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.     

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.     

Modeling Lycopene Degradation and Isomerization in the Presence of Lipids

The kinetics of thermally induced degradation and isomerization of lycopene in olive oil, fish oil, and an olive oil/tomato emulsion were studied in detail. Special attention was paid to the isomerization reactions using a multi-response modeling approach. The type of oil had a significant impact on lycopene degradation kinetics, being faster in fish oil compared with olive oil. The estimated kinetic parameters to describe lycopene degradation in olive oil were not significantly different from those in an olive oil/tomato emulsion. The overall Z-isomer formation and elimination in olive oil, fish oil, and olive oil/tomato emulsion was similar. Only the kinetic parameters for 13-Z-lycopene formation differed significantly in the two oils. Although the isomerization rate constants for the emulsion were lower than for olive oil, the isomerization reactions showed similar temperature dependency. This study shows that the kinetics of thermally induced degradation and isomerization of lycopene in oil and in an olive oil/tomato emulsion can be described using the same model. The food system, however, has an influence on the model parameters, especially on the rate constants.     

Lycopene (Z) – isomers enrichment and separation

(All‐E)‐ Lycopene undergoes geometrical isomerisation into (Z)‐lycopene isomers with thermal treatment. Influence of three isomerisation methods including ethyl acetate reflux, microwave‐assisted reflux and ultrasound/microwave‐assisted reflux, and isolation of (all‐E)‐lycopene from other carotenoids and (Z) lycopene isomers through selective inclusion by deoxycholic acid (3α, 12α dihydroxy‐5βcolan‐24‐oic‐acid, DCA) were investigated. The results showed that microwave and ultrasound/microwave‐assisted reflux were not significantly different at P < 0.05, but both were significantly different (P < 0.05) over refluxing in ethyl acetate, proportion of (Z)‐lycopene isomers reached 54% after refluxing for 5 h. Heterogeneous mixture of isomerised tomato oleoresin containing 54% (Z)‐lycopene isomers and 40% (all‐E)‐lycopene and deoxycholic acid in dichloromethane was incubated at 25 °C for 2 h. Then, the mixture was filtered and from the filtrate 96.6% (Z)‐isomers enriched lycopene was obtained. The processes can be used in the production of enriched (Z)‐lycopene isomers for food supplements and functional food industry as a natural bioactive ingredient.     

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.     

The impact of industrial processing on health-beneficial tomato microconstituents

The effect of industrial processing was investigated on the stability of tomato carotenoids, phenolic compounds and ascorbic acid. A deep insight in the processed products allowed the quantification of caffeic acid hexosides, which are far more important contributors than the well-known chlorogenic acid, dicaffeoylquinic acids and quercetin oligosaccharides (new feruloyl, sinapoyl and syringoyl derivatives of quercetin apiosylrhamnosylglucoside). (E)-β-Carotene and (E)-lycopene were also quantified along with different mono- and di-(Z)-isomers of lycopene which were tentatively assigned. Processing of fresh tomato into paste had an overall positive effect on the contents in phenolic compounds, no effect on lycopene and a slight and high detrimental effect on β-carotene and ascorbic acid, respectively. The balance between the increase in tomato matrix extractability and microconstituent catabolism was further observed in two contrasted transformations of paste into sauce. Overall, the nutritional quality of tomato-processed products, except for ascorbic acid, is mainly preserved through manufacture.     

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.     

Thermally-induced geometrical isomerisation of lycopene and its potential influence on functional activity

About 90–98% of native lycopene exists in the all-E form, but 79–88% of the lycopene found in the human body are Z-isomeric forms. Thermally-induced geometrical isomerisation of lycopene occurred within 24 h of refluxing in ethyl acetate and the proportion of Z-isomers increased from 5.8% to 49.9%. Accordingly, the concentration of lycopene required to double quinone reductase (QR) activity in Hepa 1c1c7 cells decreased from >100 to ∼22 μg/mL following thermo-isomerisation, while cell viability was retained at >87% at levels up to 50 μg/mL. The inhibition of nitric oxide (NO) production in activated RAW 264.7 macrophages was 50% at ∼100 μg/mL thermo-isomerised lycopene and increased to >80% when the concentration in the medium was increased to 500 μg/mL. No significant inhibition of NO evolution by macrophages occurred with native (∼94% all-E) lycopene. Both QR induction and NO inhibition bioassays revealed that the structural changes evoked by thermo-isomerisation were accompanied by enhanced biological functionality.     

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.     

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.     

Characterization of E- and Z-ajoene obtained from different varieties of garlics

Synthesised E- and Z-ajoene were used to determine their amounts in food oils containing various fresh garlics. The best yield of E-ajoene (172.0 μg/g of garlic) and Z-ajoene (476.0 μg/g of garlic) was obtained from freshly prepared Japanese garlic with rice oil which was heated at 80 °C. Determination of E- and Z-ajoene from soybean oil containing 15% Japanese garlic samples prepared at 80 °C for 0.5 h gave the amount of E-ajoene (170.0 μg/g of garlic) and Z-ajoene (127.0 μg/g of garlic). After 9-month storage, 54.0% E- and 11.0% Z-ajoene remained in Japanese garlic with rice oil. Ajoene (0.1 mM) in ethyl acetate was incubated under UV-light (253.7 nm) for 3 days, 81.7% E- and 56.9% Z-ajoene remained. 4.3% and 0.5% E- and Z-ajoene remained when ajoene (0.1 mM in ethyl acetate) was incubated at 100 °C.     

Comparison of thermal,ultraviolet-c,and high pressure treatments on quality parameters of watermelon juice

The effect of thermal, ultraviolet-c, and high pressure treatments on colour, browning degree, dynamic viscosity, and lycopene content of watermelon juice was evaluated based on its pectin methylesterase residual level. Each treatment had a different impact on parameters studied. Ultraviolet-c treatments were rapid and effective to inactivate the pectin methylesterase of the watermelon juice compared to the thermal and high pressure treatments in the same time and temperature. High pressure treatments at 600 MPa kept the colour of the treated watermelon juice close to an untreated one, and that at 600–900 MPa held the browning degree and dynamic viscosity of the treated watermelon juice comparable to an untreated one. Moreover, the high pressure treatment had a slight impact on the all-trans-lycopene, total cis-lycopene, and total lycopene concentration of the watermelon juice compared to the other treatments. In summary, the high pressure treatment showed the lowest changes in colour, dynamic viscosity, browning degree, and lycopene content of the treated watermelon juice amongst the three treatments.     

Stabilization of all-trans-lycopene from tomato by encapsulation using cyclodextrins

The stabilization of all-trans-lycopene from tomato by encapsulation using α-, β- and γ-cyclodextrins (CDs) was evaluated. To that end, two different encapsulation methods were comparatively studied: a conventional method and a supercritical fluid extraction (SFE) process. An optimization procedure considering distinct molar ratios of CD/lycopene (1/0.0026, 1/0.005 and 1/0.05) as well as the type of cyclodextrin to be used was accomplished. The encapsulation was determined by using micro-Raman spectroscopy. All-trans-lycopene employed was obtained by SFE with a purity around 90–95%. As a result, a molar ratio CD/lycopene of 1/0.0026 was selected as it provided the best complexation yields (93.8%) whilst β-CD seemed to be the most favorable to be used to stabilize lycopene. A comparison of the two methods studied reflected higher encapsulation yields from the conventional method. However, the supercritical fluid approach offers numerous advantages such as the possibility of performing the extraction, fractionation and encapsulation of lycopene from tomato in one step, shortening notably the overall procedure time and minimizing the sample handling.     

Lycopene extraction from tomato peel by-product containing tomato seed using supercritical carbon dioxide

This work discusses the extraction of lycopene from tomato peel by-product containing tomato seed using supercritical carbon dioxide. The presence of tomato seed in the peel by-product improved the yield of extracted lycopene. Extraction was carried out at temperatures of 70-90 °C, pressures of 20-40 MPa, a particle size of 1.05 ± 0.10 mm and flow rates of 2-4 mL/min of CO₂ for 180 min extraction time. Oil from tomato seed was extracted under similar operating conditions and analyzed using GC-MS and GC-FID, while carotenoids extracted were analyzed by HPLC. The optimum operating condition to extract lycopene, under which 56% of lycopene was extracted, was found to be 90 °C, 40 MPa, and a ratio of tomato peel to seed of 37/63. The presence of tomato seed oil helped to improve the recovery of lycopene from 18% to 56%. The concentration of lycopene in supercritical carbon dioxide as a function of density at various temperatures was determined.     

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.     

Optimisation of biological and physical parameters for lycopene supercritical CO2 extraction from ordinary and high‐pigment tomato cultivars

BACKGROUND: Lycopene is used for several industrial applications. Supercritical CO₂ (SC‐CO₂) extraction from red‐ripe tomato fruits is an excellent technique to replace the use of harmful solvents. In this study, starting from red‐ripe tomatoes of ordinary and high‐lycopene cultivars, the effect of different agronomical and technical aspects on lycopene content, stability and yield was evaluated throughout the production process from fresh tomatoes to the final SC‐CO₂‐extracted oleoresin containing lycopene. RESULTS: Red‐ripe tomato cultivars differed in their lycopene content. Irrigation excess or deficit caused an increase in the amount of lycopene in the fruits. Fresh tomatoes were processed into a lyophilised matrix suitable for SC‐CO₂ extraction, which could be stored for more than 6 months at ? 20 °C without lycopene loss. Under the optimal extraction conditions, efficiencies of up to 80% were achieved, but the recovery of lycopene in the extracted oleoresin was very low (～24%). Co‐extraction of the tomato matrix mixed with a lipid co‐matrix allowed the recovery of ～90% of lycopene in the oleoresin. Using the high‐lycopene cultivars, the yield of total extracted lycopene increased by ～60% with respect to the ordinary cultivars. Lipids and other biologically active molecules were present in the oleoresin. CONCLUSION: A method for extracting, from a tomato matrix, a natural and solvent‐free oleoresin containing lycopene dissolved in a highly unsaturated vegetable oil has been described. The oleoresin represents an excellent product for testing on cancer and cardiovascular disease prevention. Copyright © 2010 Society of Chemical Industry     

Radical scavenging and reducing properties of extracts of cashew shoots (Anacardium occidentale)

The total phenolic content and antioxidant activities of methanol, hexane and ethyl acetate extracts of the shoots of Anacardium occidentale were measured. Total phenolic content was assessed by the Folin–Ciocalteau assay whereas antioxidant activities were assessed by measuring the ability of the extracts to scavenge the ABTS^·+ and DPPH^· radicals, superoxide anion radicals and nitric oxide radicals as well as their ability to reduce ferric ions. Results indicated that the methanol extract of A. occidentale was the most potent reducing agent and radical-scavengers compared to the other two extracts. The ethyl acetate extract exhibited some antioxidant activities whereas the hexane extract is the least reactive. The order of the antioxidant potency of the plant extract is methanol > ethyl acetate > hexane. The methanol extract contained more than 7 fold of total phenolic content compared to the hexane and ethyl acetate extracts indicating the likely possibility that the observed antioxidant activities were partly contributed by the phenolics. The results suggest that the shoots of A. occidentale are a source of natural antioxidants.     

Innovative extraction procedure for obtaining high pure lycopene from tomato

Many researchers have studied the biological effects of carotenoids and the more appropriate procedure for extracting them from vegetable sources. In this work we propose a rapid and low-cost procedure to extract lycopene from tomato in order to by-pass the problems related to the high cost of this molecule. Following this procedure we have obtained over 95% pure all-trans-lycopene checked by DAD-HPLC coupled with mass-spectrometer equipped with APCI source and by UV–Vis spectroscopy. Moreover, in order to evaluate the effectiveness of this procedure, we have assayed the capacity of the extracted lycopene to inhibit proliferation in T-lymphocyte jurkat J32 cells in comparison with authentic standard all-trans-lycopene. On this cellular line both standard lycopene and extracted lycopene tended to be dose-dependent but this latter seems to be more active even at lowest concentration.     

Evaluation of microbial inactivation and physicochemical properties of pressurized tomato juice during refrigerated storage

Effects of high pressure processing (300-500 MPa/25 °C/10 min) on microbial inactivation and processing qualities of tomato juices during refrigerated storage at 4 °C for 28 days were investigated to compare with those of conventionally thermal processing. Conventionally, thermal processing almost inactivated all the microorganisms and pectolytic enzymes and produced microbially and consistency stable tomato juices; however, they also reduced the color, extractable carotenoids and lycopene and vitamin C compared with fresh juice. During storage, all the pressure processing could improve the extractable carotenoids and lycopene contents compared with fresh juice, and they also retained more vitamin C contents than thermal processing. Although 300- and 400-MPa processing could retain a/b values of tomato juices as fresh juice during storage for 21 and 28 days, 500-MPa processing could improve the color of juices even after storage. Syneresis occurred in the 300- and 400-MPa processing juices by storing for 7 and 14 days; however, viscosity stable juice was produced by 500-MPa processing. Moreover, 400- and 500-MPa processing significantly inactivated microorganisms and the juices were microbially stable during storage. This study demonstrated that 500-MPa processing would be an alternative for conventionally thermal processing for tomato juice with improvement of some processing quality attributes.     

Dose-effect study on the antioxidant properties of leaves and outer bracts of extracts obtained from Violetto di Toscana artichoke

Artichoke (Cynara scolymus L.) is an edible vegetable largely used in the Mediterranean diet and in folk medicine. The present paper discusses the analysis of the polyphenol content of leaves and outer bracts of Violetto di Toscana artichoke using different extraction procedures with the aim of establishing a correlation between polyphenol subclasses and antioxidant activity measured on human LDL oxidized by copper ions. HPLC/DAD and HPLC/MS analyses revealed that both the matrixes contain identical polyphenol subclasses, with mainly quantitative differences. The antioxidant effect of four artichoke extracts decreases in the following order when the sum of total phenolic compounds was considered: ethanolic extract from leaves (IC₅₀ = 2.92 ± 0.46 μM); ethanolic extract from outer bracts (IC₅₀ = 4.04 ± 0.21 μM); ethyl acetate extract from leaves (IC₅₀ = 4.91 ± 0.11 μM); ethyl acetate extract from outer bracts (IC₅₀ = 10.18 ± 1.6 μM). IC₅₀ were also calculated considering the concentrations of single polyphenol subclasses. In both cases, the potency of antioxidant properties was not related to the amount of total polyphenols or the single subclasses.