High-pressure Size Exclusion Chromatography Research Articles

Chemical characterization of polysaccharides from Gracilaria gracilis from Bizerte (Tunisia)

Polysaccharides were extracted from Gracilaria gracilis collected from Manzel Jemil Lake in Bizerte Tunisia, with two different solvents (water and NaOH 0.3 M). Different assays were performed on samples (total sugars, neutral sugars, uronic acids, anhydrogalactose, proteins, sulphates, pyruvates), followed by high performance anion-exchange chromatography (HPAEC) to observe the monosaccharide composition, high pressure size exclusion chromatography with multi-angle laser light scattering (HPSEC-MALS) to obtain the molecular mass, Fourier transform infrared spectroscopy (FTIR), and 1D and 2D nuclear magnetic resonance (NMR) to access to structural data. Results have shown that the polysaccharide extracted from Gracilaria gracilis collected from Manzel Jemil Lake in Bizerte Tunisia, is of agar type but with high molecular mass and some original structural features. Hence, the sample was found to contain 9 % of pyruvate groups and is partly sulphated at the C4 of β-d-galactose and methylated on C2 of anhydro-α-l-galactose. The polymer from G. gracilis from Bizerte thus presents a never described structure that could be interesting for further rheological or biological activities applications.

Aggregate Formation and Antibody Stability in Infusion Bags: The Impact of Manual and Robotic Compounding of Monoclonal Antibodies

Monoclonal antibodies (mAbs) can be damaged during the aseptic compounding process, with aggregation being the most prevalent form of degradation. Protein aggregates represent one of several risk factors for undesired immunogenicity of mAbs, which can potentially lead to severe adverse drug reactions and less effective treatments. Since data on aggregate and particle formation by robotic compounding is missing, we aimed to compare the antibody stability between robotic- and manual compounding of mAbs with regard to formation of (sub)visible aggregates. Infliximab and trastuzumab were compounded into infusion bags with the APOTECAchemo robot or manually by nurses or pharmacy technicians. The products were analyzed by quantifying (sub)visible particles with nanoparticle tracking analysis, dynamic light scattering (DLS), light obscuration, micro-flow imaging, high pressure size exclusion chromatography (HP-SEC), and visual inspection. HP-SEC showed high percentages monomers in trastuzumab (99.4 % and 99.4 %) and infliximab (99.5 % and 99.6 %) infusion bags for both manual and robotic compounding, respectively. DLS indicated more consistent and reproducible results with robotic compounding, and confirmed monodisperse samples with a higher polydispersity index for manual compounding (0.16, interquartile range; IQR 0.14–0.18) compared to robotic compounding (0.12, IQR 0.11–0.15). This study shows that the studied compounding methods had a minor impact on the number of aggregates and particles, and that robotic compounding of mAbs provided at least similar quality as manual compounding.

Extraction and Characterization of Acidolysis Lignin from Turkey Oak (Quercus cerris L.) and Eucalypt (Eucalyptus camaldulensis Dehnh.) Wood from Population Stands in Italy.

Acidolysis lignins from the species Quercus cerris L. and Eucalyptus camaldulensis Dehnh. were isolated and characterized using high pressure size exclusion chromatography (HP-SEC), Fourier-transform (FTIR) infrared spectroscopy, analytical pyrolysis-gas chromatography-mass spectrometry (Py-GCMS), and two-dimensional heteronuclear single quantum coherence (2D HSQC) NMR spectroscopy. The acidolysis lignins from the two different species varied in chemical composition and structural characteristics, with Q. cerris L. lignin having a higher S/G ratio and higher molar mass averages with a bimodal molar mass distribution. The different analytical techniques FTIR spectroscopy, Py-GCMS, and 2D NMR spectroscopy provided consistent results regarding the S/G ratio of the lignins from the two wood species. Based on the determined high S/G ratio of both oak and eucalypt lignin, the two wood sources could be promoted as substrates for efficient lignin isolation in modern forest biorefineries in order to develop innovative lignin-based value-added biorefinery products.

Novel Nanomaterials Made of Humic Substances from Green Composts and Chitosan Exerting Antibacterial Activity

Green compost represents a sustainable source of humic substances (HS), which are supramolecular associations of heterogeneous natural compounds bearing a variety of functional groups. Novel humic-chitosan nanoconjugates (NC) were synthesized by using HS from three green composts [coffee husks (HS-COF), artichoke residues (HS-CYN), and fennel residues (HS-FEN)]. Solid-state NMR spectra showed that HS-CYN and HS-FEN contained the largest relative amount of polysaccharidic and phenolic carbons, whereas HS-COF had the greatest relative content of alkyl and carboxyl groups. While size and z-potential of NC depended upon the HS origin, NC-HS-FEN revealed the greatest thermal stability, followed by NC-HS-CYN and NC-HS-COF. Scanning electron microscopy and transmission electron microscopy analyses suggested the formation of spherical nanoparticles only for NC-HS-FEN and NC-HS-CYN. This was explained by more stable conformations of HS-FEN and HS-CYN that enabled regular spherical nanoparticles, as assessed by high-pressure size-exclusion chromatography measurements. NC bioactivity against bacterial human pathogens was strain-specific, and the inhibition of bacterial development was attributed to the positive z-potentials that facilitated NC adhesion on bacterial cell walls, smaller nanosizes favoring cell penetration, and subsequent release in the cell of NC toxic components that altered microbial biochemical functions. This study indicates that not only novel NCs can be obtained by humic matter derived from recycled biomass, such as green compost, but they can also be employed as effective and sustainable antimicrobial agents.

Impact of aluminum adjuvants on the stability of pneumococcal polysaccharide-protein conjugate vaccines

Development of a vaccine drug product requires formulation optimization to ensure that the vaccine’s effectiveness is preserved upon storage throughout the shelf-life of the product. Although aluminum adjuvants have been widely used in vaccine formulations to safely and effectively potentiate an immune response, careful attention must be directed towards ensuring that the type of aluminum adjuvant does not impact the stability of the antigenic composition. PCV15 is a polysaccharide-protein conjugate vaccine comprising the pneumococcal polysaccharide (PnPs) serotypes (1, 3, 4, 5, 6A, 6B, 7F, 9V, 14, 18C, 19A, 19F, 22F, 23F and 33F), each individually conjugated to the protein carrier CRM197. PCV15 was formulated with either amorphous aluminum hydroxyphosphate sulfate adjuvant (AAHS) or aluminum phosphate adjuvant (AP) and examined for both stability and immunogenicity. Using a collection of methods to evaluate vaccine stability, it was discovered that certain PCV15 serotypes (e.g., 6A, 19A, 19F) formulated with AAHS resulted in a reduction of immunogenicity in vivo and a reduction in recoverable dose as tested by an in vitro potency assay. The same polysaccharide-protein conjugates formulated with AP were stable regarding all measures tested. Moreover, the reduction in potency of certain serotypes correlated with chemical degradation of the polysaccharide antigen caused by the aluminum adjuvant as measured by reducing polyacrylamide gel electrophoresis (SDS-PAGE), High-Pressure Size Exclusion Chromatography coupled with UV detection (HPSEC-UV) and ELISA immunoassay. This study suggests a formulation, which includes AAHS, may negatively impact the stability of a pneumococcal polysaccharide-protein conjugate vaccine that contains phosphodiester groups. This decrease in stability would likely result in a decrease in the “active” concentration of antigen dose, and herein, it is shown that such instability directly compromised vaccine immunogenicity in an animal model. The results presented in this study help to explain critical degradation mechanisms of pneumococcal polysaccharide-protein conjugate vaccines.

Spectroscopic evidence for adsorption of natural organic matter on microplastics

AbstractThe interaction of microcroplastics (MP) with dissolved organic matter, especially humic substances, is of great importance in understanding the behavior of microplastics in aquatic ecosystems. Surface modification by humic substances plays an essential role in transport and interaction of MP with abiotic and biotic components. Previous studies on the interaction between MP and humic substances were largely based on a model compound, humic acid (Sigma‐Aldrich). In our work, we therefore investigated the interaction of natural organic matter (NOM) sampled from a German surface water with low‐density polyethylene particles (LDPE). High‐pressure size exclusion chromatography (HPSEC) and UV/vis absorption and fluorescence spectroscopy were used to characterize the incubation solutions after modifications due to the presence of LDPE, and Raman spectroscopy was used to characterize the incubated microplastics. While the studies of the solutions generally showed only very small effects, Raman spectroscopic studies allowed clear evidence of the binding of humic fractions to MP. The comparison of the incubation of NOM and a lignite fulvic acid which also was tested further showed that specific signatures of the humic substances used could be detected by Raman spectroscopy. This provides an elegant opportunity to conduct broader studies on this issue in the future.

Description of the Wild Strain Rhizobium rosettiformans DSM26376, Reclassified under Peteryoungia rosettiformans comb.nov., for Producing Glucuronan.

Glucuronan is a polysaccharide composed of β-(1,4)-linked d-glucuronic acids having intrinsic properties and biological activities recoverable in many fields of application. Currently, the description of Sinorhyzobium meliloti M5N1CS mutant bacterial strain as the sole source of glucuronan makes it relevant to the exploration of new microorganisms producing glucuronan. In this study, the Peteryoungia rosettifformans strain (Rhizobia), was identified as a wild producer of an exopolysaccharide (RhrBR46) related to glucuronan. Structural and biochemical features, using colorimetric assays, Fourier infrared spectroscopy, nuclear magnetic resonance, high pressure size exclusion chromatography coupled to multi-angle light laser scattering, and enzymatic assays allowed the characterization of a polyglucuronic acid, having a molecular mass (Mw¯) of 1.85 × 105 Da, and being partially O-acetylated at C-2 and/or C-3 positions. The concentration of Mg2+ ions in the cultivation medium has been shown to impact the structure of RhrBR46, by reducing drastically its Mw¯ (73%) and increasing its DA (10%). Comparative structural analyses between RhrBR46 and the glucuronan from Sinorhyzobium meliloti M5N1CS strain revealed differences in terms of molecular weight, degree of acetylation (DA), and the distribution of acetylation pattern. These structural divergences of RhrBR46 might contribute to singular properties or biological activities of RhrBR46, offering new perspectives of application.

Structural characteristics, emulsifying and foaming properties of laccase-crosslinked bovine α-lactalbumin mediated by caffeic acid

In this study, laccase (LA) was chosen as a commonly employed enzyme to research the impacts of enzyme-catalyzed crosslinking (polymerization) on the structural, emulsifying and foaming properties of bovine α-lactalbumin (α-LA) in the presence of caffeic acid (CA). High pressure size exclusion chromatography (HPSEC) and sodium dodecyl sulfate–polyacrylamide gel electrophoresis (SDS-PAGE) demonstrated the formation of α-LA aggregates (dimers, trimers, and polymers) by LA-induced crosslinking with CA, consistent with the particle size distribution results. LA-induced treatment exhibited pronounced influences on the conformation, secondary and tertiary structure of α-LA, as confirmed by circular dichroism (CD), and fluorescence spectroscopy. For α-LA-LA-CA, α-helix content was progressively decreased from 33.3% (0 h) to 24.7% (24 h). LA-catalyzed crosslinking resulted in the exposure of interior hydrophobic groups, and the increase of zeta-potential values of α-LA. Apparent viscosity of α-LA was considerably enhanced by LA-induced crosslinking with CA. The emulsifying activity and stability of α-LA can be considerably improved with LA-catalyzed crosslinking with CA except at 24 h incubation time. Compared with controls, LA-catalyzed polymerizations of α-LA molecules with CA led to the increase of foaming activity and stability regardless of incubation time. After 24 h incubation, the foaming stability (FS) of α-LA was 81.0%, whereas the value was 88.0% for α-LA-LA-CA. This research indicates that LA-induced modification possesses great potential in ameliorating the emulsifying and foaming capacities of α-LA. • Laccase led to the significant polymerization of α-lactalbumin with caffeic acid. • Laccase-catalyzed crosslinking led to the changes of the structure of α-lactalbumin. • Laccase-catalyzed crosslinking increased the emulsifying properties of α-lactalbumin. • Laccase-catalyzed crosslinking increased the foaming activity of α-lactalbumin. • Laccase-crosslinked α-lactalbumin aggregates showed potential as functional ingredients.

Changes in the structural characteristics of EfOM during coagulation by aluminum chloride and the effect on the formation of disinfection byproducts

The effects of coagulation on the removal efficiency of different fractions of effluent organic matter (EfOM) from wastewater treatment plants were investigated to identify changes in their structural characteristics and the influences on trihalomethane formation potential (THMFP) and haloacetic acid formation potential (HAAFP). The results indicated that coagulation performed better for the removal of hydrophobic base (HOB) and hydrophobic neutral (HON) fractions than hydrophilic (HI) and hydrophobic acid (HOA) fractions. The removal efficiency was higher under neutral than under acidic conditions for all fractions. As a result, lower levels of THMFP and HAAFP were detected at pH7. The excitation-emission matrix spectra indicated that the HI fraction contained humic acid-like substances that reacted with chlorine to form THMs. The HON fraction contained soluble microbial byproduct-like substances with a higher potential to create HAAs. The results of Fourier transform infrared (FT-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and high-pressure size exclusion chromatography (HP-SEC) of the raw and coagulated water indicated that a higher molecular weight, α-carbon, COOH, aromatic structures, and polysaccharides were associated with a higher production of disinfection byproducts (DBP). These results elucidate the coagulation efficiencies of EfOM fractions associated with different mechanisms and facilitate the prediction of DBP formation by each fraction based on specific structural characteristics.

Effects of malting process on molecular weight distribution and content of total and water-extractable arabinoxylan in barley

This work aims to evaluate the effects of the malting process on the malt total and water-extractable (WE) arabinoxylan (AX), also considering the barley cultivar and year of cultivation. The WEAX molecular properties were characterized by high-pressure size exclusion chromatography (HPSEC) - triple detector array (TDA). Most of the barley malt WEAX showed a molecular weight over 4.0 × 105 Da with a random coil conformation. Compared to raw barley, the malts show analogous content of AX and WEAX, similar intrinsic viscosity, less rigid conformation, and higher polydispersity. The WEAX content of malt was highly and negatively related to the common quality parameters, resulting in a useful indicator of malt modification, even more representative than the total AX content. WEAX is highly positively related to the Congress wort viscosity, and thus, lautering could be more significantly affected by WEAX rather than total AX content.

Adsorption of Fulvic Acid and Water Extractable Soil Organic Matter on Kaolinite and Muscovite

The interaction of organic matter with mineral components of the solid phase of soils is the most important process that regulates the cycle and balance of carbon in the biosphere. The adsorption of humic acids on minerals is accompanied by their fractionation in size, composition, and amphiphilicity, thus decreasing their heterogeneity. Despite a strong interest in studying the regularities and mechanisms of the interaction between natural organic matter and layered aluminosilicates, it is necessary to take into account the natural diversity of soil organic matter, adsorption conditions, and mineral composition. This study was designed to investigate the adsorption regularities of fulvic acid (FA) and water-extractable organic matter (WEOM) isolated from horizon H of peaty-podzolic-gleyic soil on kaolinite and muscovite. Sorbates and sorbents were examined by the following methods: high-pressure size exclusion chromatography (HPSEC), high-performance liquid chromatography (HPLC), and potentiometric titration. The specific surface areas of the sorbents were determined by the sorption of N2 molecules. We found that hydrophobic components of FA and WEOM are mainly adsorbed on mineral surfaces. The adsorption of FA and WEOM on kaolinite and muscovite is followed by decreased hydrophobicity of organic matter and decreased heterogeneity of its amphiphilic properties in an equilibrium solution. At pH levels around 6, sorption of organic matter from FA solution containing 19% and 81% hydrophilic and hydrophobic components, respectively, onto kaolinite and muscovite occurs mainly due to hydrophobic components. Hydrophobic interactions on siloxane surfaces are the main mechanism to fix FA on both minerals. Kaolinite adsorbs slightly more organic carbon per unit area than muscovite. The adsorption of WEOM from a solution with 41% hydrophilic and 59% hydrophobic components results not only from hydrophobic and hydrophilic components but also from hydrophobic and electrostatic interactions and depends on pH. The most hydrophobic fractions of organic matter are adsorbed from the hydrophobic components on the surface of both minerals. Under conditions of the performed experiments at pH < 5, more WEOM is adsorbed on muscovite than on kaolinite.

Reductive Catalytic Depolymerization of Semi-industrial Wood-Based Lignin.

The current work studies the reductive catalytic depolymerization (RCD) of lignin from a novel semi-industrial process. The aim was to obtain aromatic mono-, di-, tri-, and tetramers for further valorization. The substrate and products were characterized by multiple analytical methods, including high pressure size-exclusion chromatography (HPSEC), gas chromatography–mass spectrometry, GC-flame ionization detector (FID), GC-FID/thermal conductivity detector (TCD), and NMR. The RCD was studied by exploring the influence of different parameters, such as lignin solubility, reaction time, hydrogen pressure, reaction temperature, pH, type and loading of the catalyst, as well as type and composition of the organic/aqueous solvent. The results show that an elevated temperature, a redox catalyst, and a hydrogen atmosphere are essential for the depolymerization and stability of the products, while the reaction medium also plays an important role. The highest obtained mono- to tetramers yield was 98% and mono- to dimers yield over 85% in the liquid phase products. The reaction mechanisms influenced the structure of the aliphatic chain in the monomers, but left the phenolic structure along with the methoxy groups largely unaltered. The current work contributes to the development and debottlenecking of the novel and sustainable overall process, which utilizes efficiently all the fractions of wood, in line with the principles of green engineering and chemistry.

Optimizing the production of biodiesel from palm olein (Elaeis guineensis Jacq.) using a strong basic anionic resin as a heterogeneous catalyst

In this study, the performance of the Purolite A503S anion exchange resin as a heterogeneous catalyst in the transesterification reaction of palm olein (Elaeis guineensis Jacq.) for ethyl biodiesel production was investigated, and the independent variables were optimized based on the maximum conversion to fatty acid ethyl esters. The response surface methodology (RSM) coupled to a factorial design (2³) with a central composite rotatable design (CCRD) was used for optimization. The effects of temperature, catalyst percentage, palm olein:ethanol molar ratio, and their interactions were evaluated. A reaction time of 10 h was established relating conversion versus time, and the stirring speed was determined by assessing the conversion potential ranging from 250 to 1000 rpm. The reactions were performed in a jacketed reactor coupled to a thermostatic bath. The mixtures of triacylglycerols (TAG), diacylglycerols (DAG), monoacylglycerols (MAG), fatty acid ethyl esters (FAEE), and ethanol were quantified by high-pressure size exclusion chromatography (HPSEC), and glycerol content was determined by stoichiometry. A second-order model was adjusted to explain the experimental data from the 18 factorial design trials. A conversion of approximately 98.10 % in ethyl esters was obtained from the optimised variables using a 17.6 % catalyst, palm olein:ethanol molar ratio of 1:12.85 at 49.4 °C. Despite the long reaction time, the Purolite A503S resin is a potential heterogeneous catalyst in transesterification reactions.

Thermal degradation of stigmasterol under the deodorisation temperature exposure alone and in edible corn oil

Phytosterols are commonly found in vegetable oils and possess health benefits for humans. While investigating the chemical conversion of stigmasterol at deodorisation temperatures, gas chromatography-mass spectrometry (GC-MS) and ultra-high performance liquid chromatography coupled to high-resolution mass spectrometry (UHPLC-HRMS) experiments led to the identification of 5-ethyl-6-methyl-3-heptene-2-one, 3-hydoxy-steroid, 3-ketostigmasterol, and 3,7-diketostigmasterol as by-products. The identification of these compounds assisted in the interpretation of the stigmasterol oligomers characterised by high-pressure size exclusion chromatography (HPSEC). A similar analysis was conducted in stripped corn oil at the deodorisation temperatures. As such, 5-ethyl-6-methyl-3-heptene-2-one, 3-hydoxy-steroid, 3-ketostigmasterol and 3,7-diketostigmasterol were also detected in stripped corn oil, while the contents of 3-hydoxy-steroid and 5-ethyl-6-methyl-3-heptene-2-one were higher than those of 3-ketostigmasterol, as revealed by quantum chemical simulations. In addition, stripped corn oil exhibited the characteristic of preventing stigmasterol degradation below 200 °C, whereas it enhanced the chemical conversion (such as esterification and degradation) of stigmasterol at higher temperatures.

Dissolved organic matter characterization in high and low ammonium groundwater of Dongting Plain, central China

High levels of ammonium in groundwater is a potential threat to drinking water security and ecological status. The role of dissolved organic matter (DOM) in mobilization of natural ammonium in groundwater is crucial but the intrinsic link between them has still been poorly understood. This study used high-pressure size exclusion chromatography (HPSEC) and fluorescence excitataion-emission-matrix spectra (EEMs) with parallel factor analysis (PARAFAC) to elucidate the influence of DOM characteristics in groundwater systems having contrastive ammonium levels in Dongting Plain, central Yangtze River. The results indicate that NH4+-N concentration in groundwater of western plain (0–16.75 mg/L) are much higher compared with southern plain (0–1.5 mg/L). The groundwater in western plain is in a more reductive environment and characterized by larger molecular weight (MW) of DOM and lower polydispersity (ρ), whereas DOM with relatively small molecular weight and high polydispersity is detected in the south with a more oxidative condition. The groundwater in western plain is characterized by lower fluorescence index (f450/500) and biological index (BIX), and dominated by the high molecular weight terrestrial humic-like component and larger amounts of microbial humic-like components. Protein-like is the main component in groundwater of southern plain with higher f450/500 and BIX. The ammonium concentration in groundwater correlates well with molecular weight and increases significantly with the content of high molecular weight terrestrial humic-like component, indicating that mobilization of ammonium is more closely associated with the terrestrial organic matter of high molecular weight. This study further enriches the theory on mobilization of ammonium in Quaternary alluvial-lacustrine aquifer systems and provides theoretical basis for the local water supply security.

Exploring the Microalga Euglena cantabrica by Pressurized Liquid Extraction to Obtain Bioactive Compounds.

In the present study, the chemical composition of the microalga Euglena cantabrica was investigated. The extraction of bioactive compounds was done using pressurized liquid extraction (PLE) at different temperatures (40–180 °C) and using green solvents (ethanol-water mixtures). A statistical design of experiments was used to optimize the maximum antioxidant capacity of the extracts by response surface methodology. The antioxidant capacity was determined through the inhibition of 2,2’-azino-bis-3-ethylbenzothiazoline-6-sulfonic acid (ABTS) and 1,1-diphenyl-2-picrylhydrazyl (DPPH) radicals, while the chemical analyses of the extracts were carried out using different chromatographic techniques. Chlorophylls and carotenoids were analyzed by high-performance liquid chromatography coupled to a diode array detector and mass spectrometry (HPLC-DAD-MS/MS) and carbohydrates by gas chromatography with flame ionization detection (GC-FID) and high-pressure size-exclusion chromatography coupled to an evaporative light-scattering detector (HPSEC-ELSD). The results showed different possibilities for the extraction conditions, depending on the desired bioactivity or chemical composition. Briefly, (i) mixtures of ethanol-water containing around 40% ethanol at 180 °C gave the best antioxidant capacity, (ii) mixtures containing around 50% ethanol at 110 °C gave the best yield of β-glucan paramylon, and (iii) the use of pure ethanol at a low temperature (40 °C) is the best choice for the recovery of carotenoids such as diatoxanthin. Summing up, E. cantabrica seems to be a good candidate to be used in biorefinery to obtain different bioactive compounds.

Reversible associations between human plasma fibronectin and fibrinogen γγ’ heterodimer observed by high pressure size exclusion chromatography and dynamic light scattering

We previously reported on a novel fibrin matrix having increased viscoelastic strength derived from human plasma fibronectin (pFN) and γγ′-fibrinogen (γγ′-FI). Here we use high pressure size exclusion chromatography (HPSEC) and dynamic light scattering (DLS) to observe interactions between the linearly extended conformation of γγ′-FI and random coiled pFN. Distinct γγ′-FI:pFN subpopulations were fractionated where each maintained unique retention times when individually reprocessed by HPSEC. The hydrodynamic sizes by HPSEC and DLS for these reprocessed subfractions were intermediate to that of pure γγ′-FI and pFN. SDS-PAGE analysis showed that the majority of these subfractions contained intact γγ′-FI and pFN. Importantly, after disruption and isolation using Gelatin Sepharose affinity chromatography, new complexes rapidly formed between pFN and γγ′-FI when mixed back together. This also occurred in analogous mixing experiments between Des-Aα γγ′-FI and pFN where both Aα-chains are reduced by about 15 kDa due to proteolysis. The reversible complexation observed using HPSEC and DLS was not observed in prior studies using SPR indicating that unrestricted freedom of motion is needed to efficiently form these compact associations. The presence of a γ′ chain, but not the carboxy terminal portions of either Aα chain are needed for complexation phenomena between pFN and γγ′-FI.

Autocatalytic Fractionation of Wood Hemicelluloses: Modeling of Multistage Operation

Eucalyptus globulus wood samples were treated with hot, compressed water (autohydrolysis) in consecutive stages under non-isothermal conditions in order to convert the hemicellulose fraction into soluble compounds through reactions catalyzed by in situ generated acids. The first stage was a conventional autohydrolysis, and liquid phase obtained under conditions leading to an optimal recovery of soluble saccharides was employed in a new reaction (second crossflow stage) using a fresh wood lot, in order to increase the concentrations of soluble saccharides. In the third crossflow stage, the best liquid phase from the second stage was employed to solubilize the hemicelluloses from a fresh wood lot. The concentration profiles determined for the soluble saccharides, acids, and furans present in the liquid phases from the diverse crossflow stages were employed for kinetic modeling, based on pseudohomogeneous reactions and Arrhenius-type dependence of the kinetic coefficients on temperature. Additional characterization of the reaction products by High Pressure Size Exclusion Chromatography, High Performance Anion Exchange Chromatography with Pulsed Amperometric Detection, and Matrix Assisted Laser Desorption/Ionization Time of Flight Mass Spectrometry provided further insight on the properties of the soluble saccharides present in the various reaction media.

Structural Features and Rheological Properties of a Sulfated Xylogalactan-Rich Fraction Isolated from Tunisian Red Seaweed Jania adhaerens

A novel sulfated xylogalactan-rich fraction (JSP for J. adhaerens Sulfated Polysaccharide) was extracted from the red Tunisian seaweed Jania adhaerens. JSP was purified using an alcoholic precipitation process and characterized by Attenuated Total Reflectance-Fourier-transform infrared spectroscopy (ATR-FTIR), high-pressure size exclusion chromatography (HPSEC) with a multi-angle laser light scattering (MALLS), gas chromatography coupled to mass spectrometry (GC-MS) and nuclear magnetic resonance spectroscopy (NMR, 1D and 2D). JSP was then evaluated regarding its physicochemical and rheological properties. Results showed that JSP was mainly composed of an agar-like xylogalactan sharing the general characteristics of corallinans. The structure of JSP was mainly composed of agaran disaccharidic repeating units (→3)-β-d-Galp-(1,4)-α-l-Galp-(1→)n and (→3)-β-d-Galp-(1,4)-3,6-α-l-AnGalp-(1→)n, mainly substituted on O-6 of (1,3)-β-d-Galp residues by β-xylosyl side chains, and less with sulfate or methoxy groups. (1,4)-α-l-Galp residues were also substituted by methoxy and/or sulfate groups in the O-2 and O-3 positions. Mass-average and number-average molecular masses (Mw) and (Mn), intrinsic viscosity ([η]) and hydrodynamic radius (Rh) for JSP were, respectively, 8.0 × 105 g/mol, 1.0 × 105 g/mol, 76 mL/g and 16.8 nm, showing a flexible random coil conformation in solution. The critical overlap concentration C* of JSP was evaluated at 7.5 g/L using the Williamson model. In the semi-diluted regime, JSP solutions displayed a shear-thinning behavior with a great viscoelasticity character influenced by temperature and monovalent salts. The flow characteristics of JSP were described by the Ostwald model.

Effects of Growth Conditions and Cultivar on the Content and Physiochemical Properties of Arabinoxylan in Barley.

The present study aims to evaluate the effect of the growth conditions and the cultivar on the total and water-extractable (W-E) arabinoxylan (AX) in barley. For this purpose, nine barley varieties from two different years were analyzed. The total AX content ranged from 5.97 to 8.98 wt % d.m., while the W-E AX ranged from 0.06 to 0.35 wt % d.m. The W-E AX molecular properties were characterized by high-pressure size exclusion chromatography (HPSEC)-triple detector array (TDA). The molecular weight was between 2.3 × 105 and 12.6 × 105 Da, the polydispersity was between moderate and broad (1.1 < Mw/Mn < 4.3), and the conformation was a stiff semiflexible coil (0.5 < α < 1.3). The results indicate that the year influences the content of total AX and W-E AX and some molecular characteristics of W-E AX, such as its polydispersity and its conformation. Finally, the results demonstrated that the W-E AX can be used as an index of the malting attitude of barley because it positively correlates with germinative energy and kernel dimension.