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International audience; The mechanism responsible for the appearance of the light-struck fault upon exposure of white wines and Champagnes to natural or artificial light is examined in light of new experiments involving methionine analogues. The latter show that the formation of volatile sulfur species upon irradiation of riboflavin in the presence of methionine in model wine solutions at pH 3 is not dependent on the existence of neighboring group stabilization of the sulfur-centered cation radical through a 5-or 6-membered cyclic intermediate. Instead, the formation of a dimer radical cation is proposed in agreement with the formation of oxidation products such as dimethyldisulfide at early reaction times and the observed steric effect upon product distribution. The limiting quantum yield for the release of sulfur atoms from a solution of methionine in model wine solutions at pH 3 containing riboflavin was found to be 0.26 (435 nm irradiation). No dependance of the quantum yield or product distribution on the irradiation wavelength was found over the range 365-490 nm.

Over wood aging, matured spirits developed a complex aromatic bouquet where roasted-like notes were often perceived. Since many nitrogen heterocycles were related to these olfactory nuances, a headspace solid-phase microextraction (HS-SPME) coupled to gas chromatography–mass spectrometry was developed and validated to quantify them in both spirit and wood matrices. The various parameters affecting the extraction of the analytes from both spirit and wood samples were first investigated (i.e., fiber coating phase, dilution, pH and volume sample, adding salt, extraction time and temperature, and incubation time) to determine the best compromise for a single-run analysis of the whole set of studied compounds. Good linearity (R2 > 0.99), repeatability, reproducibility, accuracy and low detection, and quantification limits were obtained, making this analytical method a suitable tool for routine analysis of the selected nitrogen compounds. Fifteen pyrazines, three pyrroles, and three quinolines were quantified i...

Iodoperfluooralkylation of terminal alkenes and alkynes is effectively photo-promoted by benzophenone 2 (BP) or the photoreducible copper(II) complex 1. In particular, BP at 1 mol% in methanol upon 365 nm irradiation with a low-pressure mercury lamp (type TLC=thin layer chromatography, 6 W) results in a fast reaction with excellent reaction yields. Complex 1 and BP 2 exhibited very similar reactivity, suggesting that the reactions involving 1 are likely to be governed by the benzophenone photoactivation processes, rather than copper(I)/(II) redox processes. Mechanistic investigations using transient absorption spectroscopy revealed that a deactivation pathway of the benzophenone triplet (3BP*) is via its reaction with the methanol solvent. We propose that the generated radicals, in particular .CH2OH, play a key role in the initiation step forming Rf. by reacting with RfI, Rf. then entering a radical chain cycle. 1H NMR studies provided evidence that a substantial amount (∼7% NMR yield) of the hemiacetal CH3OCH2OH is formed, i.e., the possible by-product of the reaction between .CH2OH and RfI. Finally, DFT calculations indicate that a triplet-triplet energy transfer (TTET) process from 3BP* to perfluorooctyl iodide (C8F17I) is unlikely or should be rather slow under the reaction conditions, consistent with the transient absorption studies.

The objective of the present study was to monitor total lipids, fatty acids and triacylglycerols accumulation during development and ripening of Sayali olive fruit (of Olea europaea L.). Results showed that the accumulation of both major fatty acids and total lipids were slightly influenced by the ripeness stages of olive fruit. Moreover, the weight and the lipid content of the olive seem to be influenced by the climatic conditions of the studied area. The greatest changes in fatty acids content occurred early during the six firsts weeks after the flowering date of the fruit. Also, the results revealed important correlations on the fatty acids accumulation patterns during the olive development and ripening. Moreover, some of triacylglycerol species as OOO (oleyl O), LOO (linoleyl L) and POO (palmityl P) showed notable variations in their percentages during the maturity process. However, LOP, POP and SOO (stearyl S) seem to be invariable during the development of Sayali olive. Oleic acid (C18:1), which has numerous healthy properties, was found at highest level (more than 70% of total fatty acids) at all stages of olive maturity. These results revealed that olive fruit was a potential source of beneficial unsaturated fatty acids which have particular attention from the food industry.

Degradable dendrimer-like PEO's were designed using an original ABC-type branching agent featuring a cleavable ketal group, following an iterative divergent approach based on the anionic ring opening polymerization (AROP) of ethylene oxide and arborization of PEO chain ends. A seventh generation dendrimer-like PEO carrying 192 peripheral hydroxyls and exhibiting a molar mass of 446 kg -1 mol-1 was obtained in this way. The chemical degradation of these dendritic scaffolds was next successfully accomplished under acidic conditions, forming linear PEO chains of low molar mass (2kg. mol-1), as monitored by 1H NMR, SEC, and MALDI-TOF mass spectrometry as well as by AFM.

Summary The present investigation was carried out for the analysis of hydrocarbon compounds of Tunisian Meski olives. The hydrocarbon fraction of the oils was found to contain twelve n-alkanes (C22–C36) and squalene. Results from the quantitative characterisation of the oils revealed that squalene was the most abundant hydrocarbon compound, at all development stages of Meski olive, accounting for more 92% of total hydrocarbons. Pentacosane (C25), heptacosane (C27) and tricosane (C23) represented the major compounds of n-alkanes. The highest accumulation of n-alkanes and squalene was observed at early stages of olive development [before 21st week after the flowering date (WAFD)]. The greatest decrease of these components occurred between 21st and 26th WAFD of the olives. At complete maturity of the fruit, the level of squalene and total n-alkanes was 126.52 and 9.13 mg per 100 g oil, respectively. Hence, the content of n-alkanes and squalene was remarkably influenced by the ripeness process of olive.

The study concerns the interactions between (+)-catechin and a representative oak wood aldehyde (5-(hydroxymethyl)furfuraldehyde for furanic aldehydes and vanillin for phenolic aldehydes) in a wine-like model solution in presence or not of SO2. The formed condensation products were characterised by LC/MS, LC/ESI/MSn, and ESI/HR/MS and we studied the effect of SO2 on these condensation reactions.

The analysis of the total lipid fraction from the Sayali variety of olive oil was accomplished in the present investigation. Glyceridic, unsaponifiable and flavour fractions of the oil were isolated and identified using several analytical methods. Chromatographic techniques have proven to be suitable for these determinations, especially capillary gas chromatography. Gas chromatography coupled to mass spectrometry was successfully used to identify sterols, triterpenes alcohols, 4-monomethylsterols, aliphatic alcohols and aroma compounds in our samples. Furthermore, solid phase microextraction was used to isolate volatiles from the total lipid fraction. Results from the quantitative characterization of Sayali olive oil showed that oleic acid (77.4%) and triolein (47.4%) were the dominant glyceridic components. However, the main compounds of the unsaponifiable fraction were β-sitosterol (147.5 mg/100 g oil), 24-methylene cycloartenol (146.4 mg/100 g oil) and hexacosanol (49.3 mg/100 g oil). Moreover, results showed that the aldehydic compounds were the major flavours present in Sayali olive oil.

A new two-step synthesis of polyisobutylene (PIB) with precisely one thymine functionality per chain (PIB-T) is reported. The primary hydroxyl-functionalized PIB (PIB-OH) precursor was prepared by direct functionalization via living carbocationic polymerization of isobutylene initiated by the α-methylstyrene epoxide/TiCl4 system. Matrix assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-ToF MS) of a low molecular weight PIB-OH precursor demonstrated the effectiveness of direct functionalization by this method. A PIB-acrylate precursor (PIB-Ac) was obtained from such a PIB-OH, and the PIB-T was subsequently prepared by Michael addition of thymine across the acrylate double bond. MALDI-ToF MS of the products verified that all polymer chains carried precisely one thymine group. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3501–3506, 2010

MALDI-TOFMS and HPLC are two analytical methods that were used to characterize triacylglycerols (TAG) of the Meski, Sayali, and Picholine Tunisian olive varieties. The HPLC chromatograms of the oils showed the presence of 15 TAG species, among which triolein (OOO) was the most abundant (21–48%). In the Sayali cultivar, OOO was the predominant TAG species followed by POO and LOO. However, the minor TAG molecules were represented by LnLO and LnLP. MALDI mass spectra produced sodiated ([M + Na]+) and potassiated ([M + K]+) TAG molecules; only the major TAG were potassiated [OOO + K] ([OOO + K]+, [POO + K]+, and [LOO + K]+). In contrast to the HPLC chromatograms, the MALDI mass spectra showed 13 peaks of TAG. The major peak was detected at m/z 907, which corresponds to OOO with an Na+ adduct. The results from both HPLC and MALDI techniques predict the fatty acid composition and their percentages for each olive variety. Practical applications: TAG are the main components in vegetable oils. These biomolecules determine the physical, chemical, and nutritional properties of the oils. The nutritional benefits of TAG are related to DAG (moderate plasma lipid level) and esterified FA, which are intermediate biosynthetic molecules of TAG. TAG analysis is necessary to discriminate between oils of different origin, since some oils have similar FA profiles. Olive products, oils, and table olives, are the main diet sources of TAG in the Mediterranean countries. In this work, chromatographic and spectrometric methods were used for TAG analysis and characterization of Tunisian olive varieties.

Policosanol is a mixture of bioactive molecules shown to have beneficial effects in treating hypercholesterolemia. Food products enriched in policosanol are currently available in the US market. In the present study, eight policosanol components were identified by GC-MS during the ripening of Meski olives. The quantitative characterization of these compounds was performed using GC-FID. The results showed that the maximum level of total policosanol components (947.20 mg/100 g oil) was reached at the 26 th week after the flowering date of Meski olives. Hexacosanol and tetracosanol were the predominant policosanol components at Meski olive maturity. However pentacosanol, heptacosanol and tricosanol were less present in the olives and they accounted for 14% of the total policosanol at complete maturity of the fruit. The total policosanol content of Meski olives was higher than that of beeswax and whole sugar cane, which belong to the sources of dietary supplements containing policosanol. These findings indicate that olive is a potential source of these health-enhancing compounds for functional foods and nutraceutical applications.

International audience; The present study describes innovations in the ring-opening polymerization (ROP) of ethylene oxide (EO) using N-heterocyclic carbenes (NHCs) as organocatalysts, which enables the synthesis of alpha,omega-heterodifunctionalized poly(ethylene oxide)s (PEOs). Two representative NHC catalysts, namely, 1,3-bis(diisopropyl)imidazol-2-ylidene (1) and 1,3-bis(di-tert-butyl)imidazol-2-ylidene (2), were efficiently employed in conjunction with a variety of chain regulators of general structure NuE, where Nu and E are the nucleophilic and the electrophilic part, respectively, with E = H or SiMe3 (e.g., PhCH2OH, HC CCH2OH, N3SiMe3, and PhCH2OSiMe3). Catalytic amounts of the NHC (typically [NHC]/[NuE]/[EO] = 0.1/1/100 in moles) were indeed utilized to trigger the metal-free ROP of EO at 50 C in dimethyl sulfoxide, allowing the polymerization to proceed to completion. In this way, PEOs of dispersities lower than 1.2 and molar masses perfectly matching the [EO]/[NuE] ratio were obtained, attesting to the controlled/living character of these NHC-catalyzed polymerizations. Characterization of alpha,omega-difunetionalized PEOs by combined techniques such as H-1 NMR spectroscopy, MALDI-TOF mass spectrometry, and size exclusion chromatography confirmed the quantitative introduction of the nucleophilic moiety (Nu) and its electrophilic component (E = H Or SiMe3) in the alpha- and omega-position of the PEO chains, respectively, and the formation of polymers with narrowly distributed molar masses. These results are discussed in the light of the existence of two possible mechanisms. The first one involves a direct attack of the NHC catalyst onto EO and the formation of a zwitterionic intermediate (activated monomer mechanism). The second possibility is the activation by the NHC of the E moiety of the NuE chain regulator first and then of the alpha-Nu,omega-OE PEO chain (activated chain end mechanism).

Five triterpene alcohols and four 4-monomethylsterols were identified by GC–MS during the ripening of Picholine olive. The quantitative characterisation of these compounds was performed using GC–FID. The results showed that the maximum level of total triterpene alcohols (263.68 mg/100 g oil) was reached at 26th week after the flowering date (WAF) of olive; whilst the highest level of total 4-monomethylsterols (234 mg/100 g oil) was attained at 24th WAF of fruit. The percentage of these two classes represented 20–33% of total phytosterols during olive maturity. 24-Methylene cycloartenol (12–207 mg/100 g oil) and cycloartenol (27–198 mg/100 g oil) were the predominant triterpene alcohols during the ripening of Picholine olive; whereas citrostadienol (30–161 mg/100 g oil) and cycloeucalenol (11–74 mg/100 g oil) were the main 4-monomethylsterol compounds followed by obtusifoliol and gramisterol. β-Amyrin, δ-amyrin and traroxerol were less present in Picholine olive and they accounted for 14% of total triterpene alcohols at complete maturity of fruit. The level of these methylsterols was overwhelmed by the amount of 4-desmethylsterols at each stage of Picholine olive maturity.

Eleven 4-desmethylsterols and two phytostanols were identified by GC–MS during the ripening of Meski olive. The maximum levels of 4-desmethylsterols (1300 mg/100 g oil) and phytostanols (7.5 mg/100 g oil) were reached at the 26th week after the flowering date (WAFD) of fruit. β-Sitosterol (72–86% of total 4-desmethylsterols) was the major 4-desmethylsterols during the maturity of fruit, while sitostanol was the predominant phytostanols (75–85% of total phytostanols). Δ5-Avenasterol (2–18%) and campesterol (1.6–4%) were the second and the third 4-desmethylsterol levels detected, respectively, during the ripening of Meski olive. The levels of campestanol varied from 15% to 25% of phytostanols. The rate of accumulation of those compounds occurred before 30th WAFD. Some of these compounds (4-desmethylsterols and phytostanols) showed nearly the same profile during the ripening of Meski olive which could be linked to the relation between these compounds during their biosynthetic pathway.

The reactions between (+)-catechin and a representative oak wood aldehyde (furfuraldehyde, 5-(hydroxymethyl)furfuraldehyde, 5-methylfurfuraldehyde, vanillin, or syringaldehyde) in a wine-like model solution were studied and the formed condensation products were characterized by LC/MS and LC/MS/MS.

Analytical pyrolysis was applied to oak wood to provide useful information concerning the structure of oak wood components and the corresponding extractable polymers (lignins, polysaccharides). We have established the aromatic profile of the formed products during heating and also the chemotaxonomy of different oak wood species, focusing on the qualitative and quantitative aspects.

This paper introduces a new fractionation method by selective extractions and precipitations making it possible to collect the three groups of oak heartwood extractable polymers in a single operation. The three families, lignins, polysaccharides and ellagitannins, were obtained and each was characterized by different techniques. We grouped together the techniques used to characterize these different oak wood groups of polymers: IR, GC, GC-MS, LC-MS, 1H NMR, SEC, MALDI-TOF/MS. This work focuses on the qualitative aspect only. Copyright © 2004 Society of Chemical Industry

To control and identify with confidence the principal enological tannins (ETs), we have devised a specific method based on the characterization of proanthocyanidin composition. We started by controlling the red colouring produced by hydrochloric acid butanolysis (e.g. Bate–Smith reaction), due to the formation of anthyocyanidins, typical of proanthocyanidin tannins. Using thioacidolysis/liquid chromatography/electrospray ionization mass spectrometry we were able to identify: (i) the nature of the flavan-3-ols (catechin, epicatechin for procyanidins tannins; gallocatechin, epigallocatechin for prodelphinidins tannins), (ii) the degree of galloylation, (iii) the average degree of polymerization (mDP). We also performed a complete structural study by matrix-assisted laser desorption/ionization-time-of-flight mass spectrometry (MALDI-TOF-MS). By comparing the chromatographic profiles of standard proanthocyanidins prepared in our laboratory with those of a variety of commercial enological tannins, we were able to identify their origin: seed proanthocyanidins (PA): only procyanidins, high level of galloylation, with a large amount of epicatechin, and a low mDP corresponding to a majority of oligomeric tannins; skins PA: a mixture of procyanidins and prodelphinidins, with a predominance of procyanidins, a low level of galloylation, with a large amount of epicatechin, and a very variable mDP; stems PA, mixture of procyanidins and prodelphinidins, little galloylation, with a very low level of epicatechin in the terminal unit, and a medium value for mDP (>5); Quebracho PA: results show no known flavan-3-ols, and according to MALDI-TOF-MS, the main structure is attributed to a large amount of profisetinidin, corresponding to a resorcinol proanthocyanidin.

International audience; Chromatographic separation using fluorescence as a detection mode revealed, besides a series of flavan-3-ols, the recurrent presence of an undefined compound in Bordeaux red wine. Its isolation and structure characterization by complementary means (high-resolution mass spectrometry, nuclear magnetic resonance, and chemical synthesis) has permitted us to identify it as the nitrogen-containing glycoconjugate 3-indolyl-(2R)-O-β-D-glucosyl-lactic acid. Its quantification was performed for different wines of different vine varieties and terroirs with the aim to assess whether this compound may be used as a terroir, variety, or wine process tag.

Monomeric flavan-3-ols and dimeric procyanidins of red wine were oxidised by two processes, chemical and enzymatic. Unstable quinonic forms were stabilised by sulphonation, and the resulting sulphones were quantified by coupled HPLC/ESI-MS. The effects of temperature and UV light on the oxidation of phenolic compounds were also investigated. The concentration of quinones increased with increasing temperature, but the kinetics of the reaction was independent of temperature. Likewise, more quinones were formed in the presence of UV light than in its absence, but UV light also did not affect the kinetics of the reaction. Thus temperature and UV light affect the quantity of quinones formed but not the rate at which they appear. Les composes phenoliques dans le vin proviennent des grains et des peaux de raisin et du bois s'ils sont vieillis en fut. Ils peuvent etre sous forme polymerisee, complexee ou oxydee. Cette etude demontre la presence de procyanidines oxydees dans le vin. Tout d'abord, les formes quinoniques des composes phenoliques sont etudiees. Les resultats montrent la presence de flavan-3-ols monomeriques et de procyanidines dimeriques. Ces composes sont oxydes dans le vin par 2 procedes: enzymatique et chimique. Les formes oxydees de ces composes sont identifiees et quantifiees apres sulfonation par HPLC/ESI-MS. Les effets de la temperature et de la lumiere UV sont aussi etudies et les resultats montrent qu'ils affectent la quantite de quinones formes.

As a consequence of their structure, ellagitannins have a high level of activity in terms of their oxidative properties. In particular, their scavenging activity is often presented as a noteworthy parameter, since polyphenols have a beneficial impact on human health. A large variety of spirits, brandies and whiskeys are aged in barrels or receive a wood extract rich in polyphenols. Although spirits (alcoholic beverages) represent a very dynamic market with significant growth, very few scientific papers have been published on this topic, or have justified specific research in this field. Firstly, the scavenging properties of ellagitannins when measured in a solution are presented. An oak wood extract was fractionated by gel chromatography to obtain different fractions with different polymeric levels. It is particularly clear that the oligomer forms are the most efficient by comparison with low-weight and high-weight fractions. A mixture of ellagitannins has a higher scavenging intensity than the pure molecule; this illustrates the synergic effect of polyphenols. The scavenging activity of different commercial spirits depends on the presence and quantities of ellagitannins. As an example, the percentage of scavenged superoxide anion radicals represents 70 and 18%, respectively, for spirits aged in a barrel (12 years) and white spirits. In a second step, details of the influence of ethanol on the antioxidant properties of ellagitannins are provided. In particular, alcohol increases the scavenging activity of ellagitannins from 0 to 25% vol., and higher concentrations present a certain degree of pro-oxidant activity. The chemical study of ellagitannin scavenging properties in solution is confirmed by means of a specific in vitro investigation on the DNA extracted from cells, and directly on the cells. Copyright © 2013 The Institute of Brewing & Distilling

International audience; Fern (Pterisvittata L.) fronds were collected in the Reppel small-scale field experiment aiming at arsenic phytoextraction. Three organic fractions, i.e. holocellulose, hemicelluloses, and lignin, were extracted from the fronds. The frond biomass as well as the holocellulose, hemicelluloses, and lignin fractions were converted by sub- and supercritical water treatments at low temperatures, 300 °C and 400 °C with 25 MPa, and organic products were identified. This study highlighted that hemicelluloses and lignin are reported as the major sources of cyclopentenones and furfurals, 5 carbons-containing products. The degradation of carbohydrates part (holocellulose and α-cellulose) provided the largest range of by-products due to the thermal resistance of the lignin. The control of biochemical families's content and temperature should determine the presence of required by-products. The fact that no 'synthetic' materials but original materials, i.e. holocellulose, α-cellulose and lignin directly extracted from control fern fronds have been converted revealed the presence of benzenes and cyclopentenones, by-products which have not been reported by the literature.

Degradable dendrimer-like PEOs were designed using an original ABC-type branching agent featuring a cleavable ketal group, following an iterative divergent approach based on the anionic ring opening polymerization (AROP) of ethylene oxide and arborization of PEO chain ends. A seventh generation dendrimer-like PEO carrying 192 peripheral hydroxyls and exhibiting a molar mass of 446 kg · mol(-1) was obtained in this way. The chemical degradation of these dendritic scaffolds was next successfully accomplished under acidic conditions, forming linear PEO chains of low molar mass (≈2 kg · mol(-1)), as monitored by (1)H NMR, SEC, and MALDI-TOF mass spectrometry as well as by AFM.

International audience; The cationic polymerization of isoprene using the 1-(4-methoxyphenyl)ethanol (1)/B(C6F5)(3) initiating system in solution (dichloromethane or alpha,alpha,alpha-trifluorotoluene) and in aqueous media. (suspension, dispersion, or emulsion) is reported. In organic solvents the reaction proceeded by controlled initiation via 1, followed by irreversible termination, thus affording polymers with a number-average molar mass M-n = 70%) in the polymer backbone. In particular, using alpha,alpha,alpha-trifluorotoluene as polymerization solvent in place of dichloromethane promoted the synthesis of polyisoprene chains with M-w/M-n similar to 1.4 and larger content of intact double bonds (up to 88%). In the absence of 1, polyisoprenes with fairly high molar mass (M-n up to 18 000 g mol(-1)) and M-w/M-n < 24 were synthesized through adventitious water/B(C6F5)(3)-initiated cationic polymerization of isoprene. In aqueous media, the cationic polymerization of isoprene with 1/B(C6F5)(3) proceeded without any side reactions (cyclization, branching). However, aqueous conditions afforded only moderate yield (up to 60% monomer conversion) and polyisoprenes with low M-n (

A family of rigid ferrocenyl-terminated redox stars has been synthesized--by Negishi coupling, including hexa(ferrocenethynyl)benzene complexes, a dodecaferrocenyl star, and stars with extended rigid tethers--and fully characterized. Cyclic voltammetry (CV) studies of the parent complex hexa(ferrocenylethynyl)benzene, 1, show a single wave for the six-electron oxidation of 1 using Nn-Bu(4)PF(6) as the supporting electrolyte on a Pt anode in CH(2)Cl(2), whereas three distinct two-electron reversible CV waves are observed using Nn-Bu(4)BAr(F)(4) (Ar(F) = 3,5-C(6)H(3)-(CF(3))(2)). The CV of 1,3,5-tris(ferrocenylethynyl)benzene, 11, also shows only one wave for the three-electron transfer with Nn-Bu(4)PF(6) and three one-electron waves using Nn-Bu(4)BAr(F)(4). This confirms the lack of electronic communication between the ferrocenyl groups and a significant electrostatic effect among the oxidized ferrocenyl groups. This effect is not significant between para-ferrocenyl groups in 1,4-bis(ferrocenylethynyl)benzene for which only a single wave is observed even with Nn-Bu(4)BAr(F)(4) as the supporting electrolyte. The para-ferrocenyl substituents are quite independent, which explains that two para-ferrocenyl groups are oxidized at about the same potential in a single CV wave of 1. With the additional steric bulk introduced with a methyl substituent on the ferrocenyl group, however, even the para-methylferrocenyl groups are submitted to a small electrostatic effect splitting the six-electron transfer into six single-electron waves, probably because of the overall steroelectronic constraints. Contrary to 11, 1,3-bis(ferrocenylethynyl)benzene and related complexes with a third, different substituent in the remaining meta position different from a ferrocenylethynyl only show a single two-electron wave using Nn-Bu(4)BAr(F)(4), which is attributed to the transoid conformation of the ferricinium groups minimizing the electrostatic effect. This shows that, in 11, it is the steric frustration that is responsible for the electrostatic effect, and the same occurs in 1. In several cases, ΔE(p) is much larger than the expected 60 mV value, characterizing a quasi-reversible (i.e., relatively slow) redox process. It is suggested that this slower electron transfer be attributed to conformational rearrangement of the ferrocenyl groups toward the transoid position in the course of electron transfer. Thus both the thermodynamic and kinetic aspects of the electrostatic factor (isolated from the electronic factor), including the frustration effect, are characterized. The distinction between the electronic communication and through-space electrostatic effect was made possible in all of these complexes in which the absence of wave splitting using a strongly ion-pairing electrolyte shows the absence of significant electronic communication, and was confirmed by the new frustration phenomenon.

International audience; A prototype for a new class of macromolecules with a high fraction of fullerene is proposed. Their facile synthesis, modular structure, electronic activity, and novel solid-state behavior make them promising materials for photovoltaic applications. Controlled reversible-deactivation radical additions of the sterically bulky 1,4-bis(methylcyclohexyl ether)-2,5-dibronlomethyl benzene to fullerene are indicated by GPC, NMR, and TGA Studies to yield oligomers and polymers containing C-60 in the main chain. UV and cyclic voltammetry indicate that the C60 undergoes mainly 1,4-additions and a minority (ca. 20%) of 1,2-additions to make a regio-irregular macromolecule. The same reaction performed in the presence of 1,4-bis(methylcyclohexyl ether)-2-bromomethyl benzene, resulting in macromolecules with bromomethyl-tree chain ends, permitted confirmation of the aforementioned characteristics. The unusual reptation of the poly {(1,4-fullerene)-alt-[14-dimethylene-2,5-bis(cyclohexylmethyl ether) phenylene]}s (PFDP) in an Al/Ca/poly(3-hexylthiophene)-blend-PFDP/PEDOT-blend-PSS/ITO/glass structured device is demonstrated by AFM to yield nanoclusters at a scale (ca. 20 run) favorable to exciton capture. Even without optimization of the chemical structure or the device, this prototype reached promising power conversion efficiencies of 1.6%.

International audience; An N-heterocyclic carbene (NHC), namely, 1,3-bis-(diisopropyl)imidazol-2-ylidene (1), was demonstrated to bring about the metal-free ring-opening polymerization of ethylene oxide at 50 degrees C in dimethyl sulfoxide, in absence of any other reagents. Poly(ethylene oxide) (PEO) of polydispersities < 1.2 and molar masses perfectly matching the [monomer]/[(1)] ratio could thus be obtained in quantitative yields, attesting to the controlled/living character of such carbene-initiated polymerizations. It is argued that (1) adds to ethylene oxide to form a zwitterionic species, namely 1,3-bis-(diisopropyl)imidazol-2-ylidinium alkoxide, that further propagates by a zwitterionic ring-opening polymerization (ZROP) mechanism. Through an appropriate choice of terminating agent NuH or NuSiMe(3) at the completion of the polymerization, a variety of end-functionalized PEO chains could be generated. In particular, alpha,omega-bis(hydroxy)-telechelic PEO, alpha-benzyl,omega-hydroxy, and alpha-azido,omega-hydroxy-difunctionalized PEOs were synthesized by NHC (1)-initiated ZROP, using H2O, PhCH2OH, and N3SiMe3 as terminating agent, respectively. Characterization of these alpha,omega-difunctionalized PEOS by techniques such as H-1 NMR spectroscopy, MALDI-TOF spectrometry, and size exclusion chromatography confirmed the quantitative introduction of functional groups at both alpha and omega positions of the PEO chains and the formation of very narrow molar mass polymers. Finally, the synthesis of a poly(ethylene oxide)-b-poly(epsilon-caprolactone) diblock copolymer by sequential ZROP of the corresponding monomers was successfully achieved using (1) as organic initiator without isolation of the PEO block intermediate.

[EN] This paper describes the formation and diversity of new compounds resulting from the polymerisation of furanic and phenolic flavanol-aldehydes with HPLC¿DAD and LC¿ES/MS analysis. Polymerisation, resulting from nucleophilic reactions, formed dimers, trimers, soluble and insoluble polymers. Reactions in hydroalcoholic solution with pure aldehydes (phenolic and furanic) and flavanols (catechin) were studied. The study was repeated with different aldehydes in white wine. This research focused particularly on the colour properties of the released products and their potential impact on the colour of white wine. Some products were purified and isolated; these were mainly catechinfurfuraldehyde, catechin-methyl-5-furfuraldehyde, catechin-hydroxymethyl-furfuraldehyde, catechin-vanillin, and catechin-syringaldehyde dimers. The most powerful coloured products resulted from furanic aldehydes. Over the course of the experiment, the reaction produced dimers, trimers and oligomers. After 50 to 60 days, the colour of the solution was mainly due to soluble polymeric forms. In addition, the role of SO2 , generally used during vinification and ageing, was studied. The influence of SO2 on the kinetics of the reaction was limited.

A new alkaloid of Aconitum karacolicum Rapcs, from the Ranunculaceae family, collected in Kirghizstan, was isolated from the roots of this plant, using a purification scheme based upon its in vitro antiproliferative properties against three human tumour cell lines in culture. Structural identification was performed using high resolution MS-MS mass spectrometry and (1)H, (13)C, 2D NOESY NMR spectroscopy analysis. This compound consists of a 14-benzoylaconine moiety substituted on C-8 by an azeloyl chain. It presents in vitro cytotoxicity with an IC(50) of about 10-20 microM, which warrants further investigation on its possible interest in cancer chemotherapy.

In this work, we wanted to devise a reliable method to characterize polymerized forms of tannins, their structural information and mass distribution. Size-exclusion chromatography (SEC) is a chromatographic technique used to determine molecular mass (weight) distributions of polymers. One important step in the data treatment is the modeling of the calibration curves. Polystyrenes (PS) are standards usually used because no commercial procyanidin (PC) standards are available. An off-line coupling of SEC and MALDI was carried out to measure differences between polystyrenes and procyanidins. Thus, a new calibration curve was established; from 1000 to 8000 Da, there is a good correlation between the MALDI and PS calibration curves, in this field the PS calibration is correct and enables true mass determination. For masses above 8000 Da, PS calibration overestimates the real molecular weight of PC, overestimation of 53%. And for masses below 1000 Da, PS calibration underestimates their real molecular weight (10-15%). This means that to truly characterize PC, calibration based on PC standards is required.

A straightforward synthesis of a fullerene derivative appended with a barbituric acid molecular recognition motif is described. The presence of two nonself-complementary hydrogen-bonding sites is shown to be conducive to the construction of supramolecular assemblies. In the presence of a melamine derivative possessing complementary hydrogen-bonding sites, enhanced efficiency toward photodimerization of the fullerene moiety is observed. This represents the first example of intermolecular photodimerization of a fullerene derivative in homogeneous solution, made possible by the formation of supramolecular assemblies in which the fullerenes are maintained in close proximity.

Tannins represent a key element in red wine flavors, so researchers have made a lot of effort to try to understand the role of their structure in wine taste in recent decades. We report some new routes to achieve a true structure-taste relationship for the major tannins found in wine, which are procyanidins in their monomeric or oligomeric state. All these routes use synthetic standards. New advances in their synthesis and their analyses using chromatographic methods, NMR spectroscopy, and mass spectrometry to obtain more precise information about their chemical structure, including their stereochemistry and their precise degree of polymerization and galloylation, are described.

Two types of oxidizing enzymes are present in botrytized white grapes and wines: laccase (PPO) and glucose oxidase (GOX). The evolution of these two enzymes is similar both during the over-ripening of grapes and during wine making. Yet, PPO is severely inhibited by the addition of SO2 following the alcoholic fermentation, and shows a marked instability in both the must and wine environments. GOX, however, remains free and active in solution and helps develop the main characteristics of the wine. In particular, as is to be expected from its activity, GOX oxidizes tartaric acid, ethanol and glycerol, the major components of must and wine, respectively to glyoxylic acid, acetaldehyde and glyceraldehyde. And then, by nucleophilic additions under acidic conditions, these products react with catechins and proanthocyanidins to form several new compounds, some of which appear in a colored form. These reactions can have an impact on the visual quality of the wine., VITIS - Journal of Grapevine Research, Vol. 49 No. 3 (2010): Vitis