Comparison of lycopene stability in water- and oil-based food model systems under thermal- and light-irradiation treatments

Lycopene can undergo degradation via isomerization and oxidation during processing and storage. These degradative reactions affect its bioactivity and health benefit functionality. Degradation kinetics and isomerization of lycopene in water- and oil-based tomato model systems were investigated as a function of thermal treatments and light irradiation. Results showed that 80 and 100 °C heating favoured the stability of lycopene in oil-based tomato products. The high heating temperatures (120 and 140 °C) increased isomerization of lycopene and resulting in degradation of total lycopene and cis-isomers in both water- and oil-based tomato products. However, the levels of degradation of total lycopene contents and cis-isomers were greater in water-based samples than in oil-based model systems under different treatments. Heat and light both promoted lycopene isomerization of the all-trans form to the cis-isomers and further oxidation of cis-isomers. The major effect of thermal degradation and photosensitized oxidation was a significant decrease in the total lycopene content, especially the content of cis-isomers. These research results could be useful in assisting industry to improve processing technology and to improve the nutritional value and health-benefits of tomato-based foods.     

Tomato pulp as source for the production of lycopene powder containing high proportion of cis-isomers

Cis-isomers of lycopene has been demonstrated to possess higher biological activity than its all-trans form. The objectives of this study were to compare the extraction efficiency and degree of isomerization of lycopene by employing supercritical carbon dioxide (SCD) and solvents, as well as process the lycopene extract into powder containing high proportion of cis-isomers from tomato pulp as source. Results showed that a high yield of lycopene was achieved by SCD at 350 bar and 70 °C, with cis-isomers making up 41.4% of total lycopene. However, with temperature at 80 and 90 °C, the maximum isomerization was accomplished, and cis-lycopene constituted 51.0 and 53.8% of total lycopene, respectively. For solvent extraction, the highest yield of all-trans-lycopene was attained by ethanol–hexane (4/3 v/v) at 25 and 50 °C, whereas the maximum isomerization (47.0% cis-lycopene) occurred at 75 °C. A powder product containing 34.5% cis-isomers of lycopene was obtained by spray-drying, and the total amount of lycopene in spray-dried powder was much greater than that in freeze-dried powder. The maximum yield of lycopene in the powder product could be obtained through processing by adding sodium alginate to the eluate directly after SCD extraction and open-column chromatography with formation of 41.4% cis-lycopene. The method developed in this study may be used for possible commercial production of highly active lycopene powder.     

Thermal processing of carrots: Lycopene stability and isomerisation with regard to antioxidant potential

The thermal stability of lycopene was evaluated in a carrot cultivar with a high lycopene content (Daucus carota var. Nutri Red) by (a) exposure of carrot homogenates (with/without the addition of oil) to temperatures ranging from 25 to 140 °C; (b) applying convection and microwave vacuum drying to carrot slices. Heating carrot homogenates at temperatures above 100 °C initiated isomerisation of all-trans-lycopene under non-oxidising conditions, as indicated by a significant increase in 9-cis-lycopene. Isomerisation was enhanced at short treatment times, when sunflower oil was added prior to thermal treatment. Independent from an oil supplement, all-trans-lycopene was degraded at temperatures above 70 °C. The ratio of all-trans- to total-cis-isomers changed from 90:10 to 40:60, indicating a higher lycopene bioavailability due to generated cis-isomers. In oil containing carrot homogenates antioxidant properties of the methanol-soluble components raised after heat treatment at 130 °C for 0.5 h. Lycopene remained stable in dried carrots.     

Effect of osmotic pre-treatment and microwave heating on lycopene degradation and isomerization in cherry tomato

Cherry tomato were dehydrated by a combination of different techniques (osmotic dehydration, convective drying, and microwaves assisted air drying) in order to evaluate the effect of the process variables on the degradation and isomerization of lycopene, as well as on the optical properties. Specifically, the effect of prior osmotic treatment, air drying temperature (40, 55, and 80 °C) and level of microwave energy (0, 1, and 3 W/g) were studied. Obtained results showed that the osmotic pre-treatment limited the isomerization during the later stage of drying, whereas both the loss of total lycopene and the trans–cis isomerization, mainly to the 13-cis form, were favored by an increase in temperature and the microwave power. Furthermore, a positive correlation between the degree of isomerization experienced by the samples during drying and the hue (h*) were obtained. This correlation was reflected in the colour of the sample with predominantly more orange tones and less reddish ones.     

Identification and Quantification of All-Trans-Zeaxanthin and Its Cis-Isomers During Illumination in a Model System

The degradation and isomerization of all-trans-zeaxanthin in a model system during illumination, in the absence or presence of iodine, were investigated. A high-performance liquid chromatography method was developed using the C-30 column to separate all-trans-zeaxanthin and its cis-isomers. Three mono-cis-isomers and four di-cis-isomers were assigned by high-performance liquid chromatography-photo diode array detection-atmospheric pressure chemical ionization-mass spectrometry (HPLC-DAD-APCI-MS), namely, 15/15’-cis-, 13/13’-cis-, 9/9’-cis-13,15-di-cis-, 9,15-di-cis-, 9,13-di-cis-, and 9,9’-di-cis-zeaxanthin. 13/13’-cis- and 9, 13-di-cis-zeaxanthin were the major cis-isomers of zeaxanthin formed during illumination. Di-cis-zeaxanthin was favored during illumination in the presence of iodine. The degradation of total amount of all-trans-zeaxanthin during illumination was found to fit a first-order model. The degradation rate of iodine-catalyzed photoisomerization of all-trans-zeaxanthin was faster than that of non-iodine-catalyzed photoisomerization. Isomerization and degradation of all-trans-zeaxanthin and its cis-isomers during illumination proceeded simultaneously.     

Effects of a hydrodynamic process on extraction of carotenoids from tomato

We evaluated the results of using a proprietary hydrodynamic method, which was introduced with the hope of increasing accessibility of beneficial nutrition-enhancing fruit and vegetable products. Tomato, a major dietary source of carotenoids, notably lycopene, was tested because of its many health benefits to consumers. Samples before and after treatment were compared for lycopene, phytoene, and phytofluene contents. Extractable lycopene and other carotenoids increased significantly. In nature, lycopene exists almost exclusively as the all-trans stereoisomer. Cis-lycopene isomers form during cooking and digestion, resulting in higher percentages in plasma and tissues than ingested. Cis-lycopene isomers are more bioavailable than all-trans lycopene. Extraction using this proprietary method increased extracted cis-lycopene to as high as 43% of the total lycopene, indicating increased isomerisation. This method could therefore contribute significantly to the delivery of health benefits of biologically available lycopene from tomato products for metabolic functions.     

Effects of supercritical fluid extraction parameters on lycopene yield and antioxidant activity

The effects of various parameters of supercritical carbon dioxide (SC-CO₂) fluid extractions of tomato skins on the extraction yields and antioxidant activities of lycopene-rich extracts were investigated. A Box–Behnken design was applied to study the effects of three independent variables (temperature ranging from 40 to 100 °C, pressure ranging from 20 to 40 MPa, and flow rate ranging from 1.0 to 2.0 mL/min) on lycopene yield. The model showed good agreement with the experimental results, by the coefficient of determination (r² = 0.9834). Temperature, pressure, and the quadratic term for the temperature of SC-CO₂ extraction were large significantly positive factors affecting lycopene yield (P < 0.05). The maximum total lycopene content of 31.25 μg/g of raw tomato was extracted at the highest temperature of 100 °C, 40 MPa and 1.5 mL/min. TEAC assay was applied to assess the antioxidant activity of lycopene-rich extracts from SC-CO₂ fluid extraction. The effects of SC-CO₂ fluid extraction parameters on the antioxidant activities of the extracts differed with the yield. For each unit of lycopene extract, the antioxidant activity level was constant below 70 °C, but then gradually decreased above 70 °C due to isomerization occurring as a result of the higher temperature. The ratio of all-trans-lycopene to the cis-isomers changed from 1.70 to 1.32 when the operating temperature was adjusted from 40 to 100 °C, indicating an increased bioavailability due to the generation of the cis-isomers. No significant effects of pressure or flow rate of SC-CO₂ fluid extraction on the antioxidant activity were observed.     

Cis-trans isomerisation of lycopene and colour stability of foam—mat dried tomato powder during storage

Tomato powder with ～3% moisture was obtained by foam-mat drying tomato paste (29% solids). Samples of powder were stored at various temperatures (?10° +2° +20° and +37°c), atmospheres (air, nitrogen) and humidities (with and without in-package desiccation), and colour changes were observed for periods of up to 1 year. The main cause of colour fading was the oxidation of lycopene. However, another phenomenon, trans—cis isomerisation of all-trans lycopene, can occur, with apparent loss of coloration, which is later restored by re-isomerisation. The existence of this mechanism was demonstrated by simultaneous measurements of total liposoluble colour at 420 nm and separations of carotenoid pigments by column chromatography on Al₂O₃. Neo-lycopene A (6-mono-cis-lycopene) and at least one other cis-lycopene isomer were found in fresh powder and in samples stored up to 5 months. cis-Isomers were more susceptible to oxidation. Colour changes depend upon the interplay of isomerisation and oxidation; in some cases, tomato powder was more intensively coloured after storage than when fresh. Storage at +20°c was more favourable for colour retention than storage at +2°c, or — 10°c. Excessive desiccation strongly promoted oxidation losses. Storage in an inert atmosphere improved colour retention. At +37°c non-enzymic browning, accompanied by formation of water, caused rapid darkening although carotenoid pigments were not lost to a great extent.     

Partial purification and characterization of polyphenol oxidase from Chinese parsley (Coriandrum sativum)

Rates of thermal degradation and isomerization of all-trans-β-carotenes in air and in triacylglycerols were determined. Degradation of carotenes in triacylglycerols was faster than that in air. The 13-cis-β-carotene level in triacylglycerols was higher than in air. Oxidized materials of triacylglycerols probably facilitated isomerization of carotenes and, thus, degradation. Amounts of all-trans-β-carotenes and all-trans-α-carotenes in pumpkin decreased with an increase in heating time. The proportion of 13-cis-β-carotene increased after heat treatment started, probably due to thermal isomerization of all-trans-β-carotenes to cis-isomers, and to decreases in amounts of all-trans-β-carotenes and all-trans-α-carotenes in pumpkin. Effects of heating methods on proportions of isomers; however, were not different.     

Effect of illumination and chlorophylls on stability of tomato carotenoids

Lipidic extract from tomato peels, or tomato peels plus stalks, dissolved in ethanol were submitted to illumination. Lycopene, β-carotene, phytoene and phytofluene isomerisation and degradation, during storage at room temperature for 28 days, were studied. Degradation of chlorophylls a and b were analysed in lipidic extracts from stalks. Total lycopene and all-E-lycopene degradation was found to fit to a first-order model. The degradation rate constant was lower in extracts from peels −0.0137 (all-E-lycopene) and −0.0737 (total lycopene), than in those from peel plus stalk −0.0415 (all-E-lycopene) and −0.0854 (total lycopene). Z-lycopene isomers showed an inconsistence change during storage, in all analysed samples. Concentration of β-carotene from extracts of tomato peels plus stalks decreased slightly during storage. Phytoene and phytofluene degradation were not significantly affected by both storage conditions and chlorophylls. The obtained results showed that some compounds from stalks, such as chlorophylls, could favour lycopene and β-carotene degradation during storage under illumination.     

Ultra-performance liquid chromatographic separation of geometric isomers of carotenoids and antioxidant activities of 20 tomato cultivars and breeding lines

All-trans-lutein, lycopene, β-carotene and their 22 cis-isomers in 20 tomato breeding were separated and identified by a rapid and sensitive UPLC method using a 1.7 μm C₁₈ column and a new gradient mobile phase based on methanol-MTBE-water in 15 min. All-trans-carotenoids were predominant, but 9-cis, 13-cis-lutein, 5-cis, 9-cis, 13-cis, 15-cis, di-cis-lycopene, 9-cis, 13-cis, 15-cis and di-cis-β-carotene were also found. The cis-isomers were identified using absorption around 330 nm and the Q-ratio. The total antioxidant activities as evaluated by PCL and DPPH assays were found to correlate well with the total carotenoid content, but not with the individual carotenoid or its different isomers. This paper provides an efficient analytical method for obtaining a complete picture of carotenoids in tomatoes. It can be a valuable tool for plant breeders, food processors and researchers in developing designer tomatoes and tomato-products with unique carotenoid compositions, and functional properties.     

Analysis of carotenoids with emphasis on 9-cis β-carotene in vegetables and fruits commonly consumed in Israel

Recent epidemiological studies have directed the attention from the synthetic all-trans β-carotene to natural carotenoids predominant in fruits and vegetables as possible active ingredients for prevention of cancer and cardiovascular diseases. Seventeen fruits and 17 vegetables commonly consumed in Israel and the β-car-otene-rich alga, Dunaliella bardawil, were analysed for their content of carotenoids with emphasis on 9-cis β-carotene by reversed-phase, 3D photodiode array HPLC. Fourteen carotenoids were eluted in order of decreasing polarity, from polar oxycarotenoids to lipophilic hydrocarbons, and quantified in μg carotenoid per gram freeze-dried plant sample. The richest sources of total carotenoids (>100μg/g dry weight) in Israeli fruits were pittango, mango and papaya while, in vegetables, the predominant types were carrot, dill, parsley, tomato, lettuce, sweet potato and red pepper. Red fruits and vegetables contained mainly lycopene. Yellow and orange fruits and vegetables had high contents of hydrocarbon carotenes with substantial levels of cryptoxanthins and xanthophylls. The green vegetables had high contents of both xanthophylls and hydrocarbon carotenes. Relatively high ratios (9-cis to all-trans β-carotene) of above 0.2 g/g were noted in sweet potato, papaya, parsley, lettuce, dill, apricot, pepper, prune and pumpkin, compared to the high ratio of 9-cis to all-trans β-carotene in the alga Dunaliella (~ 1.0 g/g). The high content of 9-cis β-carotene in certain fruits and vegetables and the wide variety of carotenoids and stereoisomers of carotenoids in all plants should shift nutritional and medical attention from the synthetic all-trans β-carotene toward natural carotenoids as potential candidates for chemoprevention.     

Effects of genotype and cultivation environment on lycopene content in red‐ripe tomatoes

Lycopene, a natural red pigment found in tomato, is correlated with reduced incidence of some cancers. Forty tomato varieties, including cluster F₁ hybrid tomatoes, round breeding line tomatoes (Lycopersicon esculentum Mill) and cherry tomato types (L esculentum var cerasiforme), grown under greenhouse and field conditions were evaluated for their lycopene content using high‐performance liquid chromatography (HPLC) and spectrophotometry. Lycopene content varied significantly among the tomato varieties, with cherry tomato types having the highest lycopene content. Greenhouse‐grown cluster and round tomatoes contained more lycopene (mean = 30.3 mg kg^?1) than field‐grown tomatoes (mean = 25.2 mg kg^?1), whereas cherry tomato types had a higher lycopene content in field‐grown (mean = 91.9 mg kg^?1) than in greenhouse‐grown (mean = 56.1 mg kg^?1) fruits. HPLC analysis of lycopene isomeric forms revealed a higher content of all‐trans isomers in all tomato genotypes examined. However, the cis isomeric form was exceptionally higher in the field‐ and greenhouse‐grown cherry tomato L esculentum var cerasiforme cv Gardener's Delight, which contained ～9.3 and 9.9 mg kg^?1 cis isomers respectively. Results indicate that genetics and choice of cultivation environment may have a strong influence on tomato lycopene content. Copyright © 2005 Society of Chemical Industry     

Influence of extraction with ethanol or ethyl acetate on the yield of lycopene, β-carotene,phytoene and phytofluene from tomato peel powder

This study evaluated the extraction yield of the food grade solvents ethanol and ethyl acetate by extracting lycopene, β-carotene, phytoene and phytofluene from tomato peel powder at varying heating intensities, and the influence of the solvent and heating intensity on carotenoids isomerization and degradation during extraction. The heat treatments assayed were 25, 35, 50 and 60 °C which were applied for periods of 5, 10, 20, 30 or 40 min. The carotenoid yield was higher in the extractions with ethanol than with ethyl acetate. In general, the temperature increase caused an increase in the carotenoid concentrations; however in the extractions performed with ethanol at 60 °C, the yield of (all-E)-lycopene and their (Z)-isomers was lower than at 50 °C. This could indicate that a great isomerization is produced in the high temperature extractions with ethanol but the oxidative degradation is the predominant reaction. On the contrary, the obtained results in the extractions with ethyl acetate indicate that the isomerization is the predominant reaction.     

Thermal Stability and Isomerization of Lycopene in Tomato Oleoresins from Different Varieties

ABSTRACT: Lycopene, a tomato carotenoid, has been associated with the inhibition of certain chronic diseases including prostate cancer. Tomato oleoresin is a lipid-rich material resulting from successive solvent extraction of the tomato fruit. Thermal stability and isomerization of lycopene in oleoresins prepared from 3 different tomato varieties, Roma, High Lycopene, and Tangerine, and tomato peel waste, were studied at 25 °C, 50 °C, 75 °C, and 100 °C in the dark. Thermally degraded lycopene compounds and isomers of lycopene were analyzed by a combination of C₃₀ reversed-phase high-performance liquid chromatograph with a photodiode array detector, UV-visible spectrometer, or mass spectrometer. Effects of antioxidants on lycopene were also studied at 50 °C. As the storage temperature increased from 25 °C to 100 °C, the degradation of total lycopene in oleoresin from all samples increased significantly ( P <0.05). Lycopene at 25 °C and 50 °C may degrade mainly through oxidation without isomerization. Isomerization of lycopene in tomato oleoresins increased at 75 °C and 100 °C. Tetra- cis lycopene in Tangerine tomato varieties followed different degradation and isomerization pathways compared with all -trans lycopene in other tomato varieties. Addition of α-tocopherol or butylated hydroxytoluene slowed the rate of degradation of lycopene in oleoresin.     

Beta-carotene isomerisation in mango puree as influenced by thermal processing and high-pressure homogenisation

The present study describes a case study on mango puree, in which focus is given to the effect of thermal processing (100–130 °C, 0–80 min) and high-pressure homogenisation (0–1300 bar) on the isomerisation of β-carotene. Both unit operations are of relevance for the production of mango puree. β-Carotene is an essential micronutrient which is present in a high amount in most mango cultivars, and it is important for human health due to its antioxidant and provitamin A capacity. It is known that these health-related properties of β-carotene are negatively affected by the conversion to cis-isomers. The results have shown that during high-pressure homogenisation of mango puree, β-carotene isomerisation was negligible. During thermal processing, on the other hand, an increase in β-carotene cis-isomer formation with increasing treatment intensity could be observed, although high temperatures and/or long treatment times were required to observe clear additional isomer formation. From a kinetic point of view, a fractional conversion model could be used to model the all-trans-β-carotene isomerisation in mango puree in the temperature and time range studied. In general, it can be concluded that a high percentage of β-carotene is present as cis-isomers in raw mango puree. Furthermore, only intense thermal processing of mango puree leads to the formation of additional cis-isomers in relevant amounts.     

Stability of carotenoids in tomato juice during processing

The stability of carotenoids in tomato juice as affected by various processing treatments was studied. Fresh tomatoes were crushed, hot-broken at 82 °C, screened and the juice was subjected to the following treatments: (1) heated at 90 °C for 5 min prior to canning; (2) heated in water at 100°C for 30 min after canning; (3) heated at 121°C for 40 s before canning (high-temperature-short-time treatment). The results showed that 16 carotenoids, including all-trans plus cis forms of lutein, lycopene and -carotene, were present in tomato juice. Most cis isomers of carotenoids showed inconsistent change during heating. The high-temperature-short-time treatment generated the highest yield of all-trans plus cis forms of lutein and lycopene, followed by heating at 90 °C for 5 min and heating in water at 100 °C for 30 min. Only a minor change in -carotene was observed for these heating treatments.     

Volatile chemical and carotenoid profiles in watermelons [Citrullus vulgaris (Thunb.) Schrad (Cucurbitaceae)] with different flesh colors

Twelve watermelon [Citrullus vulgaris (Thunb.) Schrad (Cucurbitaceae)] cultivars with different flesh colors were analyzed by HPLC, GC-FID, and GC-MS for their differences in carotenoid, soluble sugar, organic acid, and flavor. Results showed that all-trans violaxanthin, 9-cis-violaxanthin, and luteoxanthin were the main carotenoid esters in watermelons with yellow flesh. However, watermelons with red flesh were rich in all-trans lycopene and their cis-isomers. High concentrations of β-carotene and pro-lycopenes were found in watermelon with orange-yellow flesh. Large variations in the sucrose concentration were observed among the different watermelons. Sucrose and/or fructose were the dominant sugars, while citric acid and malic acid were the main organic acids in watermelon flesh. Limonene was detected in the watermelon flesh of all investigated genotypes. Interestingly, partial correlation analysis of the chemical concentrations revealed 2 significant (p<0.01) positive correlations between β-ionone and β-carotene, and between (E)-geranyl acetone and prolycopenes.     

The physico-chemical characteristics of extruded snacks enriched with tomato lycopene

Adding tomato derivatives to traditional starchy extruded snacks can improve their nutritional properties by adding lycopene and fibre; however the physico-chemical properties of these products must also be considered. Ingredients and extrusion parameters, including temperature, alter these properties, but their effect on lycopene content is not known. In this study, crisp low density extruded snacks were manufactured from corn, wheat and rice, with or without dried tomato skin or paste powder extruded at temperatures of 140, 160 or 180 °C. Lycopene content and the physico-chemical properties (expansion, density, hardness, colour parameters and percentage of moisture loss) of the extruded products were measured. Lycopene retention was higher in products containing tomato skin powder and significantly lower when wheat flour was used to make the snacks. Increases in the processing temperature improved the physico-chemical characteristics of the snacks but had no significant effect on lycopene retention (P > 0.05).     

Optimization of osmotic dehydration of tomatoes in a ternary system followed by air-drying

Osmotic dehydration and air drying technology represent a technique that can reduce post-harvest loss of fruits and vegetables. In this work the influence of osmotic solution composition (water/sugar/salt) and temperature on the osmotic dehydration of tomatoes (Lycopersicum esculentum) were examined. Tomatoes with and without skin were studied. The process of osmotic dehydration followed by air-drying was studied and modeled, so it could be optimized aiming the reduction of total processing time. The results showed the advantage of two different processes for the tomatoes with skin and without skin. Tomatoes without skin are processed faster using air-drying without submitting the fruit to osmotic dehydration. Whereas, the tomatoes with skin dry faster when submitted to an osmotic solution consisting of 35% of sucrose and 5% of salt at 60 °C prior to air-drying.