CN110128234B - Quick green preparation method of high cis-isomer lycopene - Google Patents
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Abstract
The invention relates to the technical field of preparation processes of cis-isomer lycopene, in particular to a rapid green preparation method of high-cis-isomer lycopene. The invention takes high-purity lycopene or lycopene oleoresin or all-trans-lycopene as raw material, and the high cis-isomer lycopene is prepared by ball milling under the conditions of no oxygen and no light, and the solvent-free process ensures that the lycopene is green and environment-friendly compared with the prior process, better meets the requirements of solvent-free and non-toxic of functional food, has short process time, higher preparation efficiency, and is simple in process and easier to realize industrial production.
Description
Technical Field
The invention relates to the technical field of preparation processes of cis-isomer lycopene, and discloses a rapid green preparation method of high cis-isomer lycopene.
Background
Lycopene is a natural lipophilic carotenoid rich in lycopene in red fruits and vegetables, such as tomatoes, rosehips, watermelons and the like. The 87% lycopene is from tomatoes, especially the higher content of dark red fresh tomatoes. Lycopene is one of the main carotenoids in human serum and tissues, and studies have found that 65% of lycopene is distributed in fat, the remaining 20% is distributed in liver, 5% is distributed in plasma, and about 60% of lycopene in plasma is cis-isomer due to the strong lipid solubility of lycopene. Lycopene is one of the strongest antioxidants, and it inhibits the carcinogenesis of animal and human cells, prevents cancer and chronic diseases, reduces the incidence of cancer and alleviates the extent of cancer progression.
Lycopene is a highly unsaturated hydrocarbon compound whose chemical formula mainly contains 11 conjugated double bonds and 2 non-conjugated double bonds in a linear arrangement, and thus has a longer chain length than other carotenoids. In naturally occurring lycopene, the all-trans isomer accounts for 94% to 96% of the total amount of lycopene in red tomatoes. The cis-isomer and the all-trans-isomer of lycopene have different physical and chemical properties, the cis-isomer has lighter color, the melting point is reduced, the lycopene is not easy to crystallize, and the maximum absorption peak value is shifted. The cis-isomer of lycopene has strong lipid solubility and is easily dissolved in oil and other hydrocarbon solvents. The cis isomer is thermodynamically more stable and more readily absorbed by the human body and has better bioavailability than the all-trans isomer. Thus a simple and efficient process for the isomerization of all-trans lycopene to the high cis isomer is necessary. Wherein the (5Z) -cis isomer has higher bioavailability, oxidation resistance and storage stability than other cis isomers, so that the increase of the content of the (5Z) -cis isomer is very necessary.
The methods for isomerizing lycopene with high cis-isomer reported in the literature mainly comprise the following steps: traditional heating, microwave heating, light irradiation. These methods have the characteristics of relatively low cis-isomerization efficiency, easy degradation and the like, and require organic solvents and chemical additives, which are not very environment-friendly for the production process of functional food ingredients.
The all-trans lycopene is dissolved in n-hexane and benzene organic solvent, nitrogen is blown in, and the mixture is heated in an oil bath at 50 ℃ in a dark place, wherein the cis-isomer accounts for 87.5 percent and 69.1 percent. The method has too long processing time in the actual process production, which not only increases the operation cost, but also reduces the production efficiency (Honda, M., et al. Spectral characteristics of Z-isomers of depends formed into a reduced heat efficiency and solution efficiencies on the E/Z isomerization process. Food Chemistry, 2015.171: p. 323-9.).
The Lycopene Oleoresin is heated in microwaves to improve the trans-cis Isomerization efficiency, but this method is difficult to implement in the actual industrial production of functional food ingredients (Honda, m., et al., Microwave-assisted Z-isometrization of (all-E) -lycopen in the Tomato oil and production of the Conversion by Microwave available resins contacting filtration Compounds Eur. J. Lipid Sci. Technol, 2018.120 (7)).
At present, the domestic patent about the preparation research of the high cis-isomer lycopene is mainly disclosed as CN101314554, which is named as a method for synthesizing the cis-lycopene isomer from all-trans lycopene by photochemical isomerization reaction, and the patent adopts ultraviolet irradiation, and uses a tile high-pressure mercury lamp and a cut-off filter to induce the isomerization of the lycopene under the protection of nitrogen, so that the proportion of the cis-isomer in the obtained product is 60wt% to 73wt%, but the light energy utilization rate of the high-pressure mercury lamp in the method is lower, and a cold trap needs to be added to cool the high-pressure mercury lamp at the same time, so that the operation cost is increased, the actual industrial production is difficult to realize, and in addition, a polar solvent is introduced, so that the prepared functional food has solvent residue, and the safety of the food is influenced.
Disclosure of Invention
The invention provides a rapid green preparation method of high cis-isomer lycopene, overcomes the defects of the prior art, and can effectively solve the problems of high cost and solvent residue in the existing preparation process of high cis-isomer lycopene.
The technical scheme of the invention is realized by the following measures: a fast green preparation method of high cis-isomer lycopene is carried out according to the following steps: ball milling lycopene oleoresin or natural lycopene or all-trans lycopene under the conditions of light and oxygen free, wherein the ball milling speed is 200-1300 r/min, the ball milling temperature is 15-50 ℃, and the ball milling time is 1-2 hours to obtain the lycopene with the mass percentage of (5Z) -cis isomer reaching 60-65%.
The following is further optimization or/and improvement of the technical scheme of the invention:
the lycopene oleoresin or natural lycopene or all-trans lycopene is subjected to ball milling in a nitrogen atmosphere and in a dark condition.
Grinding balls with different sizes are placed in a ball milling tank of the ball mill, then lycopene oleoresin or natural lycopene or all-trans lycopene is added into the ball milling tank, the ball milling tank is filled with nitrogen, a gland is sealed, and the ball milling tank is placed in the ball mill and subjected to ball milling.
After the ball milling, the temperature of the obtained lycopene with high cis-isomer was returned to room temperature within 3 minutes.
The invention takes high-purity lycopene or lycopene oleoresin or all-trans-lycopene as raw material, and the high cis-isomer lycopene is prepared by ball milling under the conditions of no oxygen and no light, and the solvent-free process ensures that the lycopene is green and environment-friendly compared with the prior process, better meets the requirements of solvent-free and non-toxic of functional food, has short process time, higher preparation efficiency, and is simple in process and easier to realize industrial production.
Drawings
FIG. 1-1 shows HPLC-DAD (high performance liquid chromatography) chromatography of the product obtained by ball milling all-trans lycopene in nitrogen for 60min in example 7 of the present invention.
Fig. 1-2 are HPLC-DAD spectra of all-trans lycopene retained in a product obtained after ball milling of all-trans lycopene under nitrogen protection for 60min in example 7 of the present invention.
Fig. 1-2-1 is an enlarged view of a portion of the upper view of fig. 1-2.
Fig. 1-2-2 is an enlarged view of a portion of the lower view of fig. 1-2.
FIGS. 1-3 are HPLC-DAD spectra of (5Z) -cis isomer in the product obtained after ball milling of all-trans lycopene in nitrogen for 60min in example 7 of the present invention.
Fig. 2 is an infrared spectrum of all-trans lycopene and infrared spectra of products obtained after ball milling of all-trans lycopene for 60min, 90 min and 120 min under nitrogen protection in example 7 of the present invention.
In fig. 2, a is all-trans lycopene, b is ball-milled for 60min under nitrogen protection, c is ball-milled for 90 min under nitrogen protection, and d is ball-milled for 120 min under nitrogen protection.
Detailed Description
The present invention is not limited by the following examples, and specific embodiments may be determined according to the technical solutions and practical situations of the present invention. The various chemical reagents and chemical articles mentioned in the invention are all the chemical reagents and chemical articles which are well known and commonly used in the prior art, unless otherwise specified; the percentages in the invention are mass percentages unless otherwise specified; the normal temperature and room temperature in the present invention generally mean a temperature of 15 ℃ to 25 ℃.
The invention is further described below with reference to the following examples:
example 1: the rapid green preparation method of the high cis-isomer lycopene is carried out according to the following steps: ball milling lycopene oleoresin or natural lycopene or all-trans lycopene under the conditions of light and oxygen free, wherein the ball milling speed is 200-1300 r/min, the ball milling temperature is 15-50 ℃, and the ball milling time is 1-2 hours to obtain the lycopene with the mass percentage of (5Z) -cis isomer reaching 60-65%.
The invention takes high-purity lycopene (natural lycopene) or lycopene oleoresin or all-trans-lycopene as raw materials, and prepares the high-content cis-isomer lycopene by the process of 'anaerobic atmosphere + ball milling', the process without solvent is more environment-friendly than the prior process, better meets the requirements of functional food on no solvent and no toxicity, and the process time is short, thereby the preparation efficiency is higher, in addition, the process is simple, and the industrial production is easier to realize.
Example 2: the rapid green preparation method of the high cis-isomer lycopene is carried out according to the following steps: ball milling lycopene oleoresin or natural lycopene or all-trans lycopene under the conditions of light and oxygen resistance, wherein the ball milling speed is 200 revolutions per minute or 1300 revolutions per minute, the ball milling temperature is 15 ℃ or 50 ℃, and the ball milling is carried out for 1 hour to 2 hours to obtain the lycopene with the mass percentage of (5Z) -cis isomer reaching 60 percent to 65 percent.
Example 3: as an optimization of the above examples, the lycopene oleoresin or natural lycopene or all-trans lycopene was ball milled under nitrogen atmosphere and in the dark.
The nitrogen has the advantages of low cost and safety, and the method is easier to operate and realizes industrial production.
Example 4: as the optimization of the above example 3, grinding balls with different sizes are put into the ball milling tank of the ball mill, then the lycopene oleoresin or natural lycopene or all-trans lycopene is added into the ball milling tank, the ball milling tank is filled with nitrogen, the gland is sealed, and the ball milling tank is placed into the ball mill and ball milling is carried out.
The grinding balls with different sizes are adopted, so that the raw materials can be more sufficiently ball-milled, the conversion rate of the raw materials is further improved, and the process time is shortened.
Example 5: as an optimization of the above example, the temperature of the obtained high cis-isomer lycopene was returned to room temperature within 3 minutes after the completion of the ball milling.
The following examples use all-trans lycopene as the starting material.
Example 6: the rapid green preparation method of the high cis-isomer lycopene is carried out according to the following steps: putting 4, 20 and 30 stainless steel grinding balls with the diameters of 3 mm, 5 mm and 8 mm into a stainless steel ball milling tank, weighing 0.5 g of all-trans lycopene into the stainless steel ball milling tank, ball milling the all-trans lycopene in the stainless steel ball milling tank at the rotation speed of 1100 r/min under the nitrogen atmosphere at the ball milling temperature of 30 ℃, ball milling for 60min respectively, sampling after 120 min, and performing nuclear magnetic resonance hydrogen spectrum and infrared analysis.
The nuclear magnetic resonance hydrogen spectrum of a sample after ball milling for 60min and 120 min according to the method described in example 6 shows that the chemical shift of the low field region is 5.9ppm to 6.7 ppm of olefin hydrogen disappears, and the chemical shift is 2.50ppm to 3.50 ppm, so that multiple peaks appear; infrared functional group region 3035cm-1，3019 cm-1The stretching vibration of olefin hydrocarbon disappears, and the fingerprint area is 956 cm-1The bending vibration of the disubstituted olefin disappears and becomes 1024 cm-1And the nuclear magnetic resonance hydrogen spectrum and the infrared result show that the all-trans lycopene is oxidized and decomposed.
After ball milling for 60min, the mass percent of the (5Z) -cis isomer reaches 60 percent by adopting the method described in the embodiment 6; the mass percent of the (5Z) -cis isomer is up to 62 percent after ball milling for 120 min.
Example 7: the rapid green preparation method of the high cis-isomer lycopene is carried out according to the following steps: putting 4, 20 and 30 large, medium and small grinding balls into a ball milling tank, weighing 0.5 g of all-trans-lycopene into a stainless steel ball milling tank, ball milling at the rotating speed of 1100 r/min, ball milling under the protection of nitrogen gas at the temperature of 40 ℃, ball milling for 60min, 90 min and 120 min respectively, and sampling to obtain a nuclear magnetic resonance hydrogen spectrum, an infrared spectrum, an ultraviolet spectrum and a liquid chromatogram.
According to the NMR and IR spectra data of the reference (Takehara, M., et al, chromatography and thermal ionization of (all-E) -lycopen. Journal of Agricultural and Food Chemistry, 2014.62 (1): 264-269.), all-trans lycopene is treated by the method described in example 7, the infrared functional group region 3035 cm-1 and 3019 cm-1 olefin hydrocarbon stretching vibration become 3035 cm-1, and the structure of all-trans lycopene is proved to be changed, and the HPLC is shown in FIG. 1-1.
The hydrogen spectral data indicate a single peak added to the chemical shift of about 2.19 ppm, which is known as (5Z) -cis isomer lycopene by comparison with the data in the literature (Takehara, M., et al. Characterization and thermal Characterization of (all-E) -lycopen. Journal of Agricultural and Food Chemistry, 2014.62 (1): 264-.
The ultraviolet absorption characteristic wavelength (nm) of all-trans lycopene is 296, 362, 444, 469, 499 by high performance liquid chromatography (such as figure 1-2, figure 1-2-1, figure 1-2-2); the ultraviolet absorption characteristic wavelength (nm) of the (5Z) -cis isomer is 296, 361, 443, 469, 500 (shown in figure 1-3).
After ball milling for 60min, 90 min and 120 min according to the method described in example 7, the (5Z) -cis isomer lycopene content was about 60%.
After ball milling for 60min, the mass percent of the (5Z) -cis isomer reaches 63 percent by adopting the method described in the embodiment 7; after ball milling for 90 min, the mass percent of the (5Z) -cis isomer reaches 65 percent; the mass percentage of the (5Z) -cis isomer reaches 60 percent after ball milling for 120 min.
Example 8: the rapid green preparation method of the high cis-isomer lycopene is carried out according to the following steps: putting 4, 20 and 30 stainless steel grinding balls with the diameters of 3 mm, 5 mm and 8 mm into a stainless steel ball milling tank, weighing 0.5 g of all-trans lycopene into the stainless steel ball milling tank, ball milling at the rotating speed of 1100 r/min under the protection of nitrogen, ball milling at the temperature of 50 ℃ for 60min and 120 min respectively, sampling, and performing nuclear magnetic resonance hydrogen spectrum and infrared analysis.
The hydrogen nuclear magnetic resonance spectrum of the ball-milled product obtained by the method described in example 8 shows that a broad multiplet appears at chemical shifts of 2.50ppm to 3.50 ppm;
956 cm infrared fingerprint area-1In order to weaken the bending vibration of the disubstituted olefin, an absorption peak of 1024 cm is added-1The results show partial oxidative decomposition of all-trans lycopene.
After ball milling for 60min, the mass percent of the (5Z) -cis isomer reaches 61 percent by adopting the method described in the embodiment 8; the mass percentage of the (5Z) -cis isomer reaches 64 percent after ball milling for 120 min.
In conclusion, the invention takes high-purity lycopene or lycopene oleoresin or all-trans-lycopene as a raw material, and the high-content cis-isomer lycopene is prepared by ball milling under the oxygen-free and light-proof conditions, and the solvent-free process is green and environment-friendly compared with the prior process, better meets the solvent-free and non-toxic requirements of functional foods, has short process time, higher preparation efficiency, simple process and easier realization of industrial production.
The technical characteristics form an embodiment of the invention, which has strong adaptability and implementation effect, and unnecessary technical characteristics can be increased or decreased according to actual needs to meet the requirements of different situations.
Claims (4)
1. A fast green preparation method of high cis-isomer lycopene is characterized by comprising the following steps: ball milling lycopene oleoresin or natural lycopene or all-trans lycopene under the conditions of light and oxygen free, wherein the ball milling speed is 200-1300 r/min, the ball milling temperature is 15-50 ℃, and the ball milling time is 1-2 hours to obtain the lycopene with the mass percentage of (5Z) -cis isomer reaching 60-65%.
2. The method for preparing lycopene with high cis-isomer according to claim 1, wherein lycopene oleoresin or natural lycopene or all-trans lycopene is ball milled under nitrogen atmosphere and in dark.
3. The method for preparing lycopene with high cis-isomer according to claim 2, wherein grinding balls with different sizes are put in a ball milling tank of a ball mill, and then lycopene oleoresin or natural lycopene or all-trans lycopene is added into the ball milling tank, and the ball milling tank is filled with nitrogen, sealed by a gland, placed in the ball mill and ball milled.
4. The method for the rapid green production of high cis-isomer lycopene according to claim 1 or 2 or 3, characterized in that the temperature of the obtained high cis-isomer lycopene is returned to room temperature within 3 minutes after the end of ball milling.
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