Stability of black carrot anthocyanins in various fruit juices and nectars

Fruit juices (apple, grape, orange, grapefruit, tangerine and lemon) and nectars (apricot, peach and pineapple) were coloured with black carrot juice concentrate and stability of black carrot anthocyanins in these matrices was studied during heating at 70–90 °C and storage at 4–37 °C. Anthocyanin degradation, in all coloured juices and nectars, followed first-order reaction kinetics. During heating, black carrot anthocyanins in apple and grape juices showed higher stability than those in citrus juices at 70 and 80 °C. High stability was also obtained for the anthocyanins in peach and apricot nectars at these temperatures. Black carrot anthocyanins were the least stable in orange juice during both heating and storage. During storage, degradation of anthocyanins was very fast at 37 °C, especially in pineapple nectar. Refrigerated storage (4 °C) markedly increased the stability in all samples. Activation energies for the degradation of black carrot anthocyanins in coloured juices and nectars ranged from 42.1 to 75.8 kJ mol⁻¹ at 70–90 °C and 65.9–94.7 kJ mol⁻¹ at 4–37 °C.     

The effect of pre-treatment on the anthocyanin and flavonol content of black currant juice (Ribes nigrum L.) in concentration by reverse osmosis

Reverse osmosis process for the concentration of black currant juice was carried using AFC-99 tubular membrane at 30 °C and 45 bar. The contents of selected flavonols and anthocyanins were analyzed after centrifugation; enzyme treatment by Panzym Super E and by Rohapect berry followed by centrifugation; and ultrafiltration black currant juices and juice concentrates. The total soluble solid (TSS) content of the juices increased from the initial 17.6–17.9 °Brix to 24–24.8 °Brix in the case of the centrifuged juice in the concentration process. Similarly, it increased from 14.5–15.5 °Brix to 23.1–23.4 °Brix for the Panzym Super E treated juice, and from 16.1–16.9 °Brix to 22.5–23.1 °Brix for the Rohapect berry treated black currant juices. The ultrafiltered juice had the lowest initial TSS content between 14.1 and 14.9 °Brix and it increased to 22.1–23.1 °Brix. The average permeate fluxes during the concentration process were 7.3 L m⁻² h⁻¹ for the centrifuged juice, 11.9 L m⁻² h⁻¹ for the Panzym Super E treated juice, 9.2 and 13.1 L m⁻² h⁻¹ for the Rohapect berry treated and ultrafiltered juice, respectively. Analysis indicated that the enzymatic treatment resulted in the increase of anthocyanin and flavonol content of the juices. The centrifugation process decreased the amount of anthocyanins and flavonols to some extent. The juice clarified by ultrafiltration had significantly lower concentrations of anthocyanins and flavonols, while the juices treated by Panzym Super E had the highest levels of these flavonoids. This study recommends enzymatic pre-treatment by Panzym Super E, since it improves the permeate flux in reverse osmosis during the concentration process, and results in a juice concentrates highest in anthocyanins and flavonols.     

Effects of temperature,solid content and pH on the stability of black carrot anthocyanins

Anthocyanin stability of black carrots was studied at various solid contents (11, 30, 45 and 64° Brix) and pHs (4.3 and 6.0) during both heating, at 70–90 °C, and storage at 4–37 °C. Monomeric anthocyanin degradation fitted a first-order reaction model. Degradation of monomeric anthocyanins increased with increasing solid content during heating, while it decreased during storage. For example, at pH 4.3, half-life periods for anthocyanins at 30, 45 and 64° Brix were, respectively, 8.4, 6.9 and 5.2 h during heating at 80 °C and 18.7, 30.8 and 35.9 weeks during storage at 20 °C. At 30–64° Brix, increasing pH from 4.3 to 6.0 enhanced the degradation of anthocyanins during heating. The effect of pH on thermal stability of anthocyanins was also studied at six different pHs (2.5–7.0) in citrate-phosphate buffer solutions and significant decrease in anthocyanin stability was observed at pHs above 5.0. Higher activation energies (E_a) were obtained during heating than during storage with increasing solid contents. At 30–64° Brix, E_a values ranged from 68.8 to 95.1 kJ mol⁻¹ during heating and from 62.1 to 86.2 kJ mol⁻¹ during storage. Q₁₀ values at 20–37 °C were as high as 3.1 at 45° Brix and 3.6 at 64° Brix.     

Thermal inactivation of lactoperoxidase in goat,sheep and bovine milk – A comparative kinetic and thermodynamic study

Using isothermal heating, inactivation of lactoperoxidase (LPO) in goat, sheep and cow milk was studied in the temperature range of 70–77 °C. Kinetic and thermodynamics studies were carried out at different time–temperature combination in order to evaluate the suitability of LPO as marker for the heat-treatment of milk and dairy products from different species. The thermal inactivation of LPO followed the first-order kinetics. D- and k-values decreased and increased, respectively with increasing temperature, indicating a more rapid LPO inactivation at higher temperatures. The influence of temperature on the inactivation rate constant was quantified using the Arrhenius and thermal death time models. The corresponding z-values were 3.38 ± 0.013, 4.11 ± 0.24 and 3.58 ± 0.004 °C in goat, sheep and cow milk, respectively. Activation energy values varied between milk species with 678.96 ± 21.43 kJ mol⁻¹ in goat milk, 560.87 ± 28.18 kJ mol⁻¹ in sheep milk and 641.56 ± 13.12 kJ mol⁻¹ in cow milk, respectively.     

Changes in anthocyanins in arils of chitosan-coated pomegranate (Punica granatum L. cv. Rabbab-e-Neyriz) fruit during cold storage

Edible coatings as chitosan treatments (0%, 1% and 2%) were applied to ‘Rabbab-e-Neyriz’ pomegranate (Punica granatum L.). The effect of chitosan coating on individual anthocyanins and colour parameters of the juice during storage at 2 °C or 5 °C was examined. Six predominant anthocyanins were identified in the juice, with up to 935 mg/L total anthocyanins at the time of harvest. Cyanidin 3,5-diglucoside (402 mg/L) was the major pigment. The total anthocyanin content and chroma decreased with storage time in all applied treatments, although lightness and hue angle increased. These changes were reduced with chitosan treatments and at lower storage temperature (2 °C as compared to 5 °C). Based on the obtained results, the diglucoside anthocyanins were more stable than the monoglucosides. Chitosan coating followed by cold storage delayed anthocyanin degradation and prevented colour deterioration in the pomegranate arils.     

Aqueous extraction of anthocyanins from Hibiscus sabdariffa: Experimental kinetics and modeling

Solid-liquid extraction of anthocyanins from calyces of Hibiscus sabdariffa L. was studied to evaluate the influence of the operating parameters. Solid-to-solvent ratio and particle size had the main impact on anthocyanin extraction efficiency. Maximum yield of anthocyanins (88%) was obtained at 25 °C with the highest solid-to-solvent ratio (1/25). The decrease in the particle size of the calyces from 2 cm to 150 μm drastically reduced the extraction time. The increase of temperature reduced the extraction time by increasing the diffusion coefficient (3.9 × 10⁻¹¹-1.35 × 10⁻¹⁰ m² s⁻¹ between 25 and 90 °C) but did not modify the extraction yield. A simple extraction model that integrated anthocyanin thermo-degradation kinetic was proposed. A good agreement between the predicted results of the models and experimental data was demonstrated. From a solid-to-solvent ratio of 1/5, an extraction yield of 63% and an anthocyanin concentration of 0.3 g L⁻¹ could be obtained in less than 10 min.     

High hydrostatic pressure protection of a pectinase cocktail against thermal inactivation

Pectinase cocktails, containing pectinases, hemicellulases, and cellulases are used in the production of commercial apple juice to reduce juice viscosity, increase yield, and to clarify the final product. The kinetics of inactivation of a commercial pectinase formulation was studied at 0.1–400 MPa and 55.0–85.0 °C. High hydrostatic pressure slowed the rate of inactivation of the pectinase cocktail treated at inactivating temperature conditions by up to 19-fold at 77.0 °C, 350 MPa compared to inactivation at atmospheric pressure at the same temperature. Apparent activation energies of enzyme inactivation at 200–400 MPa were lower (107.3–154.4 kJ mol⁻¹) than at 0.1 MPa (195.6 kJ mol⁻¹).     

Chemical stability of açai fruit (Euterpe oleracea Mart.) anthocyanins as influenced by naturally occurring and externally added polyphenolic cofactors in model systems

The influence of different classes of naturally occurring and externally added polyphenolic cofactors on the phytochemical and colour stability of anthocyanins in açai fruit (Euterpe oleracea) was investigated. Model systems were based on anthocyanin isolates from açai fruit, rich in cyanidin-3-rutinoside (311 ± 27 mg/l) and cyanidin-3-glucoside (208 ± 18 mg/l), and isolated groups of naturally occurring polyphenolic cofactors in açai fruit (phenolic acids, procyanidins, and flavone-C-glycosides, each adjusted to ∼50 mg/l). Anthocyanin degradation kinetics were assessed as a function of pH (3.0, 3.5, and 4.0) and storage temperature (5, 20 and 30 °C). During storage, anthocyanins experienced pH and temperature-dependent losses, and the half life cyanidin-3-rutinoside (t_1/2 = 2.67–210 days) was consistently longer than cyanidin-3-glucoside (t_1/2 = 1.13–144 days). The presence of flavone-C-glycosides induced significant hyperchromic shifts and enhanced anthocyanin stability at all pH and temperature combinations, while no significant effects were attributed to the presence of phenolic acids or procyanidins. Additional models using externally added cofactors from rooibos tea, also rich in flavone-C-glycosides, resulted in up to 45.5% higher anthocyanin colour and up to 40.7% increased anthocyanin stability compared to uncopigmented anthocyanin isolates and had similar copigmentation effects to a commercial rosemary-based colour enhancer. Results suggest flavone-C-glycosides offer potential for their use as colour enhancers and stabilizing agents in products rich in cyanidin glycosides, particularly açai fruit-containing foods, juice blends, and beverages.     

Optimisation of the aqueous extraction conditions of phenols from meadowsweet (Filipendula ulmaria L.) for incorporation into beverages

Meadowsweet was extracted in water at a range of temperatures (60–100 °C), and the total phenols, tannins, quercetin, salicylic acid content and colour were analysed. The extraction of total phenols followed pseudo first-order kinetics, the rate constant (k) increased from 0.09 ± 0.02 min⁻¹ to 0.44 ± 0.09 min⁻¹, as the temperature increased from 60 to 100 °C. An increase in temperature from 60 to 100 °C increased the concentration of total phenols extracted from 39 ± 2 to 63 ± 3 mg g⁻¹ gallic acid equivalents, although it did not significantly affect the proportion of tannin and non-tannin fractions. The extraction of quercetin and salicyclic acid from meadowsweet also followed pseudo first-order kinetics, the rate constant of both compounds increasing with an increase in temperature up until 90 °C. Therefore, the aqueous extraction of meadowsweet at temperatures at or above 90 °C for 15 min yields extracts high in phenols, which may be added to beverages.     

Thermal degradation kinetics of anthocyanins and visual colour of Urmu mulberry (Morus nigra L.)

Urmu mulberry (Morus nigra L.) juice was concentrated from 15.02 to 45.20 °Brix by rotary vacuum evaporator at 40 °C. The objectives of this study were to determine the titratable acidity, soluble solid content, antioxidant capacity, total monomeric anthocyanins and total phenolic matter in prepared concentrate, to investigate the thermal degradation kinetics of anthocyanins and Hunter colour parameters (L^∗, a^∗, b^∗) and total colour difference (TCD^∗) and to develop a relationship between visual colour and anthocyanin during thermal processing at 60, 70 and 80 °C. Monomeric anthocyanin degradation showed a first order reaction kinetics. The zero order, first order and a combined kinetics model were applied to the changes in Hunter colour parameters (L^∗, a^∗ and b^∗) and total colour difference (TCD^∗). All colour parameters followed an apparent combined kinetics model. The degradation of anthocyanins showed positive correlation with a^∗, b^∗ and L^∗ and negative correlation with TCD^∗.     

Kinetics of ascorbic acid degradation in fruit-based infant foods during storage

The kinetics of ascorbic acid (AA) degradation in a fruit-based beikost product added with AA were determined after storage at 4, 25, 37 and 50 °C during 4, 8, 12, 16 and 32 weeks in plastic polypropylene/ethylene–vinyl alcohol vacuum packaging. It was confirmed that AA degradation followed an Arrhenius first-order kinetics, with an activation energy of 20.11 ± 0.33 kcal mol⁻¹. No AA losses at 4 °C were recorded during the entire storage period. In contrast, a time- and temperature-dependent decrease (p < 0.05) in AA was observed at the other tested temperatures – the degradation rate decreasing from 50 °C to 25 °C, as expected. AA percentage retention at the end of storage ranged between 6.4% (50 °C/16 weeks) and 100.9% (4 °C/32 weeks).     

Kinetic study on the thermal and pressure degradation of anthocyanins in strawberries

The degradation of anthocyanins (pelargonidin-3-glucoside) in a strawberry paste during high-temperature/high-pressure treatments was investigated over a temperature range of 80–130 °C and a pressure range of 200–700 MPa, compared to 0.1 MPa. A first-order kinetic model fitted well to all data. At constant pressure, anthocyanin concentration decreased as a function of time and the degradation was accelerated at higher temperatures. At constant temperature, anthocyanins were more rapidly degraded as the pressure increased, but the effect of increasing pressure was smaller than the effect of increasing temperature. Temperature dependence of the degradation rate constants, described by the Arrhenius equation, was higher at atmospheric pressure than at elevated pressures, where all activation energies were comparable. Activation volumes, estimated by the Eyring equation, demonstrated a small pressure dependence of the reaction rate constants. Finally, a model to describe the combined temperature–pressure dependence of the degradation rate constants was proposed.     

Kinetics of formation of acrylamide and Schiff base intermediates from asparagine and glucose

From the concentration of glucose and asparagine as reactants and of acrylamide as product each determined by LC–MS during reaction in an acetonitrile/water (68:32) model system at pH 7.6 (0.04 M phosphate buffer) and from the relative concentration of the Schiff base intermediate, the decarboxylated Schiff base intermediate, the Amadori product and aminopropionamide determined in the same reaction mixtures at 120 °C, 140 °C, 160 °C and 180 °C for up to 16 min, the energy of activation for formation of the Schiff base intermediate was found to have the value 50 ± 2 kJ mol⁻¹, while the apparent activation energy for formation of acrylamide was 64.4 ± 0.6 kJ mol⁻¹, for formation of the decarboxylated Schiff base intermediate 92 ± 2 kJ mol⁻¹, and for formation of the Amadori compound 59 ± 4 kJ mol⁻¹, respectively. At high temperature conditions, formation of the Schiff base is accordingly rate determining, while at lower temperatures, decarboxylation becomes rate determining. Aminopropionamide was only detected at reaction times at which acrylamide formation already is significant in favor of, a reaction path including direct formation of acrylamide from the decarboxylated Schiff base, rather than including dissociation of ammonia from aminopropionamide.     

Thermodynamic analysis of the thermal stability of sulphonamides in milk using liquid chromatography tandem mass spectrometry detection

The present study investigates the kinetics of the degradation of eight sulphonamides in skimmed milk when heated at 60, 70, 80, 90 and 100 °C using an LC–MS/MS methodology. To determine the thermal stability of these compounds, the first-order kinetic model was applied and the activation energies, half-lives and degradation percentages were calculated. Application of kinetic equations to the different heat treatments used in dairy processing indicates that sulphonamides are very stable during pasteurisation (63 °C; 30 min and 72 °C; 15 s) as well as UHT sterilisation (140 °C; 4 s). In contrast, the calculations performed with the kinetic model estimated losses in concentrations between 6.5% (sulfadimethoxine) and 85.1% (sulfamethazine) for the sterilisation at 120 °C for 20 min. The existence of thermodynamic compensation was also tested for sulphonamide degradation. Results show that enthalpy and entropy values displayed a good linear relationship, and thermodynamically we can establish that the thermal degradation of sulphonamides in skimmed milk exhibits enthalpy–entropy compensation.     

Kinetics of quality changes of pumpkin (Curcurbita maxima L.) stored under isothermal and non-isothermal frozen conditions

The effects of freezing process and frozen storage at isothermal (−7, −15 and −25 °C) and non-isothermal (accelerated life testing with step-stress methodology; temperature range from −30 to −5 °C) conditions on pumpkin quality were investigated. Storage temperature conditions were selected to embrace the limits practiced in the cold chain. Quality changes, such as texture, colour CIE Lab and vitamin C (ascorbic acid) content, were evaluated for both frozen storage regimes. The freezing process (that included a pre-blanching step) and subsequent frozen storage had significant impacts on all quality parameters analysed.A fractional conversion kinetic model was adequate in colour, texture and vitamin C data fits. The storage temperature effect was successfully described by the Arrhenius law.This study shows that non-isothermal frozen storage has a marked effect on pumpkin quality.     

Weight loss of frozen bread dough under isothermal and fluctuating temperature storage conditions

Evaporative weight loss from food leads to both loss of saleable weight and quality deterioration so it need to be minimized. The effect of isothermal and fluctuating conditions on frozen dough weight loss was measured and compared with kinetic, physical and artificial neural network (ANN) models. Frozen dough samples were regularly weighed during storage for up to 112 days in loose-fitting plastic bags. The storage temperatures were in the range of −8 to −25 °C with fluctuations of ±0.1 °C (isothermal), ±1, ±3 or ±5 °C about the mean. For each combination of temperature and fluctuation amplitude, the rate of dough weight loss was constant. The rate of weight loss at constant temperature was nearly proportional to water vapour pressure consistent with standard theories for evaporative weight loss from packaged foods but was also accurately fitted by Arrhenius kinetics. Weight loss increased with amplitude of temperature fluctuations. The increase could not be fully explained by either the physic model based on water vapour pressure differences or the kinetic model alone. An ANN model with six neurons in the input layer, six neurons in hidden layers and one neuron in the output layer, achieved a good fit between experimental and predicted data for all trials. However, the ANN model may not be accurate for product, packaging and storage systems different to that studied.     

Caffeic acid copigmentation of anthocyanins from Cabernet Sauvignon grape extracts in model systems

Caffeic copigmentation of anthocyanins from Cabernet Sauvignon grape extracts in model system and yoghurt model system was investigated, as well as the influence of copigmentation on the stability of these pigments. In the model system, the dependence of anthocyanin stability on added caffeic acid was evaluated at temperatures (4 ± 1 °C and 29 ± 3 °C) and in the presence or absence of light, at two pH values: 3.0 and 4.0; in the yoghurt model system, the stability of the anthocyanins was evaluated at 4 ± 1 °C in the dark. The half-life and percentage of color retention of the anthocyanins in all treatments was calculated. The spectrophotometric results (Δλ, ΔA) revealed that interaction occurred between the crude extract of anthocyanins and caffeic acid suggesting copigmentation. The addition of caffeic acid (1:1 w/v) significantly increased (p < 0.05) the stability of anthocyanins in both model and yoghurt systems. In the model system the temperature and presence of light significantly influenced the stability of anthocyanins (p < 0.05), where the highest values for half-life were obtained for anthocyanins with caffeic acid at pH 3.0, stored in the dark at a temperature of 4 ± 1 °C (6.930 h). In the yoghurt system the caffeic acid increased the half-life time of anthocyanins to 6673 h.     

Anthocyanin stability studies in Tibouchina semidecandra L.

The effects of pH, storage period, temperature, light and dark conditions on the stability of anthocyanins extracted from Tibouchina semidecandra flowers of different developmental stages was evaluated. Fully formed but unopened flower bud had the highest amount of total anthocyanin extracted from fresh petals. The anthocyanin contents for all flower developmental stages were stable at pH 0.5–3.0 but the colour of the extracts faded at higher pH values. Degradation percentages of total anthocyanins in the extracts kept at 25 °C were 7–20% lower than that maintained at 31 °C. Extracts stored in darkness at 25 °C maintained their purple colour for 26 days while light exposure reduced it to an average of 10 days. The study shows that suitable storage condition for coloured anthocyanin pigments in extracted form is in acidic conditions in the dark. This implies the potential usage of coloured anthocyanins as natural food colourants and shelf life indicator for acidic foods.     

Anthocyanin and glucosinolate occurrences in the roots of Chinese red radish (Raphanus sativus L.), and their stability to heat and pH

Roots of three unique Chinese radish cultivars were evaluated as potential sources for anthocyanin-type colourants or value-added products. These cultivars showed high variation in anthocyanins (63.77–160.74 mg/100 g FW). Seventeen pigments were tentatively identified by mass spectroscopy as pelargonidin-3-sophoroside-5-glucoside derivatives with multiple acylation of hydroxycinnamic acids. A bright colour (CIELab) of radish anthocyanins has been shown at a wide pH range, comparably stable at pH < 4.2. Those anthocyanins also showed a remarkable thermal stability, following a zero-order kinetics at pH 2.5 with half-lives of 14.5 or 8.7 h at 90 or 100 °C, respectively. Additionally, those cultivars varied in glucosinolate contents (59.69–163.91 mg/100 g FW), whereas their degradation was sensitive to pH and followed a first-order kinetics at pH 5.8 with half-lives of 11.44 or 7.05 h at 90 or100 °C, respectively. However, the stable pH ranges for anthocyanins and glucosinolates were different: pH < 4.2 and pH > 3.6, respectively. In a radish juice model (pH 5.8/2.5), thermal degradation of anthocyanins or glucosinolates was associated closely with media pH values. In conclusion, cultivar selection, and thermal and pH conditions during processing or storage should be taken into account for quality, stability, and health benefits of radish derived natural colourants or nutraceutical products.     

Degradation kinetics of anthocyanins in acerola pulp: Comparison between ohmic and conventional heat treatment

Degradation kinetics of monomeric anthocyanins in acerola pulp during thermal treatment by ohmic and conventional heating was evaluated at different temperatures (75–90 °C). Anthocyanin degradation fitted a first-order reaction model and the rate constants ranged from 5.9 to 19.7 × 10⁻³ min⁻¹. There were no significant differences between the rate constants of the ohmic and the conventional heating processes at all evaluated temperatures. D-Values ranged from 116.7 to 374.5 for ohmic heating and from 134.9 to 390.4 for conventional heating. Values of the free energy of inactivation were within the range of 100.19 and 101.35 kJ mol⁻¹. The enthalpy of activation presented values between 71.79 and 71.94 kJ mol⁻¹ and the entropy of activation ranged from −80.15 to −82.63 J mol⁻¹ K⁻¹. Both heating technologies showed activation energy of 74.8 kJ mol⁻¹ and close values for all thermodynamic parameters, indicating similar mechanisms of degradation.