Bioaccessibility of Maillard Reaction Products from Biscuits Formulated from Buckwheat Flours Fermented by Selected Lactic Acid Bacteria.

The in vitro bioaccessibility of the soluble protein and Maillard reaction products (MRPs) such as furosine (an early indicator of the MR), free FIC (fluorescent intermediate compounds), and FAST index (fluorescence of advanced MRPs and tryptophan), and the level of melanoidins defined by the browning index were analyzed in biscuits formulated from raw and roasted common buckwheat flours fermented by select lactic acid bacteria (LAB). The content of soluble proteins in fermented buckwheat flour and biscuits before and after digestion in vitro was significantly dependent on the LAB applied and the type of flour used and was the highest in the digested biscuits, indicating increased bioaccessibility. Generally, in all analyzed biscuits a lower furosine content was observed as compared to control samples, and its high bioaccessibility was noted after digestion. The free FIC in biscuits was strain-dependent, resulting in low bioaccessibility with the exception of biscuits obtained from both types of flours fermented by Streptococcus thermophilus MK-10. Compared to control biscuits obtained from raw buckwheat flour, the almost twice-increased FAST index was found for samples fermented by L. plantarum IB or Streptococcus thermophilus MK-10. After digestion, at least a fivefold higher value of the browning index was noted in control and tested biscuits, indicating the high bioaccessibility of melanoidins. This study indicates that fermentation of buckwheat flours by selected lactic acid bacteria seems to be a good way to obtain a product with high bioaccessibility of MRPs. However, further research on their functional properties is needed.

Identification and Bioaccessibility of Maillard Reaction Products and Phenolic Compounds in Buckwheat Biscuits Formulated from Flour Fermented by Rhizopus oligosporus 2710.

The identification and potential bioaccessibility of phenolic compounds using the highly sensitive micro-HPLC-QTRAP/MS/MS technique and Maillard reaction products (MRPs) in buckwheat biscuits formulated from flours, raw and roasted, fermented by Rhizopus oligosporus 2710 was addressed in this study after in vitro digestion. The content of the analyzed MRPs such as furosine, FAST index, and the level of melanoidins defined by the browning index was increased in the biscuits prepared from fermented flours as compared to the control biscuits prepared from non-fermented ones. After in vitro digestion higher content of furosine was observed in control and tested biscuits providing its high potential bioaccessibility. The fermented buckwheat flours used for baking affected the nutritional value of biscuits in comparison to the control biscuits in the context of the twice-increased FAST index. More than three times higher value of the browning index was noted in control and tested biscuits after digestion in vitro indicating the high bioaccessibility of melanoidins. Our results showed the presence of ten phenolic acids and eight flavonoids in the investigated biscuits. Among phenolic acids, vanillic, syringic, and protocatechuic were predominant while in the group of flavonoids, rutin, epicatechin, and vitexin were the main compounds in analyzed biscuits. Generally, the lower potential bioaccessibility of phenolic acids and higher potential bioaccessibility of flavonoids was found for biscuits obtained from buckwheat flours fermented by fungi compared to control biscuits obtained from non-fermented flours. Fermentation of buckwheat flour with the fungus R. oligosporus 2710 seems to be a good way to obtain high-quality biscuits; however, further research on their functional properties is needed.

Bioaccessibility of Phenolic Acids and Flavonoids from Buckwheat Biscuits Prepared from Flours Fermented by Lactic Acid Bacteria.

The literature reports that the consumption of common buckwheat (Fagopyrum esculentum Moench), exactly the polyphenols it contains, is associated with a wide spectrum of health benefits. Therefore, the determination of the bioaccessibility of phenolic acids and flavonoids from buckwheat biscuits formulated from liquid-state fermented flours (BBF) by selected lactic acid bacteria (LAB) after gastrointestinal digestion was addressed in this study. Bioaccessibility could be defined as the fraction of a compound that is released from the food matrix in the gastrointestinal lumen and used for intestinal absorption. The bioaccessibility of eight phenolic acids (protocatechuic, vanillic, syringic ferulic, caffeic, sinapic, p-coumaric, and t-cinnamic) and six flavonoids (epicatechin, vitexin, orientin, apigenin, kaempferol, and luteolin) were provided for BBF and BBC (buckwheat biscuits prepared from fermented and unfermented flours, respectively). The bioaccessibility indexes (BI) indicated the high bioaccessibility of phenolic acids and improved bioaccessibility of flavonoids from BBF. Moreover, the data provide evidence for the suitability of selected LAB strains to be used as natural sour agents for further bakery product development rich in phenolic acids and flavonoids with LAB-dependent bioaccessibility.

An Electrochemical Determination of the Total Reducing Capacity of Wheat, Spelt, and Rye Breads.

The most interesting activities associated with bread components such as phenolic compounds, fibre, tocols, or newly formed compounds in the Maillard reaction, are their reducing properties responsible for the formation of the overall reducing capacity of bread. Among the electrochemical methods, the cyclic voltammetry (CV) technique has been recently adapted for this purpose. In this study, the application of the CV assay for the determination of the total reducing capacity of flours, doughs, and breads as well as their crumbs and crusts, originated from wheat, spelt, and rye formulated on white flours (extraction rate of 70%) and dark flours (extraction rate of 100%) and baked at 200 °C for 35 min and at 240 °C for 30 min was addressed. The reducing capacity of hydrophilic extracts from white flours and breads as well as their crumbs and crusts showed double values when compared to that of lipophilic ones whilst hydrophilic and lipophilic extracts from dark breads and their parts revealed comparable levels. The dark wheat, spelt, and rye breads showed an approximately threefold higher total reducing capacity than white breads. Baking at higher temperature slightly increased the total reducing capacity of breads and the highest value was found for dark rye bread as well as its crust baked at 240 °C for 30 min. The cyclic voltammetry methodology showed to be especially suitable for screening the bread technology and allows for obtaining rapid electrochemical profiles of bread samples.

In Vitro Expanded Bioaccessibility of Quercetin-3-Rutinoside and Quercetin Aglycone from Buckwheat Biscuits Formulated from Flours Fermented by Lactic Acid Bacteria.

The expanded bioaccessibility of rutin (Ru) and quercetin (Q) from buckwheat biscuits (BBs) formulated from liquid-state fermented flours by selected lactic acid bacteria (LAB) were determined after gastrointestinal digestion. Fermentation of buckwheat flours caused a LAB-dependent variation in Ru and Q content. BBs baked at 220 °C for 30 min showed lower content of Ru and Q, and no correlation was found between the content of these compounds in fermented flours and BBs. The expanded bioaccessibility of Ru from BBs was low when its content in the soluble and insoluble fractions remaining after digestion in vitro was taken into account. Contrary results were found for Q bioaccessibility which had an index greater than 1, indicating the high Q bioaccessibility from BBs. Since very low Q content was noted in the insoluble fraction remaining after BBs digestion, the high Q bioaccessibility was determined to be due to its concentration in the soluble fraction.

ACE Inhibitory Properties and Phenolics Profile of Fermented Flours and of Baked and Digested Biscuits from Buckwheat.

The angiotensin converting enzyme (ACE) inhibitory activity and phenolics profile of fermented flours and of baked and digested buckwheat biscuits was studied. The fermentation of buckwheat flour by select lactic acid bacteria (LAB) caused a decrease in ACE inhibitory activity as compared to the non-fermented flour. The baking process significantly reduced the ACE inhibitory activity of biscuits obtained from fermented flours, whereas digestion significantly increased these properties. In non-fermented and fermented flours and buckwheat biscuits before and after in vitro digestion samples, ten phenolic acids and eight flavonoids were found. Highly significant correlations were found between sample concentration of 50% inhibition of ACE (IC50) and total phenolic compounds of fermented flour and biscuits before and after digestion for each applied LAB, thus indicating a link between phenolic compound content and ACE inhibitory activity. In the digested biscuits, the input to ACE inhibitory activity was provided by p-coumaric, sinapic, syringic, vanillic, and protocatechuic acids as well as by kaempherol, quercetin, apigenin, and orientin. Therefore, it can be concluded that cumulative action of those phenolic acids and flavonoids released after digestion is responsible, in part, for the bioaccessible ACE inhibitory activity of buckwheat biscuits.

Changes in protein quality and antioxidant properties of buckwheat seeds and groats induced by roasting.

This study focused on the evaluation of changes in protein quality and antioxidant properties of buckwheat seeds and groats induced by roasting. Changes in protein quality were indirectly measured by Maillard reaction chemical indicators such as furosine, FAST index, and browning. Characterization of antioxidant profiles of raw whole seeds, roasted whole seeds, raw groats, and roasted groats was undertaken by determining the extractable total phenolic compounds (TPC), extractable total flavonoids (TF) and individual flavonoids, lipophilic and hydrophilic peroxyl radical scavengers by ORAC(FL) assay, and scavengers of ABTS radical cations by TEAC assay. Roasting significantly decreased the total protein content of groats, whereas this parameter was not affected by the thermal treatment of whole seeds. The formation of MRPs was induced by the thermal treatment of both whole seeds and groats, thus suggesting deterioration of protein quality due to this chemical event. A significant degradation in natural antioxidants due to thermal processing was observed. Most of the peroxyl radical scavenging activity of samples was associated with hydrophilic compounds because L-ORAC(FL) values were on average 9% of the H-ORAC(FL) values. The H-ORAC(FL) values were positively correlated with extractable TPC contents (r = 0.51) and extractable TF contents (r = 0.93), whereas they showed a negative correlation with furosine (r = -0.87), FAST index (r = -0.85), and browning (r = -0.98) results.

Determination of the relative contribution of quercetin and its glucosides to the antioxidant capacity of onion by cyclic voltammetry and spectrophotometric methods.

This paper describes the use of cyclic voltammetry (CV), spectrophotometric methods [Trolox equivalent antioxidant capacity (TEAC), peroxyl radical trapping capacity (PRTC), DPPH radical scavenging activity (RSA), and Folin-Ciocalteu reagent (FCR) reducing capacity], and photochemiluminescence (PCL) for the measurement of the antioxidant capacity of onion var. Sochaczewska and var. Szalotka. The antioxidant and reducing activity of the dominant onion flavonoids quercetin (Q), quercetin-3- O-beta-glucoside (Q3G), quercetin-4'- O-beta-glucoside (Q4'G), and quercetin-3,4'-di- O-beta-glucoside (Q3,4'G) were determined by spectrophotometric (TEAC and PRTC) and CV methods, respectively. The contribution of quercetin and its glucosides to the antioxidant capacity of onion was calculated in consequence of the qualitative and quantitative analysis of onion flavonoids by high-performance liquid chromatography-ultraviolet-mass spectrometry. The dominant forms of quercetin in the onion var. Sochaczewska and Szalotka included Q4'G (61 and 54%), Q3,4'G (37 and 44%), Q3G (1.4 and 1.1%), and free quercetin (1.1 and 0.7%), respectively. The CV experiment showed the highest reducing activity of Q while Q3G, Q4'G, and Q3,4'G exhibited about 68, 51, and 30% of the reducing power noted for Q. The order of the reducing activity of onion flavonoids was confirmed by their free radical scavenging activity and evaluated by TEAC and PRTC assays as follows: Q > Q3G > Q4'G > Q3,4'G. The Q4'G and Q3,4'G showed poor antioxidant activity under both applied spectrophotometric assays but still exhibited reducing activity based on CV experiments. The reducing capacity of onions determined by CV method was twice higher than the antioxidant capacity formed by water-soluble compounds (ACW) evaluated by PCL, and it was about 50% higher than PRTC and DPPH RSA results and the converted FCR reducing capacity. In contrast, the reducing capacity of onions determined by the CV method was 3-fold and about four times lower when compared to the antioxidant capacity evaluated by the TEAC method and that formed by lipid-soluble compounds (ACL) provided by PCL, respectively. The highest antioxidant capacity of onion was found under cumulative consideration of PCL (ACW + ACL) and TEAC assays. The relative contribution of Q and its glucosides to the antioxidant capacity of onions showed a low contribution of Q, Q3G, and Q3,4'G derived from CV, TEAC, and PRTC assays while the highest contribution to the antioxidant capacity of onions was provided by Q4'G.

Antioxidant contents and antioxidative properties of traditional rye breads.

The purpose of this research was to find out the effect of flour extraction rate on the antioxidative properties of traditional rye bread and then to compare the bioactive compounds content and antioxidant properties of rye breads with commercial wheat roll. Four types of rye flour with different extraction rates of 100 (whole meal dark flour), 95 (brown flour), 90 (brown flour), and 70% (light flour) originated from Warko rye cultivar were used for traditional bread baking with sourdough fermentation. Four types of the respective rye breads were analyzed for their potentially beneficial components, including tocopherols and tocotrienols, total phenolics and flavonoids, reduced glutathione, and inositol hexaphosphates. Moreover, the phenolic acids profile was provided. The Trolox equivalent antioxidant capacity (TEAC) of the breads was evaluated using free radical scavenging activities of 80% methanol extracts against ABTS*+ radical cation (ABTS radical cation decolorization method) whereas radical scavenging activity (RSA) was determined against 2,2-diphenyl-1-picrylhydrazyl radical (DPPH*). The superoxide dismutase-like activity (SOD-like activity) was evaluated as free radical scavenging activities of PBS extracts against superoxide anion radicals (O2*-). The results were compared to whole meal rye bread as well as to wheat roll taken as representative example of wheat based bakery product. The studies showed that flour extraction rates strongly affected the content of bioactive compounds and antioxidative properties of traditionally baked rye breads. The incorporation of the rye flours with extraction rates from 100 down to 70% in the formulation caused decrease in tocopherol (T), tocotrienol (T3), inositol hexaphosphate (IP6), and phenolic compound (TPC) contents in rye breads. No changes in reduced glutathione (GSH) contents were noted between each type of rye bread. A significant decrease in Trolox equivalent antioxidant capacity and radical DDPH scavenging activity was also found in bread formulated on flour with an extraction rate of 70% in comparison to the breads formulated on flour with extraction rates from 100 to 90%. The highest SOD-like activity was noted for rye bread formulated on flour with an extraction rate of 70%. The four types of rye breads showed better antioxidative properties and higher antioxidant contents when compared to wheat roll with one exception made to tocopherols and tocotrienols.