Search

Motivated by the fugitive and undisclosed nature of eosin-derived pigments as used by Vincent van Gogh, this paper presents the syntheses of monometallic and historical bimetallic eosin-based lakes and structural elucidation by MS, ATR-FTIR and NMR. Specifically two monometallic (Al, Pb) and several bimetallic lakes (on varying Al and Pb constituents) have been synthesized and examined alongside two reference compounds: eosin disodium salt and eosin Y. Resulting monometallic lake complexes are 2:1 adducts (dye:metal) with the carboxylic group coordinating the metal. In historical lake preparations, no correlation between the coordinating metals and the resulting lake color can be made. On production and investigations of different eosin lake substrates, two main anchored species have been distinguished: H-bonded for eosin onto Pb-substrates and a further bridged bidentate for eosin onto alumina. A prominent tendency to form 2:1 eosin:Pb adducts emerged in each Pb-containing recipe. Evidence concerning historical lakes suggests that eosin can diversely coordinate to metals thus producing a variety of nuances in according to experimental pH and reaction conditions. This behavior may well explain observed discrepancies between historical recipes and experimental findings regarding the coordination of eosin to one or more metals. [ABSTRACT FROM AUTHOR]

Abstract: The search for innovative and well-defined organic–inorganic hybrid materials demands that the interplay between polymerization reactions, chemical reactivity, and physical adsorption be fully understood. We examine the case study of the thermal polymerization of styrene in the presence of silica, and the effect of pre-irradiation of silica with γ-rays. The effect of adsorption of styrene-derived radical species on the silica support and polymerization conditions on free and grafted (unextractable) polystyrenes and on polymerization mechanism is discussed on the basis of previous literature findings and new data. Evidence is provided of silica derivatization with various species besides polystyrene (13C CPMAS NMR), including products from a β-scission of the adsorbed radical intermediates ensuing oxygen donation from the silica network. The polymerization mechanism can be cationic as well as radical, depending on reaction conditions, and the cationic route prevails in the grafting of polystyrene from silica, resulting in a bimodal molecular weight distribution. [Copyright &y& Elsevier]

Abstract: The system described in this paper was obtained by soaking calcium alginate (CaAlg) microspheres in a water solution of poly-[(3-acrylamidopropyl)-trimethylammonium chloride-b-N-isopropylacrylamide] [poly(AMPTMA-b-NIPAAM)], a new block co-polymer recently synthesized by atom transfer radical polymerization (ATRP). The block co-polymer is characterized by a lower critical solution temperature (LCST) of 41°C in aqueous 0.1M NaCl solution, and can be anchored on the CaAlg microspheres by means of polyion interactions. Polycations (permanently positively charged blocks) and polyanions (free alginate carboxylic groups) interact, leading to microspheres with thermosensitive properties. As an effect of interaction with the microspheres the LCST of the co-polymer is lowered to 36–38°C. In this temperature range a colloidal water suspension of the microspheres collapses, forming macroscopic aggregates. The new system shows, at human body temperature, an improved ability to carry and deliver both hydrophobic and hydrophilic molecules in comparison with unmodified CaAlg microspheres. The release properties of the microspheres loaded with different model drugs can be appropriately modulated by the amount of the poly(AMPTMA-b-NIPAAM). Furthermore, the microspheres show the interesting capability of retaining the activity of a loaded enzyme (horseradish peroxidase), used as a model protein. The results obtained indicate that the proposed drug delivery system may be suitable for drug depot applications. [Copyright &y& Elsevier]

Abstract: Precipitated amorphous silica has been γ radiolyzed at 333, 666 and 1000kGy in air. The structural changes undergone during irradiation have been studied by 29Si CP-MAS NMR spectroscopy. The spectra suggest that silica looses the hydrogen atoms attached to the silanol groups and the resulting silanol radicals undergo a crosslinking reaction by forming peroxysiloxane groups or by reacting with E′ centres yielding siloxane groups. [Copyright &y& Elsevier]

• "sedano bianco di Sperlonga" PGI celery was investigated by a multi-methodological approach. • A detailed phytochemical profile of the edible part (petioles and blade leaves) was obtained. • Biogenic amine and mycotoxin low contents confirmed celery quality and freshness. • Ethanolic extract of blade leaves showed antimutagenic and radical scavenger power. Celery is a widely used vegetable known for its peculiar sensorial and nutritional properties. Here, the white celery (Apium graveolens L.) "sedano bianco di Sperlonga" PGI ecotype was investigated to obtain the metabolic profile of its edible parts (blade leaves and petioles) also related to quality, freshness and biological properties. A multi-methodological approach, including NMR, MS, HPLC-PDA, GC–MS and spectrophotometric analyses, was proposed to analyse celery extracts. Sugars, polyalcohols, amino acids, organic acids, phenols, sterols, fatty acids, phthalides, chlorophylls, tannins and flavonoids were detected in different concentrations in blade leaf and petiole extracts, indicating celery parts as nutraceutical sources. The presence of some phenols in celery extracts was here reported for the first time. Low contents of biogenic amines and mycotoxins confirmed celery quality and freshness. Regarding the biological properties, ethanolic celery extracts inhibited the oxidative-mediated DNA damage induced by tert -butylhydroperoxide and scavenged DPPH and ABTS radicals. [ABSTRACT FROM AUTHOR]

In this study a multi-analytical approach has been performed to characterise the constitutive materials of an ancient painted barkcloth or Tapa. Originating from Wallis Island, Polynesia, this cloth likely served utilitarian or ceremonial purposes and is part of the Felice Junck collection at the Pigorini, Muciv museum of Rome. During a recent conservation project, some micro-samples were taken from the support, brown and black painted areas and were investigated using the complementarity of SEM-EDX, FT-IR, Raman/SERS and solid-state 13C NMR and 1H HR-MAS spectroscopy. The combination of these techniques allowed the chemical characterization of the constitutive materials, from distinguishing the lignin and cellulose content of the support to the use of organic materials including condensed tannins (catechin, anthocyanidins, alkaloids), phlobaphene and vegetal anthraquinone based Morinda genus dyes for the decorations. A primary focus was placed on an understanding of its state of conservation where data of alteration products collected, namely metal carboxylates and oxalates can serve to formulate apt restoration efforts for this specific artefact. [ABSTRACT FROM AUTHOR]

The dispute over the paternity of western paper is a longstanding problem. In Italy, a country that has a long tradition of papermaking, many cities compete for the leadership in the production of this material; on the other hand, several studies attribute to Fabriano (13th century), a little center in Marche region, the birth of modern paper and its diffusion throughout Europe. During the 14thcentury, the nearby town of Camerino imposed itself on the paper market, triggering a historic rivalry with the manufacture of Fabriano. As scientific studies on these different productions are missing, a comparative, multidisciplinary investigation has been carried out to characterize a set of thirteenth-fifteenth century handmade papers from Camerino-Fabriano area. Several analytical techniques–some non-invasive such as Fourier-transform infrared spectroscopy (FTIR) and portable magnetic resonance (unilateral NMR), joined to micro-destructive ones such as scanning electron microscopy (SEM), 13C CPMAS NMR spectroscopy, thermo-gravimetric analysis (TGA), sodium dodecyl sulphate-polyacrylamide gel electrophoresis (SDS-PAGE) and reverse-phase liquid chromatography (RP-HPLC)–have been employed in order to study the morphology of the paper documents, to identify the substances used in production process and to define their preservation state. Moreover principal component analysis (PCA) has been applied to the spectroscopic data, allowing the clustering of Fabriano documents with respect to Camerino ones and dividing the samples in two sets. This work improves and confirms knowledges on paper production in Marche region, and the experimental data collected highlight similarities and differences between Camerino and Fabriano manufactures. [ABSTRACT FROM AUTHOR]

A multi-methodological approach was applied to study red sweet peppers ( Capsicum annuum L.) ecotype “Cornetto di Pontecorvo” grown in a greenhouse or in open field. This approach includes morphological analysis, chemical composition determination, and biological activity evaluation of different extracts from pepper fruits. Untargeted analyses, namely NMR spectroscopy and mass spectrometry, allowed the comprehensive pepper metabolite profile of pepper pulp, peel and seeds hydroalcoholic and organic extracts to be determined, showing the presence of sugars, organic acids, amino acids and other secondary metabolites. Targeted analyses, such as HPLC-PDA, HPLC-TLC and spectrophotometric analyses allowed polyphenols, tannins, flavonoids and pigments content to be determined. Samples quality and freshness were verified by the low content of biogenic amines and mycotoxins, as determined using HPLC-FLD and HPLC-MS, respectively. Preliminary biological results demonstrated the ability of the organic extracts to inhibit α-amylase, a key enzyme in the control of glucose metabolism. [ABSTRACT FROM AUTHOR]

Abstract: Nanosized α-layered monohydrogen zirconium phosphate (ZP) has been organically modified by reacting the monohydrogen phosphate groups with of 1,2 epoxydodecane solutions in tetrahydrofuran. The materials thus obtained (ZP(C12) x , with x in the range 0.74–2.1) have been characterized by TEM, thermogravimetric analysis, X-ray powder diffraction and solid state 13C CPMAS NMR. The functionalization leads to a disordered layer packing without substantial alteration of the inorganic framework of the α-layer of pristine ZP. Samples with x=0.74 and 1.15 have been used as fillers of membranes based on a recast short side chain perfluorinated ionomer with EW=830. Composite membranes with 5–15wt% filler loadings have been characterized by stress–strain mechanical tests, proton conductivity measurements and water uptake determinations under controlled conditions of temperature and relative humidity (RH). The presence of the filler results in a significant increase in the Young׳s modulus of the neat ionomer up to a maximum of 55% and 67% at room temperature and at 80°C/70% RH, respectively. At 100°C and in the RH range 50–90%, the conductivity of the composite membranes is higher than that of the neat ionomer, and the proportional increase in conductivity (+72% for RH=50% and +32% for RH=90%) is maximum for 10wt% filler loading. Surprisingly, under the same conditions of temperature and RH, the hydration of the most conductive composite membrane is lower than the hydration of the neat ionomer. [Copyright &y& Elsevier]

Abstract: The aerobic metabolism of a mixture of acetate and starch was studied with main emphasis on their interaction and the effect on their storage as PHB and glycogen, respectively. Pulse feeding strongly increased the storage of both substrates; however, the presence of starch decreased PHB storage whereas the presence of acetate did not affect glycogen storage. Indeed, 13C NMR isotopomer analysis suggested an increase of acetate utilization towards TCA cycle, due to an increased request of ATP production for glycogen biosynthesis regulated by ADP-GlcPPase. This in turn influenced the partition flux for pyruvate synthesis between TCA cataplerosis and glyoxylate shunt. The corresponding reduction of PHB synthesis was in agreement with the competition for HS-CoA between KGDH activity and acetyl-CoA for PHB synthesis pathway. As a practical consequence, bioprocesses for PHA production from volatile fatty acids could be negatively affected from other carbon sources, such as unfermented carbohydrates. [Copyright &y& Elsevier]

Abstract: The NMR spectra of the tritiated isotopologues of methane dissolved in several nematic liquid-crystalline solvents are measured. The spectral parameters obtained agree extremely well with those predicted from earlier NMR studies of the deuterated isotopologues, providing excellent confirmation of the theory for vibration–reorientation interaction developed earlier. [Copyright &y& Elsevier]

Abstract: Atom transfer radical polymerization (ATRP) was used to prepare thermosensitive cationic block copolymers of (3-acrylamidopropyl)-trimethylammonium chloride (AMPTMA) and N-isopropylacrylamide (NIPAAM) with different block lengths. By using ethyl-2-chloropropionate (ECP) as initiator and CuCl/CuCl2/tris(2-dimethylaminoethyl)amine (Me6TREN) catalytic system in DMF:water 50:50 (v/v) mixtures at 20°C the polymerization was controlled. The association properties in NaCl aqueous solution were studied as a function of temperature and polymer concentration by dynamic light scattering, NMR spectroscopy, fluorescence spectroscopy and energy filtered-transmission electron microscopy. The block copolymers formed micellar aggregates above the lower critical solution temperature (LCST) of pNIPAAM. The LCST is strongly influenced by the relative length of the two blocks and is significantly higher than that of pure pNIPAAM. The size of core and shell of the micelles is discussed in terms of block copolymer composition. [Copyright &y& Elsevier]

Abstract: NMR and statistical procedures were used to analyse olive oils obtained from trees grown in different areas of Lazio, an Italian region, under different irrigation conditions. In order to obtain information on “real” commercial olive oils and to study the effects of some agronomical and ecological factors on the olive oil composition, we studied commercial multi-varietal olive oils, all produced in well-characterized areas of Lazio. 1H and 13C NMR techniques, coupled to a suitable multivariate statistical procedure, were used to analyse 72 multi-varietal extra virgin and PDO (Protected Denomination of Origin) olive oils harvested in 2003, from the northern area, the centre and the southern area of Lazio. The intensity of selected 1H and 13C NMR variables were submitted to three different statistical methods, namely, analysis of variance (ANOVA), principal component analysis (PCA) and linear discriminant analysis (LDA). 1H and 13C NMR spectroscopy allowed us to obtain a good chemical characterization of the samples, giving information on major and minor compounds with an experimental error exactly the same and always extremely low for all the analyzed components. As a result of the statistical analysis, olive oils from the same geographical areas were well grouped. Since the amounts of some minor volatile components, such as aldehydes, terpenes and squalene, as well as, the content of β-sitosterol, the most important sterol present in olive oils, are sensitive to the pedoclimatic conditions, the intensity of the corresponding NMR signals turned out to be the most discriminating factors in the geographic classification. Moreover, the NMR and statistical protocol allowed us to investigate the roles of irrigation and altitude on the olive oil composition: the contents of oleic and saturated fatty acids turned out to be strongly influenced by the irrigation practice, whereas the content of volatile compounds was sensitive to the altitude of the olive trees. As a result of our study, olive oils were well grouped according to the irrigation practice as well as to the altitude at which olive trees were grown. [Copyright &y& Elsevier]

Abstract: The structure of polymeric gel membranes to be used as electrolytes in the recording of bioelectrical signals has been investigated by means of ATR–FTIR and 7Li and 13C MAS NMR spectroscopies. The membranes, based on PMMA, 1,2-diethoxyethane and lithium perchlorate, showed different ionic conductivity as a function of their composition. Such differences have been analyzed on the basis of spectroscopic data and the existence of interactions with the ester function in the polymeric matrix was determined. Spectroscopic data allowed to establish the optimal lithium concentration needed to achieve best ionic conductivity. [Copyright &y& Elsevier]

A new type of hyaluronan based polymeric network has been prepared applying the well known cross-linking processes based on aqueous Ugi condensation reactions. In this study lysine has been used as a cross-linking agent.The structural and physico-chemical properties of the resulting hydrogels have been studied using solid state NMR spectroscopy and measurements of swelling in water and in aqueous NaCl solution. [Copyright &y& Elsevier]

NMR targeted and untargeted methodologies are widely recognized as important tools for food authentication and the detection of counterfeit products. Targeted approaches allow the identification of specific markers of identity/adulteration for a given foodstuff. In the untargeted approach, the chemical profile of the whole foodstuff is used to create a unique fingerprint as a reference for suspect samples. The untargeted analysis methodology typically follows the metabolomics approach. In this manuscript we discuss how both targeted and untargeted NMR methodologies are applied in routine use for food fraud monitoring. The cost-effective approaches for routine application are discussed using examples of Food Screener™ and benchtop low-field instruments. Several examples of routine consolidated NMR targeted and untargeted applications are reported and the food matrices that are problematic for the NMR application are discussed. The future NMR implementation into routine practice will rely on the further exploration of FoodScreener™ like platforms for simultaneous targeted and untargeted applications and the continued development of applications for low-field benchtop instrumentation. • NMR methodologies are powerful tools to characterize foodstuffs and determine their authenticity. • NMR is now in the portfolio of routine methods in several food control laboratories. • FoodScreener™ NMR platforms for routine use can reveal counterfeits. • NMR benchtop instrumentations represent a new frontier in food authentication field. [ABSTRACT FROM AUTHOR]

Abstract Surface modified CeO 2 nanoparticles were prepared by reacting nanometric CeO 2 with a fluoroalkyl (C 8 F 17 -C 2 H 4 -PO(OH) 2) or a fluorobenzyl phosphonic acid (C 6 F 5 -CH 2 -PO(OH) 2). Both non-modified and fluorophosphonic acid modified CeO 2 were used as fillers of composite Aquivion membranes, with loadings up to 5 wt%. Ex situ accelerated ageing using the Fenton reaction shows that non-modified CeO 2 is a more efficient radical scavenger than the two fluorophosphonic acid modified fillers. Fluoride emission rate data for pristine Aquivion and for the composite membranes are consistent with the corresponding changes in the values of ion exchange capacity (IEC) and elastic modulus. The conductivity of membranes containing non-modified CeO 2 , measured as a function of relative humidity at 80 and 110 °C, decreases with increasing filler loading. For loadings > 2 wt%, an increase in temperature from 80 to 110 °C results in further conductivity drop and in the concomitant IEC decrease, due to partial filler solubilization, thus indicating that the composite membranes are unstable at temperature > 80 °C. However such conductivity drops are strongly reduced, especially at 80 °C, for composites with fluorophosphonic acid modified CeO 2. Graphical abstract fx1 Highlights • Nanosized CeO 2 was surface modified by using two fluorinated phosphonic acids. • Pure CeO 2 and modified CeO 2 were used as radical scavengers in Aquivion membranes. • Pure CeO 2 is more efficient radical scavenger than organically modified CeO 2. • Aquivion/CeO 2 is less conductive than Aquivion/modified CeO 2 composites. • Fluorobenzyl modified CeO 2 is highly conductive and good radical scavenger. [ABSTRACT FROM AUTHOR]

Abstract The metabolite profiling of extracts from Adansonia digitata L. (baobab) fruit pulp and leaf, and the quantification of their major components, was conducted by means of reverse-phase, high-performance liquid chromatography with photodiode array detection, coupled to electrospray ion-trap mass spectrometry (RP-HPLC-PDA-ESI-MS/MS) and high field nuclear magnetic resonance (NMR) spectroscopy. Water-soluble metabolites from chemical classes including sugars, amino acids, organic acids, and phenolic compounds, were identified, in addition to metabolites soluble in organic solvents such as triacylglycerides, sterols, and fatty acids, and most of these were quantified. The profiling of the primary and secondary metabolites of baobab fruit and leaves addresses the limited knowledge of the chemical composition of baobab, and helps support and explain the growing evidence on its nutritional and biological properties, and provide suggestions about the possible uses of baobab fruit and leaves by food, pharmaceutical and cosmetic industries. [ABSTRACT FROM AUTHOR]

The knowledge of changes in the properties of foods that occur with processing is needed for designing better drying methods that preserve desirable characteristics and minimize/eliminate undesirable ones. To this aim, this study analysed the effect of convective drying at 45–55 °C on physicochemical properties of pear. The drying kinetics, shrinkage and SEM images were evaluated. Portable-NMR was used to determine the drying moisture profile of pears and thickness reduction. Portable-NMR also allowed to investigate water mobility in fresh and dried pears by measuring the longitudinal and transverse relaxation times, and the self-diffusion coefficient. Results showed that at 55 °C the faster drying rate and corresponding energy saving were combined with a more uniform water distribution in pear tissues. Finally, a diffusion model considering the shrinkage during drying was developed. It assumes that all water in pear is free-water, according to NMR result that most of the water lost was from vacuole. [ABSTRACT FROM AUTHOR]

Agar is an interesting and versatile biopolymer capable of forming hydrogels useful in different applications. In particular, in the field of Cultural Heritage agar gels are often used as tools for cleaning the surfaces of artifacts. Agar gels are thermoreversible, peelable materials, exhibiting high retention of water and an intrinsic cleaning capability that can be increased and modulated by loading different cleaning agents. Agar gels are able to solubilize and retain dirt, and allow a confined release of the liquid phase, which is especially important when they are applied on water sensitive substrates. A detailed knowledge of the role of water in agar gels and of water/agar interactions is important to fully understand the properties and performances of agar gels as cleaning materials. Here we report the results of a systematic study aimed at exploring the water state and the types of water (i.e. bound non-freezable, bound freezable and freezable bulk-like) in agar hydrogels prepared from four different types of commercial agar powders. The influence of agar concentration on the water behaviour in the hydrogels was also investigated. The total water content, the identification and quantification of the different types of water was carried out by gravimetric, thermogravimetric and calorimetric analyses, while water mobility and localization in the gel network were investigated by unilateral 1 H NMR. Moreover, 1 H NMR depth profiles of agar gels applied on Noto stone specimens were collected to monitor the gel deformation due to water release and to evaluate the ability of the gel in controlling the water release into a porous material. [ABSTRACT FROM AUTHOR]

Isotope Ratio Mass Spectrometry (IRMS), 1 H Nuclear Magnetic Resonance ( 1 H NMR), conventional chemical analysis and chemometric elaboration were used to assess quality and to define and confirm the geographical origin of 177 Italian PDO (Protected Denomination of Origin) olive oils and 86 samples imported from Tunisia. Italian olive oils were richer in squalene and unsaturated fatty acids, whereas Tunisian olive oils showed higher δ 18 O, δ 2 H, linoleic acid, saturated fatty acids β-sitosterol, sn -1 and 3 diglyceride values. Furthermore, all the Tunisian samples imported were of poor quality, with a K 232 and/or acidity values above the limits established for extra virgin olive oils. By combining isotopic composition with 1 H NMR data using a multivariate statistical approach, a statistical model able to discriminate olive oil from Italy and those imported from Tunisia was obtained, with an optimal differentiation ability arriving at around 98%. [ABSTRACT FROM AUTHOR]

Highlights: [•] A two-step-one-pot procedure was used to prepare brush-type chiral stationary phases. [•] The new chiral phases showed excellent hydrolytical stability at high pH values. [•] An H min of 9.57μm and 104,500 theoretical plates per meter were obtained on Crab like columns. [•] The Crab-like columns are highly suitable for the resolution of N-derivatized amino acids. [•] Direct resolution of chiral samples was obtained in normal phase and polar organic mode. [ABSTRACT FROM AUTHOR]

Abstract: Paper and papyrus endurance depends on their intrinsic properties that are related to the manufacture processes and to the environmental conditions (temperature, humidity, presence of micro-organisms, etc.). During the time, paper and papyrus undergo unavoidable ageing processes causing mainly the degradation of the cellulose. In the framework of the European Project “PAPERTECH” a multi-analytical approach was selected to carefully study the behaviour, properties, and the quality of different samples of paper with different provenience, before and after artificial ageing. This work was focused to understand and explain the degradation processes occurring in paper during the time. Portable EDXRF, NMR, Raman, FTIR, ATR, mechanical properties, colour measurement and XRD analyses were performed before and after the accelerated weathering. The light and the chemical oxidation were found to cause the most aggressive ageing processes. [Copyright &y& Elsevier]

Abstract: Hydrogels have been widely used in tissue engineering as a support for tissue formation and/or to deliver drug locally. A novel procedure for the in situ rapid chemical gelation of aqueous solutions of hyaluronan (HA) was employed. HA was functionalised with an arm bearing a terminal azido group (HAAA). When HAAA was mixed with a series of dialkyne reagents of different length, a 1,3-dipolar cycloaddition (“click-chemistry”) reaction took place in the presence of catalytic amount of Cu(I) resulting in fast gelation at room temperature. The resulting gels were characterised in terms of degree of cross-linking by 1H HR-MAS NMR. The kinetic of gelation and the determination of elastic moduli as well as the degree of swelling and the controlled release of a model drug, were studied as a function of chemical nature of the dialkyne group, catalyst concentration, HAAA concentration and temperature. All these variables allowed the swelling ratio and the extent of release of a drug, doxorubicin, entrapped within the gel, to be modulated. In all cases the kinetic of release reached the stationary state within 150h. The height of the plateau was dependent on the overall (chemical and topological) degree of cross-linking. [Copyright &y& Elsevier]

Abstract: Grafting of methyl methacrylate and ethyl acrylate onto cellulose chains of textiles with oxidized sites has been carried out. To this aim, carboxyl and carbonyl groups have been introduced by oxidation of the cellulose and used as photosensitive agents, allowing the formation of radical sites. The copolymerization has been started irradiating the substrate with ultraviolet light for a short time. With the grafting of acrylic monomers the mechanical strength and the thermal stability of cellulose based textiles may be improved, as well as the resistance to chemical and biological agents. The method has been successfully tested performing the grafting on a naturally aged cotton sample. It is worth to note that the grafting does not affect the aspect of the material. All samples have been characterized with 13C solid state NMR spectroscopy. A semi-quantitative evaluation of the grafting has been performed either studying the cross-polarization dynamic process, or by direct integration of resonances in 13C single pulse excitation spectra. [Copyright &y& Elsevier]

A high-field NMR study of the polysaccharidic fraction extracted from Lentinula edodes mycelium grown on olive mill waste waters is reported. Diffusion-ordered NMR spectroscopy (DOSY) was applied to the polysaccharidic fraction. The results showed the presence of two polysaccharides of different sizes, whose structures were revealed using one- and two-dimensional NMR techniques. These two polysaccharides were identified as xylan and lentinan. [Copyright &y& Elsevier]

The worldwide-cultivated chicory (Cichorium intybus L.) produces food and beneficial compounds, and young pre-flowering inflorescence stems are newly marketed vegetables. These sink-organs undergo growth by metabolizing sugars of leaf origin; the carbohydrate content and sweetness are crucial aspects for consumers' nutrition and acceptance. NMR profiling of 31 hydrosoluble phytochemicals showed that stem contents varied as influenced by genotype, environment and interaction, and that higher sucrose levels were associated with the sweeter of two landraces. Integrative analyses of metabolic and transcriptomic profile variations allowed the dissection of sucrose pathway. Overall, 427 and 23 unigenes respectively fell into the categories of sucrose metabolism and sugar carriers. Among 10 differentially expressed genes, the 11474/sucrose synthase , 53458/fructokinase , 9306 and 17035/hexokinases , and 20171/SWEET-type genes significantly associated to sugar content variation, and deduced proteins were characterised in silico. Correlation analyses encompassing sugar level variation, expressions of the former genes and of computationally assigned transcription factors (10938/NAC , 14712/bHLH , 40133/TALE and 17846/MIKC) revealed a gene network. The latter was minimally affected by the environment and accomplished with markers, representing a resource for biological studies and breeding. Integrative analysis combining metabolic and gene transcription profiles were used to give insights into chicory stem sugar metabolism of two landraces grown in different sites in order to define a gene network subtending sugar content differences. Image 1 • Sugar sink of stems was studied in chicories diverging for sugar content. • Sucrose level and sweetness were affected by the genotype, site and interactions. • Catabolism/transport gene expression variations associated to sucrose differences. • Transcription factors were in silico assigned to build a gene-metabolite network. • The network was unaffected by the environment and provided gene markers. [ABSTRACT FROM AUTHOR]