CN109053843A - One plant sterols polyacid mesoinositol and preparation method thereof - Google Patents
One plant sterols polyacid mesoinositol and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to food, the technical fields such as medicine and cosmetics, a more particularly to plant sterols polyacid mesoinositol and preparation method thereof, the present invention uses lipase-catalyzed synthesis phytosterol succinic acid mesoinositol in organic phase, the yield for obtaining phytosterol succinic acid mesoinositol is 64.7%, purity is 80.5%, the Production by Enzymes reaction condition that the method for the present invention uses is mild, step is simple, the features such as products therefrom purity and high income, without protective group, the raw material of selection, catalysts and solvents also all can security application in food, it is environmentally friendly, Product Safety is high.
Description
Technical field
The invention belongs to food, medicine and cosmetic technical field more particularly to a plant sterols polyacid mesoinositols
And preparation method thereof.
Background technique
Phytosterol is a kind of abundance and the natural products with different physiological roles, is with perhydrocyclopentanophenanthrene
The steroid compound of main body framework.Phytosterol has many important physiological functions, is known as " key of life ", most
Significant function is to reduce the content of cholesterol and low-density lipoprotein in serum, effectively prevents the generation of cardiovascular disease.
In addition, also having oxidation-resisting and caducity, anticancer, anti-inflammatory, prevention and treatment prostatic disorders, antiviral, raising immunity etc. a variety of important
Physiological function is a kind of important food function factor, is widely used in the fields such as food, medicine, chemical industry and cosmetics.
Phytosterol molecule C-3 are connected with a hydroxyl, the hydrophobic side of C-17 9-10 carbon atom compositions of ining succession
Chain, the unique chemical structure of phytosterol determine its water-insoluble and low oil-soluble, the interior suction to free phytosterol of human body
Yield is only 3%, limits its application in the food industry, so how to improve the solubility and biological utilisation of phytosterol
Rate is matter of utmost importance.It is modified under the premise of not influencing phytosterol physiological function, improve its bioavilability at
For the hot spot of research.It is known as sterol ester after sterol esterification, is one kind of most study in phytosterol derivative, compared to plant
Sterol, the variation of chemical structure have no effect on its physiological function, and there are also certain humidifications for some.
There are many document reports to be modified research to phytosterol for the purpose of the solubility for improving sterol in recent years, such as
Sterol and lauric acid, glutamic acid etc. are esterified or are prepared microcapsules etc..But there is energy consumption height, step in these methods mostly
It is cumbersome, the problems such as safety is unknown, it is restricted its practical application.Therefore, if can select it is some can security application in food
The functional materials and phytosterol in product field carry out mild single step reaction, can not only improve lacking in respective physicochemical property
It falls into, its bioavilability is improved, and respective function can be retained again or acted synergistically, to realize that modified synergistic mentions
Matter.
Inositol is that human and animal maintains the indispensable low molecule organic matter of normal physiological function, widely used.Its
Significant function is to reduce the content of cholesterol and low-density lipoprotein in serum, effectively prevents the generation of cardiovascular disease.
Inositol has the metabolism for promoting cell, improves cytotrophy, prevent and treat fat accumulation in liver, foster growth, improve a poor appetite
The effects of with regaining one's strength, can be used for the drugs such as vitamins and hypolipidemic and be widely used in food and beverage additive side
Face.
Phytosterol and the significant function of inositol are all to reduce the content of cholesterol and low-density lipoprotein in serum, are had
The generation of effect prevention cardiovascular disease.The synthetic method that a plant sterols polyacid mesoinositol can such as be developed, will have significantly
Beneficial to improving the availability of phytosterol and inositol, but there is presently no the correlations about phytosterol polyacid inositol Lipase absobed
Report.
Summary of the invention
In order to solve the above technical problems, the purpose of the present invention is to propose to a plant sterols polyacid mesoinositol and its preparations
Method, phytosterol polyacid mesoinositol obtained can be analyzed to free phytosterol and inositol through absorption of human body, in human body
Function that is interior while playing both substances plays synergistic effect, and will not generate side effect, phytosterol to human body
Polyacid mesoinositol can increase the solubility of phytosterol and inositol, improve bioavailability, addition that can be more convenient
The texture and flavor of food itself are not influenced into the food of various systems and.
The first purpose of the invention is to provide a plant sterols polyacid mesoinositol, general structure is as follows:
Wherein, n=0~6；.
Alternatively, its general structure are as follows:
Alternatively, its general structure are as follows:
Alternatively, its general structure are as follows:
Alternatively, its general structure are as follows:
Wherein, R includes
A second object of the present invention is to provide the preparation methods of above-mentioned phytosterol polyacid mesoinositol, pass through plant steroid
The polynary acid monoester of alcohol prepares the polynary vinyl acetate of phytosterol, and the polynary vinyl acetate of phytosterol is reacted with inositol generates plant steroid
Alcohol polyacid mesoinositol.
In one embodiment of the invention, the preparation step of the polynary acid monoester of the phytosterol are as follows: by plant steroid
Pure and mild multicomponent organic acid or its acid anhydrides, catalyst a mixing, are added organic solvent a, by controlling temperature, real-time monitoring react into
Journey is heated by stopping after sufficiently reacting, is cooled to room temperature, and is taken out sample removing organic solvent a and is obtained reaction product plant
The polynary acid monoester of sterol.
In one embodiment of the invention, the phytosterol includes stigmasterol, campesterol, cupreol and dish
One of seed sterol is a variety of.
In one embodiment of the invention, the phytosterol in the preparation step of the polynary acid monoester of phytosterol is dense
Degree is 0.5-0.7mmol/mL.
In one embodiment of the invention, described polynary organic in the preparation step of the polynary acid monoester of phytosterol
Acid include citric acid, malic acid, tartaric acid, butene dioic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid,
One of suberic acid is a variety of, and the multicomponent organic acid acid anhydride includes one of corresponding acid anhydrides of the multicomponent organic acid or more
Kind, phytosterol is 1.0:1.2~1.0:1.7 with the molar ratio of multicomponent organic acid or acid anhydrides.
In one embodiment of the invention, the catalyst a in the preparation step of the polynary acid monoester of phytosterol includes
One of dimethylamino naphthyridine, pyridine, diethylamine, lauryl sodium sulfate, dodecyl sulphate copper are several, plant steroid
The molar ratio of alcohol and dimethylamino naphthyridine is 1.0:0.1~1.0:0.5.
In one embodiment of the invention, the organic solvent a packet in the preparation step of the polynary acid monoester of phytosterol
Include one of toluene, methylene chloride, benzene, diformazan toluene, pyridine or a variety of.
In one embodiment of the invention, the reaction temperature in the preparation step of the polynary acid monoester of phytosterol is
100~110 DEG C.
In one embodiment of the invention, the reaction time in the preparation step of the polynary acid monoester of phytosterol is 9
~10h.
In one embodiment of the invention, the preparation step of the polynary vinyl acetate of phytosterol are as follows: by phytosterol
Polynary acid monoester is mixed with vinyl acetate, adds organic solvent b, and alkalescent metal salt is added as catalyst b, lazy
Property gas under react a period of time after be added strong acid starting reaction, heating reacted, reaction terminate stop heating, be cooled to room
Temperature is added excessive salt of weak acid and neutralizes and stop reacting, and takes out sample removing solvent and obtains reaction product.
In one embodiment of the invention, the catalyst b in the preparation step of the polynary vinyl acetate of phytosterol is
Mol ratio of metal acetate or carbonic acid metal salt.
In one embodiment of the invention, the catalyst b in the preparation step of the polynary vinyl acetate of phytosterol is
Mercuric acetate or carbonic acid mercury.
In one embodiment of the invention, the catalyst b in the preparation step of the polynary vinyl acetate of phytosterol is
Additive amount be the polynary acid monoester dosage of phytosterol 2%~10% (w/w).
In one embodiment of the invention, the catalyst b in the preparation step of the polynary vinyl acetate of phytosterol is
Additive amount be the polynary acid monoester dosage of phytosterol 4%~6% (w/w).
In one embodiment of the invention, the phytosterol in the preparation step of the polynary vinyl acetate of phytosterol is more
The molar ratio of first acid monoester and vinyl acetate is 1.0:1.0~0.5:1.0.
In one embodiment of the invention, the phytosterol in the preparation step of the polynary vinyl acetate of phytosterol is more
The initial concentration of first acid monoester is 100~200mmol/L.
In one embodiment of the invention, the phytosterol in the preparation step of the polynary vinyl acetate of phytosterol is more
The molar ratio of first acid monoester and vinyl acetate is 0.2~0.3:1.0.
In one embodiment of the invention, the organic solvent b in the preparation step of the polynary vinyl acetate of phytosterol
Including one or more of tetrahydrofuran, pyridine, n,N-Dimethylformamide.
In one embodiment of the invention, the reaction temperature in the preparation step of the polynary vinyl acetate of phytosterol is
40~50 DEG C.
In one embodiment of the invention, stirring in the preparation step of the polynary vinyl acetate of phytosterol under a nitrogen
30~60min of reaction is mixed, strong acid is then added, the reaction time is 10~12h after strong acid is added.
In one embodiment of the invention, the acidic materials in the preparation step of the polynary vinyl acetate of phytosterol are
The concentrated sulfuric acid, additive amount are 2~5 μ L/10mL organic solvent b.
In one embodiment of the invention, the salt of weak acid in the preparation step of the polynary vinyl acetate of phytosterol is vinegar
Sour sodium.
In one embodiment of the invention, the preparation step of phytosterol polyacid mesoinositol are as follows: by phytosterol
Polynary vinyl acetate, inositol, biocatalyst are added separately in the reaction flask of the pre- solvent for first passing through dehydration, closed,
And shake reaction flask, and control reaction temperature, the process of regular sample detection reaction stops heating after reaction, cold
But it to room temperature, takes out sample removing solvent and obtains reaction product phytosterol polyacid mesoinositol.
In one embodiment of the invention, the biocatalyst is lipase catalyst.
In one embodiment of the invention, the lipase catalyst is that Novi believes immobilized lipase
(Novozyme435), immobilized lipase RM IM (Lipozyme RM IM) or fold lipase from candida sp (Candida
Rugosa).In one embodiment of the invention, the additive amount of the biocatalyst is the polynary vinyl acetate of phytosterol
The 8%~12% of quality.
In one embodiment of the invention, the dehydration mode of the solvent is addition molecular sieve, the molecule
The additive amount of sieve is 10g/L, and the molecular sieve is 4A molecular sieve.
In one embodiment of the invention, the solvent include n-hexane, 2- butanone, methylene chloride, in acetone
It is one or more.
In one embodiment of the invention, the concentration of the polynary vinyl acetate of phytosterol is 100~200mmol/L.
In one embodiment of the invention, the molar ratio of the polynary vinyl acetate of the phytosterol and inositol is 1.0:
2.0~1.0:4.0.
In one embodiment of the invention, in the preparation step of phytosterol polyacid mesoinositol, reaction temperature is
40~50 DEG C.
In one embodiment of the invention, in the preparation step of phytosterol polyacid mesoinositol, concussion speed is
150rpm~200rpm.
In one embodiment of the invention, in the preparation step of phytosterol polyacid mesoinositol, the reaction time is
120~168h.
Third object of the present invention is to provide the isolation and purification method of a plant sterols polyacid mesoinositol, the sides
Method specifically: catalyst is first removed, after removing solvent using Rotary Evaporators, dissolves solute with the solvent of thin-layer chromatography, then
It after silica gel column chromatography, is detected by thin-layer chromatography, collects different sections of component, the phytosterol polyacid of purifying can be obtained
Mesoinositol.
In one embodiment of the invention, the silica gel column chromatography mobile phase includes petroleum ether, ethyl acetate, hexamethylene
One of alkane, methanol or several mixtures.
In one embodiment of the invention, the preparation method of phytosterol polyacid mesoinositol passes through following formulas
It carries out, wherein multi-anhydride is by taking succinic acid glycosides as an example:
First step reaction:
Second step reaction:
Third step reaction:
Fourth object of the present invention be propose phytosterol polyacid mesoinositol made from a kind of above method food,
The application of medicine, chemical industry and cosmetic field.
Beneficial effects of the present invention:
(1) present invention has synthesized a plant sterols polyacid mesoinositol, improves the solubility of sterol, improves sterol
With the bioavilability of inositol, the application range of phytosterol and inositol has greatly been widened.
(2) method that phytosterin ester is prepared using chemo-enzymatic process reaction in organic solvent using the present invention, Ke Yi great
The big esterification yield for improving ester, esterification yield is more than 64.7%, and purity is 80.5% or more.
(3) present invention process is simple, and the reaction condition requirement of each step is low, is easy to realize industrial production, wherein enzyme process is raw
Produce that reaction condition is mild, step is simple, products therefrom purity and the features such as high income.
Detailed description of the invention
Fig. 1 is the HPLC map of stigmasterol hemisuccinate and stigmasterol amber vinyl acetate.
Fig. 2 is the infrared spectrogram of stigmasterol amber vinyl acetate.
Fig. 3 is the mass spectrogram of stigmasterol amber vinyl acetate.
Fig. 4 is the HPLC map of stigmasterol succinic acid mesoinositol.
Fig. 5 is the infrared spectrogram of stigmasterol succinic acid mesoinositol.
Fig. 6 is the mass spectrogram of stigmasterol succinic acid mesoinositol.
Specific embodiment
The identification method of product: using Fourier transform infrared spectroscopy and Mass Spectrometric Identification phytosterol polyacid mesoinositol
Structure.FT-IR analysis uses Thermo Scientific Nicolet i S10 Fourier Transform Infrared Spectrometer, selects KBr
Pressed disc method, scanning times: 32 times, resolution ratio: 4cm-1.Mass spectral analysis uses Waters UPLC-TQD mass spectrograph, will isolate and purify
Sample after 0.22 μm of miillpore filter sample introduction, ion source be electron spray (ESI) ion source, capillary voltage 3.5kV, desolventizing
250 DEG C of temperature, Desolvention gas velocity 500L/h, taper hole gas velocity 50L/h, orifice potential 20V, collision energy 6V, detector electricity
Press 1700V, 50~1000m/z of mass range.
The calculation method of esterification yield and product purity: the present invention is pure using HPLC measurement phytosterol polyacid mesoinositol
Degree and yield, HPLC-ELSD analysis system include Waters1525 high performance liquid chromatograph, Alltech3300 evaporative light-scattering
Detector (ELSD) and Empower data processing software.Chromatographic column be Waters symmetry C18 reversed-phase column (4.6 ×
150mm, 5 μ L), column temperature: 45 DEG C, mobile phase: methanol/formic acid (1000/1, v/v), flow velocity: 1mL/min, constant speed elution, sample introduction
Amount: 10 μ L；ELSD parameter: temperature is 55 DEG C, and carrier gas is nitrogen, flow velocity 1.5L/min, gain 1.
The calculation method of specific esterification rate are as follows: the polynary vinyl acetate of the phytosterol isolated and purified and phytosterol is polynary
Sour mesoinositol prepares a series of solution of various concentrations respectively, each peak area is measured using HPLC, according to pair of sample peak area
The linear relationship of the logarithm of numerical value and concentration makes standard curve.After the reaction solution sample introduction after esterification, further according to peak area
The concentration for calculating the polynary vinyl acetate of phytosterol in reaction solution and phytosterol polyacid mesoinositol, further according to following equation
Esterification yield can be calculated.
XPSE2(%)=CPSE2/CPSE1×100 (1)
XPSE3(%)=CPSE3/CPSE2×100 (2)
X in formula (1)PSE2For the esterification yield of the polynary vinyl acetate of phytosterol, CPSE2For the polynary vinyl acetate of phytosterol
Concentration (mol/L), CPSE1Start the concentration (mol/L) of the polynary acid monoester of phytosterol for reaction.
X in formula (2)PSE3For the esterification yield of phytosterol polyacid mesoinositol, CPSE3For phytosterol polyacid mesoinositol
Concentration (mol/L), CPSE2Start the concentration (mol/L) of the polynary vinyl acetate of phytosterol for reaction.
The purity (%) of phytosterol polyacid mesoinositol=phytosterol polyacid mesoinositol peak area/all samples
Total peak area × 100
The preparation of 1 intermediate product of embodiment, 1 phytosterol monomester succinate
Weigh phytosterol (cupreol of purity > 97%, 63% and 37% stigmasterol) 2.00g, succinic anhydride
0.7506g, 4-dimethylaminopyridine (DMAP) 0.12217g measure toluene 10mL, are added in the conical flask of 125mL, are added
Stirrer installs condensation reflux unit, and oil bath heating is reacted 10 hours at 110 DEG C, stops heating, is cooled to room temperature, and takes out
Sample removes solvent through rotary evaporation and obtains reaction product phytosterol monomester succinate.
The preparation and identification of 2 intermediate product of embodiment, 2 phytosterol amber vinyl acetate
The preparation and analysis of the polynary vinyl acetate of phytosterol are by taking phytosterol amber vinyl acetate as an example.It is pure to weigh separation
Phytosterol monomester succinate 5.12g, mercuric acetate 0.2g after change measure vinyl acetate 0.15moL, tetrahydrofuran 10mL,
It is added in the conical flask of 125mL, reaction 30min is stirred at room temperature in the case where logical nitrogen, the 2uL concentrated sulfuric acid is then added, so
It is reacted at 40 DEG C afterwards, detects reaction process at interval of the tlc silica gel plate point sample of sampling in 2 hours, react 12 hours, stop
It only heats, is cooled to room temperature, the sodium acetate that 20mg is added neutralizes and stops reacting, and takes out sample and obtains through rotary evaporation removing solvent
To reaction product phytosterol amber vinyl acetate.
The liquid phase map analysis of phytosterol amber vinyl acetate is by taking stigmasterol amber vinyl acetate as an example.By phytosterol amber
Amber vinyl acetate carries out efficient liquid phase chromatographic analysis, wherein the appearance time of stigmasterol amber vinyl acetate (b in Fig. 1) is
16.473, the appearance time of stigmasterol hemisuccinate (a in Fig. 1) is 12.223, as shown in Figure 1.
The infrared spectrum of phytosterol amber vinyl acetate is analyzed by taking stigmasterol amber vinyl acetate as an example.Stigmasterol amber
The infrared spectroscopy of vinyl acetate is as shown in Fig. 2, be analyzed as follows: 2924.38cm-1For-CH3Asymmetric stretching vibration absorb (ν
as-CH3), 2849.70cm-1For-CH2Symmetrical stretching vibration absorb (ν s-CH2), 1730.20cm-1Strong absworption peak is ester group
The stretching vibration of C=O absorbs (ν C=O) in functional group, 1601.20cm-1For the stretching vibration absworption peak of C=C, 1465.24cm-1For-CH2Bending vibration absorption peak, 1379.59cm-1For-CH3Bending vibration absorb (δ-CH3), 1184.99cm-1With
1146.63cm-1(ν C-O) is absorbed for the stretching vibration of C-O.
The mass spectral analysis of phytosterol amber vinyl acetate is by taking stigmasterol amber vinyl acetate as an example.Stigmasterol succinic acid second
The mass-spectrogram of enester is as shown in figure 3, be analyzed as follows: the relative molecular mass of stigmasterol monoesters is 512, the phase of vinyl acetate
It is 86 to molecular mass, therefore the relative molecular mass of stigmasterol amber vinyl acetate is 538.Stigmasterol amber vinyl acetate exists
ES+ ionization under, it is understood that there may be [M+H] of stigmasterol amber vinyl acetate+, [M+NH4]+and [M+Na]+molecular ion peak, figure
In 3 561.5 for stigmasterol amber vinyl acetate [M+Na]+mass signal.Therefore, product is stigmasterol succinic acid ethylene
Ester.
The preparation and identification of 3 final product phytosterol succinic acid mesoinositol of embodiment
The preparation and analysis of phytosterol polyacid mesoinositol are by taking phytosterol succinic acid mesoinositol as an example.It is pure to weigh separation
Phytosterol amber vinyl acetate 0.16g, inositol 0.25g, fold Candida (CandidaRugosa) 0.1g after change, point
It is not added to the reaction of mixed solution (85/15, V/V) 10mL of the pre- n-hexane for first passing through molecular sieve dehydration processing and 2- butanone
It is closed in bottle, and the concussion speed that reaction flask is put into 200rpm in constant temperature oscillator is shaken, and controlling reaction temperature is 45
DEG C, the process of regular sample detection reaction stops heating, is cooled to room temperature by the reaction of 120h, takes out sample and steams through rotation
Hair removes solvent and obtains reaction product.
The liquid phase map analysis of phytosterol succinic acid mesoinositol is by taking stigmasterol succinic acid mesoinositol as an example.Pass through efficient liquid phase
Chromatography, the appearance time of stigmasterol succinic acid mesoinositol is 11.299 in phytosterol succinic acid mesoinositol, such as Fig. 4 institute
Show.
The infrared spectrum of phytosterol succinic acid mesoinositol is analyzed by taking stigmasterol succinic acid mesoinositol as an example.Stigmasterol amber
The infrared spectroscopy of sour mesoinositol is as shown in figure 5, be analyzed as follows: 3385.02cm-1For the stretching vibration absworption peak of-OH,
2916.21cm-1For-CH3Asymmetric stretching vibration absorb (ν as-CH3), 2846.77cm-1For-CH2Symmetrical stretching vibration
Absorb (ν s-CH2), 1722.77cm-1Strong absworption peak is that the stretching vibration of the upper C=O of ester functional groups absorbs (ν C=O),
1461.68cm-1For-CH2Bending vibration absorption peak, 1381.45cm-1 be-CH3Bending vibration absorb (δ-CH3),
1216.68cm-1And 1168.14cm-1(ν C-O) is absorbed for the stretching vibration of C-O.
The mass spectral analysis of phytosterol succinic acid mesoinositol is by taking stigmasterol succinic acid mesoinositol as an example.Phytosterol amber acid flesh
The analysis of alcohol ester is by taking stigmasterol succinic acid mesoinositol as an example.The mass-spectrogram of stigmasterol succinic acid mesoinositol is as shown in fig. 6, analysis
As follows: the relative molecular mass of stigmasterol amber vinyl acetate is 538, and the relative molecular mass of inositol is 180, therefore stigmasterol
The relative molecular mass of succinic acid mesoinositol is 674.Stigmasterol succinic acid mesoinositol is under ES+ ionization, it is understood that there may be stigmasterol
[M+H] of succinic acid mesoinositol+, [M+NH4]+and [M+Na]+molecular ion peak, 697 be stigmasterol succinic acid inositol in Fig. 6
[M+Na] of ester+mass signal.Therefore, product is stigmasterol succinic acid mesoinositol.
4 intermediate product of embodiment, 2 phytosterol amber vinyl acetate response parameter optimization process
1) influence of the reaction temperature to synthesis 2 phytosterol amber vinyl acetate of intermediate product
On the basis of embodiment 2, variable is set by reaction temperature, other reaction conditions are constant, respectively control reaction
Temperature be 20 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, when reaction reach 12 it is small when, carry out sample detecting, calculate esterification
Rate.The result shows that esterification yield reaches highest when temperature reaches 50 DEG C, continue to improve temperature, esterification yield no longer rises.Not equality of temperature
Esterification yield under degree is as shown in table 1:
Influence of 1 reaction temperature of table to synthesis intermediate product 2
2) influence of the reaction time to synthesis 2 phytosterol amber vinyl acetate of intermediate product
On the basis of embodiment 2, the reaction time it will be set as variable, other reaction conditions are constant, respectively in reaction
Between to 6,8,10,12,14h carry out sample detecting, calculate esterification yield.The result shows that when the reaction time reaches 12h, esterification yield
Reach highest.The esterification yield of different time is as shown in table 2:
Influence of 2 reaction time of table to synthesis intermediate product 2
3) influence of the catalyst amount to synthesis 2 phytosterol amber vinyl acetate of intermediate product
On the basis of embodiment 2, variable is set by catalyst amount, other reaction conditions are constant, respectively by second
The additive amount of sour mercury is set as 2,3,4,5,6%w/w, to carry out sample detecting after reaction, calculates esterification yield.The result shows that
When catalyst loading is 5%w/w, esterification yield highest.The esterification yield of different catalysts additive amount is as shown in table 3:
Influence of 3 reaction time of table to synthesis intermediate product 2
4) influence of the substrate molar ratio to synthesis 2 phytosterol amber vinyl acetate of intermediate product
On the basis of embodiment 2, variable is set by substrate molar ratio, other reaction conditions are constant, respectively by second
The additive amount of vinyl acetate is set as 5,10,15,20,25mol, to carry out sample detecting after reaction, calculates esterification yield.Knot
Fruit shows vinyl acetate: when phytosterol monomester succinate is 20:1.0, esterification yield highest.The esterification of different mol ratio
Rate is as shown in table 4:
Influence of 4 reaction time of table to synthesis intermediate product 2
5) phytosterol mono succinate ester concentration pairing at 2 phytosterol amber vinyl acetate of intermediate product influence
On the basis of embodiment 2, variable is set by the concentration of phytosterol monomester succinate, other reaction conditions are not
Become, carry out sample detecting after the completion of reaction respectively, calculates esterification yield.The result shows that phytosterol mono succinate ester concentration is
When 0.6mmol/mL, esterification yield highest.The esterification yield of different phytosterol mono succinate ester concentrations is as shown in table 5:
5 phytosterol mono succinate ester concentration pairing of table at intermediate product 2 influence
The preparation and identification of 5 final product phytosterol succinic acid mesoinositol of embodiment
1) influence of the reaction temperature to synthesis final product phytosterol succinic acid mesoinositol
On the basis of embodiment 3, variable is set by reaction temperature, other reaction conditions are constant, respectively control reaction
Temperature be 30 DEG C, 35 DEG C, 40 DEG C, 45 DEG C, 50 DEG C, when reaction reach 120 it is small when, carry out sample detecting, calculate esterification
Rate.The result shows that esterification yield reaches highest when reaction temperature reaches 45 DEG C.The esterification yield of different temperatures is as shown in table 6:
Influence of 6 reaction temperature of table to synthesis final product
2) influence of the reaction time to synthesis final product phytosterol succinic acid mesoinositol
On the basis of embodiment 3, the reaction time it will be set as variable, other reaction conditions are constant, respectively in reaction
Between to 40,60,80,100,120h carry out sample detecting, calculate esterification yield.The result shows that when the reaction time is 80h, esterification
Rate highest.The esterification yield of different time is as shown in table 7:
Influence of 7 reaction time of table to synthesis final product
3) influence of the enzyme dosage to final product phytosterol succinic acid mesoinositol
On the basis of embodiment 3, variable is set by enzyme dosage, other reaction conditions are constant, respectively by lipase
Additive amount be set as 20,40,60,80,100g/L, to carry out sample detecting after reaction, calculate esterification yield.Work as lipase
Additive amount when being set as 80g/L, esterification yield reaches highest.The esterification yield of different enzyme additive amounts is as shown in table 8:
Influence of 8 enzyme dosage of table to synthesis final product
4) influence of the substrate molar ratio to synthesis final product phytosterol succinic acid mesoinositol
On the basis of embodiment 3, variable is set by substrate molar ratio, other reaction conditions are constant, respectively by flesh
The additive amount of alcohol is set as 0.090,0.1350,0.1800,0.2250g, to carry out sample detecting after reaction, calculates esterification
Rate.The result shows that phytosterol amber vinyl acetate: esterification yield highest when inositol is 1.0:3.0.Different substrate molar ratios
Esterification yield is as shown in table 9:
Influence of the 9 substrate molar ratio of table to synthesis final product
5) influence of the phytosterol amber vinyl acetate concentration to synthesis final product
On the basis of case study on implementation 2, variable is set by the concentration of phytosterol monomester succinate, other reaction conditions
It is constant, it carries out sample detecting after the completion of reaction respectively, calculates esterification yield.The result shows that phytosterol amber vinyl acetate concentration
Esterification yield highest when for 0.025mmol/L.Esterification yield is as shown in table 10:
Influence of the 10 phytosterol amber vinyl acetate concentration of table to synthesis final product
The purification process of 6 intermediate product of embodiment, 2 phytosterol amber vinyl acetate
By taking stigmasterol amber vinyl acetate as an example, is explored by thin-layer chromatography and silica gel column chromatography is suitble to separate stigmasterol amber
The eluting solvent of vinyl acetate are as follows: petrol ether/ethyl acetate/formic acid: 9/2/0.01.By 320g 100-200 mesh column chromatography silica gel
G is put into beaker, and certain eluting solvent is added, sufficiently stirs evenly, and is in homogenate state, impregnates 3h at room temperature.The silica G that will sufficiently impregnate
It is slowly packed into flaring chromatographic column (2.5cm × 100cm), bubble is avoided to occur, after silica gel sufficiently settles, stands an evening, for use.
4g sample is dissolved in 20mL eluting solvent, loading collects eluent, 8min/ with automatic collector with eluent silicagel column
Pipe, and eluted product is tracked with thin-layer chromatographic analysis, by Rf value (Rf) consistent product merges and collect, remove through rotary evaporation
It is stigmasterol amber vinyl acetate after solvent.
The purification process of 7 final product phytosterol succinic acid mesoinositol of embodiment
By taking stigmasterol amber vinyl acetate as an example, is explored by thin-layer chromatography and silica gel column chromatography is suitble to separate stigmasterol amber
The eluting solvent of vinyl acetate are as follows: petrol ether/ethyl acetate/formic acid: 13/7/0.02.320g 100-200 mesh column is chromatographed into silicon
Glue G is put into beaker, and certain eluting solvent is added, sufficiently stirs evenly, and is in homogenate state, impregnates 3h at room temperature.The silicon that will sufficiently impregnate
Glue G is slowly packed into flaring chromatographic column (2.5cm × 100cm), and bubble is avoided to occur, and after silica gel sufficiently settles, stands an evening, to
With.4g sample is dissolved in 20mL eluting solvent, loading collects eluent with automatic collector with eluent silicagel column,
8min/ pipe, and eluted product is tracked with thin-layer chromatographic analysis, by Rf value (Rf) consistent product merges and collect, steam through rotation
Hair is stigmasterol succinic acid mesoinositol after removing solvent.
Although the present invention has been described by way of example and in terms of the preferred embodiments, it is not intended to limit the invention, any to be familiar with this skill
The people of art can do various change and modification, therefore protection model of the invention without departing from the spirit and scope of the present invention
Enclosing subject to the definition of the claims.
Claims (10)
1. a plant sterols polyacid mesoinositol, it is characterised in that: general structure is as follows:
Wherein, n=0~6；
Alternatively, its general structure are as follows:
Alternatively, its general structure are as follows:
Alternatively, its general structure are as follows:
Alternatively, its general structure are as follows:
Wherein, R includes
2. the preparation method of phytosterol polyacid mesoinositol described in claim 1, it is characterised in that: more by phytosterol
First acid monoester prepares the polynary vinyl acetate of phytosterol, and it is more that the polynary vinyl acetate of phytosterol reacts generation phytosterol with inositol
First acid mesoinositol.
3. preparation method according to claim 2, it is characterised in that: the preparation step of the polynary acid monoester of phytosterol
Are as follows: phytosterol and multicomponent organic acid or its acid anhydrides, catalyst a are mixed, organic solvent a is added, by controlling temperature, in real time
Reaction process is monitored, heats, is cooled to room temperature by stopping after sufficiently reacting, taking-up sample removes organic solvent a and obtains instead
Answer the polynary acid monoester of product phytosterol.
4. preparation method according to claim 3, it is characterised in that: the multicomponent organic acid include citric acid, malic acid,
One of tartaric acid, butene dioic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid are a variety of,
The multicomponent organic acid acid anhydride includes one of corresponding acid anhydrides of the multicomponent organic acid or a variety of, phytosterol with it is polynary organic
The molar ratio of acid or its acid anhydrides is 1.0:(1.2~1.7).
5. preparation method according to claim 2, it is characterised in that: the preparation step of the polynary vinyl acetate of phytosterol
Are as follows: the polynary acid monoester of phytosterol is mixed with vinyl acetate, adds organic solvent b, and alkalescent metal salt work is added
For catalyst b, strong acid starting reaction is added after reacting a period of time under an inert gas, heating is reacted, and reaction terminates to stop
It only heats, is cooled to room temperature, excessive salt of weak acid is added and neutralizes and stops reacting, take out sample removing solvent and obtain reaction production
Object.
6. preparation method according to claim 5, it is characterised in that: the additive amount that catalyst b is is that phytosterol is polynary
2%~10% (w/w) of acid monoester dosage.
7. preparation method according to claim 2, it is characterised in that: the preparation step of phytosterol polyacid mesoinositol
Are as follows: the polynary vinyl acetate of phytosterol, inositol, biocatalyst are added separately to the anti-of the pre- solvent for first passing through dehydration
It answers in bottle, it is closed, and reaction flask is shaken, and control reaction temperature, the process of regular sample detection reaction, reaction terminates
Afterwards, stop heating, be cooled to room temperature, take out sample removing solvent and obtain reaction product phytosterol polyacid mesoinositol.
8. preparation method according to claim 7, it is characterised in that: the biocatalyst is lipase catalyst,
Including Novi's letter immobilized lipase (Novozyme 435), immobilized lipase RM IM (Lipozyme RM IM) or fold
Lipase from candida sp (Candida Rugosa).
9. preparation method according to claim 7, it is characterised in that: the additive amount of the biocatalyst is phytosterol
The 8%~12% of polynary vinyl acetate quality.
It is planted 10. any one of phytosterol polyacid mesoinositol described in claim 1 and claim 2-9 the method is obtained
Application of the object sterol polyacid mesoinositol in food, medicine, chemical industry and cosmetic field.
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| CN101886100A (en) * | 2010-07-12 | 2010-11-17 | 江南大学 | Method for preparing sucrose-6-acetic ester by enzymatic method |
| CN102936613A (en) * | 2012-11-20 | 2013-02-20 | 江南大学 | Enzymatic catalysis method for preparing phytosterol-beta-D-glucoside |
| CN102978272A (en) * | 2011-09-06 | 2013-03-20 | 江南大学 | Novel phytosterol or/and phytostanol derivative preparation method |
| CN103044363A (en) * | 2012-04-17 | 2013-04-17 | 湘北威尔曼制药股份有限公司 | Paclitaxel derivative as well as preparation method and application thereof |
| CN103965278A (en) * | 2014-04-16 | 2014-08-06 | 江南大学 | Preparation method for water-soluble phytosterin organic dibasic acid sugar ester |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101886100A (en) * | 2010-07-12 | 2010-11-17 | 江南大学 | Method for preparing sucrose-6-acetic ester by enzymatic method |
| CN102978272A (en) * | 2011-09-06 | 2013-03-20 | 江南大学 | Novel phytosterol or/and phytostanol derivative preparation method |
| CN103044363A (en) * | 2012-04-17 | 2013-04-17 | 湘北威尔曼制药股份有限公司 | Paclitaxel derivative as well as preparation method and application thereof |
| CN102936613A (en) * | 2012-11-20 | 2013-02-20 | 江南大学 | Enzymatic catalysis method for preparing phytosterol-beta-D-glucoside |
| CN103965278A (en) * | 2014-04-16 | 2014-08-06 | 江南大学 | Preparation method for water-soluble phytosterin organic dibasic acid sugar ester |
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