CN101575256A - Cis-isomerism method for lycopene and lycopene product with high cis-isomer content - Google Patents

Abstract

The invention discloses a cis-isomerism method for lycopene and a lycopene product with high cis-isomer content, and belongs to the technical field of production of functional food ingredients. The method comprises the following steps: using lycopene oleoresin extracted from plant or microbe or purified lycopene as a raw material, firstly dissolving the raw material into an organic solvent A to prepare a lycopene organic solution; under the condition of protection of introduced high-purity nitrogen, adding an organic solvent B with high boiling point into the lycopene organic solution, gradually heating the system, and carrying out reflux reaction; after the reaction is finished, removing a heat source, increasing the introduction amount of the nitrogen, directly reducing the pressure to reclaim the solvent B or using an organic solvent C to extract the lycopene in the system, and separating the organic solvent B to obtain a lycopene/solvent C solution; and reducing the pressure, reclaiming the solvent B or C, and then obtaining the lycopene product with high cis-isomer content, wherein in the product, the mass content of the high cis-isomer lycopene is 10 to 70 percent.

Description

The lycopene product of Lyeopene cis isomerism method and high-cis content of isomer

Technical field

The extract or the high purity Lyeopene behind the purifying that the present invention relates to contain Lyeopene are raw material, carry out the method for cis isomerismization and the lycopene product of the high-cis content of isomer that obtained through subsequent disposal, belong to the functional food ingredient production technical field.

Background technology

Lyeopene is intermediates of the multiple carotenoid of biosynthesizing by 11 conjugated double bonds and two straight chain type hydrocarbon polymers that unconjugated double bond is formed.Though do not have β-ionone ring structure in its structure, do not have the vitamin a source activity, Lyeopene is the most effective singlet oxygen scavenging agent in the carotenoid, has very strong anti-oxidant activity.Self can not synthesize Lyeopene people and higher animal, but they can significantly improve the concentration of Lyeopene in its tissue and the blood by food intake (as tomato or tomato product, planktonic organism etc.), and epidemiology and trophology are discovered, lycopene concentration and its are suffered between the initiation potential of malignant tumours such as prostate cancer and mammary cancer and presented remarkable negative correlation in when injected organism tissue and the blood.

Owing to exist the conjugated double bond that has high degree of rigidity in a large number in the Lyeopene molecule, molecular chain can not internal rotation, and tomato red have 72 kinds of steric isomers in theory.In recent years discover that the Lyeopene in the natural food raw material is based on alltrans (all-trans) structure, its quantity accounts for the 90%-98% of Lyeopene total amount; The accounting of all-trans lycopene is generally more than 90% in the Lyeopene extract that can buy on the market; Through concentrating or the Lyeopene of purification process also exists based on the alltrans structure and with the crystalline form, its biological value can lower than the Lyeopene in the food (crystallization be difficult for being absorbed); The biological value that content increases, this based article is overall of cis (cis-) isomer is also apparently higher than all-trans lycopene in the goods such as the heat treated tomato-sauce of process.

With alltrans structure in the foodstuff raw material be that principal phase is anti-, Lyeopene in human body and animal tissues, the blood is based on various cis-isomerides, the 79%-88% that accounts for the Lyeopene total amount is (comprising 5-cis, 9-cis, 13-cis and 15-cis etc.), alltrans structure proportion then has only 12%-21%.The biological value that relatively is rich in the tomato-sauce of all-trans lycopene or its cis-isomeride finds that thermal treatment can improve the content of Lyeopene cis-isomeride in the product, promotes the digestion and the absorption of Lyeopene; Also have cis-isomeride that result of study shows Lyeopene than alltrans structure easier by microemulsified, absorbed easilier by intestinal cells.

So, be the Lyeopene that raw material prepares the high-cis content of isomer based on the Lyeopene extract (or the purifying thing that obtains on this basis) of alltrans structure, will have important research and be worth and huge market outlook.

Summary of the invention

The lycopene product (accounting of All-cislycopene content in total Lyeopene is at 10%-70%) and the preparation method that the purpose of this invention is to provide the high-cis content of isomer, this product has the physicochemical characteristics similar to all-trans lycopene, but the Lyeopene that contains with human body on its sterie configuration consistent (cis-isomeride is main).

Technical scheme of the present invention: a kind of Lyeopene cis isomerism method is a raw material with lycopene oleo-resinous or the Lyeopene behind the purifying that extracts from plant or microorganism, earlier it is dissolved in the organic solvent A, is prepared into Lyeopene organic solution; Under the condition that feeds the high pure nitrogen protection, gradually this organic solution system heating evaporation is gone out solvent orange 2 A, and adding has the organic solvent B of higher simultaneously, to keep this organic solution system volume constant substantially; Continue heating and back flow reaction; After reaction finishes, remove thermal source, strengthen nitrogen feeding amount, direct decompression and solvent recovery B or with the Lyeopene in the non-polar organic solvent C extraction system, and divide to fall organic solvent B, obtain Lyeopene/solvent C solution; Promptly get the Lyeopene goods of high-cis content of isomer behind decompression and solvent recovery B or the C; The preparation process condition of high-cis content of lycopene goods is:

(1) getting the Lyeopene mass concentration at 1%～90% lycopene oleo-resinous or purified Lyeopene, is solvent with the organic solvent A, and the preparation content of lycopene is the organic solution of 0.01～10g/100mL;

Organic solvent A is selected one or more in ether, acetone, ethyl acetate, normal hexane, sherwood oil, methylene dichloride, dithiocarbonic anhydride, benzene or the chloroform for use;

(2) under the condition of lucifuge, feeding high pure nitrogen, add organic solvent B and also gradually this organic solution system is heated to evaporate solvent orange 2 A with higher, keep this organic solution system constancy of volume in the process as far as possible; To system heating and backflow, when the boiling point of B was higher than 120 ℃, temperature of reaction system maintained 120 ℃, and backflow or 120 ℃ of insulations are held time and are 2-72 hour;

Organic solvent B is selected one or more in ethyl acetate, normal hexane, ethanol, Virahol, ethylene glycol, propylene glycol or the glycerol for use;

(3) after reaction finishes, remove thermal source, strengthen nitrogen feeding amount;

When organic solvent B is the solvent of boiling point≤80 ℃, when removing thermal source, direct decompression and solvent recovery B;

Or when the boiling point of organic solvent B during in the Virahol more than 80 ℃, ethylene glycol, propylene glycol or glycerol, after the system for the treatment of naturally cools to room temperature,, and divide to fall solvent B with the Lyeopene in the organic flux C extraction system, obtain Lyeopene/solvent C solution, again decompression and solvent recovery C;

Organic flux C selects ether, acetone, ethyl acetate, normal hexane, sherwood oil, methylene dichloride, dithiocarbonic anhydride, benzene or chloroform for use;

(4) the resulting Lyeopene goods that are the high-cis content of isomer behind decompression and solvent recovery B or the C.

The Lyeopene goods of the high-cis content of isomer that makes, wherein the mass content of high-cis isomer Lyeopene is 10%-70%.

The sample preparation of Lyeopene and HPLC detection method:

Measure the preceding or processing back Lyeopene sample of processing of a certain amount of (containing Lyeopene 0.02g approximately), be dissolved in in the ethyl acetate solution behind the 0.45 μ m membrane filtration and be settled to 100mL, in lucifuge, filled under the condition of nitrogen concussion 2 minutes, analysis more promptly is available on the machine after 0.22 μ m organic system filtering head filters.

Chromatographic condition:

Chromatographic instrument: Agilent 1100,

Chromatographic column: Cosmosil cholester, 4.6 * 250mm, 5 μ m (Nacalai USA, Inc.),

Detect column temperature: 27 ℃,

Moving phase: tetrahydrofuran (THF): acetonitrile=10: 90 (V/V),

Flow velocity: 1mL/min detects wavelength: 472nm.

Beneficial effect of the present invention: what the present invention carried out proves with the all-trans lycopene crystallization and as the anti-inflammatory that sample the was carried out test (NO that carries out with RAW264.7 clone generates inhibition test) and anthraquinone reductase activity induction experiment (test of the 1c1c7 cell QR activity inducement) result of raw material after isomerization is handled, it is that natural lycopene generates 355% of inhibiting rate to NO to NO generation inhibiting rate that the back Lyeopene is handled in isomerization, and QR activity inducement ability has also been improved more than 400%.

This shows that the Lyeopene behind Lyeopene extract or the purifying is after isomerization is handled, its biological activity can significantly improve.

Description of drawings

Fig. 1 handles prolycopene sample HPLC analytical results, and all-trans lycopene (appearance time 33.8min) accounts for 90.6% of total amount, and cis accounts for 9.4%.

Back Lyeopene sample HPLC analytical results is handled in Fig. 2 isomerization, and all-trans lycopene in the product (appearance time 33.8min) accounts for 51.2% of total amount, and cis accounts for (other several peaks) 48.8%.

Embodiment

Embodiment 1

Get a certain amount of lycopene concentration and be 1% oleo-resinous, be dissolved in the ether, making content of lycopene is the Lyeopene diethyl ether solution of 0.01g/100mL;

Continue to feed high pure nitrogen and improve system temperature gradually in solution, when evaporating ether, add the ethanol of equal volume, the continuation heating makes the ethanol boiling and refluxed 48 hours;

Remove thermal source, treat that system temperature is reduced to room temperature after, with dichloromethane extraction wherein Lyeopene and separate ethanol;

The reclaim under reduced pressure methylene dichloride obtains the Lyeopene of cis-structure ratio 10%-70%.

Embodiment 2

Get a certain amount of lycopene concentration and be 90% high-purity lycopene, be dissolved in the ethyl acetate, making content of lycopene is the Lyeopene ethyl acetate solution of 0.5g/100mL;

In solution, continue to feed high pure nitrogen and improve system temperature gradually, to the ethyl acetate boiling, reflux 72 hours;

Remove thermal source, treat that ethyl acetate evaporation obviously weakens after, change system over to decompression distillation system rapidly, reclaim ethyl acetate.The resulting Lyeopene that is the cis-structure ratio at 10%-70%.(be equivalent to solvent orange 2 A, B is ethyl acetate)

Embodiment 3

Get a certain amount of lycopene concentration and be 10% oleo-resinous, be dissolved in the methylene dichloride, making content of lycopene is the Lyeopene dichloromethane solution of 10g/100mL;

Continue in the solution to feed high pure nitrogen and improve system temperature gradually, when evaporating methylene dichloride, add the ethylene glycol of equal volume, continue to be heated to 120 ℃ and kept 2 hours;

Remove thermal source, treat that system temperature is reduced to room temperature after, with n-hexane extraction wherein Lyeopene and separate ethylene glycol.

The reclaim under reduced pressure normal hexane obtains the Lyeopene of cis-structure ratio 10%-70%.The HPLC analytical results of the content of trans Lyeopene and All-cislycopene as shown in Figure 2 in the product.

Claims (2)

1, a kind of Lyeopene cis isomerism method is characterized in that lycopene oleo-resinous or the Lyeopene behind the purifying to extract is raw material from plant or microorganism, earlier it is dissolved in the organic solvent A, is prepared into Lyeopene organic solution; Gradually this organic solution system is heated to evaporate solvent orange 2 A under the condition that feeds the high pure nitrogen protection, adding simultaneously has the organic solvent B of higher to keep this organic solution system volume constant substantially; Continue heating and back flow reaction; After reaction finishes, remove thermal source, strengthen nitrogen feeding amount, direct decompression and solvent recovery B or with the Lyeopene in the non-polar organic solvent C extraction system, and divide to fall organic solvent B, obtain Lyeopene/solvent C solution; Promptly get the Lyeopene goods of high-cis content of isomer behind decompression and solvent recovery B or the C; The preparation process condition of high-cis content of lycopene goods is:

(1) getting the Lyeopene mass concentration at 1%～90% lycopene oleo-resinous or purified Lyeopene, is solvent with the organic solvent A, and the preparation content of lycopene is the organic solution of 0.01～10g/100mL;

Organic solvent A is selected one or more in ether, acetone, ethyl acetate, normal hexane, sherwood oil, methylene dichloride, dithiocarbonic anhydride, benzene or the chloroform for use;

(2) under the condition of lucifuge, feeding high pure nitrogen, add organic solvent B and also gradually this organic solution system is heated to evaporate solvent orange 2 A with higher, keep this organic solution system constancy of volume in the process as far as possible; To system heating and backflow, when the boiling point of B was higher than 120 ℃, temperature of reaction system maintained 120 ℃, and backflow or 120 ℃ of insulations are held time and are 2-72 hour;

Organic solvent B is selected one or more in ethyl acetate, normal hexane, ethanol, Virahol, ethylene glycol, propylene glycol or the glycerol for use;

(3) after reaction finishes, remove thermal source, strengthen nitrogen feeding amount;

When organic solvent B is the solvent of boiling point≤80 ℃, when removing thermal source, direct decompression and solvent recovery B;

Or when organic solvent B when being boiling point in the Virahol more than 80 ℃, ethylene glycol, propylene glycol or glycerol, after the system for the treatment of naturally cools to room temperature,, and divide to fall solvent B with the Lyeopene in the organic flux C extraction system, obtain Lyeopene/solvent C solution, again decompression and solvent recovery C;

Organic flux C selects ether, acetone, ethyl acetate, normal hexane, sherwood oil, methylene dichloride, dithiocarbonic anhydride, benzene or chloroform for use;

(4) the resulting Lyeopene goods that are the high-cis content of isomer behind decompression and solvent recovery B or the C.

2, the Lyeopene goods of the high-cis content of isomer that makes with the described method of claim 1, the mass content that it is characterized in that high-cis isomer Lyeopene in the goods is 10%-70%.

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