Mechanisms of flavonoid inhibition of Maillard reaction product formation in relation to whole grains processing.

Whole grains (WG) are beneficial to health but have reduced sensory quality, partly attributable to inhibition of Maillard reaction products (MRP) by WG phenolics. The study investigated how major flavonoid classes in cereals affect Maillard reaction pathways. Flavonoids were reacted with xylose-lysine aqueous system at 160 °C/12 min. Additionally, breads were made with catechin, and wheat and sorghum bran fortification. Low Mw MRP were profiled using UPLC-MS/MS, while melanoidins were characterized using fluorescence spectroscopy and HPSEC-MALS. The flavonoids significantly (p < 0.05) reduced both melanoidin content (by 33-86%) and Mw (3.5-15 kDa vs 20 kDa control), leading to lighter bread crust. Flavonoids inhibited MRP via direct condensation with early-stage amines and carbonyls into stable adducts, and reduction of late-stage polymerization reactions, increasing accumulation of cyclic N-containing intermediates. Inhibitory trend was flavones>flavanones>flavanols. C-Ring π-bond dramatically enhance flavonoid MRP inhibition; thus flavone-rich cereal grains are likely to strongly impact MRP-dependent sensory attributes of WG products.

Polyphenol recovery from sorghum bran waste by microwave assisted extraction: Structural transformations as affected by grain phenolic profile.

Sorghum milling waste stream (bran), contains diverse phenolic compounds with bioactive properties. The study determined the potential of microwave assisted extraction (MAE) to recover the bran phenolic compounds. Red, white, and lemon-yellow pericarp sorghum brans were subjected to MAE and phenolic yield and structural transformation vs conventional extraction (control) assessed by UPLC-MS/MS, Folin-Ciocalteu and Trolox equivalent antioxidant capacity methods. Phenols yield increased from 3.7-20.3 to 12.6-75.5 mg/g, while antioxidants capacity increased average 3.3X in MAE extracts vs controls. Hydroxycinnamic acids increased most dramatically (3.0-32X) in MAE extracts (0.08-2.64 to 2.57-8.01 mg/g), largely driven by release of cell-wall derived feruloyl- and coumaroyl-arabinose. MAE hydrolyzed flavonoid glycosides into aglycones, and depolymerized condensed flavonoid heteropolymers into flavanones, flavanols and (deoxy)anthocyanidins. Thus, MAE dramatically enhances yield of valuable phenolics from sorghum bran waste, but also alters the phenolic profile in ways that may influence their chemical and biological properties.

Effect of cereal bran phenolic profile on Maillard reaction products formation during hydrothermal treatment.

Maillard reaction products (MRP) contribute to sensory quality of various foods. Whole grains (WG) are rich in phenols which may influence Maillard reaction pathways during thermal processing and impact WG product sensory attributes. This study investigated how WG phenolic profile affects MRP formation. Amylase-hydrolyzed wheat (white and red) and sorghum (white, red, tannin) brans were hydrothermally processed at 150 °C/6 min, and characterized for MRP using colorimetry, fluorescence spectroscopy, HPLC-MS/MS, and HS-SPME/GC-MS. Bran phenolic structure, and to a lesser extent content, had larger influence on MRP formation than protein/amino acid profile. Polymeric tannins (both in situ and when added to wheat brans) strongly inhibited volatile and non-volatile MRP intermediates and melanoidin formation, likely via their carbocation depolymerization intermediates trapping furans. Principle component analysis demonstrated clear segregation of volatiles formation based on bran phenolic profile. Phenolic composition should be considered in WG product formulation and processing to achieve desired MRP formation.

Stability of starch-proanthocyanidin complexes to in-vitro amylase digestion after hydrothermal processing.

Proanthocyanidins (PA) form poorly digestible complexes with starch. The study examined amylase degradation mechanism and hydrothermal stability of starch-PA complexes. Sorghum-derived PA was complexed with wheat starch, reconstituted into flour (10% gluten added) and processed into crackers and pancakes. In vitro digestion profile of the complexes and products were characterized. The starch-PA complexes retained more (34-84%) fragments with degree of polymerization (DP) > 6,000 after 120 min digestion than controls (0-21%). Debranching further revealed higher retention of DP 11 - 30 chains in the digested starch-PA complexes than controls, suggesting amylopectin complexation contributed to reduced starch digestion. Starch-PA complexes retained reduced digestibility (50-56% higher resistant starch vs controls) in the cracker, but not pancake model. However, removing gluten from the pancake formulation restored the reduced digestibility of the starch-PA complexes. The starch-PA complexes are stable to hydrothermal processing, but can be disrupted by hydrophobic gluten proteins under excess moisture conditions.

Effect of protein-starch interactions on starch retrogradation and implications for food product quality.

Starch retrogradation is a consequential part of food processing that greatly impacts the texture and acceptability of products containing both starch and proteins, but the effect of proteins on starch retrogradation has only recently been explored. With the increased popularity of plant-based proteins in recent years, incorporation of proteins into starch-based products is more commonplace. These formulation changes may have unforeseen effects on ingredient functionality and sensory outcomes of starch-containing products during storage, which makes the investigation of protein-starch interactions and subsequent impact on starch retrogradation and product quality essential. Protein can inhibit or promote starch retrogradation based on its exposed residues. Charged residues promote charge-dipole interactions between starch-bound phosphate and protein, hydrophobic groups restrict amylose release and reassociation, while hydrophilic groups impact water/molecular mobility. Covalent bonds (disulfide linkages) formed between proteins may enhance starch retrogradation, while glycosidic bonds formed between starch and protein during high-temperature processing may limit starch retrogradation. With these protein-starch interactions in mind, products can be formulated with proteins that enhance or delay textural changes in starch-containing products. Future work to understand the impact of starch-protein interactions on retrogradation should focus on integrating the fields of proteomics and carbohydrate chemistry. This interdisciplinary approach should result in better methods to characterize mechanisms of interaction between starch and proteins to optimize their food applications. This review provides useful interpretations of current literature characterizing the mechanistic effect of protein on starch retrogradation.

Determination of basic criteria that influence the functionality of gluten protein fractions and gluten complex on roll bread characteristics.

Determinations of basic criteria that influence the functionality of gluten protein fractions on roll bread characteristics were investigated. SE-HPLC and RP-HPLC methods were used to quantification of protein/gluten composition of six different wheat flour samples with unique quality characteristics. Consequently, following new findings were reached: The ratio of HMW-GS/LMW-GS is more important than the amounts of HMW-GS and LMW-GS in flour. And as this rate increases, bread characteristics improve. In determining dough resistance, bread elasticity and height; the ratio of insoluble to soluble glutenin is influential factor and this ratio should be at the level of 1.3-1.4. When the pointer changes towards to insoluble glutenin; the dough is more resistant, the bread is more elastic and heighten, but the viscosity is weaker. Best bread flour had balance not only between gliadin and glutenin; but also, soluble glutenin and insoluble glutenin (1:1). Strong flours had 25-30%, whereas weak flours had 16% insoluble glutenin, as a percentage of flour protein.

Hepatocyte Adenosine Kinase Promotes Excessive Fat Deposition and Liver Inflammation.

BACKGROUND & AIMS: Nonalcoholic fatty liver disease is highly associated with obesity and progresses to nonalcoholic steatohepatitis when the liver develops overt inflammatory damage. While removing adenosine in the purine salvage pathway, adenosine kinase (ADK) regulates methylation reactions. We aimed to study whether hepatocyte ADK functions as an obesogenic gene/enzyme to promote excessive fat deposition and liver inflammation. METHODS: Liver sections of human subjects were examined for ADK expression using immunohistochemistry. Mice with hepatocyte-specific ADK disruption or overexpression were examined for hepatic fat deposition and inflammation. Liver lipidomics, hepatocyte RNA sequencing (RNA-seq), and single-cell RNA-seq for liver nonparenchymal cells were performed to analyze ADK regulation of hepatocyte metabolic responses and hepatocyte-nonparenchymal cells crosstalk. RESULTS: Whereas patients with nonalcoholic fatty liver disease had increased hepatic ADK levels, mice with hepatocyte-specific ADK disruption displayed decreased hepatic fat deposition on a chow diet and were protected from diet-induced excessive hepatic fat deposition and inflammation. In contrast, mice with hepatocyte-specific ADK overexpression displayed increased body weight and adiposity and elevated degrees of hepatic steatosis and inflammation compared with control mice. RNA-seq and epigenetic analyses indicated that ADK increased hepatic DNA methylation and decreased hepatic Ppara expression and fatty acid oxidation. Lipidomic and single-cell RNA-seq analyses indicated that ADK-driven hepatocyte factors, due to mitochondrial dysfunction, enhanced macrophage proinflammatory activation in manners involving increased expression of stimulator of interferon genes. CONCLUSIONS: Hepatocyte ADK functions to promote excessive fat deposition and liver inflammation through suppressing hepatocyte fatty acid oxidation and producing hepatocyte-derived proinflammatory mediators. Therefore, hepatocyte ADK is a therapeutic target for managing obesity and nonalcoholic fatty liver disease.

Identifying the Genetic Basis of Mineral Elements in Rice Grain Using Genome-Wide Association Mapping.

Mineral malnutrition is a major problem in many rice-consuming countries. It is essential to know the genetic mechanisms of accumulation of mineral elements in the rice grain to provide future solutions for this issue. This study was conducted to identify the genetic basis of six mineral elements (Cu, Fe, K, Mg, Mn, and Zn) by using three models for single-locus and six models for multi-locus analysis of a genome-wide association study (GWAS) using 174 diverse rice accessions and 6565 SNP markers. To declare a SNP as significant, -log10(P) ≥ 3.0 and 15% FDR significance cut-off values were used for single-locus models, while LOD ≥ 3.0 was used for multi-locus models. Using these criteria, 147 SNPs were detected by one or two GWAS methods at -log10(P) ≥ 3.0, 48 of which met the 15% FDR significance cut-off value. Single-locus models outperformed multi-locus models before applying multi-test correction, but once applied, multi-locus models performed better. While 14 (~29%) of the identified quantitative trait loci (QTLs) after multiple test correction co-located with previously reported genes/QTLs and marker associations, another 34 trait-associated SNPs were novel. After mining genes within 250 kb of the 48 significant SNP loci, in silico and gene enrichment analyses were conducted to predict their potential functions. These shortlisted genes with their functions could guide future experimental validation, helping us to understand the complex molecular mechanisms controlling rice grain mineral elements.

Baking Process Effects and Combined Cowpea Flour and Sorghum Bran on Functional Properties of Gluten-Free Cookies.

Gluten-related disorders, including celiac disease and non-celiac gluten sensitivity, are growing worldwide. The only treatment for both disorders is a lifelong gluten-free diet. However, gluten-free foods are generally poorer in nutrients, less healthy, and have a high cost. Sorghum and cowpea are gluten-free grains with high levels of phenolic compounds (PC) and a low cost. Their phenolic profile is structurally different; thus, the blend of both can provide synergistic/complementary health benefits to the final product. This study analyzed the effect of baking process and the blend of cowpea flour (CP) and sorghum bran (SB) on the levels of PC, resistant starch (RS), neutral detergent fiber (NDF), and antioxidant capacity (AC) of gluten-free cookies. Eleven rice or cowpea cookie formulations were made with or without white sorghum bran (WSB) or black sorghum bran (BSB). Baking increased the extractability of PC, AC, and the NDF of almost all formulations. The PC and AC were, respectively, about twice and 3-5 times higher in cookies containing BSB compared to the others. There was a minor effect of WSB on the PC and AC. Although there were losses, the retention of RS of cookies after the baking process was between 49.8 and 92.7%. Sorghum bran has excellent potential for use as a functional ingredient in healthy food production. The combined CP and SB have great potential to improve the nutritional and functional properties of gluten-free products, especially the PC, RS, and NDF contents.

CRISPR/Cas9-Mediated Mutagenesis of the Granule-Bound Starch Synthase Gene in the Potato Variety Yukon Gold to Obtain Amylose-Free Starch in Tubers.

Potato (Solanum tuberosum L.) is the third most important food crop after rice and wheat. Its tubers are a rich source of dietary carbohydrates in the form of starch, which has many industrial applications. Starch is composed of two polysaccharides, amylose and amylopectin, and their ratios determine different properties and functionalities. Potato varieties with higher amylopectin have many food processing and industrial applications. Using Agrobacterium-mediated transformation, we delivered Clustered regularly interspaced short palindromic repeats and CRISPR-associated protein 9 (CRISPR/Cas9) reagents to potato (variety Yukon Gold) cells to disrupt the granule-bound starch synthase (gbssI) gene with the aim of eliminating the amylose component of starch. Lugol-Iodine staining of the tubers showed a reduction or complete elimination of amylose in some of the edited events. These results were further confirmed by the perchloric acid and enzymatic methods. One event (T2-7) showed mutations in all four gbss alleles and total elimination of amylose from the tubers. Viscosity profiles of the tuber starch from six different knockout events were determined using a Rapid Visco Analyzer (RVA), and the values reflected the amylopectin/amylose ratio. Follow-up studies will focus on eliminating the CRISPR components from the events and on evaluating the potential of clones with various amylose/amylopectin ratios for food processing and other industrial applications.

Interactions of 3-deoxyanthocyanins with gum arabic and sodium alginate contributing to improved pigment aqueous stability.

3-Deoxyanthocyanins (3DXA) are of interest as food colorants but readily precipitated in aqueous solutions, limiting their potential applications. This work investigated ability of gum arabic vs alginate to stabilize 3DXA in aqueous systems and mechanisms involved. Apigeninidin and luteolinidin, and sorghum extracts dominant in these compounds, API-EX and LUT-EX, respectively, were prepared in pH 3 and 5 polysaccharide solutions (0.5-1.0 g/L), and colloidal properties and 10-week stability measured. Alginate equally stabilized both pigments at pH 5 (75% retention), but only LUT-EX at pH 3 (65%); viscosity and H-bonding contributed to the effects. By contrast, gum arabic highly stabilized API-EX (100%, pH 5), but not LUT-EX. Gum arabic formed a stable complex with apigeninidin via hydrophobic encapsulation, but much weaker complex with luteolinidin due to its more hydroxylated B-ring. Structure of 3DXA is critical to its interaction with hydrocolloids, thus pigment profile must be considered when selecting stabilizing polysaccharides.

Effect of tannins on microwave-assisted extractability and color properties of sorghum 3-deoxyanthocyanins.

Sorghum derived 3-deoxyanthocyanins (3-DXA) are of growing interest as natural food colors due to their unique stability compared to anthocyanins, but are generally difficult to extract. Microwave-assisted extraction (MAE) can dramatically improve extraction efficiency of 3-DXA from sorghum tissue. However, condensed tannins common in some sorghums could impact MAE extractability and color properties of 3-DXA. The objective of this work was to determine how presence of condensed tannins affect MAE extractability, stability, and color properties of sorghum 3-DXA. Sorghums of varying 3-DXA profile and tannin content, as well as purified tannins, were subjected to MAE and pigment yield and profile, aqueous color properties and stability at pH 1 - 5 monitored over time using, UV-vis spectroscopy, colorimetry, and UPLC-MS. The relative yield of 3-DXA from tannin sorghums was higher (3 - 10-fold) after MAE than from non-tannin sorghum (2-fold). During MAE, condensed tannins underwent extensive oxidative depolymerization to anthocyanidins (cyanidin and 7-O-methylcyanidin), which caused the tannin-sorghum pigment extracts to have a redder hue (12-43H°) compared to the non-tannin pigment extract (58H°). The tannin-derived anthocyanidins transformed over time into xanthylium pigments, resulting in increased extract H°. Tannins enhanced both color intensity (pH 1) and stability (pH 3-5) of the 3-DXA over 14 days, indicating they acted as copigments. The presence of tannins in sorghum enhances MAE extractability of 3-DXA from sorghum tissue, and could also potentially enhance their functionality in aqueous food systems. However, the initial changes in extract hue properties due to tannin-derived anthocyanidins should be considered.

Changes in extractable phenolic profile during natural fermentation of wheat, sorghum and teff.

Whole grain polyphenols are associated with structure-specific bioactive properties. However, the phenolic profile of grain ingredients can be significantly altered by processes like fermentation. This study investigated how polyphenol profiles in different cereal grains respond to microbial metabolism during sourdough fermentation. Whole grain wheat (white and red), sorghum (white and lemon-yellow), and teff (white and brown) flours were subjected to natural sourdough fermentation for 48-96 h, and phenolic profiles and their metabolites monitored using UPLC-tandem quadrupole MS. Flavonoid O-glycosides (dominant in sorghum) were rapidly metabolized (66% reduction in 48 h) to release aglycones (2.5 fold increase). O-Glycoside groups in mixed O/C-glycosides (dominant in teff) were selectively hydrolyzed, but more slowly (11-32% reduction in 48 h) than homo-O-glycosides, suggesting steric hindrance from the C-glycoside groups. Flavonoid C-glycosides (dominant in wheat) and aglycones (white sorghum) were generally stable to microbial degradation. Extractable phenolic acids and their esters (most abundant in white sorghum) were extensively degraded (80% reduction in 48 h) with few metabolites detected at the end of fermentation. Thus, extractable phenolics in sorghum were generally most extensively metabolized, whereas those in wheat were the least impacted by sourdough fermentation. New microbial metabolites, putatively identified as O-methylcatechol-vinyl-isoflavans, were detected in all fermented samples, with levels increasing with fermentation time. Based on structure, these compounds were likely derived from cell wall C-C linked diferulic acid metabolism. As expected, Folin reactive phenols and antioxidant capacity increased in fermented samples, but the extent was distinctly smaller in sorghums (1.3-1.9 fold) vs teff (2.4-3.2 fold) and wheat (2.0-6.1 fold), likely due to higher presence of easily metabolizable phenolics in sorghum. The phenolic profile of a cereal grain affects the products of microbial metabolism during fermentation, and may thus alter phenolic-dependent bioactive properties associated with a specific grain.

Impact of condensed tannin interactions with grain proteins and non-starch polysaccharides on batter system properties.

Proanthocyanidins (PA) cross-link wheat gluten proteins and dramatically enhance batter viscosity; PA could similarly affect related grains. This study aimed to determine PA effect on viscosity and pasting properties of barley, rye, and oat flours, and the relative contributions of PA interactions with proteins and non-starch polysaccharides (NSP). PA significantly increased batter viscosity, stability, and RVA peak viscosity in rye and barley flours (2.8× and 1.2×, respectively). Interestingly, viscosity peaked distinctively ~75 °C in PA-treated rye and barley flours, and their isolated protein-starch systems, indicating prolamins unravelled and complexed with PA during heating. Oat was largely unaffected by PA, likely because of its protein composition. Furthermore, water-soluble rye NSP and arabinoxylans, but not barley ß-glucans, significantly increased starch pasting viscosity with PA; oxidative gelation was not a factor. Thus, rye flour viscosity dramatically increased through interactive effects of PA on rye proteins and NSP, which could expand its food applications.

The effect of cooling and rehydration methods in high moisture meat analogs with pulse proteins-peas, lentils, and faba beans.

Pulse proteins (PLP) can be ideal alternative-sources that produce a meat-like textured product, known as a high moisture meat analog (HMMA). In this research, each commercial PLP: pea (16%), lentil (16%), and faba-bean (20%) was mixed with pea isolate (63%, 63%, and 59%, respectively) and constant ingredients which are canola oil (6%) and wheat gluten (15%) and texturized to produce HMMA using a twin-screw extruder (TX-52) with a cooling die. Soy concentrate and soy isolate were mixed with the constant ingredients and texturized into an HMMA and used as a control. Before freezing for storage, each sample was cooled by air, water, or a brine solution (2% or 4%) for 10 min. Frozen samples were thawed at room temperature (25 °C) for 3 hr and rehydrated by soaking at 25 °C for 2 hr, warm-soaking at 50 °C for 12 hr, or boiling for 2 min. Color, moisture content (MC), specific density (SD), water absorption index (WAI), water solubility index (WSI), and texture were measured. Compared to the control, samples with PLP had less lightness and texture and greater redness, yellowness, MC and WSI. The 2% brine solution used for cooling reduced WSI without textural change compared to other cooling methods. Boiling for rehydration increased lightness while warm-soaking decreased lightness and increased yellowness. In addition, boiling resulted in the least MC, SD, WSI, and WAI following soaking and warm-soaking. Therefore, these PLP can be used as alternative meat sources to soy proteins and a 2% brine solution for cooling and rehydration by boiling are recommended to reduce the WSI. PRACTICAL APPLICATION: Pulses are an excellent food ingredient because they are rich in protein and have an exceptional nutritional profile. In this study, high moisture meat analogs containing pea proteins, lentil proteins, faba bean proteins, and pea isolate instead of soy concentrate and soy isolate were produced. According to the results, pulse proteins can be an alternative source to soy proteins. Since they formed relatively well-defined orientation. Further research can be conducted using modified processing conditions for texturization to improve its quality. In addition, this research can help researchers and product developers understand proper handling methods for HMMA products after production such as cooling before freezing for storage and thawing and rehydrating after freezing.

Application of a novel microwave energy treatment on brewers' spent grain (BSG): Effect on its functionality and chemical characteristics.

The effect of a new microwave energy treatment on brewers' spent grain (BSG) functionality and its application in a bakery product was evaluated. The physicochemical modifications of BSG were studied with special emphasis on the analysis of non-enzymatic browning reactions. Microwave treatment induced the formation of Maillard reaction products with a high antioxidant activity. The structure of these compounds was fully analyzed and it was concluded that melanoidins were formed by polymerization of furanose rings. Results indicated that chlorogenic acids were also reactants involved in the development of this reaction, leading to the formation of new bioaccesible compounds with important antioxidant activity. Although the addition of BSG in cookie formulations negatively affect their texture, this effect was successfully reduced when the microwave treatment was applied on BSG. This was associated to the disrupting effect that the microwaves had on BSG fiber, which significantly reduced its water absorption index (p ≤ 0.05).

Effects of edible plant polyphenols on gluten protein functionality and potential applications of polyphenol-gluten interactions.

Expanding plant-based protein applications is increasingly popular. Polyphenol interactions with wheat gluten proteins can be exploited to create novel functional foods and food ingredients. Polyphenols are antioxidants, thus generally decrease gluten strength by reducing disulfide cross-linking. Monomeric polyphenols can be used to reduce dough mix time and improve flexibility of the gluten network, including to plasticize gluten films. However, high-molecular-weight polyphenols (tannins) cross-link gluten proteins, thereby increasing protein network density and strength. Tannin-gluten interactions can greatly increase gluten tensile strength in dough matrices, as well as batter viscosity and stability. This could be leveraged to reduce detrimental effects of healthful inclusions, like bran and fiber, to loaf breads and other wheat-based products. Further, the dual functions of tannins as an antioxidant and gluten cross-linker could help restructure gluten proteins and improve the texture of plant-based meat alternatives. Tannin-gluten interactions may also be used to reduce inflammatory effects of gluten experienced by those with gluten allergies and celiac disease. Other potential applications of tannin-gluten interactions include formation of food matrices to reduce starch digestibility; creation of novel biomaterials for edible films or medical second skin type bandages; or targeted distribution of micronutrients in the digestive tract. This review focuses on the effects of polyphenols on wheat gluten functionality and discusses emerging opportunities to employ polyphenol-gluten interactions.

Stability of 3-deoxyanthocyanin pigment structure relative to anthocyanins from grains under microwave assisted extraction.

Sorghum derived 3-deoxyanthocyanin (DXA) pigments are stable relative to their anthocyanin analogs, and are of growing interest in food applications. However, the 3DXA are poorly extractable from grain tissue. This work aimed to determine the relative stability and extractability of sorghum 3-DXA vs anthocyanins from maize and cowpea under microwave-assisted extraction (MAE). UV-Vis and UPLC-MS/MS spectrometry were used to characterize the properties. The 3-DXA remained structurally stable to MAE conditions up to 1200 W/100 °C/30 min. MAE increased sorghum 3-DXA yield 100% versus control (3100 vs 1520 mg/g). On the other hand, both maize and cowpea anthocyanins were unstable and rapidly degraded under MAE. Cell wall-derived ferulate esters were detected in sorghum and maize MAE extracts, indicating cell wall degradation occurred during MAE. Thus the enhanced extraction of 3-DXA under MAE was due to their structural stability, along with improved diffusion from cell matrix due to microwave-induced sorghum cell wall disruption.

Rye flavonoids - Structural profile of the flavones in diverse varieties and effect of fermentation and heat on their structure and antioxidant properties.

Flavones are important bioactive flavonoids in cereal grains, but are poorly characterized. This study investigated rye flavone profile as influenced by phenotype (grain color), sourdough fermentation, and subsequent heat processing. Twelve rye varieties belonging to 4 phenotypes were characterized using UPLC-tandem quadrupole MS before and after fermentation and baking. Antioxidant properties were also assessed. Rye flavones (range 57-137 µg/g) were dominated by O-glycosides (50-68%), present as derivatives of tricin (exclusively O-glycosides), chrysoeriol (O-/C-glycosides), and apigenin (exclusively C-glycosides). Phenotype did not influence flavone content. Fermentation partially hydrolyzed O-glycosides to their aglycones, but did not affect C-glycosides. Extractable phenols and antioxidants increased 1.9-3.6X after 96-h fermentation; baking further increased these components by 36-96% in fermented samples, likely via enhanced cell wall disruption. The high proportion of flavone-O-glycosides in rye is of interest due to their known higher bioavailability relative to typical cereal grain C-glycosides.

Resistant starch formation through intrahelical V-complexes between polymeric proanthocyanidins and amylose.

Reducing starch digestibility can significantly benefit efforts to combat obesity and associated chronic diseases. Polymeric proanthocyanidins (PA) form complexes with starch via unknown mechanisms, resulting in dramatically decreased starch digestibility. We hypothesized that V-type complexes are involved in these interactions. Sorghum derived PA was complexed with amylose, amylopectin, and granular maize starches in regular and deuterated solvents, and structural properties and in vitro digestibility of the complexes investigated. Based on iodine binding, X-ray diffraction patterns, crystallinity, and thermal properties, we demonstrated, for the first time, that type II semi-crystalline V-complexes are formed between amylose and PA. Furthermore, suppression of H-bonding led to amorphous complexes, suggesting extensive H-bonding facilitate and/or stabilize the V-complexes. We speculate that the complexation involves inclusion of B-rings of the PA units into the amylose helical cavity. The V-complex formation significantly increased resistant starch in gelatinized normal starch and pure amylose (by 35-45%), indicating likely physiological benefits.