Rye phenolics in nutrition and health

Dietary intake of whole-grain foods is associated with a decreased risk of chronic diseases such as diabetes, obesity and heart disease. In addition to dietary fibre, various phytochemicals have been suggested to contribute to the health effects of whole grain products. This review focuses on phenolic compounds in rye (Secale cereale L.), which is one of the major bread grains in Europe. Data on phenolic concentrations in rye grain and foods, their bioavailability to tissues and effects in vivo, and their potential contributions to health are presented. Phenolic compounds in rye, such as phenolic acids, alkylresorcinols and lignans, are concentrated in the outer layers of the grain. Phenolic acids are the major phenolic compounds in whole grain rye (103–300 mg/100 g grain), ferulic acid being the most abundant. Rye lignans are present at concentrations of 2 mg/100 g grain and had been shown to be converted by the intestinal microflora to the mammalian lignans enterodiol and enterolactone in human intervention studies. Alkylresorcinols (36–320 mg/100 g grain), which have been found to be incorporated into human erythrocyte membranes, are of particular interest due to their potential use as biomarkers of the intake of rye and wheat.     

Fermentation-induced changes in the nutritional value of native or germinated rye

Processing is important both for the sensory and nutritional quality of grains. In the case of whole grains, it especially may influence the levels and bioavailability of the bioactive compounds. Yeast, lactic acid and mixed fermentation were shown to vary in their effects on native and germinated wholemeal rye flour. The presence of Saccharomyces cerevisiae was important for enhanced levels of the analysed compounds. The levels of folates, free phenolic acids, total phenolic compounds, lignans and alkylresorcinols were increased especially by fermentation of germinated rye, which also resulted in lower pH when compared with native rye flour, the level of folate was increased up to seven-fold and that of free phenolic acids by up to ten-fold after germination and fermentation. Tailored fermentation thus offers a tool to further increase the bioactive potential of wholemeal rye.     

Low molecular phytochemicals of Indian dwarf (Triticum sphaerococcum Percival) and Persian wheat (T. carthlicum Nevski) grain

Ancient wheat grain is considered by consumers to be more natural, pro-healthy and better tolerated, so these genotypes are being steadily reintroduced to cultivation. This study presents the content and composition of phenolic acids, alkylresorcinols, sterols, tocols and carotenoids in the grain of Indian dwarf and Persian wheats, extended by characteristics of their kernels (weight, dimensions and colour). To compare these features, four other wheat species (bread, spelt, durum and einkorn wheats) were used. It was found that the grain of Indian dwarf and Persian wheat is similar in weight and dimensions to grain of einkorn wheat, while in colour to bread wheat. Among the tested samples, grain of both new genotypes was the richest source of total low molecular phytochemicals, especially phenolic acids and alkylresorcinols, while being the weakest source of carotenoids. For these wheats, an enhanced share of ferulic acid (93–95%) was found, accompanied by higher quantitative and qualitative variability of homologues within sterols, tocols and carotenoids. In turn, the alkylresorcinol composition was related to wheat ploidy level.     

Lignans in triticale grain and triticale products

This study determined the lignan content of seven varieties of triticale grain and compared these values with wheat and rye grain, with triticale milling fractions (bran, shorts, and refined flour), and triticale products (sprouted grain, malt, fermented bread dough, baked dough, dried pasta and cooked pasta). Acid hydrolysis and enzymatic hydrolysis were used to release the lignans in extracts. We carried out qualitative and quantitative analysis of secoisolariciresinol, matairesinol, lariciresinol, syringaresinol, and pinoresinol levels using an Acquity UPLC liquid chromatograph with photodiode and mass Acquity TQD detectors. The most abundant lignan in all samples was syringaresinol, which made up 80% of all lignans. The lignan content of triticale grain varied from 392 to 792 μg·100gd·m⁻¹ (acid hydrolysis) and from 685 to 1189 μg·100gd·m⁻¹(enzymatic hydrolysis), depending on the variety. The lignan levels in triticale bran were almost three times those found in the grain; in flour, there was one fifth or even one tenth as much, whereas the shorts had similar levels as the grain. After three days of germination, the amount of lignans in the triticale grain increased by 17%–32%. A greater increase in lignan content (by factors of 1.4 and 2.3) was found in triticale after extrusion cooking. Fermentation led to lignan concentrations increasing slightly (2–14%), but this was then reduced in the baking process. Extracts from dry pasta contained similar or lower amounts than did the raw material, but the concentration was higher in cooked pasta (14%–47%). The enzymatic hydrolyzed extracts contained on average 36% higher lignan content than did the acid hydrolyzed samples.     

Recent findings on certain bioactive components in whole grain wheat and rye

Whole grain wheat and rye are important sources of many bioactive compounds and contribute significantly to the total intake of cereals in many countries. Alkylresorcinols, benzoxazinoids, lignans, phenolic acids, phytosterols and tocols are common bioactive compounds present in these cereals. In this review, we report recent findings (mainly from 2010 onwards) regarding their content, composition, effects of food processing and their uptake, elimination and bioactivities with implications for health.     

Localization of alkylresorcinols in wheat,rye and barley kernels

Cereal alkylresorcinols (AR), a group of phenolic lipids mainly found in the outer parts of wheat and rye kernels, are currently being studied for the possibility to use them as biomarkers for the intake of whole grain wheat and rye foods. In this work, AR were localised in grains by using light microscopy and gas chromatographic analysis of hand-dissected botanical and pearling fractions. GC-analysis of hand-dissected fractions showed that more than 99% of the total AR content was located in an intermediate layer of the caryopsis, including the hyaline layer, testa and inner pericarp. Microscopic examination showed that the outer cuticle of testa/inner cuticle of pericarp was the exact location, and that no AR were found in the endosperm or in the germ, suggesting that AR could be used as a selective marker of testa.     

Identification and quantification of phenolic acids and anthocyanins as antioxidants in bran,embryo and endosperm of white,red and black rice kernels (Oryza sativa L.)

Whole rice grain comprising endosperm, embryo (or germ), and bran has potential beneficial health effects in addition to provision of nutrients. The distribution of phenolic acids and anthocyanins in endosperm, embryo, and bran of white, red, and black rice grains was investigated in this study. The total phenolic content (TPC) was highest in the bran, averaging 7.35 mg GAE/g and contributing 60%, 86% and 84% of phenolics in white, red and black rice. The average TPC of the embryo and endosperm were 2.79 and 0.11 mg GAE/g accounting for 17% and 23%, 4% and 10% and 7% and 9% in white, red and black rice, respectively. The antioxidant capacity determined using DPPH and ORAC displayed a trend similar to TPC. Free/conjugated phenolic acids in white, red and black rice bran accounted for 41%, 65% and 85% of total acids. Bound phenolic acids in rice bran accounted for 90% of total acids in whole grain. Cis-p-coumaric was detected in bound form in bran while cis-sinapic acid was detected in the free/conjugated form in embryo and bran. Cyanidin-3-O-glucoside and peonidin-3-O-glucoside were identified mainly in black rice bran as the total anthocyanins. Cyanindin-3-O-rutinoside was also detected in black rice bran.     

Extraction and in vitro Fermentation of Rye Bran Fractions

Rye bran was fractionated on a pilot scale into water-extractable, alkali-extractable and unextractable fractions. The fractions were enzymatically digested to partially remove starch and protein. The enzyme treated substrates were fermented in vitro using a human faecal inoculum. The water- and alkali-extractable fractions were fermented faster than the unextractable fraction and rye bran itself. However, the extent of fermentation after 24 h was similar in each case. The production of gases and short-chain fatty acids correlated well with the consumption of neutral sugars. All the rye substrates enhanced the molar proportion of propionic and butyric acids, among the short chain fatty acids.     

Biochemical markers: Efficient tools for the assessment of wheat grain tissue proportions in milling fractions

To produce safe and healthy whole wheat food products, various grain or bran dry fractionation processes have been developed recently. In order to control the quality of the products and to adapt these processes, it is important to be able to monitor the grain tissue proportions in the different milling fractions produced. Accordingly, a quantitative method based on biochemical markers has been developed for the assessment of grain tissue proportions in grain fractions. Grain tissues that were quantified were the outer pericarp, an intermediate layer (including the outer pericarp, the testa and the hyaline layer), the aleurone cell walls, the aleurone cell contents, the endosperm and the germ, for two grain cultivars (Tiger and Crousty). Grain tissues were dissected by hand and analysed. Biochemical markers chosen were ferulic acid trimer, alkylresorcinols, para-coumaric acid, phytic acid, starch and wheat germ agglutinin, for outer pericarp, intermediate layer, aleurone cell walls, aleurone cell contents, endosperm and germ respectively. The results of tissue quantification by hand dissection and by calculation were compared and the sensitivity of the method was regarded as good (mean relative errors of 4% and 8% for Crousty and Tiger outer layers respectively). The impact of the analytical variability (maximum 13% relative error on coarse bran) was also regarded as acceptable. Wheat germ agglutinin seems to be a promising marker of wheat germ: even if the quantification method was not able to quantify the germ proportions in milling fractions, it was able to classify these fractions according to their germ content. The efficiency of this method was tested, by assessing the grain tissue proportions of fractions exhibiting very different compositions such as flour, bran and aleurone-rich fractions obtained from three different grain or bran dry fractionation processes (conventional milling, debranning process, production of aleurone-rich fractions from coarse bran). By calculation of the composition of the different products generated, it was possible to study the distribution of the different tissues among fractions resulting from the different fractionation processes. This quantitative method is thus a useful tool for the monitoring and improvement of processes, and allows the effects of these processes to be understood and their adaption to reach the objectives.     

The antioxidant potential of milling fractions from breadwheat and durum

The effect of primary processing, namely milling, on the phenolic content and antioxidant capacity of two wheat cultivars, namely Canada Western Amber Durum (Triticum turgidum L. var. durum) and Canada Western Red Spring (Triticum aestivum L.) was studied. The milling products: bran, flour, shorts and feed flour fractions were examined. In addition, semolina was an end-product of durum wheat milling. Antioxidant activity of wheat phenoliocs was evaluated using oxygen radical absorbance capacity, inhibition of photochemiluminescence, the Rancimat method, and inhibition of oxidation of low-density lipoprotein cholesterol and deoxyribonucleic acid. The phenolic composition of wheat extracts was determined using high performance liquid chromatography. Bran showed the highest antioxidant activity whereas the endosperm possessed the lowest in both cultivars examined. The phenolic compounds are concentrated in the outermost layers namely the bran. The consumption of wheat with bran in the form of whole grain may provide beneficial health effects.     

Evaluation of Tissue Dissociation of Durum Wheat Grain (Triticum durum Desf.) Generated by the Milling Process

The three major botanical components (starchy endosperm, aleurone layer and pericarp) of eight durum wheat samples exhibited significantly different compositions and concentrations in phenolic acids. The starchy endosperm, the aleurone layer and the pericarp were respectively characterised by a low content in ferulic acid (FA), a high content intrans -sinapic acid (t -SA), and a high content in ferulic acid dehydrodimers (DHD). These three chemical markers can be exploited to differentiate the three grain botanical parts within milling fractions and to evaluate the milling efficiency, particularly the separation between bran and endosperm. The histological dissociation of the wheat grain generated by the milling process can be investigated further into details using the three phenolic acids markers. A separability index (S i) was proposed in order to quantify the ease of dissociation of endosperm from bran. Differences in S i values between wheat varieties grown under various agricultural conditions demonstrated the relevant variability of this character. The structural and molecular factors implied in the control of tissue dissociation are discussed in details.     

Validation of an extraction method for the quantification of soluble free and insoluble bound phenolic compounds in wheat by HPLC-DAD

Wheat is one of the three most widely grown grain crops and the most consumed in Europe. Wheat contains different phenolic compounds, mainly phenolic acids and flavonoids that are not evenly distributed in the wheat, being most abundant in the bran. These phenolic compounds are antioxidants against free radicals and other reactive oxygen species. Therefore, over the last few decades, there is a great interest to study and quantify these compounds present in wheat.This work proposes a HPLC-DAD method that allows a good separation of different phenolic compounds occurring as soluble free and insoluble bound compounds in wheat brand and flour. The extraction and the chromatographic conditions allowed the characterization of forty-two phenolic compounds, among phenolic acids (HBA, HCA, DFA and TFA), phenolic aldehydes, phenolic alcohols and flavonoids (flavones). This method is simple, sensitive, reproducible and accurate, and only a HPLC-DAD equipment is required. Thirty-four soluble and insoluble phenolic compounds can be quantified in wheat flour and brand. Hydroxytyrosol, a potent antioxidant compound, has been identified and quantified in wheat for the first time.     

Determination of phenolic acid concentrations in wheat flours produced at different extraction rates

High-performance liquid chromatography (HPLC) was used to determine the distribution of phenolic acids in wheat flours produced from five milling extraction rates ranging from 60% to 100% in four cultivars sown in two locations in the 2008–2009 season. Considerable variation was observed in free and bound phenolic acids, and their components in flours with different extraction rates. Most phenolic acids, including the component ferulic, were present in the bound form (94.0%). Ferulic (51.0%) was the predominant phenolic acid in wheat grain, and caffeic (22.8%) and p-coumaric (17.6%) acids were abundant. The phenolic acids and their components were all significantly influenced by effects of cultivar, milling, location, and cultivar × milling interaction, with milling effect being the predominant. The proportions of phenolic compounds varied considerably among milling extractions and cultivars, and their levels depended on both initial grain concentrations and on selection of milling extraction that was incorporated into the final product. The grain phenolic acid concentrations determined ranged from 54 μg g⁻¹ in flour produced at 60% extraction rate to 695 μg g⁻¹ in flour produced at 100% extraction rate, indicating their higher concentrations in bran associated with cell wall materials. Therefore, wholemeal wheat products maximize health benefits and are strongly recommended for use in food processing.     

Antioxidant properties of wheat and rye bran extracts obtained by pressurized liquid extraction with different solvents

Rye and wheat brans are valuable sources of bioactive compounds, which could be used for the development and commercialization of high added value functional ingredients such as dietary antioxidants. The aim of this study was to evaluate antioxidant potential of rye and wheat bran using different polarity solvents. Cereal brans were ground to four different particle size fractions and extracted at 10.3 MPa pressure and 80 °C temperature by consecutive application of hexane, acetone and methanol:water (80:20%). The highest extract yield was obtained from rye bran using methanol-water; particle size in most cases had a significant effect. Antioxidant potential of extracts was assessed by ABTS^+•, DPPH^• scavenging, ORAC and total phenols content (TPC) assays. Extraction solvent had a major influence on TPC and antioxidant activity of the extracts. The most active extracts were obtained using methanol:water; rye bran extracts, in general, were stronger antioxidants than wheat bran extracts. For the majority of assays, reduction of particle size resulted in higher antioxidant activity values. However, ABTS^+• scavenging was found to decrease by decreasing particle size of rye bran used for extraction.     

Buckwheat Seed Milling Fractions: Description, Macronutrient Composition and Dietary Fibre

The structure of the mature buckwheat achene and groat is discussed in relation to milling fractions and nutritional composition. Whole groats contain 55% starch, 12% protein, 4% lipid, 2% soluble carbohydrates, 7% total dietary fiber (TDF), 2% ash, and 18% other components (organic acids, phenolic compounds, tannins, phosphorylated sugars, nucleotides and nucleic acids, unknown compounds). The composition of the milling fractions reflects the relative abundance of seed tissues. Starch is concentrated in the central endosperm. Protein, oil, soluble carbohydrates and minerals are concentrated in the embryo. Commercial «Fancy» flour, a light-coloured flour, is mostly central endosperm and contains 75% starch, 6% protein, 1% lipid, 1% soluble carbohydrates, 3% TDF, 1% ash, and 13% other components. Although the embryo traverses the central endosperm, during milling parts of the embryo separate with the aleurone and seed coat in the bran fraction. Bran, with little central endosperm, contains 18% starch, 36% protein, 11% lipid, 6% soluble carbohydrates, 15% TDF, 7% ash, and 7% other components. Buckwheat bran also is a rich source of TDF and soluble dietary fibre (SDF), particularly bran with hull fragments (40% TDF of which 25% is SDF), while bran without hull fragments has 16% TDF of which 75% is SDF.     

Influence of phenolic acid content on sensory perception of bread and crackers made from red or white wheat

Despite the health benefits of wholegrain, consumer acceptance of wholegrain products remains an issue due to the presence of characteristic flavours that some consumers consider to be unacceptable. It was hypothesized that phenolic acids could be contributing to the perceived unacceptable flavours described in wholegrain products. The purpose of this study was to examine the relationship between total phenolic acid content (TPAC) and phenolic acids as quantified by HPLC, to the sensory properties of wholegrain products using partial least squares (PLS) mapping. Red and white wheat flours were investigated in an intermediate (bread) and low (cracker) moisture product system. Red and white wheat demonstrated different phenolic acid profiles despite having similar TPAC. Within the bread crumb, the free and bound phenolic acids provided the best predictive scores; whereas only bound phenolic acids provided high predictive scores in crackers. This suggests that the contribution of phenolic acids to flavour characteristics of wholegrain products varies depending upon the product moisture.     

Fractionation and characterisation of arabinoxylans from brewers' spent grain and wheat bran

Two agro-industrial co-products, brewers' spent grain and wheat bran, were fractionated by sequentially extracting with alkali of increasing strength. Over 60% of the brewers' grain biomass was solubilised by these treatments, compared with only 25% for wheat bran. The carbohydrate and phenolic composition of the solubilised fractions were determined, highlighting two compositionally different sets of fractions. In both co-products arabinoxylan was the main polysaccharide released. The degree of arabinose substitution of the extracted arabinoxylan diminished as the alkali strength increased. Insoluble residues contained both cellulose and non-cellulosic polysaccharides. In spent grain, the composition of the arabinoxylan in the residue was similar to that of the starting material. In wheat bran, the residual xylan was very highly substituted with arabinose. Both ferulic acid and three forms of diferulic acid (5,5′, 8-O-4′ and 8,5′) were present in the solubilised material, even after treatment with 4 M KOH. Esterified acetate was also present on polymers solubilised with KOH at concentrations up to 1 M. The more soluble fractions of spent grain represented a heterogeneous aggregation of feruloylated arabinoxylans with a broad molecular mass range, but the fractions extracted with stronger base were separated into low molecular weight moieties, presumably due to cleavage of covalent cross-links. Potential food and non-food uses for the isolated fractions from the cereal co-products are discussed.     

Antioxidant activity of small grain cereals caused by phenolics and lipid soluble antioxidants

In this study, the content of soluble, free forms of phenolic compounds (total phenolics, flavonoids, PVPP (polyvinylpolypyrrolidone) bound phenolics, proanthocyanidins and phenolic acids), as well as the content of carotenoids and tocopherols, were determined in whole grains of bread and durum wheat, rye, hull-less barley and hull-less oat, each represented with four genotypes. Antioxidant activity was evaluated as radical scavenging activity with DPPH (2,2-diphenyl-1-picrylhydrazyl) reagent, as well as by hydrogen transfer reaction (reduction power) based on the reduction of Fe³⁺. Generally, a considerable variation in antioxidant activities and phytochemical contents was observed between the cereals. Remarkably higher DPPH radical scavenging ability and reducing power were detected in hull-less barley, followed by rye and hull-less oat and durum and bread wheat, indicating that small grain species have different major antioxidants with different properties. Hull-less barley had the highest content of total free phenols, flavonoids, PVPP bound phenolics and contained flavan-3-ols, not found in other species. Hull-less oat had the highest content of tocopherols, very high content of yellow pigments and PVPP bound phenolics. Ferulic acid was the major free phenolic acid in small grain cereals tested. The relationship between the content of soluble phenols, as well as reducing power and DPPH^• scavenging activity are also considered.