A method for promoting the cis-isomerization of lycopene using food ingredients

Abstract

This invention discloses a method for promoting the conversion of lycopene from the all-trans configuration to the cis isomer using naturally occurring components in food, belonging to the field of food functional factor activity enhancement technology. This invention employs a method for catalyzing the isomerization of lycopene using food-grade plant extracts and food components, comprising the following steps: adding plant extracts or pre-treated food components to tomato products containing vegetable oil, and reacting under heating conditions to obtain tomato products with high cis-lycopene content. The cis-lycopene content can reach over 35%, providing an efficient, economical, and green method for preparing tomato products with high cis-lycopene content.

Description

Technical Field

[0001] This invention belongs to the field of food functional factor activity enhancement technology, and relates to a method for promoting cis isomerization of lycopene using food components. Background Technology

[0002] Lycopene is a natural carotenoid widely found in fruits and vegetables such as tomatoes, carrots, and watermelons. As a multifunctional natural ingredient, lycopene is believed to have functions such as preventing cardiovascular disease, delaying aging, preventing metabolic disorders, and preventing obesity. Functional foods, health foods, and cosmetics with lycopene as their main active ingredient are increasingly being developed.

[0003] Because its molecule contains 11 conjugated double bonds, lycopene can exist in both cis and all-trans configurations and has multiple isomers. More than 90% of naturally occurring lycopene-containing fruits, vegetables, and processed products are in the all-trans configuration, but its cis isomer is abundant in the human body—cis-lycopene accounts for more than 50% of serum and tissues. Studies have found that for dietary lycopene, cis-lycopene is more easily absorbed by the body than all-trans-lycopene, exhibiting higher bioavailability; cis-lycopene also has stronger antioxidant activity than trans-lycopene. Since lycopene is a fat-soluble substance, its absorption rate in the human body is relatively low. Isomerization, converting trans-lycopene to cis-lycopene, can improve the physiological activity and bioavailability of lycopene and its related products.

[0004] A search revealed that currently published patents such as CN102627521A and CN104549377A describe isomerization methods for converting trans-lycopene to cis-lycopene using short-time thermal reflux / cholate adsorption or iodine-doped titanium dioxide nanoparticles as non-photocatalysts. These isomerization methods require the use of organic solvents and chemical reagents, resulting in chemical residues. Furthermore, these methods all focus on lycopene extracts, which, after isomerization, differ from ordinary lycopene extracts and cannot be directly used as food additives in food processing. Therefore, this application attempts to develop a method that uses food-grade raw materials containing lycopene as a starting point and utilizes naturally occurring chemical components in food to catalyze the isomerization of natural (all-trans) lycopene to cis-lycopene, thereby increasing the proportion of cis-configured lycopene in the product. Summary of the Invention

[0005] Technical issues

[0006] Currently, mainstream lycopene isomerization methods use organic reagents, but the amount of catalyst added is limited, and problems such as organic reagent residue and catalyst removal exist. Therefore, to meet the current market and consumer demands for green products, a lycopene isomerization method using food-grade raw materials is needed to obtain lycopene products with high cis-lycopene content.

[0007] Technical solution

[0008] To address the above problems, this invention provides a method for preparing a product with high cis-lycopene content, comprising the following steps:

[0009] Plant extracts and vegetable oils are added to products containing lycopene, and the mixture is heated to produce a product with a high cis-lycopene content.

[0010] Furthermore, the lycopene in the product containing lycopene includes two types: all-trans lycopene and cis-lycopene.

[0011] Alternatively, the lycopene in products containing lycopene may be all-trans lycopene.

[0012] Furthermore, the lycopene-containing product is prepared from a plant containing lycopene.

[0013] Furthermore, plants containing lycopene include one or more of the following: tomatoes, carrots, watermelons, papayas, and guavas.

[0014] Specifically, optional products containing lycopene include tomato paste, tomato sauce, tomato powder, and tomato juice.

[0015] Furthermore, the plant extract contains garlic extract and broccoli extract.

[0016] Furthermore, the broccoli-containing extract includes broccoli extract and broccoli sauce.

[0017] Specifically, optional steps for preparing broccoli sauce include:

[0018] Broccoli sprouts cultivated for 3-6 days were mixed with an ascorbic acid aqueous solution with a concentration of 0.03-6 mg / ml at a mass ratio of 1:0.5-2. The mixture was then hydrolyzed at 30-37°C for 1-3 hours, followed by freeze-drying for 4-6 hours to obtain broccoli sprout sauce.

[0019] Furthermore, the ratio of the amount of plant extract added to the mass of the product containing lycopene is 25-100 mg: 1 g.

[0020] Furthermore, vegetable oils include one or more of olive oil, rapeseed oil, peanut oil, and sesame oil.

[0021] Specifically, the vegetable oil that can be selected is olive oil.

[0022] Furthermore, the mass ratio of the vegetable oil to the product containing lycopene is 1g:5-15g.

[0023] Furthermore, the heating is carried out at 80℃ to 120℃, and the reaction time is 0.5 to 2 hours.

[0024] Furthermore, the cis-lycopene in the product with high cis-lycopene content is one or more of 13-cis-lycopene, 9-cis-lycopene, and 5-cis-lycopene.

[0025] Furthermore, the total cis-lycopene content in the product exceeds 35% of the total lycopene.

[0026] The method provided by this invention has applications in the fields of cis-isomerization of lycopene and food.

[0027] This invention provides a product with high cis-lycopene content obtained by the above method.

[0028] The application of the product with high cis-lycopene content provided by this invention in the food industry.

[0029] Beneficial effects

[0030] The isomerization method of this invention can produce lycopene with a high cis-proportion in a non-toxic, safe, rapid and efficient manner using natural food components. The proportion of cis-lycopene in the product can reach more than 35%, providing an efficient, economical and safe method for preparing lycopene products with high physiological activity and high cis-lycopene content. Attached Figure Description

[0031] Figure 1 This is a liquid phase chromatogram of the reaction product cis-lycopene detected in Example 1.

[0032] Figure 2 This is a liquid phase chromatogram of the reaction product cis-lycopene detected in Example 2.

[0033] Figure 3 This is a liquid phase chromatogram of the reaction product cis-lycopene detected in Example 3.

[0034] Figure 4 The liquid phase diagram shows lycopene in Comparative Example 1.

[0035] Figure 5 The liquid phase diagram shows lycopene in Comparative Example 2.

[0036] Figure 6 The liquid phase diagram shows lycopene in Comparative Example 3.

[0037] Figure 7 The liquid phase diagram shows lycopene in Comparative Example 4.

[0038] Figure 8 The liquid phase diagram shows lycopene in Comparative Example 5.

[0039] Figure 9 The liquid phase diagram shows lycopene in Comparative Example 6.

[0040] Figure 10 Q-value calculation method (DB / D) || ). Detailed Implementation

[0041] The preferred embodiments of the present invention are described below. It should be understood that the embodiments are for better explanation of the present invention and are not intended to limit the present invention.

[0042] Source of raw materials

[0043] Allicin is from Langde Biotechnology Co., Ltd.; glucosinolates are from Jiashengkangze Biotechnology Co., Ltd.; tomato sauce is from Shanghai Zhiying Biotechnology Co., Ltd.; broccoli seeds are from Jingyan Yinong (Beijing) Seed Industry Technology Co., Ltd.'s Lvjian Xiya No. 1; garlic extract: Langde Biotechnology Co., Ltd.; broccoli extract: Xinlu Biotechnology Co., Ltd.; horseradish extract: Zhuorui Biotechnology Co., Ltd.; other ingredients, unless otherwise specified, are commercially available.

[0044] Broccoli sprout cultivation:

[0045] (1) Before cultivation, wash the seeds with water, add 700ml of water to the seedling tray and cover it with sowing paper (the amount of water should not be more than the sowing paper);

[0046] (2) Spread the seeds evenly on the seeding paper, and place the seedling tray indoors, away from direct sunlight. Maintain the indoor temperature between 15℃ and 25℃;

[0047] (3) Spray water 4 times a day to keep the sowing paper moist, and change the water in the seedling tray every 24 hours;

[0048] (4) Harvest broccoli sprouts after 4 days of cultivation.

[0049] Test methods

[0050] The liquid chromatography method for analyzing cis-lycopene in tomato sauce is as follows:

[0051] 1) Extraction of lycopene: Take 5g of the reacted tomato paste, add 20ml of n-hexane:methanol:acetone (2:1:1, v / v / v), and extract magnetically for 20min. Filter and collect the supernatant. Repeat the above steps twice with the residue until the color of the residue becomes lighter. Combine the obtained supernatants. Transfer the combined supernatant to a separatory funnel and add 5ml of water. After standing, take the n-hexane layer, remove the organic phase by vacuum rotary evaporation at 45℃, dissolve in ethyl acetate, and bring the volume to 10ml.

[0052] 2) Liquid chromatography analysis conditions for lycopene cis isomers:

[0053] High-performance liquid chromatography-diode array detector (HPLC-PDA) was used for separation and detection, and qualitative identification was performed based on retention time and spectral characteristics. Detection conditions: Column: C30 (5μm, 250mm×4.6mm); Liquid chromatography conditions: Column temperature 30℃; Flow rate 1mL / min; Injection volume 20μL; Mobile phase A: methanol-methyl tert-butyl ether-water (450:25:25, v / v / v); Mobile phase B: methyl tert-butyl ether-methanol (400:100, v / v); Gradient elution was used. The gradient changes of mobile phase B were as follows: 0min–20min, B changed from 45% to 50%; 20min–28min, B changed from 50% to 95%; 28min–32min, B phase maintained at 95%; 32min–34min, B phase changed from 95% to 100%; 34min–37min, B phase maintained at 100%; 37min–40min, B phase changed from 100% to 45%, for a total run time of 45min; Detection wavelength: 471nm.

[0054] 3) Identification of lycopene isomers

[0055] The identification of lycopene was achieved by comparing it with relevant data reported in the literature, including retention time, Z peak (the peak near 360 nm, which is the characteristic cis absorption peak of lycopene), Q value (the ratio of Z peak to the main absorption peak). The peak identification results are shown in Table 10. The 13-cis, 5-cis, 9-cis and all-trans lycopene isomers can all be identified well.

[0056] Table 1 Identification of Lycopene Isomerization

[0057]

[0058] The present invention will be further explained and described below with reference to specific embodiments.

[0059] Example 1

[0060] A method for promoting cis-isomerization of lycopene using food components includes the following steps:

[0061] Garlic extract was added to 10g of tomato sauce containing olive oil, placed in a capped sample vial, and the air was purged with nitrogen. The mixture was heated in an oil bath at 80℃ with stirring for 1 hour. Immediately after heating, it was cooled in an ice-water bath. A tomato sauce with high cis-lycopene content was obtained, wherein the amount of garlic extract added to the tomato sauce was 100mg / g, and the amount of olive oil added to the tomato sauce was 0.1g / g. The sample was stored at -20℃ before analysis.

[0062] The lycopene in the extracted tomato sauce was tested, and the test results are as follows: Figure 1 ;

[0063] from Figure 1 It can be seen that after isomerization, all-trans lycopene yields three main cis products: 13-cis-lycopene with a retention time of 30.35 min, 9-cis-lycopene with a retention time of 32.29 min, and 5-cis-lycopene with a retention time of 35.20 min. The results indicate that all-trans lycopene can be isomerized to cis-lycopene via allicin catalysis, with the highly bioavailable 5-cis-lycopene being the predominant product, accounting for 21.32%, and the total cis-lycopene accounting for 58.12%. The total cis-lycopene includes 13-cis-lycopene, 9-cis-lycopene, and 5-cis-lycopene, among other cis-lycopene products.

[0064] Example 2

[0065] A method for promoting cis-isomerization of lycopene using food components includes the following steps:

[0066] Broccoli extract was added to 10g of tomato sauce containing olive oil, placed in a capped sample vial, and the air was purged with nitrogen. The mixture was heated in an oil bath at 100℃ for 1 hour. Immediately after heating, it was cooled in an ice-water bath. A tomato sauce with high cis-lycopene content was obtained, with broccoli extract added at 25mg / g and olive oil added at 0.1g / g. The sample was stored at -20℃ before analysis.

[0067] The lycopene in the extracted tomato sauce was tested, and the test results are as follows: Figure 2 ;

[0068] from Figure 2It can be seen that after isomerization, all-trans lycopene yields three main cis products: 13-cis-lycopene (retention time 30.48 min), 9-cis-lycopene (retention time 32.65 min), and 5-cis-lycopene (retention time 36.11 min). The results indicate that all-trans lycopene can be isomerized to cis-lycopene via sulforaphane-catalyzed isomerization, with the highly bioavailable 5-cis-lycopene being the predominant product, accounting for 19.3%, and the total cis-lycopene accounting for 39%. The total cis-lycopene includes 13-cis-lycopene, 9-cis-lycopene, and 5-cis-lycopene, among other cis-lycopene products.

[0069] Example 3

[0070] A method for promoting cis-isomerization of lycopene using food components includes the following steps:

[0071] Fresh broccoli sprouts harvested after four days of cultivation were mixed with water containing 0.05 mg / ml ascorbic acid at a 1:1 mass ratio. The mixture was then thoroughly crushed using a juicer and hydrolyzed at 35°C for 2 hours. The resulting broccoli sprout juice was then freeze-dried for 5 hours to obtain broccoli sprout sauce.

[0072] Add 1g of dried and concentrated broccoli sprout paste to 10g of tomato sauce containing olive oil. Place the mixture in a capped sample bottle and purge the air with nitrogen. Heat in an oil bath at 100℃ for 1 hour. Immediately after heating, cool in an ice-water bath. A tomato sauce with high cis-lycopene content is obtained, with 0.1g / g of olive oil added. Store the sample at -20℃ before analysis.

[0073] The lycopene in the extracted tomato sauce was tested, and the test results are as follows: Figure 3 ;

[0074] from Figure 3 It can be seen that after isomerization, all-trans lycopene yields three main cis products: 13-cis-lycopene with a retention time of 29.90 min, 9-cis-lycopene with a retention time of 31.88 min, and 5-cis-lycopene with a retention time of 34.95 min. The results indicate that all-trans lycopene can be isomerized to cis-lycopene via the addition of broccoli bud juice, with the highly bioavailable 5-cis-lycopene being the predominant product, accounting for 26.04%, and the total cis-lycopene accounting for 61.87%. The total cis-lycopene includes 13-cis-lycopene, 9-cis-lycopene, and 5-cis-lycopene, among other cis-lycopene products.

[0075] Comparative Example 1

[0076] Olive oil was omitted from Example 1, while other aspects remained the same as in Example 1, to obtain the reaction product.

[0077] The obtained reaction products were tested, and the test results are as follows: Figure 4 :

[0078] from Figure 4 It can be seen that after the tomato sauce was heated, only a small amount of cis-lycopene was detected. Specifically, 13-cis-lycopene was retained for 31.32 min, 9-cis-lycopene for 33.84 min, and 5-cis-lycopene for 37.22 min. The proportion of 13-cis-lycopene was 2.13%, the proportion of 9-cis-lycopene was 2.51%, and the proportion of 5-cis-lycopene was only 2.98%. The total proportion of cis-lycopene was 8.06%, which is much lower than the total proportion of cis-lycopene in the example.

[0079] Comparative Example 2

[0080] The garlic extract in Example 1 was omitted, the heating temperature was adjusted to 100°C and the heating time was 1 hour, and other aspects remained the same as in the example to obtain the reaction product.

[0081] The obtained reaction products were tested, and the test results are as follows: Figure 5 :

[0082] from Figure 5 It can be seen that after the tomato sauce was heated, only a small amount of cis-lycopene was detected. Specifically, 13-cis-lycopene was retained for 31.50 min, 9-cis-lycopene for 34.06 min, and 5-cis-lycopene for 37.62 min. The proportion of 13-cis-lycopene was 0.62%, the proportion of 9-cis-lycopene was 2.74%, and the proportion of 5-cis-lycopene was only 3.32%. The total proportion of cis-lycopene was 6.68%, which is much lower than the total proportion of cis-lycopene in the example.

[0083] Comparative Example 3

[0084] The garlic extract in Example 1 was replaced with an equal amount of horseradish extract. Everything else remained the same as in Example 1, and the reaction product was obtained.

[0085] The obtained reaction products were tested, and the test results are as follows: Figure 6 :

[0086] from Figure 6It can be seen that after the tomato sauce was heated, only a small amount of cis-lycopene was detected. Specifically, 13-cis-lycopene was retained for 29.984 min and 9-cis-lycopene for 32.114 min. The proportion of 13-cis-lycopene was 6.339%, the proportion of 9-cis-lycopene was 8.645%, and the proportion of 5-cis-lycopene was only 2.202%. The total proportion of cis-lycopene was 17.19%, which is much lower than the proportion of total cis-lycopene in the example.

[0087] Comparative Example 4

[0088] The garlic extract in Example 1 was replaced with an equal amount of radish seed extract. Everything else remained the same as in Example 1, and the reaction product was obtained.

[0089] The obtained reaction products were tested, and the test results are as follows: Figure 7 :

[0090] from Figure 7 It can be seen that after the tomato sauce was heated, only a small amount of cis-lycopene was detected. Specifically, 13-cis-lycopene was retained for 31.322 min and 9-cis-lycopene for 33.393 min. The proportion of 13-cis-lycopene was 8.513%, the proportion of 9-cis-lycopene was 4.88%, and the proportion of 5-cis-lycopene was only 7.922%. The total proportion of cis-lycopene was 24.13%, which is much lower than the proportion of total cis-lycopene in the example.

[0091] Comparative Example 5

[0092] The garlic extract in Example 1 was replaced with an equal amount of alliin. Everything else remained the same as in Example 1, and the reaction product was obtained.

[0093] The obtained reaction products were tested, and the test results are as follows: Figure 7 :

[0094] As shown in Figure 8, after heating the tomato sauce, only a small amount of cis-lycopene was detected. Specifically, 13-cis-lycopene was retained for 31.372 min and 9-cis-lycopene for 33.640 min. The proportion of 13-cis-lycopene was 4.49%, and the proportion of 9-cis-lycopene was 5.72%. No 5-cis-lycopene was detected, and the total proportion of cis-lycopene was 11.54%, which is much lower than the proportion of total cis-lycopene in the example.

[0095] Comparative Example 6

[0096] The broccoli extract in Example 2 was replaced with an equal amount of glucosinolates. Everything else remained the same as in Example 2, and the reaction product was obtained.

[0097] The obtained reaction products were tested, and the test results are as follows: Figure 8 :

[0098] from Figure 9 It can be seen that after the tomato sauce was heated, only a small amount of cis-lycopene was detected. Specifically, 13-cis-lycopene was retained for 30.042 min and 9-cis-lycopene for 32.158 min. The proportion of 13-cis-lycopene was 4.132%, the proportion of 9-cis-lycopene was 9.497%, and the proportion of 5-cis-lycopene was only 6.338%. The total proportion of cis-lycopene was 19.97%, which is much lower than the proportion of total cis-lycopene in the example.

[0099] Table 2 shows the detection data for Examples 1-3 and Comparative Examples 1-6.

[0100] 5-cis-lycopene Total cis-lycopene Example 1 21.32％ 58.12％ Example 2 19.3％ 39％ Example 3 26.04％ 61.87％ Comparative Example 1 2.98％ 8.06％ Comparative Example 2 0.62％ 6.68％ Comparative Example 3 2.202％ 17.19％ Comparative Example 4 7.922％ 24.13％ Comparative Example 5 0％ 11.54％ Comparative Example 6 6.338％ 19.97％

[0101] The data from the examples and comparative examples were compiled and compared, as shown in Table 1. It can be seen that in Examples 1 to 3 of the present invention, garlic extract, broccoli extract and broccoli sprout sauce were used respectively to increase the total cis-lycopene to a high proportion, achieving excellent results.

[0102] In Comparative Example 1, olive oil was omitted. Lycopene is a fat-soluble substance, and without olive oil as a reaction medium, it is difficult to obtain a lycopene product with a high cis-lycopene content. In Comparative Example 2, the extract was omitted, and only heating was performed; it was found that it was difficult to obtain a lycopene product with a high cis-lycopene content.

[0103] Comparative Examples 3 and 4 used horseradish extract and radish seed extract, respectively. It was found that not all substances similar to garlic extract and broccoli extract could effectively catalyze lycopene isomerization. It is difficult to obtain lycopene products with high cis-lycopene content by simply selecting similar substances.

[0104] Comparative Examples 4 and 5 used sulfur-containing compounds—alliin and sulforaphane—from garlic extract and broccoli extract, respectively. It was found that using alliin and sulforaphane alone was insufficient to obtain lycopene products with high cis-lycopene content. This indicates that even though the catalytic effects of sulfur-containing compounds are generally known, not all sulfur-containing compounds have good catalytic effects. Even different sulfides from the same plant can have significantly different catalytic effects in actual operation due to the complexity of the reaction. This is because other substances in the plant extract may affect the catalytic reaction. Therefore, the effect of cis-catalysis of lycopene cannot be easily predicted.

[0105] Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Anyone skilled in the art can make various modifications and alterations without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be determined by the claims.

Claims

1. A method for preparing a product with high cis-lycopene content, characterized in that, Includes the following steps: By adding broccoli sauce and olive oil to products containing lycopene and heating to react, a product with a high cis-lycopene content is obtained. The preparation steps of the broccoli sauce are as follows: add broccoli sprouts cultivated for 3-6 days to an ascorbic acid aqueous solution with a concentration of 0.03-6 mg / ml at a mass ratio of 1:0.5-2, mix evenly, and allow the broccoli sprout juice to hydrolyze at 30-37℃ for 1-3 hours, and then freeze-dry for 4-6 hours to obtain broccoli sprout sauce. The ratio of the amount of broccoli sauce added to the mass of the product containing lycopene is 25~100mg : 1g; The mass ratio of the olive oil to the product containing lycopene is 1g : 5~15g; The heating is carried out at 100°C for 1 hour.

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