in model wine and FTIR spectroscopy characterization of the sorbent

Abstract For the first time, we report that enological yeasts or yeast cell walls can sorb (−)geosmin, an undesirable molecule that causes critical organoleptic defects in wine at low concentrations (around 50 ng l −1 ). The wine is described as “earthy” or “mouldy”. The influence of various post-harvesting processes on yeast (−)geosmin sorption capacity was studied. The dried yeast biomass obtained by the different processes was analysed by FTIR spectroscopy in ATR mode: structural differences were detected between the samples depending on the strain and the treatment used. Surface proteins and mainly phospholipids from the plasma membrane appeared to induce significantly different signals…

Sulfites and the Wine Metabolome

International audience; In a context of societal concern about food preservation, the reduction of sulfite input plays a major role in the wine industry. To improve the understanding of the chemistry involved in the SO2 protection, a series of bottle aged Chardonnay wines made from the same must, but with different concentrations of SO2 added at pressing were analyzed by ultrahigh resolution mass spectrometry (FT-ICR-MS) and excitation emission matrix fluorescence (EEMF).Metabolic fingerprints from FT-ICR-MS data could discriminate wines according to the added concentration to the must but they also revealed chemistry-related differences according to the type of stopper, providing a wine me…

Wine Oxidation and the Role of Cork

The present review aims to show the state of the art of oxidation mechanisms occurring especially in white wines by taking into account knowledge from different fields in relation to the subject. It is therefore divided into three main parts. First, the mechanisms of oxidation relevant to white wine are discussed in the light of recent scientific literature. Next, the phenomenon of oxygen solubility in wine during the winemaking process, and in particular during bottling is stated theoretically as well as practically. Finally, the aspect of wine conservation after bottling is examined with respect to mass transfers which may occur through the closure, with a special emphasis on cork. Curren…

In situ Pesticide Detection in Food Processing by Microwave Transduction Combined with Molecularly Imprinted Polymers

International audience; Since 2005, the microwave transduction coupled with a sensitive material is devoted to gas detection. In this work, we demonstrate the possibility to detect liquid pollutant (pesticide, fungicide) for food-processing industry. The principle is based on the interaction of the pollutant with a sensitive material within a microwave structure. The sensor is submitted to an electromagnetic excitation in wideband frequencies (GHz) and presents a quantitative response to liquid pollutant expositions at low concentration. The retained sensitive material is a molecularly imprinted polymer (MIP) specific to the pesticide targeted in a model wine. The coupling with this materia…

Expressing forest origins in the chemical composition of cooperage oak woods and corresponding wines by using FTICR-MS.

A non-targeted, ultra-high-resolution mass spectrometric, direct analysis of oak-wood extracts from two species (Quercus robur L. and Quercus petraea Liebl.) from three French forests, and of a wine aged in barrels derived therefrom has been performed to identify families of metabolites that could discriminate both the species and the geographical origin of woods. From 12 T ultra-high-resolution Fourier transform ion cyclotron resonance mass spectra of wood extracts, hundreds of mass signals were identified as possible significant biomarkers of the two species, with phenolic and carbohydrate moieties leading the differentiation between Q. robur and Q. petraea, respectively, as corroborated …

Systems chemical analytics: introduction to the challenges of chemical complexity analysis

Understanding complex (bio/geo)systems is a pivotal challenge in modern sciences that fuels a constant development of modern analytical technology, finding innovative solutions to resolve and analyse. In this introductory paper to the Faraday Discussion "Challenges in the analysis of complex natural systems", we aim to present concepts of complexity, and complex chemistry in systems subjected to biotic and abiotic transformations, and introduce the analytical possibilities to disentangle chemical complexity into its elementary parts (i.e. compositional and structural resolution) as a global integrated approach termed systems chemical analytics.

Interaction Mechanisms between guaiacols and lignin: the conjugated double bond makes the difference.

Lignin is considered to be responsible for a selective sorption of phenolic compounds on wood. In order to investigate the mechanisms involved, two similar guaiacol compounds--only differing by the nature of the para side chain--were adsorbed on oak wood extracted lignin. Vapor sorption-desorption isotherms indicated that about 3.5 wt % of 4-vinylguaiacol is adsorbed near saturation whereas it is only 0.8% for 4-ethylguaiacol. For both compounds, the isotherms displayed a hysteresis though significantly greater for 4-vinylguaiacol. Analyses of the hydroxyl stretching region of FTIR spectra of the lignin/4-ethylguaiacol and lignin/4-vinylguaiacol complexes indicated that physisorption via hy…

Unexpected high production of biohydrogen from the endogenous fermentation of grape must deposits

International audience; The aim of this work was to assess the performances of wine byproduct biomass for hydrogen production by dark fermentation. Grape must deposits from two grape varieties (Pinot Gris and Chardonnay) were considered, either with external microbial inoculum or without. We show that grape must residues contain endogenous microflora, well adapted to their environment, which can degrade sugars (initially contained in the biomass) to hydrogen without any nutrient addition. Indeed, hydrogen production during endogenous fermentation is as efficient as with an external heat-treated inoculum (2.5 ± 0.4 LH2.L-1reactor and 1.61 ± 0.41 molH2.mol-1consumed hexose, respectively) with…

Solid-state NMR investigation on the interactions between a synthetic montmorillonite and two homopolypeptides.

Abstract Interactions of two homopolypeptides (polylysine and polyglutamic acid) with a synthetic montmorillonite were studied by 1H MAS, 1H–27Al HETCOR and 1H–13C CP-MAS NMR experiments. 1H–27Al HETCOR with 1H spin-diffusion NMR appears to be a powerful probe for the identification of the polypeptide fragments, which interact with the montmorillonite interlayer surfaces. In particular, selective interactions were observed between the polypeptide side-chains and the montmorillonite octahedral aluminum atoms. 1H–13C CP-MAS NMR experiments were used to assess the dynamics of the two polypeptides through the measurement of the t1/2 characteristic time of selected carbons. Results indicate that…

Measurement of white wines resistance against oxidation by Electron Paramagnetic Resonance spectroscopy

International audience; Free radical theory of aging hypothesizes that oxygen-derived radicals are responsible for the storage-related flavor instability in wine. In an optimal situation, a balanced-distribution exists between oxidants and antioxidants among wines intrinsic/extrinsic metabolites. Based on the kinetic study of POBN-1-hydroxyethyl spin adduct (POBN-1-HER) formation in wines initiated via the Fenton reaction, a novel tool based on EPR spin trapping methodology was developed to quantify wines resistance against oxidation. Antioxidant capacities of wines were evaluated according to POBN-1-HER maximum signal intensity (Imax POBN-1-HER) and rate formation (r(POBN-1-HER)) kinetic p…

Direct NMR evidence for the dissociation of sulfur-dioxide-bound acetaldehyde under acidic conditions: Impact on wines oxidative stability

Abstract SO2 reaction with electrophilic species present in wine, including in particular carbonyl compounds, is responsible for the reduction of its protective effect during wine aging. In the present study, direct 1H NMR profiling used to monitor the reactivity of SO2 with acetaldehyde under wine-like oxidation conditions. The dissociation of acetaldehyde bound SO2 was evidenced suggesting that released free SO2 can further act as an antioxidant. EPR and DPPH assays showed an increasing antioxidant capacity of wine with the increase in the concentration of acetaldehyde sulfonate. The presence of acetaldehyde sulfonate in wines was correlated with the overall antioxidant activity of wines.…

Design of new sensitive α,β-unsaturated carbonyl 1,8-naphtalimide fluorescent probes for thiol bioimaging

International audience; We report herein an efficient synthesis of news naphtalimide-based fluorescent derivatives functionalized with an a,(3-unsaturated carbonyl group. Probes were synthesized from reaction of an amino-naphtalimide precursor with maleic anhydride. Photophysical study of fluorescent probes and cells labelling were performed, and showed that the reactive derivatives exhibit rich turn on fluorescence properties in presence of different biological thiol (Glutathione and Cysteine) making these systems a very promising way for thiol bioimaging.