CN106755254B - Method for synthesizing lipoic acid sterol ester in organic phase through enzyme catalysis - Google Patents
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Abstract
The invention discloses a method for synthesizing lipoic acid sterol ester in an organic phase through enzyme catalysis, and belongs to the technical fields of food, medicine, cosmetics and the like. The lipoate sterol ester is synthesized in an organic phase by lipase catalysis, the yield of the lipoate sterol ester is 71.2%, and the purity of the lipoate sterol ester is 99.3%. The method has the characteristics of mild reaction conditions, simple steps, high purity and yield of the obtained product and the like, does not need functional group protection, only needs one-step reaction, can safely apply the selected raw materials, the catalyst and the solvent to food, is environment-friendly and has high product safety.
Description
Technical Field
The invention relates to a method for synthesizing lipoic acid sterol ester in an organic phase through enzyme catalysis, belonging to the technical fields of food, medicine, cosmetics and the like.
Background
The phytosterol is a natural product with rich sources and multiple physiological functions, belongs to steroid compounds, and is characterized in that a hydroxyl is connected to a C-3 position of a molecule, and a hydrophobic side chain consisting of 9-10 carbon atoms is connected to a C-17 position. The phytosterol is an important food functional factor, and has a plurality of important physiological functions, such as effectively preventing cardiovascular diseases, resisting oxidation and aging, resisting cancer, diminishing inflammation and the like.
The unique chemical structure of phytosterols determines their water-insolubility and low oil-solubility, limiting their use in the food industry. In addition, the absorption rate of free phytosterol in human body is only 3%, and the excessive intake of phytosterol can cause a new disease, namely hyperphytosterolaemia, so that how to improve the solubility and bioavailability of phytosterol is the primary problem. The modification of the phytosterol on the premise of not influencing the physiological function of the phytosterol and the improvement of the bioavailability of the phytosterol become a hotspot of research. The esterified sterol is called sterol ester, which is the most studied kind of phytosterol derivatives, and compared with phytosterol, the change of chemical structure does not affect the physiological function of the phytosterol and has certain enhancing effect.
In recent years, many studies have been reported on the modification of phytosterol for the purpose of improving the solubility of sterol, such as esterification of sterol with lauric acid, glutamic acid, or the like, or preparation of microcapsules. However, most of the methods have the problems of high energy consumption, complicated steps, unknown safety and the like, so that the practical application of the methods is limited. Therefore, if some functional substances which can be safely applied to the food field can be selected to carry out mild one-step reaction with the phytosterol, the defects of respective physicochemical properties can be improved, the bioavailability of the phytosterol is improved, and respective functions can be retained or synergistic effect can be generated, so that the modification, synergism and quality improvement are realized.
Lipoic acid is a natural antioxidant with very strong antioxidant capacity and plays an important role in various metabolic processes, so that the lipoic acid is widely researched and applied in the fields of medicines, foods and the like, such as medicines for treating diabetes, antioxidant health-care foods and the like. The lipoic acid sterol ester generated after esterification of sterol and lipoate can theoretically play the functions of the two substances simultaneously after being absorbed and decomposed by a human body. Currently, there are few reports about lipoic acid phytosterol ester, and only samanthir.p. madawala et al report in 2012 about a chemical preparation method of lipoic acid sterol ester, which includes: after dissolving 1g of sterol in 9mL of dichloromethane and 64mg of DMAP, 580mg of lipoic acid and 468mg of EDCI were added with stirring at 0 ℃ under introduction of nitrogen, and then the reaction was stirred at room temperature overnight to obtain a yield of 60%. The method finally uses normal hexane as a solvent, uses a solid phase extraction column for separation and purification, and verifies that the synthesized lipoic acid sterol ester has certain oxidation resistance through DPPH & free radical scavenging experiments.
Disclosure of Invention
The invention aims to provide a method for preparing and purifying lipoic acid sterol ester by an enzyme method in order to improve the physicochemical property and the efficacy of phytosterol and improve the bioavailability. The method has the advantages of mild reaction conditions, simple steps, high purity and yield of the obtained product, and safe application in the industries of food, medicine and the like.
The preparation method provided by the invention is that lipoic acid sterol ester is synthesized in an organic phase under the condition of constant temperature oscillation by using phytosterol and lipoic acid as substrates and lipase as a catalyst; the organic phase is mixed in a volume ratio of 1:1 mixed n-hexane, acetone or 1:1 mixed tert-amyl alcohol, n-hexane; the lipase is Novozyme 435 or Candida Rugosa; the initial concentration of the phytosterol is 100-200 mmol/L, the addition amount of lipase is 60-80 g/L, and the acid-alcohol molar ratio is (2-3): 1; the reaction temperature is 50-60 ℃, and the reaction time is 72-120 h.
In one embodiment of the present invention, the initial concentration of the phytosterol is 100-150 mmol/L.
In one embodiment of the invention, the initial concentration of the phytosterol is 150 mmol/L.
In one embodiment of the present invention, the amount of lipase added is 60 g/L.
In one embodiment of the invention, the acid to alcohol molar ratio is 2.5: 1
In one embodiment of the invention, the reaction concentration used is 55 ℃.
In one embodiment of the invention, 0-20 g/L molecular sieve is added into a reaction system; the molecular sieve is 3A or 4A.
In one embodiment of the invention, the lipase used is Candida Rugosa.
In one embodiment of the present invention, the amount of the molecular sieve used is 10g/L and the type of the molecular sieve is 4A.
In one embodiment of the invention, the reaction time used is 96 h.
In one embodiment of the invention, the ratio of the total amount of the components in the mixture is 1:1 mixed n-hexane and t-amyl alcohol, 60g/L of Candida Rugosa is added, the molecular sieve concentration is 10g/L, the initial sterol concentration is 150mmol/L, and the acid-alcohol molar ratio is 2.5: 1, reacting for 96 hours at the conditions of 55 ℃ and 150 rpm.
In one embodiment of the invention, the method further comprises the steps of separating and purifying the product, namely removing the enzyme and the molecular sieve, removing the solvent by using a rotary evaporator, dissolving the solute by using a developing agent of thin layer chromatography, detecting by using the thin layer chromatography after silica gel column chromatography, and collecting components of different sections to obtain the purified lipoic acid sterol ester; the silica gel column chromatography mobile phase is prepared from the following components in percentage by volume of 15: 1 mixed petroleum ether: ethyl acetate; the developing agent for thin-layer chromatography detection is prepared from the following components in percentage by volume of 15: 1 mixed petroleum ether: ethyl acetate.
In one embodiment of the invention, the method further comprises the steps of determining purity and yield by using a High Performance Liquid Chromatography (HPLC), and identifying the structure by infrared spectroscopy (FT-IR) and Mass Spectrometry (MS).
The invention has the beneficial effects that:
(1) the lipoic acid sterol ester is synthesized, the solubility of sterol is improved, the bioavailability of sterol is improved, and the lipoic acid sterol ester is beneficial to becoming a functional antioxidant.
(2) The method for preparing the lipoic acid sterol ester in the organic solvent by using lipase catalysis can greatly improve the conversion rate of the ester, the conversion rate exceeds 71.2 percent, and the purity reaches more than 99.3 percent.
(3) The method has the characteristics of mild reaction conditions, simple steps, high purity and yield of the obtained product and the like, does not need functional group protection, only needs one-step reaction, can safely apply the selected raw materials, the catalyst and the solvent to food, is environment-friendly and has high product safety.
Drawings
Fig. 1 is a structural formula of lipoic acid phytosterol ester.
Fig. 2 is an HPLC profile of stigmasterol lipoate.
Fig. 3 is an infrared spectrum of stigmasterol lipoate.
Fig. 4 is a mass spectrum of stigmasterol lipoate.
Detailed Description
The identification method of the product comprises the following steps: sulfur identification by Fourier transform infrared spectroscopy and mass spectrometryStructure of sterol octanoate. FT-IR analysis adopts Thermo Scientific Nicolet i S10 Fourier transform infrared spectrometer, selects KBr tablet method, scanning times: 32 times, resolution: 4cm-1. The mass spectrometry adopts a Waters UPLC-TQD mass spectrometer, samples of separated and purified samples are fed after passing through a 0.22 mu m microporous filter membrane, the ion source is an electrospray ionization (ESI) ion source, the capillary voltage is 3.5kV, the desolvation temperature is 250 ℃, the desolvation airflow rate is 500L/h, the cone hole airflow rate is 50L/h, the cone hole voltage is 20V, the collision energy is 6V, the detector voltage is 1700V, and the mass range is 50-1000 m/z.
The method for calculating the esterification rate and the product purity comprises the following steps: the invention adopts HPLC to determine the purity and yield of lipoic acid phytosterol ester, and an HPLC-ELSD analysis system comprises a Waters1525 high performance liquid chromatograph, an Alltech3300 Evaporative Light Scattering Detector (ELSD) and Empower data processing software. The column was a Waters symmetry C18 reverse phase column (4.6X 250mm, 5 μm), column temperature: 45 ℃, mobile phase: 100% methanol, flow rate: 1mL/min, isokinetic elution, sample size: 10 mu L of the solution; ELSD parameters: the temperature was 55 ℃, the carrier gas was nitrogen, the flow rate was 1.5L/min, and the gain was 1.
The specific esterification rate calculation method comprises the following steps: preparing a series of solutions with different concentrations from the separated and purified lipoic acid sterol ester respectively, measuring each peak area by using HPLC, and making a standard curve according to the linear relation between the logarithm of the peak area and the logarithm of the concentration of the sample to obtain the formula of lgA being 1.41lgC + 6.77. And (3) after the esterified reaction solution is injected, calculating the concentration of the phytosterol lipoic acid in the reaction solution according to the peak area, and calculating the esterification rate according to the following formula.
XPSE(％)＝CPSE/CPSX100, wherein XPSEIs the esterification rate of lipoic acid sterol ester, CPSEIs the concentration (mol/L) of lipoic acid sterol ester, CPSThe concentration of phytosterol (mol/L) was the start of the reaction.
Purity (%) of lipoic acid sterol ester ═ peak area of lipoic acid sterol ester/total peak area of all samples × 100
Example 1 Effect of reaction solvent and enzyme types on the Synthesis of lipoic acid sterol ester
To tert-butanol, tert-amyl alcohol, n-hexane, acetone/n-hexane (volume ratio 1:1), n-hexane/tert-butanol (volume ratio 1:1) and tert-amyl alcohol/n-hexane (volume ratio 1:1), 20g/L of Novozyme 435(10000PLU/g, available from Beijing Gaoreson technologies, Inc.), Lipase from Candida Rugosa (847U/mg, available from Sigma), Lipozyme TL IM (250IUN/g, available from Beijing Gaoreson technologies, Inc.), Lipozyme RM (275IUN/g, available from Beijing Gaoreson technologies, Inc.), 40g/L of 4A molecular sieve, 50mmol/L of phytosterol, respectively, were added, the molar ratio of acid to alcohol was 1.5: 1, reacting for 72 hours at 45 ℃ and 150 rpm. The esterification rate is shown in table 1 below:
TABLE 1 influence of the reaction solvent and enzyme species on the synthesis of lipoic acid sterol esters
Example 2 Effect of phytosterol initial concentration on synthetic lipoic acid sterol ester
Based on example 1, the organic phase is n-hexane/t-amyl alcohol, the enzyme is Candida Rugosa, and the initial concentrations of phytosterol are adjusted to 25mmol/L, 50mmol/L, 100mmol/L, 150mmol/L and 200mmol/L respectively, which shows that the highest esterification rate is achieved when the sterol concentration is 150 mmol/L. The esterification rates at different phytosterol concentrations are shown in table 2 below:
table 2 effect of phytosterol initial concentration on synthetic lipoic acid sterol ester
| Initial sterol concentration (mmol/L) | Esterification ratio (%) |
| 25 | 5.6 |
| 50 | 6.8 |
| 100 | 8.6 |
| 150 | 10.2 |
| 200 | 7.8 |
Example 3 Effect of acid alcohol molar ratio on the Synthesis of lipoic acid sterol ester
On the basis of example 2, the sterol concentration is 150mmol/L, and then the molar ratio of lipoic acid to phytosterol is adjusted to 1: 1.5, 1: 1. 1.5: 1. 2: 1. 2.5: 1. 3: 1 and 3.5: 1. initially, the conversion rate increases with the acid-alcohol molar ratio, but when the acid-alcohol molar ratio is greater than 2.5: at 1, the yield decreased slightly. The esterification rate under different acid-alcohol molar ratio conditions is shown in the following table 3:
table 3 effect of acid alcohol molar ratio on synthesis of lipoic acid sterol ester
| Molar ratio of acid to alcohol | Esterification ratio (%) |
| 1:1.5 | 8.3 |
| 1:1 | 5.6 |
| 1.5:1 | 9.7 |
| 2:1 | 13.1 |
| 2.5:1 | 16.1 |
| 3:1 | 11.3 |
Example 4 Effect of molecular Sieve type and amount added on synthetic lipoic acid sterol ester
On the basis of example 3, the acid-alcohol molar ratio is selected to be 2.5: 1, respectively adjusting the concentrations of the 3A type molecular sieves and the 4A type molecular sieves to be 0g/L, 10g/L, 20g/L, 30g/L and 40 g/L. The esterification rate of the sample added with the 3A type molecular sieve is obviously lower than that of the sample added with the 4A type molecular sieve, and when the concentration of the 4A type molecular sieve is 10g/L, the yield is the highest, and the reaction conversion rate is gradually reduced along with the increase of the adding amount of the molecular sieve. The esterification rates at different molecular sieve addition levels are shown in table 4 below:
TABLE 4 influence of molecular sieve type and addition amount on the synthesis of lipoic acid sterol ester
EXAMPLE 5 Effect of Lipase addition on lipoic acid sterol ester Synthesis
In addition to example 4, the amount of molecular sieve was 10g/L, and the amounts of lipase were adjusted to 20g/L, 40g/L, 60g/L and 80g/L, respectively. The results showed that the conversion was higher with the larger amount of lipase added, and that the yield tended to be stable when the amount was more than 60 g/L. The esterification rates for different enzyme additions are shown in table 5 below:
TABLE 5 Effect of lipase addition on lipoic acid sterol ester synthesis
EXAMPLE 6 Effect of reaction temperature on Synthesis of lipoic acid sterol ester
In example 5, the highest conversion rate was observed at 55 ℃ by selecting 60g/L of lipase and adjusting the reaction temperature to 40 ℃, 45 ℃, 50 ℃, 55 ℃ and 60 ℃ respectively. The esterification rates under different reaction temperature conditions are shown in table 6 below:
TABLE 6 Effect of reaction temperature on the Synthesis of lipoic acid sterol ester
| Reaction temperature (. degree.C.) | Esterification ratio (%) |
| 40 | 41.8 |
| 45 | 46.7 |
| 50 | 51.4 |
| 55 | 56.2 |
| 60 | 50.3 |
Example 7 Effect of reaction time on the Synthesis of lipoic acid sterol ester
On the basis of example 6, the reaction temperature was 55 ℃ and the reaction times were adjusted to 24h, 48h, 72h, 96h and 120h, respectively, and it was found that the reaction gradually reached equilibrium at 96 h. The esterification rates under different reaction time conditions are shown in table 7 below:
TABLE 7 Effect of reaction time on the Synthesis of lipoic acid sterol ester
| Reaction time (h) | Esterification ratio (%) |
| 24 | 21.6 |
| 48 | 42.5 |
| 72 | 55.6 |
| 96 | 71.2 |
| 120 | 68.9 |
Example 8
In the volume ratio of 1:1 mixed n-hexane and t-amyl alcohol, 60g/L Candida Rugosa, 10g/L molecular sieve, 150mmol/L phytosterol are added, and the acid-alcohol molar ratio is 2.5: 1, reacting for 96 hours at the conditions of 55 ℃ and 150 rpm.
After the reaction is finished, removing the enzyme and the molecular sieve, removing the solvent by using a rotary evaporator, dissolving the solute by using a developing agent (petroleum ether: ethyl acetate in a volume ratio of 15: 1) of thin-layer chromatography, performing silica gel column chromatography (the mobile phase condition is petroleum ether: ethyl acetate in a volume ratio of 15: 1), and collecting components of different sections through thin-layer detection to obtain the purified lipoic acid phytosterol ester. Under the condition, the product yield is 71.2 percent, and the purity is 99.3 percent.
The ir spectrum of lipoic acid sterol ester is shown in fig. 2, and the analysis is as follows: 2949cm-1is-CH3Asymmetric stretching vibration absorption (v)as-CH3)，2866cm-1is-CH2-symmetrical telescopic vibration absorption (v)s-CH2-)，1732cm-1The strong absorption peak is the stretching vibration absorption of C ═ O (v C ═ O) on the ester functional group, 1462cm-1is-CH2Bending vibration absorption peak of (1), 1366cm-1is-CH3Bending vibration absorption (v-CH)3)，1173cm-1And 1131cm-1Is the stretching vibration absorption of C-O (v C-O).
The mass spectrum of lipoic acid sterol ester is shown in fig. 4, and analyzed as follows: the relative molecular mass of stigmasterol is 412.69 and the relative molecular mass of lipoic acid is 206.32, so the relative molecular mass of lipoic acid sterol ester is 601. Under ES + ionization of stigmasterol lipoate, the [ M + H ] of the sterol lipoate may exist]+And [ M + Na]+The molecular ion peak of (1), 601.4 in FIG. 3 is the mass spectrum signal of the thioctic acid bean sterol ester, 624.4 is [ M + Na ] of the thioctic acid bean sterol ester]+The mass spectral signal of (2). Thus, the product is stigmasterol lipoate.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (4)
1. A method for preparing lipoic acid sterol ester is characterized in that in an organic phase, phytosterol and lipoic acid are used as substrates, and lipase is used as a catalyst to synthesize the lipoic acid sterol ester; the organic phase is mixed in a volume ratio of 1:1 mixed n-hexane and acetone, or 1:1 mixed tert-amyl alcohol and n-hexane; the lipase is Novozyme 435 or CandidaRugosa; the initial concentration of the phytosterol is 150mmol/L, the addition amount of lipase is 60-80 g/L, and the acid-alcohol molar ratio is 2.5: 1; the reaction temperature is 55 ℃, and the reaction time is 96 hours; the reaction system is also added with 10g/L of 4A molecular sieve.
2. The method of claim 1, wherein the lipase is added in an amount of 60g/L, and the lipase is a lipase derived from Candida Rugosa.
3. The method of claim 1, wherein the ratio of lipoic acid to sterol ester is 1:1 mixed n-hexane and t-amyl alcohol, 60g/L of lipase from Candida Rugosa is added, 10g/L of molecular sieve is added, the initial concentration of sterol is 150mmol/L, and the molar ratio of acid to alcohol is 2.5: 1, reacting for 96 hours at the conditions of 55 ℃ and 150 rpm.
4. The method of claim 1, further comprising separating and purifying the product by removing enzymes and molecular sieves, removing the solvent using a rotary evaporator, dissolving the solute using a developing solvent of thin layer chromatography, subjecting the solution to silica gel column chromatography, detecting the solution by thin layer chromatography, and collecting fractions of different fractions to obtain purified sterol lipoic acid ester; the silica gel column chromatography mobile phase is prepared from the following components in percentage by volume of 15: 1 mixed petroleum ether: ethyl acetate; the developing agent for thin-layer chromatography detection is prepared from the following components in percentage by volume of 15: 1 mixed petroleum ether: ethyl acetate.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101845473A (en) * | 2010-06-03 | 2010-09-29 | 江南大学 | Method for effectively synthesizing phytosterol ester |
| CN103352067A (en) * | 2013-08-04 | 2013-10-16 | 中国农业科学院油料作物研究所 | Method for preparing functional grease rich in phytosterol ester and diglyceride |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101845473A (en) * | 2010-06-03 | 2010-09-29 | 江南大学 | Method for effectively synthesizing phytosterol ester |
| CN103352067A (en) * | 2013-08-04 | 2013-10-16 | 中国农业科学院油料作物研究所 | Method for preparing functional grease rich in phytosterol ester and diglyceride |
Non-Patent Citations (2)
| Title |
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| Optimization of Enzymatic Synthesis of Phytosteryl Caprylates Using Response Surface MethodologyZhuliang;Tan;《Journal of the American Oil Chemists》;20111202;第89卷(第4期);第658页右栏，表1 * |
| Phytosterol and α-Lipoic Acid Conjugates: Synthesis, Free Radical Scavenging Capacity and RP-LC-MS-APCI Analysis;S.R.P. Madawala et al.;《Polish Journal of Food and Nutrition sciences》;20120931;第62卷(第3期);第159-169页 * |
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