Fine structural features and antioxidant capacity of ferulated arabinoxylans extracted from nixtamalized maize bran.

BACKGROUND: The nixtamalization process improves the nutritional and technological properties of maize. This process generates nixtamalized maize bran as a by-product, which is a source of arabinoxylans (AX). AX are polysaccharides constituted of a xylose backbone with mono- or di-arabinose substitutions, which can be ester-linked to ferulic acid (FA). The present study investigated the fine structural features and antioxidant capacity (AC) of nixtamalized maize bran arabinoxylans (MBAX) to comprehend the structure-radical scavenging capacity relationship in this polysaccharide deeply. RESULTS: MBAX presented a molecular weight, intrinsic viscosity, and hydrodynamic radius of 674 kDa, 1.8 dL g-1 , and 24.6 nm, respectively. The arabinose-to-xylose ratio (A/X) and FA content were 0.74 and 0.25 g kg-1 polysaccharide, respectively. MBAX contained dimers (di-FA) and trimer (tri-FA) of FA (0.14 and 0.07 g kg-1 polysaccharide, respectively). The main di-FA isomer was the 8-5' structure (80%). Fourier transform infrared spectroscopy confirmed MBAX molecular identity, and the second derivate of the spectral data revealed a band at 958 cm-1 related to the presence of arabinose disubstitution. 1 H-Nuclear magnetic resonance spectroscopy showed mono- and di-arabinose substitution in the xylan backbone with more monosubstituted residues. MBAX registered an AC of 25 and 20 µmol Trolox equivalents g-1 polysaccharide despite a low FA content, using ABTS (2,2'-azino-bis-3-ethylbenzthiazoline-6-sulfonic acid) and DPPH (1,1-diphenyl-2-picrylhydrazyl) methods, respectively. CONCLUSION: AC in MBAX could be related to the high A/X ratio (mainly monosubstitution) and the high 8-5' di-FA proportion in this polysaccharide. © 2023 Society of Chemical Industry.

Extraction and characterization of arabinoxylans obtained from nixtamalized brewers' spent grains.

The processes to obtain value-added products from brewers' spent grain, a contaminant industrial waste, require alkaline non-ecofriendly pre-treatments. The arabinoxylans from brewers' spent grain were extracted by nixtamalization evaluating the extraction procedure, antioxidant capacity and molecular characteristics. The best arabinoxylans yields were those extracted with CaO at 100 °C and 25 °C (6.43% and 3.37%, respectively). The antioxidant capacity by 2,2-diphenyl-1-picrylhydrazyl assay of the arabinoxylans after thermal treatment and additional arabinoxylans after thermal treatment proteolysis were 434 and 118 mg TE/g, while by 2,20'-azino-bis (3-ethylbenzothiazoline-6-sulphonic acid) diammonium salt assay the value was similar (380 µmol TE/g). The intrinsic viscosities and viscosimetric molecular weights were 69 mL/g and 13 kDa for arabinoxylans after thermal treatment, and 15 mL/g and 1.6 kDa for arabinoxylans after thermal treatment proteolysis, respectively. The protein and lignin contents were 3.1% and 6.4% for arabinoxylans after thermal treatment and, 0.9% and 4.6% for arabinoxylans after thermal treatment proteolysis, while their arabinose: xylose ratios were 0.39 and 0.36, with ferulic acid contents of 0.63 and 0.14 mg/g, respectively. Both products of arabinoxylans were molecularly identical by Fourier transform infra-red. Although the purity of the extracted arabinoxylans was improved with proteolysis, their intrinsic viscosity and viscosimetric molecular weight were affected. The extraction of arabinoxylans from brewers' spent grain by CaO nixtamalization alone or after additional proteolysis was successful to obtain purity and good antioxidant capacity.

Enzymatic cross-linking of ferulated arabinoxylan: effect of laccase or peroxidase catalysis on the gel characteristics.

Arabinoxylans (AX) gels at 4% (w/v) were prepared using laccase (LAX gels) or peroxidase (PAX gels), and their cross-linking, rheological, structural, and spectroscopic characteristics were investigated. LAX gels presented lower amount of 5,5'-diferulic acid (11%), smaller mesh size (128 nm), and higher hardness (37 N) and elasticity (430 Pa) than the PAX gels (28%, 197 nm, 7 N, and 120 Pa, respectively). Microscopy of the LAX gels showed linked strands, while the system was less connected in the PAX gels. The Raman band at 2895 cm-1 of the LAX and PAX gels was less intense, indicating enhanced hydrogen bonding compared to that of AX. This decrease was less dramatic for the PAX gels. The greater content of 5,5'-diferulic acid in PAX gels could favor intrachain bonds, affecting their rheological, structural, and spectroscopic characteristics. Laccase may be a better option than peroxidase for AX gelation intended for food and biotechnological applications.

Efecto prebiótico de los Arabinoxilanos y los Arabinoxilo-Oligosacáridos y su relación con la promoción de la buena salud / Prebiotic effect of Arabinoxylans and Arabinoxylan-Oligosaccharides and the relationship with good health promotion

RESUMEN Los arabinoxilanos son polisacáridos presentes en los granos de los cereales, y como tales, forman parte de la fibra dietética consumida por humanos y animales. La hidrólisis química o enzimática de los arabinoxilanos produce arabinoxilo-oligosacáridos, los cuales pueden estar ramificados o no, con arabinosa. El objetivo de este trabajo fue exponer el uso potencial de los arabinoxilanos y arabinoxilo-oligosacáridos, como prebióticos, y el efecto de su consumo en la promoción de la buena salud, al estimular selectivamente el crecimiento y actividad metabólica de la microbiótica colónica benéfica. La información generada indica que los arabinoxilanos y arabinoxilo-oligosacáridos actúan modificando la microbiota de manera selectiva, y estimulan la respuesta biológica, favoreciendo la buena salud del hospedero, por su efecto antiobesogénico, regulador de la glucosa, antioxidante, anticancerígeno e inmunomodulador, con resultados similares o mejores en relación a prebióticos reconocidos. No obstante, es necesario ampliar el conocimiento que se tiene de ellos para sustentar su aplicación en la industria alimentaria, farmacéutica o biomédica.

ABSTRACT Arabinoxylans are polysaccharides present in grains and as such, are part of dietary fiber intake in humans and animals. Enzymatic or chemical hydrolysis of arabinoxylans produces arabinoxilo-oligosaccharides, which can be branched or unbranched with arabinose. The objective of this work was to describe the potential use of arabinoxylans and arabinoxylan-oligosaccharides as prebiotics to promote good health, by selective enhancement of beneficial colonic microbiota growth and metabolic activity. The information generated indicates that arabinoxylans and arabinoxylan-oligosaccharides act by modifying the microbiota selectively and stimulate the biological response favoring good health in the host, by antio-obesity effect, glucose regulator, antioxidant, anticancer, immunomodulator, with similar or better results than recognized prebiotics. However, it is necessary to expand the knowledge we have about arabinoxylans in order to support their application in the food, pharmaceutical, and biomedical industry.

Rheology and microstructure of gels based on wheat arabinoxylans enzymatically modified in arabinose to xylose ratio.

BACKGROUND: Arabinoxylans (AX) are polysaccharides consisting of a backbone of xyloses with arabinose substituents ester-linked to ferulic acid (FA). The arabinose to xylose ratio (A/X) in AX may vary from 0.3 to 1.1. AX form covalent gels by cross-linking of FA but physical interactions between AX chains also contribute to the network formation. The present study aimed to investigate the rheological and microstructural characteristics of gels based on AX enzymatically modified in A/X. RESULTS: Tailored AX presented A/X ranging from 0.68 to 0.51 and formed covalent gels. Dimers of FA content and elasticity (G') increased from 0.31 to 0.39 g kg-1 AX and from 106 to 164 Pa when the A/X in the polysaccharide decreased from 0.68 to 0.51. Atomic force microscopy images of AX gels showed a sponge-like microstructure at A/X = 0.68, whereas, at lower values, gels presented a more compact microstructure. Scanning electron microscopy analysis of AX gels show an arrangement of different morphology, passing from an imperfect honeycomb (A/X = 0.68) to a flake-like microstructure (A/X = 0.51). CONCLUSION: Lower A/X values favor the aggregation of AX chains resulting in an increase in di-FA content, which improves the rheological and microstructural characteristics of the gel formed. © 2017 Society of Chemical Industry.

Navicula sp. Sulfated Polysaccharide Gels Induced by Fe(III): Rheology and Microstructure.

A sulfated polysaccharide extracted from Navicula sp. presented a yield of 4.4 (% w/w dry biomass basis). Analysis of the polysaccharide using gas chromatography showed that this polysaccharide contained glucose (29%), galactose (21%), rhamnose (10%), xylose (5%) and mannose (4%). This polysaccharide presented an average molecular weight of 107 kDa. Scanning electron microscopy (SEM) micrographs showed that the lyophilized Navicula sp. polysaccharide is an amorphous solid with particles of irregular shapes and sharp angles. The polysaccharide at 1% (w/v) solution in water formed gels in the presence of 0.4% (w/v) FeCl3, showing elastic and viscous moduli of 1 and 0.7 Pa, respectively. SEM analysis performed on the lyophilized gel showed a compact pore structure, with a pore size of approximately 150 nm. Very few studies on the gelation of sulfated polysaccharides using trivalent ions exist in the literature, and, to the best of our knowledge, this study is the first to describe the gelation of sulfated polysaccharides extracted from Navicula sp.

Water extractable arabinoxylan aerogels prepared by supercritical CO2 drying.

Water extractable arabinoxylan (WEAX) aerogels were prepared by extracting the solvent from the alcogels (WEAX hydrogels with an alcohol as the solvent) with carbon dioxide under supercritical conditions. WEAX aerogels were characterized using scanning electron microscopy and adsorption and desorption nitrogen isotherms. The micrographs indicate a heterogeneous porous network structure in WEAX aerogel. Adsorption/desorption nitrogen isotherms of this material were type IV, which confirm that this material possess a mesoporous structure. WEAX aerogels rehydration capability was evaluated and the water absorption mechanism was determined. The WEAX aerogels water absorption mechanism was non-Fickian (n = 0.54).

Maize arabinoxylan gels as protein delivery matrices.

The laccase induced gelation of maize bran arabinoxylans at 2.5% (w/v) in the presence of insulin or beta-lactoglobulin at 0.1% (w/v) was investigated. Insulin and beta-lacto-globulin did not modify either the gel elasticity (9 Pa) or the cross-links content (0.03 and 0.015 microg di- and triferulic acids/mg arabinoxylan, respectively). The protein release capability of the gel was also investigated. The rate of protein release from gels was dependent on the protein molecular weight. The apparent diffusion coefficient was 0.99 x 10(-7) and 0.79 x 10(-7) cm(2)/s for insulin (5 kDa) and beta-lactoglobulin (18 kDa), respectively. The results suggest that maize bran arabinoxylan gels can be potential candidates for the controlled release of proteins.

Isolation and partial characterization of trehalose 6-phosphate synthase aggregates from Selaginella lepidophylla plants.

Trehalose 6-phosphate synthase was purified from Selaginella lepidophylla plants and three aggregates of the enzyme were found by molecular exclusion chromatography, ion exchange chromatography and electrophoresis. Molecular exclusion chromatography showed four activity peaks with molecular weights of 624, 434, 224 and 115 kDa. Ion exchange chromatography allowed three fractions to be separated with TPS activity which eluted at 0.35, 0.7 and 1 M KCl. Native PAGE of each pool had three protein bands with apparent M(r) 660, 440 and 200 kDa. Western blot results showed that anti-TPS antibody interacted with 115 and 67 kDa polypeptides; these polypeptides share peptide sequences as indicated by internal sequence data. The effects of pH and temperature on enzyme stability and activity were studied. For fractions eluted at 0.35 and 1.0 M KCl, the optimum pH is 5.5, while an optimum pH of 7.5 for 0.7 M fraction was found. The three fractions eluted from ion exchange chromatography were stable in a pH 5-11 range. Optimal temperatures were 25, 45 and 55 degrees C for 0.7, 0.35 and 1.0 M fractions, respectively. The 0.7 M KCl fraction showed highest stability in a temperature range of 25-60 degrees C, whereas the 0.35 M KCl fraction had the lowest in the same temperature range.

Trehalose 6-phosphate synthase from Selaginella lepidophylla: purification and properties.

A protein of 440 kDa with trehalose 6-phosphate synthase activity was purified with only one purification step by immobilized metal affinity chromatography, from fully hydrated Selaginella lepidophylla plants. The enzyme was purified 50-fold with a yield of 89% and a specific activity of 7.05 U/mg protein. This complex showed two additional aggregation states of 660 and 230 kDa. The three complexes contained 50, 67, and 115 kDa polypeptides with pI of 4.83, 4.69, and 4.55. The reaction was highly specific for glucose 6-phosphate and UDP-glucose. The optimum pH was 7.0 and the enzyme was stable from pH 5.0 to 10. The enzyme was activated by low concentrations of Ca2+, Mg2+, K+, and Na+ and by fructose 6-phosphate, fructose, and glucose. Proline had an inhibitory effect, while sucrose and trehalose up to 0.4M did not have any effect on the activity. Neither the substrates nor final product had an inhibitory effect.