Moderate ferulate and diferulate levels do not impede maize cell wall degradation by human intestinal microbiota

The degradation of plant fiber by human gut microbiota could be restricted by xylan substitution and cross-linking by ferulate and diferulates, for example, by hindering the association of enzymes such as xylanases with their substrates. To test the influence of feruloylation on cell wall degradability by human intestinal microbiota, nonlignified primary cell walls from maize cell suspensions, containing various degrees of ferulate substitution and diferulate cross-linking, were incubated in nylon bags in vitro with human fecal microbiota. Degradation rates were determined gravimetrically, and the cell walls were analyzed for carbohydrates, ferulate monomers, dehydrodiferulates, dehydrotriferulates, and other minor phenolic constituents. Shifting cell wall concentrations of total ferulates from 1.5 to 15.8 mg/g and those of diferulates from 0.8 to 2.6 mg/g did not alter the release of carbohydrates or the overall degradation of cell walls. After 24 h of fermentation, the degradation of xylans and pectins exceeded 90%, whereas cellulose remained undegraded. The results indicate that low to moderate levels of ferulates and diferulates do not interfere with hydrolysis of nonlignified cell walls by human gut microbiota.     

Model studies of ferulate-coniferyl alcohol cross-product formation in primary maize walls: implications for lignification in grasses

Ferulate and diferulates mediate cell wall cross-linking in grasses, but little is known about their cross-coupling reactions with monolignols and their role in lignin formation in primary cell walls. Feruloylated primary walls of maize were artificially lignified and then saponified to release ferulate and diferulates and their cross-products with coniferyl alcohol for analysis by GC-FID, GC-MS, and NMR spectroscopy. Ferulate and 5-5-coupled diferulate had a greater propensity than 8-coupled diferulates to copolymerize with coniferyl alcohol, forming mostly 4-O-beta' and 8-beta' and some 8-O-4' and 8-5' cross-coupled structures. Some 8-beta' structures de-esterified from xylans, but these cross-links were subsequently replaced as 8-coupled diferulates formed stable cross-coupled structures with lignin. Based on the incorporation kinetics of ferulate and diferulates and the predicted growth of lignin, cross-products formed at the onset of lignification acted as nucleation sites for lignin polymerization.     

Thermal stability of texture in Chinese water chestnut may be dependent on 8,8'-diferulic acid (aryltetralyn form)

Ferulic acid (FA) cross-links have been implicated in the thermal stability of texture in Chinese water chestnut (CWC) tissues. The aim of the current study has been to investigate this concept further. CWC tissue strips were measured for their mechanical properties before and after extraction in increasing strengths of alkali. The mechanical properties were related to the associated mode of fracture (cell separation or breakage) at the fracture surfaces and the phenolic composition of the cell walls. CWC tissue softened after prolonged extraction in cold alkali due to an increase in the ease of cell separation. Analysis of wall-bound phenolics demonstrated that most FA moieties, including five of the six dehydrodimers, were released before tissue strength was reduced. Loss of strength was, however, coincident with the loss of 8,8'-diferulic acid, aryltetralin (AT) form. It has been suggested that this dehydrodimer may be particularly concentrated at the edge of the cell faces. These results provide further evidence for the involvement of this dehydrodimer in conferring thermal stability of cell-cell adhesion and hence texture in CWC. However, they do not exclude the other diferulates from involvement in cell adhesion.     

Effects of cooking on the cell walls (dietary fiber) of 'Scarlet Warren' winter squash ( Cucurbita maxima ) studied by polysaccharide linkage analysis and solid-state (13)C NMR

Cell wall polysaccharides of 'Scarlet Warren' winter squash ( Cucurbita maxima ) were investigated before and after thermal processing. Linkage analysis of polysaccharides was done by gas chromatography coupled to mass spectrometry (GC-MS). The linkage analysis showed the cell wall polysaccharide compositions of raw and cooked squash were similar. The total pectic polysaccharides (galacturonan, rhamnogalacturonan, arabinan, and arabinogalactan) contents of the cell walls of both raw and cooked squash were 39 mol %. The amounts of pectic polysaccharides and xyloglucan in the cell walls of squash showed little alteration on heating. The cellulose content of the raw and cooked cell walls was relatively high at 47 mol %, whereas the xyloglucan content was low at 4 mol %. Solid-state (13)C nuclear magnetic resonance (NMR) spectroscopy techniques were used to examine the molecular motion of the polysaccharides in the cell walls. The mobility of highly flexible galactan depends on the water content of the sample, but no difference was seen between raw and cooked samples. Likewise, the mobility of semimobile pectic polysaccharides was apparently unaltered by cooking. No change was detected in the rigid cellulose microfibrils on cooking.     

In search of a maize ideotype for cell wall enzymatic degradability using histological and biochemical lignin characterization

Grass cell wall degradability is conventionally related to the lignin content and to the ferulic-mediated cross-linking of lignins to polysaccharides. To better understand the variations in degradability, 22 maize inbred lines were subjected to image analyses of Fasga- and M?ule-stained stem sections and to chemical analyses of lignins and p-hydroxycinnamic acids. For the first time, the nearness of biochemical and histological estimates of lignin levels was established. Combination of histological and biochemical traits could explain 89% of the variations for cell wall degradability and define a maize ideotype for cell wall degradability. In addition to a reduced lignin level, such an ideotype would contain lignins richer in syringyl than in guaiacyl units and preferentially localized in the cortical region rather than in the pith. Such enrichment in syringyl units would favor wall degradability in grasses, contrary to dicots, and could be related to the fact that grass syringyl units are noticeably p-coumaroylated. This might affect the interaction capabilities of lignins and polysaccharides.     

Influence of UV Exposure on Phenolic Acid Content,Mechanical Properties of Bran,and Milling Behavior of Durum Wheat (Triticum Durum Desf.)

Durum wheat bran was exposed to UV radiation up to 48 hr and the changes in ferulic acid (FA) content in the peripheral part s of grain were measured. The treatment resulted in a 25% decrease in FA monomer and a 44% decrease in dehydrodiferulic acid (DHD) ester‐linked to the cell‐wall arabinoxylans. This reduction was partly explained by a significant increase of FA (30%) and DHD (36%) engaged in hot alkali‐labile linkages. The results suggest that UV irradiation induced the formation of new cross‐links between feruloylated arabinoxylan and lignin in the pericarp. The effects of UV treatment on bran mechanical properties and wheat milling behavior were investigated. UV irradiation for 15 hr increased the stress to rupture by 30% and decreased the extensibility of bran tissues by 54%. This stiffening was associated with an increase in bran friability during grinding. Although this effect was due in part to the hydrothermal history of the grain, chemical modification induced by UV significantly influenced the size reduction of bran particles, which can be explained by the modification of the mechanical properties of bran. Relationships between the organization of cell‐wall polymers, the mechanical properties of tissues, and the behavior of wheat grain during milling were investigated.     

Cross-linking of maize walls by ferulate dimerization and incorporation into lignin

Cross-linking of xylans and lignin by ferulates was investigated with primary maize walls acylated with 2% ferulate and with ferulate ethyl esters. Peroxidase-mediated coupling of wall ferulate and ethyl ferulate yielded mostly 8-coupled products, including three new dehydrodimers. Significant quantities of 5-5-coupled diferulate formed only within walls, suggesting that matrix effects influence dimer formation. Over 60% of wall ferulate dimerized upon H2O2 addition, suggesting that xylan feruloylation is highly regulated during wall biosynthesis to permit extensive dimer formation at the onset of lignification. During lignification, ferulate and 5-5-coupled diferulate copolymerized more rapidly and formed fewer ether-linked structures with coniferyl alcohol than 8-5-, 8-O-4-, and 8-8-coupled diferulates. The potential incorporation of most ferulates and diferulates into lignin exceeded 90%. As a result, xylans become extensively cross-linked by ferulate dimerization and incorporation to lignin, but only a small and variable proportion of these cross-links is measurable by solvolysis of lignified walls.     

Oxidation of spruce wood sawdust by MnO(2) plus oxalate: a biochemical investigation

This paper reports the modification/degradation of lignin within spruce sawdust by manganese complexes formed by the association of MnO(2) and oxalate. The Mn oxidants formed are shown to modify both the chemical and physical properties of the wood cell wall. Scanning electron microscopy analysis of oxidized tracheids revealed a smoothing of the cell wall surface from the lumen side due to the removal of some material. Thioacidolysis analysis of the oxidized lignin showed reductions of up to 30% in the recovery of ether-linked guaiacyl monomers and up to 45% for the some dimers composing the polymer. The MnO(2)/oxalate system also slightly modified polysaccharides, corresponding to a 10% loss in weight of arabinose and glucose in the oxidized sample. However, no delignification occurred, according to the acid insoluble lignin content of spruce. Oxalic acid at pH 2.5 did not induce detectable changes in the chemical structures of the lignin or of the polysaccharides.     

Cell wall polysaccharides of near-isogenic lines of melon (Cucumis melo L.) and their inbred parentals which show differential flesh firmness or physiological behavior

We characterized differences in cell wall material and polysaccharide structures, due to the quantitative trait loci associated with higher flesh firmness in a nonclimacteric near-isogenic line (NIL) SC7-2, and with the climacteric behavior of the NIL SC3-5-1, using their nonclimacteric inbred parentals, "Piel de Sapo" (PS) and PI 161375 (SC). PS was firmer and had a higher ripening index and greater hemicellulosic content than SC, with its lower wall material yield, and uronic acid, neutral sugar, cellulose and free sugar content and higher pectic content. SC3-5-1 showed lower uronic acid values, a higher soluble solid content, and similar flesh firmness to PS. SC3-5-1 yielded mainly high molecular weight polysaccharides in the imidazole-soluble fraction than PS. SC7-2 showed greater flesh firmness, a higher neutral sugar (especially galactose and mannose) and uronic acid content, together with a larger cellulose and α-cellulose residue than PS. SC7-2 also contained more polysaccharides of low molecular weight in the first pectic fraction and shifted toward higher molecular weights in the main peak of the 4 M potassium-soluble fraction compared with PS.     

Compositional Changes in Composts During Composting and Mushroom Growth: Comparison of Conventional and Environmentally Controlled Composts from Commercial Farms

Samples from conventional and environmentally controlled (EC) composts taken at various stages of composting and mushroom (Agaricus bisporus) growth were analyzed for changes in 80 percent ethanol and water extracts, monosaccharides in acid hydrolysates of polysaccharides, lignin concentrations and lignin structural features. The relative lignin content of all composts as measured by the acetyl bromide procedure increased, both during composting and mushroom growth. On the assumption that the absolute amount of lignin remains unaltered during composting and mushroom growth, the relative changes to the polysaccharide concentrations were calculated. Thus, during composting, 70, 53 and 58 percent of the initial wall polysaccharides for conventional, “cold” and “hot” EC, respectively, were consumed by compost microorganisms. During spawn running and fruiting, about 15 percent of wall polysaccharides were utilized from all types of composts. Thus, considerable amounts (17–31 percent) of polysaccharide remained at the end of mushroom production. During composting, there were changes in the degree of condensation and in the extent of oxidation of the lignins in all cases, but the rate and extent of these changes was dependent on the different composting regimes. During mushroom growth, further changes occurred, again with different patterns for the different compost types.     

龙须菜细胞壁多糖对硼的吸附性能研究

为研究龙须菜(Gracilaria lemaneiformis)细胞壁多糖对硼的吸附作用机制及官能团之间的交互作用,本试验分别采用电感耦合等离子发射光谱(ICP-OES)和傅里叶变换红外光谱(FTIR)技术对其细胞壁多糖组分在吸附试验中进行硼的测定和表征。结果表明,细胞壁去琼胶后,硼吸附量减少50.13%,半纤维素去除后,硼吸附量减少21.20%,故可得纤维素吸附量占细胞壁总硼吸附量的28.67%。同时,通过细胞壁不同组分脱硼及硼胁迫后的红外光谱表征结果可知,龙须菜细胞壁及多糖在吸附硼的过程中,羟基、羧基、多糖碳链C-C为硼离子的主要结合位点,其中,琼胶、半纤维素中起主要作用的官能团为羟基、羧基,纤维素中起主要作用的官能团为多糖碳链C-C。本研究结果为进一步探究龙须菜多糖组分与硼的内在结合机制提供了基础依据。     

Dehydrotriferulic and Dehydrodiferulic Acid Profiles of Cereal and Pseudocereal Flours

Dehydrooligomers of ferulic acid cross‐link polysaccharides such as arabinoxylans and pectic polysaccharides in cereal and certain pseudocereal grains, affecting physiological effects of these fiber components and their physicochemical properties during food processing. An HPLC‐MS method for the analysis of eight diferulic acids and five triferulic acids in low‐lignin samples such as cereal grains and pseudocereals was developed and validated. This method was applied to the analysis of ester‐linked diferulates and triferulates in maize, popcorn, wheat, rye, oats, barley, buckwheat, and amaranth, giving a complete profile of this set of diferulates and triferulates in cereals and pseudocereals. Triferulic acid contents of the cereal flours are roughly 1/10 of the diferulic acid contents, ranging between 23 (oats) and 161 (popcorn) μg/g of flour, with lower amounts for the pseudocereal flours (1–3 μg/g of flour). Dominating trimers are either the 5‐5/8‐O‐4‐ and/or the 8‐O‐4/8‐O‐4‐regioisomers with lower proportions of 8‐8cyclic/8‐O‐4‐, 8‐5noncyclic/8‐O‐4‐, and 8‐5noncyclic/5‐5‐triferulic acids. A unique diferulate pattern was found for buckwheat, with more than 90% of the dimers being 8‐5‐coupled. Amaranth contains an unusually high proportion of 8‐8cyclic‐diferulate, with 27% of the total dimers, whereas oats and barley show comparably high proportions (23%) of the 8‐8tetrahydrofuran diferulate.     

Distribution of Accumulated Aluminum and Changes in Cell Wall Polysaccharides in Eucalyptus camaldulensis and Melaleuca cajuputi under Aluminum Stress

Distribution of aluminum (Al) within plant components and Al-induced changes in cell wall polysaccharides in root tips of Eucalyptus camaldulensis Dehnh. seedlings were compared with those of Melaleuca cajuputi Powell. In E. camaldulensis , 0.5 mM Al (pH 4.2 for 40 d) reduced plant dry weight by 50%, increased callose concentration in the root tips and induced leaf necrosis. In comparison with M. cajuputi , Al concentrations were higher in roots and leaves of E. camaldulensis on both a fresh weight basis and in the cell sap, but were lower in the cell wall. Al increased pectin, hemicellulose and cellulose concentration in the cell walls of E. camaldulensis root tips. Al-induced leaf necrosis and growth reduction in E. camaldulensis is discussed in the context of potentially toxic concentrations of Al in plant tissue and changes in polysaccharide content which could reduce water and nutrient uptake and cell wall extensibility in roots.     

Changes in Cell Wall Polysaccharides and Hydroxycinnamates in Wheat Roots by Aluminum Stress at Higher Calcium Supply

The present study was conducted to investigate the cell-wall polysaccharides and hydroxycinnamates in wheat plants (Triticum aestivum L.) under aluminum (Al) stress at a higher level of calcium (Ca) supply. Seedlings were grown in nutrient solution for 7 d and then subjected to treatment solutions containing Al (0 or 100 μM) and Ca (0 or 2500 μM) in a 500 μM CaCl ₂ solution at pH 4.5 for 8 d. Calcium treatment (2500 μM) improved root growth significantly under Al-stress conditions. The contents of pectin and hemicellulose in roots were increased under Al-stress conditions, and this increase was conspicuous in the hemicellulosic fraction. The increase in the hemicellulose was attributed to increases in arabinose, xylose, and glucose in neutral sugars. High Ca treatment decreased these contents in Al-stressed cell walls. Aluminum treatment increased the content of ferulic acid, whereas Ca treatment with Al reduced the content. These results suggest that Al may modify the mechanical properties of cell-wall polysaccharides by enhancing the synthesis of arabinoxylan, β-glucan, and ferulic acid in the cell wall. High Ca treatment may maintain the normal synthesis of these materials even under Al-stress conditions.     

Decomposition and binding action of polysaccharides in soil

In recent years more attention has been given to the polysaccharide fraction of the soil humus and some progress has been made toward an understanding of its nature and function in the soil. There is good evidence that it does contribute to soil aggregate stabilization. Its presence in the soil in relatively large amounts indicates relative resistance to decomposition. Methods for extracting and determination of total polysaccharides have improved but undoubtedly, still yield low results. Progress has been made in enumerating and quantitizing different structural units but it is not known whether (1) the soil polysaccharides consist of a mixture of numerous relatively simple plant and microbial polysaccharides at all stages of decomposition which are resistant to decomposition as such or become resistant through reactions with inorganic and organic soil constituents or, (2) whether the soil polysaccharides are new, highly complex polymers, consisting of numerous structural units, and which are naturally resistant to decomposition or become resistant through reaction with other soil constituents. Careful studies requiring new approaches and great ingenuity are needed to obtain more meaningful information on the structure, mechanisms of formation, and relationship to other soil constituents of the soil polysaccharide polymers.     

Physicochemical characteristics of onion (Allium cepa L.) tissues

The structure and mechanical properties of onions are important factors affecting their textural quality. The onion bulb consists of several layers of pigmented, papery scales surrounding fleshy storage scales that comprise an upper epidermis, an intermediate parenchyma tissue, and a lower epidermis. The purpose of this study was to examine the chemical composition of cell walls from the papery scales and outer fleshy scales of onion (Allium cepa L. cv. Sturon) in relation to their mechanical properties. Cell-wall material (CWM) was prepared from the component tissues and analyzed for its carbohydrate and phenolic composition. The CWMs were rich in uronic acid and glucose, with smaller quantities of arabinose, galactose, and xylose. In the fleshy scales, the lower epidermis contained relatively more galactose-rich pectic polysaccharides, whereas the upper epidermis and the papery scales contained virtually no galactose. Analysis of mechanical properties showed that the order of strength of the tissues was papery scales > fleshy scales, which were in the order lower epidermis > upper epidermis > intermediate parenchyma. The upper epidermis of fleshy scales was stronger in the vertical than the horizontal direction, and both orientations showed negligible notch sensitivity. Cyclohexane-trans-1,2-diaminetetraacetate-induced vortex-induced cell separation of the intermediate layer of fleshy scales indicated that calcium cross-linking may play an important role in cell-cell adhesion. A small but significant amount of ferulic acid was found in the walls, predominantly in the thick cuticle of the lower epidermis of fleshy scales. Alkali-labile wall-bound flavonoids were also detected.     

REVIEW: Variability in Fine Structures of Noncellulosic Cell Wall Polysaccharides from Cereal Grains: Potential Importance in Human Health and Nutrition

Noncellulosic polysaccharides from the cell walls of cereal grains are not digested by human small intestinal enzymes and so contribute to total dietary fiber intake. These polysaccharides are becoming recognized increasingly for their potential to lower the risk of serious diet‐related conditions such as type II diabetes, cardiovascular disease, colorectal cancer, and diverticular disease. The effectiveness of noncellulosic cell wall polysaccharides in improving health outcomes is related to the fine structure and associated physicochemical properties. The two most nutritionally relevant wall polysaccharides of cereal grains are the arabinoxylans and the (1‐3,1‐4)‐β‐d ‐glucans. These polysaccharides have high molecular mass values but are nevertheless soluble in aqueous media, at least in part, where they adopt highly asymmetrical conformations and consequently form high viscosity solutions. Thus, arabinoxylans and (1‐3,1‐4)‐β‐d ‐glucans contribute to the soluble fiber component of human diets. The molecular size, solubility, and viscosity of the polysaccharides vary widely not only between different cereals but also within a single species. The variability in these properties reflects differences in the chemical structure of the polysaccharides, which in turn influences the beneficial effects of arabinoxylans and (1‐3,1‐4)‐β‐d ‐glucans in human diets. Here, we summarize information on the variability of fine structures of the arabinoxylans and (1‐3,1‐4)‐β‐d ‐glucans in common cereals and relate these to solubility, viscosity, and health benefits. The recent identification of genes involved in the biosynthesis of the (1‐3,1‐4)‐β‐d ‐glucans opens the way for the genetic improvement of cereal quality parameters that are important in human health.     

REVIEW: Developments in Our Understanding of Sorghum Polysaccharides and Their Health Benefits

The composition and structure of sorghum polysaccharides are remarkably similar to those in maize. Sorghum grain is rich in starch, cellulosic and noncellulosic polysaccharides (mainly glucuronoarabinoxylans [GAX]). Sorghum starch is similar to maize starch in terms of amylopectin, but the amylose may be more branched. This may account for sorghum starch having a generally slightly higher gelatinization temperature. The GAX in sorghum are highly substituted with glucuronic acid and arabinose, but the degree of these substitutions is lower when compared with maize GAX. Sorghum polysaccharides themselves are not sufficiently functional to allow the production of high‐quality baked goods. Sorghum has generally lower starch digestibility than maize. This is primarily due to the endosperm protein matrix, cell wall material, and tannins (if present) inhibiting enzymatic hydrolysis of the starch. Protein disulfide bond cross‐linking involving the kafirin prolamins in the protein matrix around the starch granules seems to be of major importance in reducing starch digestibility. It does not seem that sorghum polysaccharides, per se, have any unique health‐promoting effects. Any health‐promoting effects related to sorghum polysaccharides seem to be due to interactions between the polysaccharides and the endosperm matrix protein and phenolics.     

Distribution of Accumulated Aluminum and Changes in Cell Wall Polysaccharides in Eucalyptus camaldulensis and Melaleuca cajuputi under Aluminum Stress

Distribution of aluminum (Al) within plant components and Al-induced changes in cell wall polysaccharides in root tips of Eucalyptus camaldulensis Dehnh. seedlings were compared with those of Melaleuca cajuputi Powell. In E. camaldulensis, 0.5 mM Al (pH 4.2 for 40 d) reduced plant dry weight by 50%, increased callose concentration in the root tips and induced leaf necrosis. In comparison with M. cajuputi, Al concentrations were higher in roots and leaves of E. camaldulensis on both a fresh weight basis and in the cell sap, but were lower in the cell wall. Al increased pectin, hemicellulose and cellulose concentration in the cell walls of E. camaldulensis root tips. Al-induced leaf necrosis and growth reduction in E. camaldulensis is discussed in the context of potentially toxic concentrations of Al in plant tissue and changes in polysaccharide content which could reduce water and nutrient uptake and cell wall extensibility in roots.     

In vitro fermentation of bacterial cellulose composites as model dietary fibers

Plant cell walls within the human diet are compositionally heterogeneous, so defining the basis of nutritive properties is difficult. Using a pig fecal inoculum, in vitro fermentations of soluble forms of arabinoxylan, mixed-linkage glucan, and xyloglucan were compared with the same polymers incorporated into bacterial cellulose composites. Fermentation rates were highest and similar for the soluble polysaccharides. Cellulose composites incorporating those polysaccharides fermented more slowly and at similar rates to wheat bran. Bacterial cellulose and cotton fermented most slowly. Cellulose composite fermentation resulted in a different short-chain fatty acid profile, compared with soluble polysaccharides, with more butyrate and less propionate. The results suggest that physical form is more relevant than the chemistry of plant cell wall polysaccharides in determining both rate and end-products of fermentation using fecal bacteria. This work also establishes bacterial cellulose composites as a useful model system for the fermentation of complex cell wall dietary fiber.