Main polyphenols in the bitter taste of virgin olive oil. Structural confirmation by on-line high-performance liquid chromatography electrospray ionization mass spectrometry

Twenty virgin olive oils of extra quality and different bitter intensity were submitted to sensory evaluation and to the determination of polyphenols. A linear regression analysis was carried out assuming, as an independent variable, bitter intensity perceived by tasters, as an independent variable, the concentration (mmol/kg) of dialdehydic and aldehydic forms oleuropein aglycon, and dialdehydic and aldehydic forms ligstroside aglycon. Structural confirmation of these compounds was done by online high-performance liquid chromatography-electrospray ionization-collison-induced dissociation-mass spectrometry. The results obtained demonstrate the essential role played by this compound in the bitter taste of virgin olive oil.     

Influence of different dietary doses of n-3- or n-6-rich vegetable fats and alpha-tocopheryl acetate supplementation on raw and cooked rabbit meat composition and oxidative stability

This study evaluates the effects of replacing beef tallow added to rabbit feeds (3% w/w) by different doses (0%, 1.5% and 3% w/w) of n-6- or n-3-rich vegetable fat sources (sunflower and linseed oil, respectively) and alpha-tocopheryl acetate supplementation (0 and 100 mg/kg) on the fatty acid composition, alpha-tocopherol content, and oxidation levels [assessed by analyzing thiobarbituric acid (TBA) and lipid hydroperoxide values] in rabbit meat. We also measured these parameters after cooking and refrigerated storage of cooked rabbit meat. Both dietary alpha-tocopheryl acetate supplementation and the dose and source of fat added to feeds influenced meat fatty acid composition, modifying the n-6/n-3 ratio, which was more nutritionally favorable when linseed oil was used. Furthermore, the addition of linseed oil and the supplementation with alpha-tocopheryl acetate enhanced long-chain PUFA biosynthesis. However, the addition of 3% linseed oil increased meat oxidation, and although it was reduced by dietary supplementation with alpha-tocopheryl acetate in raw meat, this reduction was not as effective after cooking. Therefore, dietary supplementation with 1.5% linseed oil plus 1.5% beef tallow and with alpha-tocopheryl acetate would be recommended to improve the nutritional quality of rabbit meat.     

Characterization of an intense bitter-tasting 1H,4H-quinolizinium-7-olate by application of the taste dilution analysis, a novel bioassay for the screening and identification of taste-active compounds in foods

Thermal treatment of aqueous solutions of xylose and primary amino acids led to rapid development of a bitter taste of the reaction mixture. To characterize the key compound causing this bitter taste, a novel bioassay, which is based on the determination of the taste threshold of reaction products in serial dilutions of HPLC fractions, was developed to select the most intense taste compounds in the complex mixture of Maillard reaction products. By application of this so-called taste dilution analysis (TDA) 21 fractions were obtained, among which 1 fraction was evaluated with by far the highest taste impact. Carefully planned LC-MS as well as 1D and 2D NMR experiments were, therefore, focused on the compound contributing the most to the intense bitter taste of the Maillard mixture and led to its unequivocal identification as the previously unknown 3-(2-furyl)-8-[(2-furyl)methyl]-4-hydroxymethyl-1-oxo-1H,4H-quinolizinium-7-olate. This novel compound, which we name quinizolate, exhibited an intense bitter taste at an extraordinarily low detection threshold of 0.00025 mmol/kg of water. As this novel taste compound was found to have 2000- and 28-fold lower threshold concentrations than the standard bitter compounds caffeine and quinine hydrochloride, respectively, quinizolate might be one of the most intense bitter compounds reported so far.     

Direct spectrophotometric determination of bitterness in virgin olive oil without prior isolation by pH gradient

Bitter taste, an organoleptic characteristic of virgin olive oil, has been related to phenolic compound composition. The usual method to assess this attribute is by a sensorial panel of tasters, while in the laboratory; methods based on physicochemical properties have been assayed as K225, the most widely used one. However, a direct determination of bitterness in virgin olive oil is useful for quality-control purposes. The proposed method is supported by the observable spectral change undergone by the compounds responsible for bitterness as pH varied. This measurement was carried out directly in the oil, without prior isolation of bitter analytes. The difference of absorbance between alkaline and neutral medium showed a highly significant correlation (r = 0.988, p < 0.0001) with the conventional parameter (K225). The method was rapid, required a small sample, allowed direct determination of bitterness in virgin olive oil, and could be easily automated.     

复配亚麻籽油和辅酶Q10乳液的制备及表征

亚麻籽油和辅酶Q10都具有水中溶解度低、稳定性差、生物利用度低等缺点。将亚麻籽油和辅酶Q10(coenzyme Q10,CoQ10)同时负载于乳液中,可解决两者的应用瓶颈。使用阿拉伯胶为乳化剂,采用高压均质法制备复配亚麻籽油和CoQ10乳液。采用动态光散射、透射电子显微镜、体外模拟消化、体外释放、稀释稳定性、冻融稳定性、离子强度稳定性、光稳定性和加速氧化稳定性方法对所制备乳液的理化性质进行表征。结果显示,制备的乳液平均粒径为(284±5.6) nm,多分散指数(polydispersity index,PDI)为0.112±0.025,为均匀分散的球形液滴。制备的乳液在模拟小肠液中消化,和亚麻籽油、CoQ10混悬液相比,乳化后亚麻籽油的消化速率和CoQ10的生物可给率明显提高。乳液中CoQ10的释放表现出缓释效果。制备的乳液具有较好的稀释和冻融稳定性。Na^+和Ca^2+会造成乳液Zeta电位的下降,对乳液稳定性影响较大。乳液载体化后CoQ10的光稳定性得到了提高。CoQ10对亚麻籽油具有较好的保护作用。     

Influence of phosphorus application on yield,yield components,and quality of linseed

Abstract

Soil fertility depletion coupled with improper fertilization is one of the major constraints limiting linseed production in Ethiopia. Experiment was conducted in 2014/2015 on Nitisol in southeastern Ethiopian highlands to study the effect of phosphorus (P) fertilizer rate on yield, yield components, and oil content of linseed. It comprised of six levels of P fertilizer (0, 5, 10, 15, 20, and 25?kg?P?ha^?1) arranged in randomized complete block design with three replications. Results revealed that P fertilization brought significant effect on biomass yield, harvest index, plant height, number of capsules per plant, and kernel size. However, it didn’t significantly increase seed yield and oil content on linseed. Considering its influence on increasing biomass yield and improving yield components, application of 5?kg?P?ha^?1 has been recommended for replenishing the extracted P, maintaining soil fertility and improving linseed production on Nitisols of southeastern Ethiopian highlands and other similar agro-ecologies.     

Biodegradability Studies of Certain Wood Preservatives in Groundwater as Determined by the Respirometric Bod Oxitop Method

This study focuses on the biodegradability measurements of tall oil-based wood preservatives and their raw materials in groundwater as determined by the respirometric BOD OxiTop method. Certain substances were also analyzed in standard conditions described by OECD 301 F. Results show that creosote oil, a traditional wood preservative, does not biodegrade at all in groundwater over a period of 28 days, while tall oil and linseed oil biodegrade to some degree (13.4% and 14.8%, respectively). On the other hand, degrees of biodegradation of linseed oil, tall oil and creosote oil in the extra mineral and microbe including conditions described by OECD 301 F were 72.9%, 54.3% and 24.9% after 28 days, respectively. Studied raw materials of tall oil-based wood preservative production biodegrade to some degree in groundwater (variability from 11.9% to 18%) and quite effectively in OECD 301 F test (variability from 39% to 71.7%) over a period of 28 days. Abiotic degradation may also be significant with the studied substances.     

Development of two stable isotope dilution assays for the quantitation of acrolein in heat-processed fats

Two stable isotope dilution assays were developed for the quantitation of acrolein in fats and oils using [(13)C(3)]-acrolein as the internal standard. First, a direct GC-MS headspace method, followed by an indirect GC-MS method using derivatization with pentafluorophenyl hydrazine, was established. Analysis of six different types of oils varying in their pattern of fatty acids showed significant differences in the amounts of acrolein formed after heating at various temperatures and for various times. For example, after 24 h at 140 °C, coconut oil contained 6.7 mg/kg, whereas linseed oil was highest with 242.3 mg/kg. A comparison of the results showed that the extent of acrolein formation seemed to be correlated with the amount of linolenic acid in the oils. Although the acrolein concentrations were lowered in all six oils after frying of potato crisps, linseed and rapeseed oil still contained the highest amounts of acrolein after frying. By applying both methods on different thermally treated fats and oils, nearly identical quantitative data were obtained.     

Fourier transform infrared spectra of drying oils treated by irradiation

Drying oils, such as linseed oil and tung oil, have the potential as coating materials to improve barrier properties of biobased packaging films. Oil drying is a chemical reaction in which polyunsaturated fatty acids undergo autoxidation. During drying, oils polymerize and form water-resistant films. However, drying rates tend to be too slow for practical applications. Metal driers are used in the paint industry to accelerate drying, but often driers are not safe for food contact. The objective of this work was to investigate the effect of ionizing radiation on the oxidation or drying rate of drying oils. The effect of irradiation dose on the drying rate of linseed and tung oils was monitored by FTIR spectroscopy. The peak at 3010 cm (-1) was found to be a useful index of oxidation rate. The decrease in peak intensity with time was fitted with exponential functions of the form Abs = Abs 0 exp (- t/ k), where Abs 0 is the initial absorbance and 1/ k is the rate constant for the oxidation process. Values for k were 9.91 ( R (2) = 0.98), 6.59 ( R (2) = 0.95)n and 6.44 ( R (2) = 0.97) for radiation levels of 0, 50, and 100 kGy, respectively. The k values suggested that the oxidation rate increased as the radiation dose increased from 0 to 50 kGy. A further increase to 100 kGy had only a limited effect.     

Structural and sensory characterization of compounds contributing to the bitter off-taste of carrots (Daucus carota L.) and carrot puree

Sequential application of solvent extraction, gel permeation chromatography, and HPLC in combination with taste dilution analyses revealed that not a sole compound but a multiplicity of bitter tastants contribute to the bitter off-taste of cold-stored carrots and commercial carrot puree, respectively. Among these bitter compounds, 3-methyl-6-methoxy-8-hydroxy-3,4-dihydroisocoumarin (6-methoxymellein), 5-hydroxy-7-methoxy-2-methylchromone (eugenin), 2,4,5-trimethoxybenzaldehyde (gazarin), (Z)-heptadeca-1,9-diene-4,6-diin-3,8-diol (falcarindiol), (Z)-heptadeca-1,9-diene-4,6-diin-3-ol (falcarinol), and (Z)-3-acetoxy-heptadeca-1,9-diene-4,6-diin-8-ol (falcarindiol 3-acetate) could be identified on the basis of MS as well as 1D- and 2D-NMR experiments. Due to the low concentrations of <0.1 mg/kg and the high taste thresholds found for eugenin and gazarin, these compounds could be unequivocally excluded as important contributors to the bitter taste of carrots. Calculation of bitter activity values as the ratio of their concentration to their bitter detection threshold clearly demonstrated that neither in fresh and stored carrots nor in commercial carrot puree did 6-methoxymellein contribute to the bitter off-taste. In contrast, the concentrations of falcarindiol in stored carrots and, even more pronounced, in carrot puree were found to be 9- and 13-fold above its low bitter detection concentration of 0.04 mmol/kg, thus demonstrating that this acetylenic diol significantly contributes to the bitter taste of the carrot products investigated.     

Sensory activity,chemical structure,and synthesis of Maillard generated bitter-tasting 1-oxo-2,3-dihydro-1H-indolizinium-6-olates

Thermal treatment of aqueous solutions of xylose, rhamnose, and l-alanine led to a rapid development of a bitter taste of the reaction mixture. To characterize the key compounds causing this bitter taste, the recently developed taste dilution analysis (TDA), which is based on the determination of the taste threshold of reaction products in serial dilutions of HPLC fractions, was performed to locate the most intense taste compounds in the complex mixture of Maillard reaction products. By application of this TDA, 26 fractions were obtained, among which seven fractions were evaluated with a high taste impact. LC/MS and NMR spectroscopy as well as synthetic experiments revealed the 1-oxo-2,3-dihydro-1H-indolizinium-6-olates 1-5 as the key compounds contributing the most to the intense bitter taste of the Maillard mixture. Calculation of the taste impact of these compounds based on a dose/activity relationship indicated that these five compounds already accounted for 56.8% of the overall bitterness of the Maillard mixture, thus demonstrating this class of 1-oxo-2,3-dihydro-1H-indolizinium-6-olates as the key bitter compounds. First synthetic studies on the relationship between the chemical structure and the human psychobiological activity of 1-oxo-2,3-dihydro-1H-indolizinium-6-olates revealed that substitution of the furan rings of 1 by 5-methylfuryl moieties (compounds 3-5) or by 5-(hydroxymethyl)furyl groups (compound 6) led to a significant increase of the bitter threshold. In contrast, the substitution of the oxygen atoms in the furan rings of 1 by sulfur atoms induced a significant decrease of the detection threshold of the 1-oxo-2,3-dihydro-1H-indolizinium-6-olate; for example, the thiophene derivative 7 showed the extraordinarily low bitter detection threshold of 6.3 x 10(-5) mmol/kg (water).     

Application of hydrophilic interaction liquid chromatography/comparative taste dilution analysis for identification of a bitter inhibitor by a combinatorial approach based on Maillard reaction chemistry

Activity-directed fractionation of heated carbohydrate/alanine solutions recently led to the discovery of (+)-(S)-1-(1-carboxyethyl)-5-hydroxy-2-(hydroxymethyl)pyridinium inner salt (1, alapyridaine), and it has been shown that this compound lowers the detection thresholds of sugars, glutamate, and NaCl solutions, whereas no influence on bitter perception was observed. As this class of Maillard-derived pyridinium betaines seemed to be promising targets for further research on their taste modulatory activity, the objective of the present investigation was to screen for bitter taste-suppressing target molecules in combinatorial libraries of pyridinium betaines prepared from 5-(hydroxymethyl)furan-2-aldehyde and amino acid mixtures by use of Maillard-type reaction chemistry instead of synthesizing and purifying each derivative individually. By application of hydrophilic interaction liquid chromatography in combination with the recently developed comparative taste dilution analysis, followed by structure determination, synthesis, and sensory studies, we have now succeeded in identifying 1-carboxymethyl-5-hydroxy-2-hydroxymethylpyridinium inner salt (2) as a potential bitter-suppressing candidate. While tasteless on its own, 2 was found to reduce the bitterness of various bitter tastants such as the amino acid L-phenylalanine, the peptide Gly-Leu, the alkaloid caffeine, and the bitter glycosides salicin and naringin.     

Quantitative studies and sensory analyses on the influence of cultivar, spatial tissue distribution, and industrial processing on the bitter off-taste of carrots (Daucus carota l.) and carrot products

Although various reports pointed to 6-methoxymellein (1) as a key player imparting the bitter taste in carrots, activity-guided fractionation experiments recently gave evidence that not this isocoumarin but bisacetylenic oxylipins contribute mainly to the off-taste. Among these, (Z)-heptadeca-1,9-dien-4,6-diyn-3-ol (2), (Z)-3-acetoxy-heptadeca-1,9-dien-4,6-diyn-8-ol (3), and (Z)-heptadeca-1,9-dien-4,6-diyn-3,8-diol (falcarindiol, 4) have been successfully identified. In the present study, an analytical procedure was developed enabling an accurate quantitation of 1-4 in carrots and carrot products. To achieve this, (E)-heptadeca-1,9-dien-4,6-diyn-3,8-diol was synthesized as a suitable internal standard for the quantitative analysis of the bisacetylenes. On the basis of taste activity values, calculated as the ratio of the concentration and the human sensory threshold of a compound, a close relationship between the concentration of 4 and the intensity of the bitter off-taste in carrots, carrot puree, and carrot juice was demonstrated, thus showing that compound 4 might offer a new analytical measure for an objective evaluation of the quality of carrot products. Quantitative analysis on the intermediate products in industrial carrot processing revealed that removing the peel as well as green parts successfully decreased the concentrations in the final carrot puree by more than 50%.     

Structures, sensory activity, and dose/response functions of 2,5-diketopiperazines in roasted cocoa nibs (Theobroma cacao)

The taste compounds inducing the blood-like, metallic bitter taste sensation reported recently for a dichloromethane extract prepared from roasted cocoa nibs were identified as a series of 25 diketopiperazines by means of HPLC degustation, LC-MS/MS, and independent synthesis. Among these 25 compounds, 13 cis-configured diketopiperazines, namely, cyclo(L-IIe-L-Phe), cyclo(L-Val-L-Leu), cyclo(L-Pro-L-Pro), cyclo(L-IIe-L-Pro), cyclo(L-Val-L-Tyr), cyclo(L-Ala-L-Tyr), cyclo(L-Phe-L-Ser), cyclo(L-Ala-L-IIe), cyclo(L-Leu-L-Phe), cyclo(L-Pro-L-Val), cyclo(L-Pro-L-Thr), cyclo(L-Pro-L-Tyr), and cyclo(L-Val-L-Val) were identified for the first time in cocoa. In addition, the taste recognition thresholds for the metallic as well as the bitter taste of the diketopiperazines were determined, and after quantitative analysis by using two diastereomeric diketopiperazines as the internal standards, the sensory impact of the diketopiperazines was evaluated on the basis of their dose-over-threshold (DoT) factors calculated as the ratio of the concentration and the threshold concentration of a compound. These data revealed DoT factors above 1.0 exclusively for cis-cyclo(L-Pro-L-Val), cis-cyclo(L-Val-L-Leu), cis-cyclo(L-Ala-L-Ile), cis-cyclo(L-Ala-L-Leu), and cis-cyclo(L-Ile-L-Pro), whereas all of the other diketopiperazines were present below their individual bitter taste threshold concentrations and should therefore not contribute to the cocoa taste. Because the DoT factors do not consider the nonlinear relationship between the concentration and gustatory response of an individual compound, we, for the first time, report on the recording of dose/response functions describing the human bitter taste perception of diketopiperazines more precisely.     

Changes in the HPLC phenolic profile of virgin olive oil from young trees (Olea europaea L. Cv. Arbequina) grown under different deficit irrigation strategies

The HPLC phenolic profile of virgin olive oils obtained from young olive trees (Arbequina cv.) grown under different deficit irrigation strategies was studied. Deficit irrigation (RDI) did not affect all the phenolic compounds in the same way. Lignans, vanillic acid, vanillin, and the unknown phenolic compound named P24 increased in the oils from the most irrigated treatments. The secoiridoid derivatives and the unknown phenolic compound named P19 increased in the oils from the most stressed irrigation treatments. The period of growth where a water stress significantly affects the phenolic profile of oils was between pit hardening and the first stages of fruit growth and oil accumulation, independently of the water applied during the previous period to harvest. The phenolic profile and those parameters related to phenol content, oxidative stability, and the bitter index were significantly affected only in the most severe RDI strategies. Other strategies produced important savings in irrigation requirements and an increase in the water use efficiency without noticeably affecting the phenolic profile.     

Effect of the polyunsaturated fatty acid composition of beef muscle on the profile of aroma volatiles

The effect of n-3 polyunsaturated fatty acids (PUFAs) in beef muscle on the composition of the aroma volatiles produced during cooking was measured. The meat was obtained from groups of steers fed different supplementary fats: (i) a palm-oil-based control; (ii) bruised whole linseed, which increased muscle levels of alpha-linolenic (C18:3 n-3) and eicosapentaenoic acid (EPA, C20:5 n-3); (iii) fish oil, which increased EPA and docosahexaenoic acid (C22:6 n-3); (iv) equal quantities of linseed and fish oil. Higher levels of lipid oxidation products were found in the aroma extracts of all of the steaks with increased PUFA content, after cooking. In particular, n-alkanals, 2-alkenals, 1-alkanols, and alkylfurans were increased up to 4-fold. Most of these compounds were derived from the autoxidation of the more abundant mono- and di-unsaturated fatty acids during cooking, and such autoxidation appeared to be promoted by increased levels of PUFAs.     

Factors influencing phenolic compounds in table olives (Olea europaea)

The Mediterranean diet appears to be associated with a reduced risk of several chronic diseases including cancer and cardiovascular and Alzheimer's diseases. Olive products (mainly olive oil and table olives) are important components of the Mediterranean diet. Olives contain a range of phenolic compounds; these natural antioxidants may contribute to the prevention of these chronic conditions. Consequently, the consumption of table olives and olive oil continues to increase worldwide by health-conscious consumers. There are numerous factors that can affect the phenolics in table olives including the cultivar, degree of ripening, and, importantly, the methods used for curing and processing table olives. The predominant phenolic compound found in fresh olive is the bitter secoiridoid oleuropein. Table olive processing decreases levels of oleuropein with concomitant increases in the hydrolysis products hydroxytyrosol and tyrosol. Many of the health benefits reported for olives are thought to be associated with the levels of hydroxytyrosol. Herein the pre- and post-harvest factors influencing the phenolics in olives, debittering methods, and health benefits of phenolics in table olives are reviewed.     

Hydroxytyrosol 4-beta-D-glucoside,an important phenolic compound in olive fruits and derived products

There is increasing interest in olive polyphenols because of their biological properties as well as their contribution to the color, taste, and shelf life of olive products. However, some of these compounds remain unidentified. It has been shown that hydroxytyrosol 4-beta-D-glucoside (4-beta-D-glucosyl-3-hydroxyphenylethanol) coeluted with hydroxytyrosol [(3,4-dihydroxyphenyl)ethanol] under reversed phase conditions in the phenolic chromatograms of olive pulp, vegetation water, and pomace of olive oil processing. A method to separate this compound from hydroxytyrosol by HPLC has been developed. The concentration of this glucoside increased in olive pulp with maturation and could be the main phenolic compound in mature olives. In contrast, the presence of this compound was not detected in olive oil by using HPLC-MS. The compound must be considered both in table olives and olive oil processing because of its glucose and hydroxytyrosol contribution to these products.     

Transglycosylation of naringin by Bacillus stearothermophilusMaltogenic amylase to give glycosylated naringin.

Naringin, a bitter compound in citrus fruits, was transglycosylated by Bacillus stearothermophilus maltogenic amylase reaction with maltotriose to give a series of mono-, di-, and triglycosylnaringins. Glycosylation products of naringin were observed by TLC and HPLC. The major glycosylation product was purified by using a Sephadex LH-20 column. The sturcture was determined by using MALDI-TOF MS, methylation analysis, and (1)H and (13)C NMR. The major transglycosylation product was maltosylnaringin, in which the maltose unit was attached by an alpha-1-->6 glycosidic linkage to the D-glucose moiety of naringin. This product was 250 times more soluble in water and 10 times less bitter than naringin.     

Development of a phenol-enriched olive oil with both its own phenolic compounds and complementary phenols from thyme

Besides affecting the oil's sensorial characteristics, the presence of herbs and spices has an impact on the nutritional value of the flavored oils. The aim of the study was to develop a new product based on the phenol-enrichment of a virgin olive oil with both its own phenolic compounds (secoiridoid derivatives) plus additional complementary phenols from thyme (flavonoids). We studied the effect of the addition of phenolic extracts (olive cake and thyme) on phenolic composition, oxidative stability, antioxidant activity, and bitter sensory attribute of olive oils. Results showed that flavonoids from thyme appeared to have higher transference ratios (average 89.7%) from the phenolic extract to oil, whereas secoiridoids from olive presented lower transference ratios (average 35.3%). The bitter sensory attribute of the phenol-enriched oils diminished with an increase of the concentration of phenols from thyme, which might denote an improvement in the consumer acceptance.