Fast data preprocessing for chromatographic fingerprints of tomato cell wall polysaccharides using chemometric methods

The variability in the chemistry of cell wall polysaccharides in pericarp tissue of red-ripe tomato fruit (Solanum lycopersicon Mill.) was characterized by chemical methods and enzymatic degradations coupled to high performance anion exchange chromatography (HPAEC) and mass spectrometry analysis. Large fruited line, Levovil (LEV) carrying introgressed chromosome fragments from a cherry tomato line Cervil (CER) on chromosomes 4 (LC4), 9 (LC9), or on chromosomes 1, 2, 4 and 9 (LCX) and containing quantitative trait loci (QTLs) for texture traits, was studied. In order to differentiate cell wall polysaccharide modifications in the tomato fruit collection by multivariate analysis, chromatograms were corrected for baseline drift and shift of the component elution time using an approach derived from image analysis and mathematical morphology. The baseline was first corrected by using a "moving window" approach while the peak-matching method developed was based upon location of peaks as local maxima within a window of a definite size. The fast chromatographic data preprocessing proposed was a prerequisite for the different chemometric treatments, such as variance and principal component analysis applied herein to the analysis. Applied to the tomato collection, the combined enzymatic degradations and HPAEC analyses revealed that the firm LCX and CER genotypes showed a higher proportion of glucuronoxylans and pectic arabinan side chains while the mealy LC9 genotype demonstrated the highest content of pectic galactan side chains. QTLs on tomato chromosomes 1, 2, 4 and 9 contain important genes controlling glucuronoxylan and pectic neutral side chains biosynthesis and/or metabolism.     

Both water- and organo-soluble supramolecular polymer stabilized by hydrogen-bonding and hydrophobic interactions

A new bis-urea based supramolecular polymer is reported and shown by viscosimetry, neutron scattering (SANS), and calorimetry (ITC) to self-assemble in a wide range of solvents, encompassing the polarity scale from water to toluene. The presence of both hydrogen-bonding and hydrophobic groups ensures that self-assembly occurs in water, aprotic polar solvents, and nonpolar solvents. Both the driving force for the assembly and the exact structure of the filaments is solvent dependent, but whatever the solvent, long rigid filaments are formed in dynamic equilibrium with the monomer.     

Design of Blends with an Extremely Low Viscosity Ratio between the Dispersed and Continuous Phases. Dependence of the Dispersed Phase Size on the Processing Parameters

Summary: This work deals with the development of the dispersed phase morphology in immiscible blends of poly(ethylene glycol)/polyamide 66 (PEG/PA) with an extremely low viscosity ratio. The blends were obtained, under different operating conditions, by melt blending in an internal mixer. The objective was to examine the influence of the main processing parameters on the particles size of the minor phase (PEG). A model was elaborated to describe the dependence of the particle size on interfacial tension, PEG concentration, shear rate and viscosity ratio between the two blend components.     

Synthesis and Kinase Inhibitory Potencies of Pyrazolo[3,4-g]isoquinolines

A new series of pyrazolo[3,4-g]isoquinoline derivatives, diversely substituted at the 4- or 8-position, were synthesized. The results of the kinase inhibitory potency study demonstrated that the introduction of a bromine atom at the 8-position was detrimental to Haspin inhibition, while the introduction of an alkyl group at the 4-position led to a modification of the kinase inhibition profiles. Altogether, the results obtained demonstrated that new pyrazolo[3,4-g]isoquinolines represent a novel family of kinase inhibitors with various selectivity profiles.     

Laccase-Catalyzed Oxidation of Allylbenzene Derivatives: Towards a Green Equivalent of Ozonolysis

Laccase-based biocatalytic reactions have been tested with and without mediators and optimized in the oxidation of allylbenzene derivatives, such as methyl eugenol taken as a model substrate. The reaction primarily consisted in the hydroxylation of the propenyl side chain, either upon isomerization of the double bond or not. Two pathways were then observed; oxidation of both allylic alcohol intermediates could either lead to the corresponding α,β-unsaturated carbonyl compound, or the corresponding benzaldehyde derivative by oxidative cleavage. Such a process constitutes a green equivalent of ozonolysis or other dangerous or waste-generating oxidation reactions. The conversion rate was sensitive to the substitution patterns of the benzenic ring and subsequent electronic effects.     

Impact of Barrel Toasting on Ellagitannin Composition of Aged Cognac Eaux-de-Vie

It is well established that C-glucosidic ellagitannins contribute to wine quality, and new forms of ellagitannins have been found recently in cognac eaux-de-vie. The contribution of some ellagitannin-derived spirit compounds to eaux-de-vie taste has been demonstrated recently. However, there is a gap in our knowledge of the content, composition, and evolution of C-glucosidic ellagitannins in this matrix. Indeed, the quantification of these compounds and their evolutionary compounds have never before been researched in cognac eaux-de-vie. Thus, the aim of this study was not only to quantify these compounds, but also to study their kinetics and to observe how they are impacted by barrel toasting. For this purpose, barrels representing eight different toasting levels were used to age the same eau-de-vie during the first 18 months. Ellagitannin quantification was carried out by HPLC-Triple quadrupole. The results showed that the evolutionary trend of the eight ellagitannins is the same for all eight types of barrel toasting. The maximum concentrations of C-glucosidic ellagitannins were found after 3 months of aging (up to 23 mg/L) before decreasing to 18 months (9.7 mg/L), whereas ellagitannin-derived spirit compound concentrations increased throughout aging (up to 130.9 mg/L). In addition, barrel toasting had such an impact on ellagitannin content that barrels could be differentiated according to their levels. Eaux-de-vie in barrels with high toasting were lower in ellagitannins concentrations.     

Effect of operating conditions on water transport during the concentration of sucrose solutions by osmotic distillation

A recent membrane technique, osmotic distillation (OD), is used to concentrate binary water–sucrose solutions at ambient temperature under atmospheric pressure. The principle is based on the extraction of water vapour from a dilute aqueous solution, which is put in contact with a hypertonic salt solution by means of a macroporous hydrophobic membrane. The concentration difference between both solutions translates into a transmembrane vapour pressure drop, that constitutes the driving force for mass transfer. An experimental device is designed at laboratory scale for this study, allowing achievement of vapour fluxes of 10 kg m⁻² h⁻¹ under standard conditions. The effect of various operating parameters on vapour flux is studied. The solute content results in the most influencing variable via water activity in brine and via viscosity in sugar solutions. The effect of concentration polarisation on the brine side is not negligible and would have to be taken into account for process optimisation. This phenomenon could not be quantified on the sugar solution side due to pressure drop limits of the pilot rig. Eventually, the vapour flux can be significantly increased by adding a temperature difference to the transmembrane concentration difference, when pure water is evaporated.     

Diastereomer configurations from joint experimental-computational analysis

The potential of the approach combining nuclear magnetic resonance (NMR) spectroscopy, relaxed grid search (RGS), molecular dynamics (MD) simulations, and quantum mechanical (QM) calculations for the determination of diastereomer configurations is demonstrated using four diastereomers of a trisubstituted epoxide. Since the change in configuration of the chiral center is expected to change the distribution of conformer populations (including those of side-chain rotamers), changes in NMR parameters [chemical shifts, J couplings, and nuclear Overhauser effects (NOEs)] are expected. The method therefore relies on (1) identification of possible conformations in each diastereomer using relaxed grid search analysis and MD simulations; (2) geometry optimizations of conformers selected from step (1), followed by calculations of their relative energies (populations) using QM methods; (3) calculations of averaged NMR parameters using QM methods; (4) matching calculated and experimental values of NMR parameters of diastereomers. The diastereomer configurations are considered resolved, if three NMR parameters different in nature, chemical shifts, J couplings, and NOEs, are in agreement. A further advantage of this method is that full structural and dynamics characterization of each of the diastereomers is achieved based on the joint analysis of experimental and computational data.     

Photochemical grafting of diazonium salts on metals

4-Nitrobenzenediazonium may be photochemically grafted onto gold, copper and iron under visible and UV light. Thin nanometre layers are obtained and characterized by IRRAS, electrochemistry and ellipsometry.     

Comparative investigation of elastic properties in a trabecula using micro-Brillouin scattering and scanning acoustic microscopy

Micro-Brillouin scattering (μ-BR) and a 200 MHz scanning acoustic microscope (SAM) with similar spatial resolutions were applied to evaluate tissue elastic properties in two directions in a trabecula. Acoustic impedance measured by SAM was in the range of 5-9 Mrayl. Wave velocities determined by μ-BR were in the range of (4.75-5.11) × 10(3) m/s. Both exhibited a similar trend of variation across the trabecula and were significantly correlated (R(2) = 0.63-0.67, p < 0.01). μ-BR is useful for the evaluation of tissue stiffness within a trabecula. Combined with SAM or nanoindentation, it can provide additional information to assess elastic anisotropy at the micro-scale.