Comparison of the effects of concentration, pH and anion species on astringency and sourness of organic acids

The separate effects of concentration, pH and anion species on intensity of sourness and astringency of organic acids were evaluated. Judges rated sourness and astringency intensity of lactic, malic, tartaric and citric acid solutions at three levels of constant pH varying in normality and at three levels of constant concentration varying in pH. To assess the comparative sourness and astringency of the organic acid anions of study, binary acid solutions matched in pH and titratable acidity were also rated. As pH was decreased in equinormal solutions, both sourness and astringency increased significantly (P < 0.001). By contrast, as the normality of the equi-pH solutions was increased, only sourness demonstrated significant increases (P < 0.001) while astringency remained constant or decreased slightly. At the lowest normality tested, all solutions were more astringent than sour (P < 0.05). Although lactic acid was found to be significantly more sour than citric acid (P < 0.05), no other sourness or astringency differences among the organic acid anions were noted. This study demonstrates for the first time that astringency elicited by acids is a function of pH and not concentration or anion species, and confirms that sourness is independently influenced by concentration, pH and anion species of the acid.      

Time-course of astringent sensations

Qualitative and quantitative perceptual reactions to astringentmaterials were examined for three diverse chemical substances(alum, tannic acid and tartaric acid) at several concentrationsproducing moderate to strong levels of perceived sensation.Group discussions were held to determine language appropriateto describe the sensations arising from solutions of the threecompounds and a composite ballot of six rating scales (astringency,mouth drying, puckery feeling, mouth roughing, bitterness andsourness) was developed. For both experiments, two concentrationsof each compound were rated on the six attributes for five tosix minutes, a discrete-point time-intensity scaling procedure.All ratings showed roughly exponential decays over time. Theintensity ratings for each attribute were found to depend onboth the particular astringent substance and concentration tested.The results from experiment 2 suggested that the four tactileattributes of drying, puckery feeling, roughing, and overallastringency may not be totally interchangeable and that theremay be multiple sub-qualities in the sensory reactions groupedas astringency. It is recommended that future structure-activitystudies make use of time-intensity procedures with multiplerated attributes, using 1 g/1 alum as a reference material,since it is relatively low in perceived bitterness and sourness,but produces pronounced drying, roughing, puckery/drawing sensations.     

Sensory evaluation of acids by free-choice profiling

The technique of free-choice profiling was applied in orderto characterize the sensory properties of some common organicand inorganic acids. Analysis of panelists' scores by generalizedProcrustes Analysis (GPA) provided information on the relationshipsamong samples and assessors for both the consensus and individualconfigurations. Results indicated that on a weight basis (w/vor v/v), acids differed in their flavor and taste dynamics.Acids were described differently by individual panelists. The GPA resulted in three important principal axes (PA). Thefirst PA had astringency/mouthfeel as the most important factor,while bitterness and sourness were the most important for thesecond and the third PAs, respectively. At 0.08% (w/v or v/v),the inorganic acids, hydrochloric and phosphoric, were moreastringent than sour. The bitterness of succinic (S) was intenseas was the sourness of fumaric, malic and the combinations offumaric:malic (FM), citric:malic (CM) and citric:fumaric (CF).The sensory characteristics of adipic and quinic were perceivedto be very weak at this concentration. The relationship betweenastringency and pH was more evident than was the relationshipbetween pH and sourness.     

Interactions of astringent substances

Two-component mixtures of astringent materials were rated forperceived intensity of astringent and taste attributes overtime. Components included alum (a complex salt), gallic acid(the monomeric component of hydrolyzable tannins), catechin(the monomeric component of condensed tannins) and citric acid.Mixtures of alum and gallic acid showed mixture suppression,in that the 50/50 mixture was less intense than either componentin astringency, drying, roughing and puckery/drawing sensations.Suppression was seen at concentration levels producing moderateto strong astringency but was absent or less pronounced at lowerconcentration levels. A similar pattern held for citric acid,although the suppressive effects were less pronounced. Catechinand gallic acid mixtures were additive. Sensory interactionsbetween astringent materials appears to depend on the substancesinvolved and their concentrations (or intensity levels).     

SELECTION OF AN ASTRINGENCY REFERENCE STANDARD FOR THE SENSORY EVALUATION OF BLACK TEA

Astringent and bitter sensations are characteristic sensory qualities of black tea. Three different classes of potential astringent reference standards (two concentrations each of alum and tannic acid and three fruit juices) were evaluated in this study. The perceived astringency, bitterness and sourness of each were profiled using computerized time-intensity and compared with the astringent intensity of a standardized brew of black tea. The differences in temporal profiles of potential reference standards across taste attributes were evident and intensity ratings were found to be dependent upon the stimulus and its concentration. Both concentrations of tannic acid were evaluated as the highest in perceived bitterness. For the juices, a strong sour taste was perceived in addition to astringency. It was concluded that the best reference standard for the astringency of black tea is a solution of 0.7 g/L alum as it is low in perceived bitterness and sourness.     

Astringency of Organic Acids is Related to pH

Astringency and sourness of lactic, acetic and citric acids,each adjusted to pH 3, 5 and 7, were evaluated in two experiments,one starting at equal concentrations in wt/vol before neutralizationand the second starting at equal molarity. Astringency and sournessdecreased with increasing pH. However, acids were differentiallysour at equal pH, consistent with previous findings. In contrast,the tactile attributes associated with astringency (drying,roughing of oral tissues and puckery/tightening sensations)were similar across acids; pH was the major influence on astringency.Strong dependence on pH suggests that astringency of these acidsis a direct result of their acidic properties, and not solelydue to the hydrogen bonding mechanisms previously suggestedas an explanation of astringency in tannin interactions withsalivary proteins. Chem. Senses 21: 397–403, 1996.     

COMPARISON OF SOURNESS OF ORGANIC ACID ANIONS AT EQUAL pH AND EQUAL TITRATABLE ACIDITY

The sourness of six organic acids was compared by pair tests in binary acid solutions of equal pH and equal potential hydrogen ion concentration. Monoprotic lactic acid was more sour than three of the four acids against which it was tasted, while triprotic citric acid was less sour than the four other acids against which it was compared. Of the diprotic acid pairs which were evaluated, only one significant difference in sourness was observed; succinic acid was more sour than malic acid. No relationship between buffer capacity or hydrophobicity and intensity of sourness was observed.     

EVALUATION OF BITTERNESS AND ASTRINGENCY OF (+)-CATECHIN AND (-)-EPICATECHIN IN RED WINE AND IN MODEL SOLUTION

Two stereoisomeric phenolic compounds, (+)-catechin and (-)-epicatechin, were rated for perceived intensity of oral astringency and bitterness by trained judges using the scalar method. Mouth drying and mouth roughening were also assessed, since they are often associated with astringency. Amounts of 375, 750 and 1500 mg/L of each compound were tasted in red wine, and in a model system, similar in composition to a dry table wine. Preliminary tests showed that these concentrations were above the threshold level but within the range found in wine. A control sample (model solution or wine without the addition of the above phenolic compounds) was also evaluated. The results showed that the two compounds were both bitter and astringent. The high (-)-epicatechin concentration was significantly more bitter and astringent than the equal concentration of (+)-catechin in the model solution. Mouth drying and roughening ratings showed a similar increasing pattern with the ratings of astringency particularly at the higher concentrations. However, these attributes were rated differently from astringency suggesting that although they contribute to astringency, they are not subsumed by it.     

INTERACTION OF ASTRINGENCY AND TASTE CHARACTERISTICS1

The perception of astringency and basic taste in mixtures and their interaction effects were investigated by two procedures. In Experiment 1, focused and nonfocused testing procedures were compared using mixtures of low and high concentrations of alum and basic taste solutions. Both procedures yielded taste and astringency intensities that were modality‐dependent. Nonfocused testing was used in Experiment 2 to investigate the interactions of astringent phenolic (tannic acid) and nonphenolic (alum) compounds with each basic taste. Sweetness of sucrose increased with increased concentration with or without alum or tannin present. Changes in salty, bitter, and sour taste intensities were modality‐dependent. Astringency either remained unchanged or decreased with the addition of sucrose, sodium chloride, citric acid, or caffeine depending upon the taste concentration. Bitterness of tannin and alum at high concentrations was suppressed by the addition of sucrose, sodium chloride, or citric acid; sourness also decreased in the presence of sucrose or sodium chloride as well as a high level of caffeine.     

紫色小白菜有机酸的提取优化及UPLC定量分析

为建立一种紫色小白菜中精准的有机酸提取及定性定量分析方法。本研究在单因素试验的基础上,采用Box-Behnken的中心组合试验设计原理,设计响应面试验优化紫色小白菜有机酸的提取工艺。结果表明,紫色小白菜有机酸提取的最优工艺参数为:乙醇浓度73%,料液比1∶21,超声时间11 min,超声温度70℃。通过超高效液相色谱法(ultra performance liquid chromatography,UPLC)对紫色小白菜叶片和叶柄部位有机酸进行定性定量分析,检测出苹果酸、柠檬酸、丙二酸、琥珀酸和酒石酸,其中苹果酸含量最高,分别为15.968、5.019 mg/g;其次为柠檬酸,分别为9.293、1.385 mg/g。定性定量结果表明,紫色小白菜叶片及叶柄部位含有丰富有机酸类物质,叶片部位苹果酸、柠檬酸、丙二酸、酒石酸含量均高于叶柄部位,而琥珀酸含量较低。     

Gustatory Responsiveness to food-associated acids in the spider monkey (Ateles geoffroyi)

The gustatory responsiveness of four adult spider monkeys to five food-associated acids was assessed in two-bottle preference tests of brief duration (3 min). The animals were given the choice between a 30 mM sucrose solution and defined concentrations of citric acid, ascorbic acid, malic acid, acetic acid, or tannic acid dissolved in a 30 mM sucrose solution. With this procedure,Ateles geoffroyi was found to significantly discriminate concentrations as low as 5 mM ascorbic acid, citric acid, and acetic acid, 10 mM malic acid, and 0.1 mM tannic acid from the alternative stimulus. With the latter two substances, the monkeys rejected all suprathreshold concentrations tested, whereas with the former three substances, the animals showed an inverted U-shaped function of preference, i.e. they rejected high concentrations, but significantly preferred low but detectable concentrations of these acidic tastants over the alternative sweet stimulus. The results showed (1) the spider monkey to respond to the same range of acid concentrations as other nonhuman primate species; (2) thatAteles geoffroyi, is able to detect food-associated acids at concentrations well below those present in most fruits; and (3) that unlike most other primate species tested so far, spider monkeys do not generally reject acidic tastants but show a substanceand concentration-dependent change in responsiveness that may range from rejection to preference. The results support the assumptions that spider monkeys may use sourness and/or astringency of food-associated acids as a criterion for food selection, and that the gustatory responsiveness ofAteles geoffroyi to acidic tastants might reflect an evolutionary adaptation to frugivory.     

Perceptual Properties of Benzoic Acid Derivatives

Sensory properties of equimolar concentrations of benzoic acidderivatives were examined using time-intensity procedures. Significantdifferences in maximum intensities (P < 0.005) were foundfor astringency, bitterness, prickling, sourness and sweetness.Although these compounds differed only in the number and positionof the hydroxy groups, they exhibited quite different profiles.Gentisic acid had the highest sourness and bitterness maximumintensity, salicylic and gentisic acids were highest in astringency,and m-hydroxybenzoic acid was the sweetest sample. Benzoic acidhad the highest intensity of prickling feeling which lasted20 s longer than salicylic acid and 40 s longer than the othersamples which elicited lowest intensity of prickling sensation.Chem. Senses 20: 393–400, 1995.     

Turbidity as a measure of salivary protein reactions with astringent substances

Binding of tannins to proline-rich proteins has been proposed as an initial step in the development of astringent sensations. In beer and fruit juices, formation of tannin-protein complexes leads to the well-known effect of haze development or turbidity. Two experiments examined the development of turbidity in human saliva when mixed with tannins as a potential in vitro correlate of astringent sensations. In the first study, haze was measured in filtered human saliva mixed with a range of tannic acid concentrations known to produce supra-threshold psychophysical responses. The second study examined relationships among individual differences in haze development and the magnitude of astringency ratings. Mostly negative correlations were found, consistent with the notion that high levels of salivary proteins protect oral tissues from the drying effects of tannic acid.     

In vitro efficiency of combined acid-heat treatments for protecting sunflower meal proteins against ruminal degradation

Efficacy of combined acid-heat treatments to protect crude protein (CP) against ruminal degradation has not been extensively researched. Four in vitro trials (Daisy technology) with orthophosphoric and malic acids were performed to examine effects on protection of sunflower meal protein. In Trial 1, effects of the solution volume for adding two doses of orthophosphoric acid (0.4 and 1.2 eq/kg sunflower meal) were tested using five dilution volumes (80, 160, 240, 320 and 400 ml/kg of feed) for each acid dose. Samples were heated at 60°C. The quantity of CP that remained undegraded after 20 h in vitro (IVUCP) increased with the amount of acid added (P = 0.01). Increasing the dilution volume also tended (P = 0.065) to increase IVUCP. Therefore, a dilution volume of 400 ml/kg was employed in all further trials. In Trial 2, treatments with solutions of orthophosphoric and malic acids (1.2, 2.4, 3.6 and 4.8 eq/kg) and 60°C of drying temperature were used. Increased CP protection with increased acid doses was described. In this and further trials, higher protective effects of malic acid than orthophosphoric acid were also shown. In Trial 3, the effects of both these acids, four acid concentrations (0.6, 1.2, 1.8 and 2.4 eq/kg) and three levels of heat treatment required for drying the samples (100, 150 and 200°C for 60, 30 and 20 min, respectively) were evaluated. An interaction acid type × concentration × temperature was shown. In addition, interactions concentration × temperature was shown in each acid. With heat treatments of 100°C to 150°C, benefits were not obtained after increasing the acid dose over 0.8 eq/kg. The increase of the heat treatments to 200°C and the acid dose up to 1.2 eq/kg increased protection, but to exceed this dose did not improve protection. In Trial 4, available lysine, CP solubility in McDougall buffer and IVUCP were compared after treatment with water or solutions (0.8 eq/kg) of orthophosphoric or malic acids using 100°C and 150°C heat treatments as described in Trial 3. No effects on available lysine were observed. Both CP solubility and IVUCP were reduced to a greater degree by acids than by water treatment. The results showed a high effectiveness of acid-heat treatments. Levels of protection are dependent on the acid dose, its dilution, acid type and drying conditions.     

Influence of pH,malic acid and glucose concentrations on malic acid consumption by Saccharomyces cerevisiae

Malic acid consumption by Saccharomyces cerevisiae was studied in a synthetic medium. The extent of malic acid degradation is affected by its initial concentration, the extent and the rate of deacidification increased with initial malate concentration up to 10 g/l. For malic acid consumption, an optimal pH range of 3–3.5 was found, confirming that non-dissociated organic acids enter S. cerevisiae cells by simple diffusion. A full factorial design has been employed to describe a statistical model of the effect of sugar and malic acid on the quantity of malate degraded (g/l) by a given amount of biomass (g/l). The results indicated that the initial malic acid concentration is very important for the ratio of malate consumption to quantity of biomass. The yeast was found to be most efficient at higher levels of malate.     

Esterification Rates of Main Organic Acids in Wines

The esterification rates (ratio of the concentration of an acid in the neutral ethyl ester form to total concentration of the acid) of main organic acids in wines were determined to study the extent of ethyl ester formation of organic acids. The esterification rates ranged from zero to 24.6%. The averaged values of table wines were from 6 to 16% for acetic and lactic acid, from 0.3 to 3.6% for succinic and malic acid, and from zero to 0.1% for tartaric acid. Sherries had higher esterification rates, about 1.6 to 6 times larger, than table wines. It was found that storage time and temperature influence the formation of ethyl esters, and it was suggested that the aging period required for the ester equilibrium is about one year for acetic and lactic acid, and more than two years for succinic, malic and tartaric acid. The possibility and the procedure to control wine quality during the aging process were discussed.     

Accumulation and transport of nickel in relation to organic acids in ryegrass and maize grown with different nickel levels

Difference in Ni tolerance/accumulation in plant genotypes might be used to identify or develop plants for remediation of high Ni soils. Ryegrass was shown to be more sensitive to Ni toxicity and accumulated much more Ni in shoots than maize. The objectives of this study were to examine the relationship of organic acids to Ni accumulation and xylem transport of Ni in ryegrass (Lolium perenne L.) and maize (Zea mays L.). The results showed that accumulation of Ni in shoots was 5 to 7 fold higher in ryegrass than in maize grown at 20 to 80 µM Ni, whereas Ni concentration in ryegrass roots was only 1 to 2 fold higher at 0.1 to 40 µM Ni and 1.5-fold lower at 80 µM Ni than that of maize roots. Xylem transport rates of Ni increased with increasing Ni supply for both species, and were about 2 to 7 times higher in ryegrass than in maize. Shoot concentrations of citric, malic, oxalic and cis-aconitic acids increased at Ni levels above 20 µM, and were about 2 to 6 times higher in ryegrass than in maize. Whereas, maize roots accumulated greater amount of malic, oxalic, and cis-aconitic acids than ryegrass roots, especially at Ni levels of 40-80 µM. The rate of Ni exudation by roots in the two species was significantly correlated with root Ni concentrations. It could be concluded that high Ni accumulation in shoots was closely related to high xylem transport rates of Ni and that the accumulation of organic acids, citric and malic acid in particular. A high root exudate rate of Ni and the enhanced accumulation of organic acids, malic acid in particular, in roots might be among the important factors which are associated with the tolerance of crops to toxic Ni levels.     

Aluminum resistance in two cultivars of Zea mays L.: Root exudation of organic acids and influence of phosphorus nutrition

Root exudation of organic acids as Al-chelating compounds and P nutrition have been suggested to play a major role in Al-resistance in higher plants. Effects of Al exposure on maize plant growth, and organic acid root content and root exudation under various levels of P nutrition were examined. Sikuani, a Colombian maize cultivar tolerant to acid soils with high Al saturation, and Corso, a Swiss cultivar, were grown in sterile hydroponic conditions for 21 days. Al-caused inhibition of root growth was lower in Sikuani than in Corso. Al effect on plant growth was decreased with increasing P content in roots. Al content in roots increased with increasing P content and was higher in Sikuani than in Corso. When exposed to Al, the contents in root apices as well as the root exudation of citric and malic acids in Corso and citric, malic and succinic acids in Sikuani increased, and were higher in Sikuani than in Corso. Increased PEP carboxylase (PEPC) activity in root apices after Al exposure partially explained the variations of organic acid content in the roots. These Al-induced changes in PEPC activity, organic acid content and exudation were reduced in plants supplied with higher P concentrations during the 21 days prior to treatment. Increased secretion of organic acids after exposure to Al appeared to be specific to Al and was not totally explained by increased root content in organic acids.     

Diurnal and temporal changes in the chemical profile of xylem exudate from Vitis rotundifolia

Positive root pressure in Vitis rotundifolia Michx. cv. Noble was employed to quantify diurnal and temporal changes in the chemical profile of xylem exudate. Xylem fluid osmolarity (7.2 to 16.8 m M ), water flux (8.2 to 18.5 ml h⁻¹) and solute flux (0.7 to 2.2 mmol h⁻¹) from a cut spur exhibited a diurnal pattern with maxima during midday and minima at night. Total osmolarity was similar to the sum of all organic and inorganic entitites quantified, indicating that the major solutes have been identified. Total amino acid and organic acid concentration were about equal (2 to 7 m M ), and sugars accounted for a minor fraction of the total profile (<0.2 m M ). Glutamine represented ca 80% of the organic N and 70% of the total N transported in the xylem fluid. A circadian rhythm in water flux and net flux of most organic and inorganic entities was observed with maxima during midday and minima at night. The increase in xylem fluid osmolarity occurring during midday was primarily a consequence of increased organic acid (oxalic, citric, tartaric, malic and succinic acids) and ion (NH₄⁺, No₃⁻, P and Ca) concentration. A diurnal cycle in amino acid concentration was less clear. The concentration of individual organic and inorganic entities varied asynchronously with time. Xylem solute was comprised of 80% organic and 20% inorganic components when collected 5 min to 2 h after the commencement of bleeding, but the ratio of organic to inorganic components fell to about 50% after 7 days.     

Chemometric methods for simultaneous quantification of lactic,malic and fumaric acids

Lactic, fumaric and malic acids are commonly used in food and pharmaceutical industries. During microbial production of these compounds, it is important to determine their concentrations in the fermentation broth with a rapid and sensitive method. Spectrophotometry is commonly used. However, UV‐spectral overlap between these organic acids makes it difficult to determine each of them individually from the mixture. In order to overcome this problem, statistical methods, namely principal component regression (PCR) and partial least squares‐1 methods, were tested and compared with conventional HPLC techniques. The absorbance data matrix was obtained by measuring the absorbances of 21 ternary mixtures of lactic, fumaric and malic acids in a wavelength range of 210–260 nm. Calibration and validation were performed by using the data obtained in a mixture of these organic acids. The prediction abilities of the methods were tested by applying them to fermentation broths. The precision of the PCR method was better than that of the partial least squares‐1 method. In the PCR method, the correlation coefficients between actual and predicted concentrations of the organic acids were calculated as 0.970 for lactic acid and 0.996 for fumaric acid in fermentation broths. The concentration of malic acid was not detected due to its low concentration in samples. These results show that the PCR method can be applied for simultaneous determination of lactic, fumaric and malic acids in fermentation broths.