Stability to light, heat, and hydrogen peroxide at different pH values and DPPH radical scavenging activity of acylated anthocyanins from red radish extract

The stability of red radish extract to light, heat, and hydrogen peroxide at different pH values (3, 5, and 7) was examined, in which major anthocyanins were pelargonidin glycosides acylated with a combination of p-coumaric, ferulic, or caffeic acids. The light irradiation (fluorescence light, 5000 lx; at 25 degrees C) indicated that the red radish extract was more stable at lower pH than at higher pH. The HPLC analyses revealed that diacylated anthocyanins in the extract were more stable to light at pH 3 than monoacylated anthocyanins. No significant difference in degradation rates of acylated anthocyanins at pH 5 was observed, whereas anthocyanins acylated with p-coumaric or ferulic acids were more stable at pH 7 than ones with caffeic acids. The stability to heat (at 90-95 degrees C) showed a tendency similar to that for light. The number of intramolecular acyl units contributes to stability to light and heat at lower pH, whereas the characteristics of intramolecular acyl units influence the stability at higher pH. The degradation behavior of red radish extract to H2O2 were almost the same to those of light and heat, depending on the pH. However, HPLC analyses revealed that the stability of individual acylated anthocyanins were independent of the pH. These data suggest that the characteristics, the number, and the binding site of intramolecular acyl units affect the stability of anthocyanin to H2O2. DPPH radical scavenging activity of all acylated anthocyanins was higher than those of pelargonidin and perlargonidin-3-glucoside. The activity of acylated anthocyanins mostly depended on the activity of intramolecular acyl units (caffeic acid > ferulic acid > p-coumaric acid). However, the activity was highly affected by the binding site of intramolecular acyl units even if anthocyanins have common acyl units.     

Encapsulation of olive leaf extract in beta-cyclodextrin

Olive leaf extract, rich in oleuropein, formed an inclusion complex with beta-cyclodextrin (beta-CD) upon mixing of the components in aqueous media and subsequent freeze-drying. Inclusion complex formation was confirmed by differential scanning calorimetry (DSC). DSC thermograms indicated that the endothermic peaks of both the olive leaf extract and the physical mixture of olive leaf extract with beta-CD, attributed to the melting of crystals of the extract, were absent in DSC thermogram of inclusion complex. Moreover, DSC studies under oxidative conditions indicated that the complex of olive leaf extract with beta-CD was protected against oxidation, since it remained intact at temperatures where the free olive leaf extract was oxidized. Phase solubility studies afforded A L type diagrams, 1:1 complex stoichiometry, a moderate binding constant ( approximately 300 M (-1)), and an increase of the aqueous solubility by approximately 50%. The formation of the inclusion complex was also confirmed by nuclear magnetic resonance (NMR) studies of beta-CD solutions in the presence of both pure oleuropein and olive leaf extract. The NMR data have established the formation of a 1:1 complex with beta-CD that involves deep insertion of the dihydroxyphenethyl moiety inside the cavity from its secondary side.     

Heat stability of strawberry anthocyanins in model solutions containing natural copigments extracted from rose (Rosa damascena Mill.) petals

Thermal degradation and color changes of purified strawberry anthocyanins in model solutions were studied upon heating at 85 degrees C by HPLC-DAD analyses and CIELCh measurements, respectively. The anthocyanin half-life values increased significantly due to the addition of rose (Rosa damascena Mill.) petal extracts enriched in natural copigments. Correspondingly, the color stability increased as the total color difference values were smaller for anthocyanins upon copigment addition, especially after extended heating. Furthermore, the stabilizing effect of rose petal polyphenols was compared with that of well-known copigments such as isolated kaempferol, quercetin, and sinapic acid. The purified rose petal extract was found to be a most effective anthocyanin-stabilizing agent at a molar pigment/copigment ratio of 1:2. The results obtained demonstrate that the addition of rose petal polyphenols slows the thermal degradation of strawberry anthocyanins, thus resulting in improved color retention without affecting the gustatory quality of the product.     

Effect of storage temperature and pyruvate on kinetics of anthocyanin degradation, vitisin A derivative formation, and color characteristics of model solutions

The formation of vitisin A, an anthocyanin formed naturally in small quantities in maturing port wines, was studied in model wine solutions at several storage temperatures (10, 15, 20, and 32 degrees C). Vitisin A was formed through the interaction between malvidin 3-glucoside and pyruvic acid, Acylated forms of vitisin A, having the 6-position of the sugar acylated with acetic acid (3-acetylvitisin A) and p-coumaric acid (3-p-coumarylvitisin A), were also formed through the interaction between pyruvic acid and malvidin 3-acetylglucoside and malvidin 3-p-coumarylglucoside, respectively. A maximum degradation of the anthocyanins was obtained at higher temperatures, and it followed a first-order kinetics both with and without pyruvic acid in the solution. Whereas at low temperatures (10 and 15 degrees C) the presence of pyruvic acid accelerated the kinetic reaction, at higher temperatures (20 and 32 degrees C) it decreased it. The activation energy values for the degradation of the three anthocyanins in model solutions without and with pyruvic acid were not significantly different from each other. At low temperatures the highest concentrations of vitisin A compounds were obtained. All solutions showed a decrease in L value, indicating that all solutions became darker. This change increased with increasing temperature. All model solutions increased in the hue angle, indicating that the solutions changed from a bluish-red to an orange-red or even brownish-red color. Samples without pyruvic acid remained lighter and became browner than those with pyruvic acid. A good correlation between the amount of vitisin A in the solution and hue angle was found, indicating that vitisin A may contribute the orange-red of solutions, compared to the browner control.     

Phytochemical stability and color retention of copigmented and processed muscadine grape juice

Muscadine (Vitis rotundifolia) grape juice was assessed for color and phytochemical stability as influenced by anthocyanin copigmentation with a water-soluble rosemary extract, fortification with ascorbic acid, and processing by heat or high hydrostatic pressure (HHP). The roles of polyphenolic cofactors in the presence and in the absence of ascorbic acid were assessed as a means to improve the overall processing stability of the juice. Addition of rosemary extract from 0 to 0.4% (v/v) readily formed copigment complexes with anthocyanins and resulted in concentration-dependent hyperchromic shifts from 10 to 27% that corresponded to increased antioxidant activity. The presence of ascorbic acid was generally detrimental to juice quality, especially in the presence of rosemary extract, and resulted in overall anthocyanin, ascorbic acid, and antioxidant activity losses. Although thermal and high-pressure processing methods were detrimental to juice quality, HHP resulted in greater losses after processing, likely due to action from residual oxidase enzymes. Although physicochemical attributes were enhanced by copigmentation with rosemary extract, methods to inactivate residual enzymes should be addressed prior to copigmentation to prevent degradation of anthocyanins in the presence of ascorbic acid.     

Adsorption and desorption properties of macroporous resins for anthocyanins from the calyx extract of roselle (Hibiscus sabdariffa L.)

Adsorption of roselle anthocynins, a natural pigment, onto various macroporous resins was optimized to develop a simple and efficient process for industrial separation and purification of roselle anthocyanins. Nine different macroporous resins (AB-8, X-5, HPD-100, SP-207, XAD-4, LS-305A, DM-21, LS-610B, and LS-305) were evaluated for the adsorption properties of the anthocyanins extracted from the calyx extract of Hibiscus sabdariffa L. The influences of phase contact time, solution pH, initial anthocyanin concentration, and ethanol concentration with different citric acid amounts were studied by the static adsorption/desorption method. The adsorption isotherm data were fitted well to the Langmuir isotherm, and according to this model, LS-610B and LS-305 exhibited the highest monolayer sorption capacities of 31.95 and 38.16 mg/g, respectively. The kinetic data were modeled using pseudo-first-order, pseudo-second-order, and intraparticle diffusion equations. The experimental data were well described by the pseudo-second-order kinetic model. Continuous column adsorption-regeneration cycles indicated negligible capacity loss of LS-305 during operation. The overall yield of pigment product was 49.6 mg/g dried calyces. The content of roselle anthocynins in the pigment product was 4.85%.     

Thermal degradation of anthocyanins from purple potato (cv. Purple Majesty) and impact on antioxidant capacity

Degradation parameters of purified anthocyanins from purple-fleshed potato (cv. Purple Majesty) heated at high temperatures (100-150 °C) were determined. Purified anthocyanins, prepared by removing salts, sugars, and colorless nonanthocyanin phenolics from the crude extract, were monitored and quantified using HPLC and spectrophotometry for heat-induced degradation products. Separation of colorless phenolics from the anthocyanins was confirmed using HPLC at two wavelengths, 280 and 520 nm. The degradation kinetics of purified anthocyanins followed a first-order reaction with reaction rate constants (k values) of 0.0262-0.2855 min(-1), an activation energy of 72.89 kJ/mol, thermal death times (D values) of 8.06-8789 min, and a z value of 47.84 °C over the temperature range of 100-150 °C. The enthalpy and entropy of activation were 59.97 kJ/mol and -116.46 J/mol·K, respectively. The antioxidant capacity in the purified anthocyanins, measured by DPPH and ABTS assays, was increased after the thermal treatment, indicating antioxidant activities of degradation products in the samples.     

杨梅澄清汁及浓缩汁中花色苷热降解动力学的研究

杨梅花色苷易受温度、pH值等因素的影响而发生降解,是导致产品外观品质变劣的主要原因。本文研究了杨梅澄清汁及浓缩汁内花色苷在不同pH值和不同加热温度下的热稳定性。花色苷降解动力学数据的分析结果表明：杨梅花色苷热降解属动力学一级反应,随着pH值和温度的升高,杨梅花色苷降解的半衰期(t_1/2)和热降解活化能(Ea)显著下降,即花色苷的降解速度增大;同一处理条件下,浓缩果汁的t_1/2明显低于澄清汁。而反应速率常数k和Ea值大于澄清果汁,说明澄清汁花色苷的热稳定性优于浓缩汁。     

Preparation and comparative release characteristics of three anthocyanin encapsulation systems

Bilberries (Vaccinium myrtillus L.) and their major polyphenolic constituents, anthocyanins, have preventive activities inter alia against colon cancer and inflammatory bowel diseases. However, anthocyanins are sensitive to environmental conditions; thus their bioavailability in the gastrointestinal tract is an important determinant of their in vivo activity. In the study reported here, the potential benefits of encapsulating an anthocyanin rich bilberry extract (BE) on anthocyanin stability were investigated. Nonencapsulated BE and three different BE loaded microcapsule systems were incubated in simulated gastric fluid (SGF) and fed state simulated intestinal fluid (FeSSIF). After exposure to these media, released anthocyanins were identified and quantified by HPLC with UV/Vis detection. Although a rapid release of anthocyanins was observed within the first 20 min, encapsulation of anthocyanins doubled the amount of available anthocyanins after 150 min of incubation. These results illustrate the ability of encapsulation to inhibit early degradation of anthocyanins in the intestinal system.     

Preparation and characterization of inclusion complex of norflurazon and beta-cyclodextrin to improve herbicide formulations

The formulation of inclusion complexes of the herbicide norflurazon as guest and beta-cyclodextrin (beta-CD) as host has been studied as a first step in the use of cyclodextrins to obtain improved formulations of this herbicide. The interaction of norflurazon with beta-CD produced the formation of an inclusion complex in solution and in solid state. The inclusion of norflurazon in beta-CD in solution was studied by phase solubility, and an apparent stability constant of 360 M(-)(1), a 1:1 stoichiometric ratio for the complex, and up to 5-fold increase in norflurazon solubility were determined. Three processing methods (kneading, spray drying and vacuum evaporation) were used to prepare norflurazon-beta-CD solid inclusion complexes. X-ray diffraction, infrared spectroscopy, differential scanning calorimetry, and scanning electron microscopy techniques were used to study the solid complexes. From the different solid systems, an increase of norflurazon aqueous dissolution rate was obtained in comparison to the uncomplexed herbicide. This finding is a first step to obtain controlled release and/or protective formulations of norflurazon, which allow a more rational application of norflurazon, diminishing the use of organic solvents and increasing its efficacy.     

Stability and antioxidant activity of black currant anthocyanins in solution and encapsulated in glucan gel

The effects of ferric and ferrous ions, pH, and temperature on the stability and antioxidant activity of black currant anthocyanins (BCA) were studied, and the recovery of BCA from glucan gel [mixed linked (1-->3,1-->4)-beta-D-glucan] after using different encapsulating procedures was determined. The degradation of individual anthocyanins follows first-order kinetics and shows Arrhenius temperature dependence. The activation energies of individual anthocyanins, evaluated over the temperature range 60-100 degrees C, decrease with an increase in pH. While the antioxidant activity of BCA, measured by the ferric reducing antioxidant power assay, decreased with the degradation of anthocyanins, the completely degraded products still exhibited approximately 30% of the initial antioxidant activity. Ferric ions have a detrimental effect on the stability of BCA, especially for delphinidins. Freeze drying of encapsulated BCA gives approximately 20% higher recovery of individual anthocyanins than infrared drying.     

Preparation, stabilization, and bioefficacy of beta-cyclodextrin inclusion compounds of chloramidophos

Cyclodextrins are common compounds capable of forming inclusion complexes with a variety of pesticides to improve their solubility, bioavailability, and stability. In this study, chloramidophos (CP) was inclusion-complexed with beta-cyclodextrin (beta-CD) by a kneading method in an attempt to gain a more stable but equally effecacious formulation compared with CP alone. A 1:1 CP-beta-CD complex with an inclusion constant of 203.0 M(-1) was determined to exist by UV spectrophotometry. The structural identification, thermal stability, and biological assays of the CP-beta-CD complex were then carried out with a product with the maximum guest loading efficiency. The data measured by differential scanning calorimetry (DSC), Fourier transform infrared (FT-IR), and X-ray diffraction (XRD), where the endothermic peaks of beta-CD, the FT-IR bands, and the XRD peaks were generally changed, deduced the formation of complex. Results of the thermal stability assay showed that the degradation rate of CP in 14-day incubation was slowed by a factor of 3.6 when it was complexed with beta-CD. Then, activity and toxicity of CP influenced by the encapsulated process of beta-CD were evaluated by an in vitro acetylcholinesterase (AChE) inhibition assay and an acute aquatic toxicity assay, respectively. No significant differences were found in both the two biological assays by a t-test. This indicated that the encapsulation process greatly improved the thermal stability of the pesticide with no adverse effects on bioefficacy compared to that of CP. There is a promising outlook for CP-beta-CD to be produced as the active ingredient of various formulation additives of CP for its continued application.     

Stability of natamycin and its cyclodextrin inclusion complexes in aqueous solution

Aqueous solutions of natamycin and its beta-cyclodextrin (beta-CD), hydroxypropyl beta-cyclodextrin, and gamma-cyclodextrin (gamma-CD) inclusion complexes were completely degraded after 24 h of exposure to 1000 lx fluorescent lighting at 4 degrees C. After 14 days of storage in darkness at 4 degrees C, 92.2% of natamycin remained in active form. The natamycin:beta-CD complex and natamycin:gamma-CD complex were significantly more stable (p < 0.05) than natamycin in its free state in aqueous solutions stored in darkness at 4 degrees C. Clear poly(ethylene terephthalate) packaging with a UV light absorber allowed 85.0% of natamycin to remain after 14 days of storage under 1000 lx fluorescent lighting at 4 degrees C. Natamycin:cyclodextrin complexes can be dissociated for analysis in methanol/water/acetic acid, 60:40:5, v/v/v. Natamycin and its complexes in dissociated form were quantified by reverse phase HPLC with detection by photodiode array at 304 nm.     

Characterization of free radicals in soluble coffee by electron paramagnetic resonance spectroscopy

EPR spectra of soluble coffee display single-line free radical signals in both the solid state and aqueous solution, along with signals from the paramagnetic ions Fe(III) and Mn(II). The intensity of the free radical signal in the pure solid was estimated to be ca. 7.5 x 10(16) unpaired electrons/g, and there was no significant change on dissolution in water. In aqueous solutions, however, the free radical signal declined rapidly over ca. 10-15 min in the temperature range 20-65 degrees C, after which only slow changes were observed. This decline, which was essentially independent of atmosphere, was greatest for the lowest temperatures used, and the intensity after 1 h fitted well to an exponential curve with respect to temperature. The free radicals responsible for the single-peak EPR signal did not react with any of the spin traps tested in the present experiments, but unstable free radicals with parameters consistent with adducts of C-centered radicals were detected in coffee solutions in the presence of PBN and 4-POBN spin traps. The presence of oxygen in the solutions increased the initial rate of formation of these free radical adducts. No adducts were detected when DEPMPO was used as spin trap. However, *OH adducts of DEPMPO were shown to be unstable in the presence of coffee, a fact which illustrates the strong free radical scavenging ability of coffee solutions.     

Formation of natamycin:cyclodextrin inclusion complexes and their characterization

Natamycin is a broad spectrum antimycotic with very low water solubility, which is used to extend the shelf life of shredded cheese products. beta-Cyclodextrin (beta-CD), hydroxypropyl beta-cyclodextrin (HP beta-CD), and gamma-cyclodextrin (gamma-CD) were found to form inclusion complexes with natamycin in aqueous solution. The increase in solubility of natamycin with added beta-CD was observed to be linear (type A(L) phase solubility diagram). The 1:1 stability constant of natamycin:beta-CD complex was estimated from its phase solubility diagram to be 1010 M(-1). The phase solubility diagrams of both gamma-CD and HP beta-CD exhibited negative deviation from linearity (type A(N) diagram) and, therefore, did not allow the estimation of binding constants. The water solubility of natamycin was increased 16-fold, 73-fold, and 152-fold with beta-CD, gamma-CD, and HP beta-CD, respectively. The natamycin:CD inclusion complexes resulted in in vitro antifungal activity nearly equivalent to that of natamycin in its free state.     

Phytochemical composition and pigment stability of Açai (Euterpe oleracea Mart.)

Anthocyanin and polyphenolic compounds present in a?ai (Euterpe oleracea Mart.) were determined and their respective contribution to the overall antioxidant capacity established. Color stability of a?ai anthocyanins against hydrogen peroxide (0 and 30 mmol/L) over a range of temperatures (10-30 degrees C) was also determined and compared to common anthocyanin sources. Additionally, stability in a model beverage system was evaluated in the presence of ascorbic acid and naturally occurring polyphenolic cofactors. Cyanidin 3-glucoside (1040 mg/L) was the predominant anthocyanin in a?ai and correlated to antioxidant content, while 16 other polyphenolics were detected from 4 to 212 mg/L. Red grape anthocyanins were most stable in the presence of hydrogen peroxide, while a?ai and pigments rich in acylated anthocyanins displayed lower color stability in a temperature-dependent manner. In the presence of ascorbic acid, acylated anthocyanin sources generally had increased color stability. A?ai was recognized for its functional properties for use in food and nutraceutical products.     

Anthocyanins in wild blueberries of Quebec: extraction and identification

Anthocyanins were extracted from a mixture of berries of Vaccinium angustifolium and Vaccinium myrtillo?des at 7.7 degrees C, 26 degrees C, and 79 degrees C using ethanol alone or ethanol acidified with hydrochloric, citric, tartaric, lactic, or phosphoric acids at a solvent to solid ratio of 10. The effect of these parameters on extracted anthocyanins stability was investigated. The pH-differential and HPLC-DAD methods were used to determine anthocyanin contents. Extracted anthocyanins were purified on a C-18 solid-phase extraction cartridge and characterized by HPLC/electrospray ionization/mass spectrometry (HPLC-ESI-MS/MS). Anthocyanins were identified according to their HPLC retention times, elution order, and MS fragmentation pattern and by comparison with standards and published data. Anthocyanin extractions gave different yields depending on the type of added acid and the extraction temperature. High yields of monomeric and total anthocyanins (26.3 and 28.9 mg/g of dry matter) were obtained at 79 degrees C using phosphoric acid. Extraction using tartaric acid at 79 degrees C provided the lowest degradation index (1.05). Anthocyanins were stable and browning by polyphenol oxidase was inhibited under these conditions. Of the six common anthocyanindins, five were identified in the extracts, namely, delpinidin, cyanidin, peonidin, petunidin, and malvidin; pelargonidin was not found. In addition to well-known major anthocyanins, new anthocyanins were identified for the first time in extracts of wild blueberries from Quebec.     

Stability of copigmented anthocyanins and ascorbic acid in a grape juice model system

The stability of red grape anthocyanins (Vitis vinifera) was evaluated in a model juice system during normal (25 degrees C) and accelerated storage (35 degrees C) in the presence of ascorbic acid. Rosemary polyphenolic cofactors (0, 0.2, and 0.4% v/v) were evaluated as anthocyanin stabilizing agents. Cofactor addition resulted in concentration-dependent hyperchromic (up to 178%) and bathochromic (up to 23 nm) shifts, indicating a more intense red coloration of the models. Anthocyanin and ascorbic acid degradation followed first-order kinetics during storage. Results showed that copigmented treatments underwent a lower conversion of L-ascorbic acid into dehydroascorbic acid during storage when compared to the control, favorably impacting the vitamin retention of these models. Copigmentation did not affect anthocyanin degradation in the absence of ascorbic acid but in its presence aided to retain a higher anthocyanin content than the control. This study indicated that the addition of anthocyanin cofactors could be used to reduce the pigment and vitamin degradation while masking detrimental color changes in anthocyanin containing products.     

Impact of preferential interactions on thermal stability and gelation of bovine serum albumin in aqueous sucrose solutions

The influence of sucrose (0--40 wt %) on the thermal denaturation and gelation of bovine serum albumin (BSA) in aqueous solution has been studied. The effect of sucrose on heat denaturation of 1 wt % BSA solutions (pH 6.9) was measured using ultrasensitive differential scanning calorimetry. The unfolding process was irreversible and could be characterized by a denaturation temperature (T(m)), activation energy (E(A)), and pre-exponential factor (A). As the sucrose concentration increased from 0 to 40 wt %, T(m) increased from 72.9 to 79.2 degrees C, E(A) decreased from 314 to 289 kJ mol(-1), and ln(A/s(-1)) decreased from 104 to 94. The rise in T(m) was attributed to the increased thermal stability of the globular state of BSA relative to its native state because of differences in their preferential interactions with sucrose. The change in preferential interaction coefficient (Delta Gamma(3,2)) associated with the native-to-denatured transition was estimated. The dynamic shear rheology of 2 wt % BSA solutions (pH 6.9, 100 mM NaCl) was monitored as they were heated from 30 to 90 degrees C, held at 90 degrees C for either 15 or 120 min, and then cooled to 30 degrees C. Sucrose increased the gelation temperature due to thermal stabilization of the native state of the protein. The complex shear modulus (G) of cooled gels decreased with sucrose concentration when they were held at 90 degrees C for 15 min because the fraction of irreversibly denatured protein decreased. On the other hand, G of cooled gels increased with sucrose concentration when they were held at 90 degrees C for 120 min because a greater fraction of irreversibly denatured protein was formed and the strength of the protein-protein interactions increased.     

Study on the supramolecular interaction of thiabendazole and beta-cyclodextrin by spectrophotometry and its analytical application

The beta-cyclodextrin-thiabendazole (beta-CD-TBZ) inclusion complex was synthesized and its structure characterized by (1)H NMR and IR. The mechanism of the supramolecular interaction of TBZ and beta-CD has been studied and discussed by spectrophotometry. The results showed that the phenyl ring of TBZ was included in the beta-CD cavity to form a 1:1 host-guest complex with an apparent formation constant of 1.60 x 10(3) mol(-1).L. On the basis of the enhancement of the absorbance of TBZ produced through complex formation, a spectrophotometric method for the determination of TBZ in bulk aqueous solution in the presence of beta-CD was developed. The linear relationship between the absorbance and TBZ concentration was obtained in the range of 8.86 x 10(-7)-1.45 x 10(-5) mol/L. The detection limit was 2.71 x 10(-7)mol/L, and the relative standard deviation was 0.86%. The interference of 48 coexisting substances was slight. The proposed method has been successfully applied to the determination of TBZ in fruits with recoveries of 96-103%.