Health benefits of docosahexaenoic acid and its bioavailability: A review.

Docosahexaenoic acid (DHA) is the predominant omega-3 long-chain polyunsaturated fatty acid found in human brain and eyes. There are a number of studies in the literature showing the health benefits of DHA. It is critical throughout all life stages from the need for fetal development, the prevention of preterm birth, and the prevention of cardiovascular disease to the improvements in the cognitive function and the eye health of adults and elderly. These benefits might be related to the modulation of gut microbiota by DHA. In addition, there are some discrepancies in the literature regarding certain health benefits of DHA, and this review is intended to explore and understand these discrepancies. Besides the variations in the DHA contents of different supplement sources, bioavailability is crucial for the efficacy of DHA supplements, which depends on several factors. For example, DHA in phospholipid and triglyceride forms are more readily to be absorbed by the body than that in ethyl ester form. In addition, dietary lipids in meals and emulsification of DHA oil can increase the bioavailability of DHA. Estrogens stimulated the biosynthesis of DHA, whereas testosterone stimulus induced a decrease in DHA. The roles of DHA through human lifespan, the sources, and its recommended daily intake in different countries are also discussed to provide a better understanding of the importance of this review.

The size dependence of the average number of branches in amylose.

Amylose has a small but significant number of long-chain branches. Two-dimensional size-exclusion chromatography is used to obtain the first measurement of the average number of branches per amylose molecule (from potato tubers) as a function of molecular size. Molecular weight dispersity, average chain length and average amylose molecular weight all increase with increasing size. However, the average number of branches of amylose molecules is weakly, if at all, dependent on size, with 2-4 per molecule except perhaps for the very largest molecules, although for these, the data may suffer from artifacts. Differences in the sizes of amylose molecules is mostly ascribed to variations in chain length. This observation is consistent with the postulate that most branching events occur in the early stage of amylose synthesis, and afterwards the branches are further elongated by granule-bound starch synthases. This gives improved mechanistic understanding of amylose biosynthesis.

Molecular rearrangement of waxy and normal maize starch granules during in vitro digestion.

The objective of the present study is to understand the changes in starch structures during digestion and the structures contributing to slow digestion properties. The molecular, crystalline, and granular structures of native waxy maize, normal maize, high-amylose maize, and normal potato starch granules were monitored using SEC, XRD, DSC, and SEM. The amylose and amylopectin molecules of all four starches were hydrolyzed to smaller dextrins, with some having linear molecular structure. Neither the A- nor B-type crystallinity was resistant to enzyme hydrolysis. Starch crystallites with melting temperature above 120°C appeared in waxy and normal maize starches after digestion, suggesting that the linear dextrins retrograded into thermally stable crystalline structure. These crystallites were also observed for high-amylose maize starch before and after digestion, contributing to its low enzyme digestibility. On the contrary, the enzyme-resistant granular structure of native normal potato starch was responsible for its low susceptibility to enzyme hydrolysis.

Roles of GBSSI and SSIIa in determining amylose fine structure.

This study examines the relationships between genetics (single nucleotide polymorphisms (SNPs) in GBSSI and SSIIa genes), starch structure (amylose and amylopectin fine structures), and starch properties (relating to gelatinization). GBSSI and SSIIa SNPs did not alter the starch content of rice grains. GBSSI SNPs can affect the amylose content, but they are incapable of altering the chain-lengths of amylopectin and amylose. The amounts of both long and short amylose branches changed with the same trend as amylose content, and they appeared to affect starch gelatinization properties. SSIIa synthesizes intermediate single-lamella amylopectin chains (DP 16-21), and consequently impacts the gelatinization temperature. Mathematical modelling suggests that the reduction in SSIIa activity significantly increases the activity of SBEII, resulting in a decreased activity ratio of SS to SBE in the enzyme set governing an appropriate chain-length distribution range. This application of the genetics-structure-property paradigm provides selection strategies to produce rice varieties with improved qualities.

Establishing whether the structural feature controlling the mechanical properties of starch films is molecular or crystalline.

The effects of molecular and crystalline structures on the tensile mechanical properties of thermoplastic starch (TPS) films from waxy, normal, and high-amylose maize were investigated. Starch structural variations were obtained through extrusion and hydrothermal treatment (HTT). The molecular and crystalline structures were characterized using size-exclusion chromatography and X-ray diffractometry, respectively. TPS from high-amylose maize showed higher elongation at break and tensile strength than those from normal maize and waxy maize starches when processed with 40% plasticizer. Within the same amylose content, the mechanical properties were not affected by amylopectin molecular size or the crystallinity of TPS prior to HTT. This lack of correlation between the molecular size, crystallinity and mechanical properties may be due to the dominant effect of the plasticizer on the mechanical properties. Further crystallization of normal maize TPS by HTT increased the tensile strength and Young's modulus, while decreasing the elongation at break. The results suggest that the crystallinity from the remaining ungelatinized starch granules has less significant effect on the mechanical properties than that resulting from starch recrystallization, possibly due to a stronger network from leached-out amylose surrounding the remaining starch granules.

Two-dimensional macromolecular distributions reveal detailed architectural features in high-amylose starches.

Two-dimensional (2D) structural distributions based on macromolecular size and branch chain-length are obtained for three maize starches with different amylose contents (one normal and two high-amylose varieties). Data were obtained using an analytical methodology combining chemical fractionation, enzymatic debranching, and offline 2D size-exclusion chromatography with multiple detection. The 2D distributions reveal novel features in the branching structure of high-amylose maize starches. Normal maize starch shows well-resolved structural topologies, corresponding to the amylopectin and amylose macromolecular populations. However, high-amylose maize starches exhibit very complex topologies with significant features between those of amylose and amylopectin, showing the presence of distinct intermediate components. These have the macromolecular size of amylose but similar branching structure to amylopectin, except for a higher proportion of longer branches. These structural features of the intermediate components can be related to a less tightly controlled biosynthesis of the branching structures in high-amylose maize starch mutants, which may prevent these molecules from maturing into full-size amylopectin. This altered macromolecular branched architecture of high-amylose starches probably contribute to their better nutritional properties.

Structures of octenylsuccinylated starches: effects on emulsions containing ß-carotene.

Starches with different amylopectin contents and different molecular sizes prepared using acid hydrolysis were hydrophobically modified using octenylsuccinic anhydride (OSA). The OSA-modified starches were used as surfactants to stabilize emulsions of ß-carotene and canola oil dispersed in water. The objective of this study is to investigate the relationship between starch molecular structure and the chemical stability of the emulsified ß-carotene, as well as the colloidal stability of emulsion droplets during storage. The oil droplet size in emulsions was smaller when starch had (a) lower hydrodynamic volume (Vh) and (b) higher amylopectin content. The oxidative stability of ß-carotene was similar across samples, with higher results at increased amylopectin content but higher Vh. Steric hindrance to coalescence provided by adsorbed OSA-modified starches appears to be improved by more rigid molecules of higher degree of branching.

Variation in amylose fine structure of starches from different botanical sources.

The molecular structures of amylose and amylopectin have an impact on functional properties of starch-containing food. This is the first study comparing amylose size distributions from various plant sources. Chain-length distributions (CLDs) of amylose and amylopectin branches ("fine structure") are characterized using size-exclusion chromatography [sometimes termed gel permeation chromatography (GPC)] and parametrized by both biosynthesis-based and empirical fits, to understand the starch biosynthesis mechanism and identify associations with starch digestibility. All starches show bimodal amylose weight CLDs, varying with plant sources, with potato tuber and sweet potato root starch having relatively longer branches than the others. The digestograms of all starches fit first-order kinetics. Unlike what has been seen in cooked grains/flours, amylose and amylopectin fine structures have no association with the digestibility of freshly gelatinized starch. This suggests that the observed effect in cooked grains/flours arises from a secondary interaction between amylose fine structure and higher order structural features.

Freeze-drying changes the structure and digestibility of B-polymorphic starches.

Starch granules both isolated from plants and used in foods or other products have typically been dried. Common food laboratory and industry practices include oven (heat), freeze, and ethanol (solvent-exchange) drying. Starch granules isolated from maize (A-type polymorph) and potato (B-type polymorph) were used to understand the effects of different dehydration methods on starch structure and in vitro digestion kinetics. Oven and ethanol drying do not significantly affect the digestion properties of starches compared with their counterparts that have never been dried. However, freeze-drying results in a significant increase in the digestion rate of potato starch but not maize starch. The structural and conformational changes of starch granules after drying were investigated at various length scales using scanning electron microscopy, confocal laser scanning microscopy, X-ray diffraction, FTIR spectroscopy, and NMR spectroscopy. Freeze-drying not only disrupts the surface morphology of potato starch granules (B-type polymorph), but also degrades both short- and long-range molecular order of the amylopectin, each of which can cause an increase in the digestion rate. In contrast to A-polymorphic starches, B-polymorphic starches are more disrupted by freeze-drying, with reductions of both short- and long-range molecular order. We propose that the low temperatures involved in freeze-drying compared with oven drying result in greater chain rigidity and lead to structural disorganization during water removal at both nanometer and micrometer length scales in B-type polymorphic starch granules, because of the different distribution of water within crystallites and the lack of pores and channels compared with A-type polymorphic starch granules.

Extraction, isolation and characterisation of phytoglycogen from su-1 maize leaves and grain.

Phytoglycogen is a highly branched soluble α-glucan found in plants, particularly those with decreased activity of isoamylase-type starch debranching enzyme, such as sugary-1 (su-1) maize. An improved technique has been designed to extract and isolate phytoglycogen from the grain and leaves of su-1 maize with minimal degradation for structural characterisation. The structures of extracted phytoglycogen samples were analysed using size-exclusion chromatography (SEC, also termed GPC) and transmission electron microscopy (TEM) and compared with the structure of pig liver glycogen. The SEC weight molecular size distributions indicate that the extraction procedure with protease is most effective in obtaining pure phytoglycogen from grain, whereas that without protease at cold temperature followed by purification using a sucrose gradient is more effective for leaf material. The extracted and purified phytoglycogen samples from both grain and leaf contain wide distributions of molecular sizes (analysed by SEC and TEM), with the smallest being "individual" ß particles, which collectively form larger α particles; the latter are dominant in the phytoglycogen samples examined here. The results show that phytoglycogen is similar to liver glycogen in both the range of molecular size distribution and in the presence of α particles.

Improving human health through understanding the complex structure of glucose polymers.

Two highly branched glucose polymers with similar structures--starch and glycogen--have important relations to human health. Slowly digestible and resistant starches have desirable health benefits, including the prevention and alleviation of metabolic diseases and prevention of colon cancer. Glycogen is important in regulating the use of glucose in the body, and diabetic subjects have an anomaly in their glycogen structure compared with that in healthy subjects. This paper reviews the biosynthesis-structure-property relations of these polymers, showing that polymer characterization produces knowledge which can be useful in producing healthier foods and new drug targets aimed at improving glucose storage in diabetic patients. Examples include mathematical modeling to design starch with better nutritional values, the effects of amylose fine structures on starch digestibility, the structure of slowly digested starch collected from in vitro and in vivo digestion, and the mechanism of the formation of glycogen α particles from ß particles in healthy subjects. A new method to overcome a current problem in the structural characterization of these polymers using field-flow fractionation is also given, through a technique to calibrate evaporative light scattering detection with starch.

Effect of octenylsuccinic anhydride modification on ß-amylolysis of starch.

The effects of octenylsuccinic anhydride (OSA) modification of waxy maize and sorghum starches on subsequent ß-amylolysis are examined. Hydrolysis with ß-amylase is a method by which OSA starches may be structurally modified for industrial purposes. The hydrolysis of both granular and gelatinised forms of both starches follows first-order kinetics regardless of the OSA used as a percent of starch mass (0-24%). The highest hydrolysis rate coefficients for granular starches are at modification with 6% OSA/starch. The largest molecular sizes of ß-amylase hydrolysed OSA-modified gelatinised starches are found at modification with 24% OSA/starch. The results suggest that octenylsuccinyl groups have an action-blocking effect on ß-amylolysis of gelatinised starch, but the effect of semi-crystalline granular structure is more pronounced than that of OSA modification. Hence ß-amylolysis can be used under appropriate conditions to modify the structure of gelatinised OSA-modified starches.

The importance of amylose and amylopectin fine structures for starch digestibility in cooked rice grains.

Statistically and causally meaningful relationships are established between starch molecular structures (obtained by size-exclusion chromatography, proton NMR and multiple-angle laser light scattering) and digestibility of cooked rice grains (measured by in vitro digestion). Significant correlations are observed between starch digestion rate and molecular structural characteristics, including fine structures of the distributions of branch (chain) lengths in both amylose and amylopectin. The in vitro digestion rate tends to increase with longer amylose branches and smaller ratios of long amylopectin and long amylose branches to short amylopectin branches, although the statistical analyses show that further data are needed to establish this unambiguously. These new relationships between fine starch structural features and digestibility of cooked rice grains are mechanistically reasonable, but suggestive rather than statistically definitive.

Effects of lipids on enzymatic hydrolysis and physical properties of starch.

This study aimed to understand effects of lipids, including corn oil (CO), soy lecithin (SL), palmitic acid (PA), stearic acid (SA), oleic acid (OA), and linoleic acid (LA), on the enzymatic hydrolysis and physical properties of normal corn (NCS), tapioca (TPS), waxy corn (WCS), and high-amylose corn (HA7) starch, and to elucidate mechanisms of interactions between the starches and lipids. After cooking with the lipids (10%, w/w, dsb), NCS, TPS, and HA7 showed significant decreases in enzymatic hydrolysis, and their DSC thermograms displayed amylose-lipid-complex dissociation peaks except with the CO. (13)C NMR spectra of amylodextrin with CO showed downfield changes in the chemical shifts of carbons 1 and 4 of the anhydroglucose unit, indicating helical complex formation. Generally, free fatty acids (FFAs) reduced, but SL increased the peak viscosities of starches. FFAs and SL decreased, but CO increased the gel strength of NCS. These lipids displayed little impacts on the enzymatic hydrolysis and physical properties of WCS because it lacked amylose.

Milling of rice grains: effects of starch/flour structures on gelatinization and pasting properties.

Starch gelatinization and flour pasting properties were determined and correlated with four different levels of starch structures in rice flour, i.e. flour particle size, degree of damaged starch granules, whole molecular size, and molecular branching structure. Onset starch-gelatinization temperatures were not significantly different among all flour samples, but peak and conclusion starch-gelatinization temperatures were significantly different and were strongly correlated with the flour particle size, indicating that rice flour with larger particle size has a greater barrier for heat transfer. There were slight differences in the enthalpy of starch gelatinization, which are likely associated with the disruption of crystalline structure in starch granules by the milling processes. Flours with volume-median diameter ≥56 µm did not show a defined peak viscosity in the RVA viscogram, possibly due to the presence of native protein and/or cell-wall structure stabilizing the swollen starch granules against the rupture caused by shear during heating. Furthermore, RVA final viscosity of flour was strongly correlated with the degree of damage to starch granules, suggesting the contribution of granular structure, possibly in swollen form. The results from this study allow the improvement in the manufacture and the selection criteria of rice flour with desirable gelatinization and pasting properties.

Physicochemical and structural properties of maize and potato starches as a function of granule size.

Chemical composition, molecular structure and organization, and thermal and pasting properties of maize and potato starches fractionated on the basis of granule size were investigated to understand heterogeneity within granule populations. For both starches, lipid, protein, and mineral contents decreased and apparent amylose contents increased with granule size. Fully branched (whole) and debranched molecular size distributions in maize starch fractions were invariant with granule size. Higher amylose contents and amylopectin hydrodynamic sizes were found for larger potato starch granules, although debranched molecular size distributions did not vary. Larger granules had higher degrees of crystallinity and greater amounts of double and single helical structures. Systematic differences in pasting and thermal properties were observed with granule size. Results suggest that branch length distributions in both amylose and amylopectin fractions are under tighter biosynthetic control in potato starch than either molecular size or amylose/amylopectin ratio, whereas all three parameters are controlled during the biosynthesis of maize starch.

Inhibition of azoxymethane-induced preneoplastic lesions in the rat colon by a cooked stearic acid complexed high-amylose cornstarch.

This study evaluated a novel stearic acid complexed high-amylose cornstarch (SAC) for the prevention of preneoplastic lesions in the colon of azoxymethane (AOM)-treated Fisher 344 rats fed resistant starches at 50-55% of the diet for 8 weeks. Uncooked SAC (r-SAC) diet was compared with raw normal-cornstarch diet (r-CS) or raw high-amylose cornstarch diet (r-HA), and water-boiled CS (w-CS) was compared with w-HA and w-SAC, respectively. w-SAC markedly reduced mucin-depleted foci (MDF) numbers compared with w-HA or w-CS. r-HA significantly decreased aberrant crypt foci (ACF) numbers compared with r-CS or r-SAC. Increased cecum weight and decreased cecum pH were observed in the SAC or HA groups. The highest amounts of total or individual short-chain fatty acids (SCFAs) in cecum and of butyrate or propionate in feces were observed in the AOM-treated w-SAC group. This study revealed the effectiveness of a novel resistant starch in inhibiting colonic preneoplastic lesions and the importance of high-moisture cooking on the suppression of colon carcinogenesis by this resistant starch.

Milling of rice grains. The degradation on three structural levels of starch in rice flour can be independently controlled during grinding.

Whole polished rice grains were ground using cryogenic and hammer milling to understand the mechanisms of degradation of starch granule structure, whole (branched) molecular structure, and individual branches of the molecules during particle size reduction (grinding). Hammer milling caused greater degradation to starch granules than cryogenic milling when the grains were ground to a similar volume-median diameter. Molecular degradation of starch was not evident in the cryogenically milled flours, but it was observed in the hammer-milled flours with preferential cleavage of longer (amylose) branches. This can be attributed to the increased grain brittleness and fracturability at cryogenic temperatures, reducing the mechanical energy required to diminish the grain size and thus reducing the probability of chain scission. The results indicate, for the first time, that branching, whole molecule, and granule structures of starch can be independently altered by varying grinding conditions, such as grinding force and temperature.

In vivo and in vitro starch digestion: are current in vitro techniques adequate?

The time evolution of the size distributions of (fully branched and debranched) starch molecules during in vivo and in vitro digestion was analyzed using size exclusion chromatography (SEC) and compared. In vivo digesta were collected from the small intestine of pigs fed with raw normal maize starch; in vitro digestion was carried out on the same diet fed to the pigs using a method simulating digestion in the mouth, stomach, and small intestine. A qualitative difference was observed between the in vitro and the in vivo digestion. The former showed a degradation of starch molecules to a more uniform size, whereas the in vivo digestion preserved the size distribution of native starch before producing a multimodal distribution, the heterogeneous nature of which current in vitro methods do not reproduce. The use of in vitro digestion to infer in vivo digestion patterns and, hence, potential nutrition benefits need to take account of this phenomenon.

Production of resistant starch by extrusion cooking of acid-modified normal-maize starch.

The objective of this study was to utilize extrusion cooking and hydrothermal treatment to produce resistant starch (RS) as an economical alternative to a batch-cooking process. A hydrothermal treatment (110 degrees C, 3 d) of batch-cooked and extruded starch samples facilitated propagation of heat-stable starch crystallites and increased the RS contents from 2.1% to 7.7% up to 17.4% determined using AOAC Method 991.43 for total dietary fiber. When starch samples were batch cooked and hydrothermally treated at a moisture content below 70%, acid-modified normal-maize starch (AMMS) produced a greater RS content than did native normal-maize starch (NMS). This was attributed to the partially hydrolyzed, smaller molecules in the AMMS, which had greater mobility and freedom than the larger molecules in the NMS. The RS contents of the batch-cooked and extruded AMMS products after the hydrothermal treatment were similar. A freezing treatment of the AMMS samples at -20 degrees C prior to the hydrothermal treatment did not increase the RS content. The DSC thermograms and the X-ray diffractograms showed that retrograded amylose and crystalline starch-lipid complex, which had melting temperatures above 100 degrees C, accounted for the RS contents.