CN111850058A - Method for synthesizing propyl gallate through tannic acid biocatalysis - Google Patents
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Abstract
The invention belongs to the technical field of propyl gallate synthesis, and particularly relates to a method for synthesizing propyl gallate by tannic acid through biocatalysis.
Description
Technical Field
The invention belongs to the technical field of propyl gallate synthesis, and particularly relates to a method for synthesizing propyl gallate through tannic acid biocatalysis.
Background
Propyl gallate ((Propyl g gallate, PG) is white to light brown crystal powder or micro-emulsion white needle crystal, chemical name is 3,4, 5-trihydroxy benzoic acid Propyl ester, has good antioxidant performance, stronger antioxidant performance than tert-butyl hydroxy anisole and 2, 6-di-tert-butyl p-cresol, good heat resistance, is mainly used for antioxidation of grease or oil food and preservation of fruits and vegetables, can be used as biodiesel and antioxidant stabilizer or anti-aging agent of certain materials Has obvious effects on enhancing coronary blood flow and the like.
The existing method for producing propyl gallate has chemical catalysis and biotransformation, and the chemical catalysis has the disadvantages of high energy consumption, environmental pollution, long preparation time, more side reaction products and severe corrosion to equipment; the biotransformation reaction time is long, and the yield is low. More importantly, gallic acid is generally used as raw material to prepare propyl gallate through esterification in the traditional production, such as the research on the preparation of propyl gallate by aspergillus niger whole-cell biocatalysis (by the department of the amateur and the like) which utilizes aspergillus niger cells as a whole-cell biocatalyst to catalyze the production of propyl gallate, the microbiological method disclosed in the patent No. CN200410068174.8 in an organic phase synthesis mode to calculate propyl gallate, and the aspergillus niger is utilized to catalyze the synthesis of propyl gallate in an organic phase, but in fact, gallic acid is more expensive than propyl gallate, which undoubtedly increases the production cost.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for synthesizing propyl gallate by tannic acid biocatalysis.
The method is realized by the following technical scheme:
a method for synthesizing propyl gallate by tannic acid biocatalysis comprises the steps of taking tannic acid as a reaction monomer, taking sodium carboxymethylcellulose-immobilized tannase as a catalyst, performing catalytic reaction in an organic solvent in cooperation with microwaves, and then performing reduced pressure distillation, cooling crystallization and vacuum drying to obtain the propyl gallate.
In the synthesis process of the propyl gallate, the mass ratio of the reaction monomer, the organic solvent and the catalyst is 1: (2-5): (0.8-1.3).
The organic solvent is n-butanol.
The preparation method of the sodium carboxymethylcellulose-immobilized tannase comprises the following steps: mixing the tannase solution and sodium carboxymethylcellulose at constant temperature of 25-35 deg.C, and shaking.
The volume mass ratio of the tannase solution in the sodium carboxymethylcellulose solidified tannase to the sodium carboxymethylcellulose is 1: (0.3-0.6).
The tannase solution is prepared by preparing commercially available tannase and water into a solution with the mass concentration of 50-70%, and then adjusting the pH value to 6.3-6.7 by using a citric acid-sodium citrate solution.
The concentration of the tannase solution is 2000-3000U/mL.
Further, the method for synthesizing propyl gallate by tannic acid biocatalysis comprises the following steps:
1) preparing a tannic acid solution with the mass concentration of 60-80% in water, and performing ultrasonic dispersion with a catalyst for 5-10 min;
2) adding an organic solvent into the product obtained in the step 1), performing ultrasonic dispersion for 10-15min, heating to 40-45 ℃, performing heat preservation reaction for 16-20h, and filtering to recover the catalyst;
3) transferring the filtrate into a microwave kettle, performing microwave irradiation treatment for 3-5min under the condition of 120-260W, performing reduced pressure distillation to recover n-propanol, cooling, crystallizing, and vacuum drying to obtain propyl gallate.
And (3) ultrasonically dispersing, wherein the power of the ultrasonic dispersion is 50-100W.
Further, as a preferable mode, the catalyst of the present invention can also be preferably sulfonic acid resin/sodium carboxymethyl cellulose immobilized tannase, wherein the mass ratio of sodium carboxymethyl cellulose to sulfonic acid resin is 1: (0.2-0.4), uniformly mixing, and then defoaming in an oven at the temperature of 75 ℃ for 2 hours.
Has the advantages that:
the method solves the problems of long production time and low yield of a biocatalysis method, and the propyl gallate is simple and easy to operate, does not generate a large amount of waste water and waste residues, has high product activity and particularly has better oxidation resistance.
Tannase is an enzyme in a free state, has high environmental sensitivity, is unstable in strong acid, strong alkali, high temperature, high ion concentration and partial organic solvent, leads to enzyme protein denaturation, thereby reducing or even losing the catalytic activity of the tannase, and is not easy to separate from a substrate and a product after the completion of catalysis; according to the invention, sodium carboxymethylcellulose is used as a carrier to solidify tannase, so that the activity stability of the tannase can be improved, the heat-resistant range can be expanded, the enzyme activity can be ensured, the tannase can be recycled, and the tannase has lower activation energy. And the sodium carboxymethyl cellulose is insoluble in an organic solvent, so that the stability of a reaction system is facilitated. The sodium carboxymethylcellulose is utilized, and the wave absorbing frequency is wide, so that the wavelength emitted by ultrasonic treatment can be absorbed, the impurity substance can be adsorbed, the purity requirements of tannic acid and n-propanol in raw material preparation are reduced, and the oxidation resistance of the product is improved.
As a preferred scheme, the tannase is cured by using the sulfonic acid resin/sodium carboxymethyl cellulose, so that the reaction efficiency can be improved, the reaction time can be shortened, the curing capability of the tannase can be enhanced, and the phenomenon that the tannase is easy to leak or fall off from a carrier in the recycling process is effectively avoided.
The invention adopts the commercial tannase, has convenient raw material source, does not need to utilize aspergillus niger and the like for fermentation, and greatly shortens the production time.
Detailed Description
The following is a detailed description of the embodiments of the present invention, but the present invention is not limited to these embodiments, and any modifications or substitutions in the basic spirit of the embodiments are included in the scope of the present invention as claimed in the claims.
Example 1
A method for synthesizing propyl gallate by tannic acid biocatalysis comprises the following steps:
1) preparing a tannic acid solution with the mass concentration of 70% in tannic acid solution water, and performing ultrasonic dispersion on the tannic acid solution and sulfoacid resin/sodium carboxymethylcellulose solidified tannase for 7min under the condition that the power is 70W;
2) adding n-butanol into the product obtained in the step 1), performing ultrasonic dispersion for 12min under the condition of power of 70W, heating to 43 ℃, performing heat preservation reaction for 18h, and filtering to recover the catalyst;
3) Transferring the filtrate into a microwave kettle, performing microwave irradiation treatment for 4min under the condition of 200W, recovering n-propanol by reduced pressure distillation, cooling for crystallization, and vacuum drying to obtain propyl gallate;
the propyl gallate is prepared from the reaction monomers, the organic solvent and the catalyst in a mass ratio of 1: 3: 1;
the preparation method of the sulfonic acid resin/sodium carboxymethyl cellulose solidified tannase comprises the following steps: mixing the tannase solution and sodium carboxymethylcellulose at constant temperature of 30 ℃ and oscillating;
the volume-mass ratio of the tannase solution in the sodium carboxymethylcellulose solidified tannase to the sulfonic acid resin/sodium carboxymethylcellulose is 1: 0.4;
the sulfonic acid resin/sodium carboxymethyl cellulose is prepared by mixing sodium carboxymethyl cellulose and sulfonic acid resin according to a mass ratio of 1: 0.3, uniformly mixing, and then defoaming in an oven at the temperature of 75 ℃ for 2 hours;
the tannase solution is prepared by preparing commercially available tannase and water into a solution with the mass concentration of 60%, and then adjusting the pH value to be 6.5 by using a citric acid-sodium citrate solution, wherein the concentration of the tannase solution is 2500U/mL.
Example 2
A method for synthesizing propyl gallate by tannic acid biocatalysis comprises the following steps:
1) preparing a tannic acid solution with the mass concentration of 60% in tannic acid solution water, and performing ultrasonic dispersion with sodium carboxymethylcellulose-immobilized tannase at the power of 50W for 5 min;
2) Adding n-butanol into the product obtained in the step 1), performing ultrasonic dispersion for 10min under the condition that the power is 50W, heating to 40 ℃, performing heat preservation reaction for 16h, and filtering to recover the catalyst;
3) transferring the filtrate into a microwave kettle, performing microwave irradiation treatment for 3min under the condition of 120W, recovering n-propanol by reduced pressure distillation, cooling for crystallization, and vacuum drying to obtain propyl gallate;
the propyl gallate is prepared from the reaction monomers, the organic solvent and the catalyst in a mass ratio of 1: 2: 0.8;
the preparation method of the sodium carboxymethylcellulose-immobilized tannase comprises the following steps: mixing the tannase solution and sodium carboxymethylcellulose at a constant temperature of 25 ℃ and oscillating;
the volume mass ratio of the tannase solution in the sodium carboxymethylcellulose solidified tannase to the sodium carboxymethylcellulose is 1: 0.3;
the tannase solution is prepared by preparing commercially available tannase and water into a solution with the mass concentration of 50%, and then adjusting the pH value to be 6.3 by using a citric acid-sodium citrate solution, wherein the concentration of the tannase solution is 2000U/mL.
Example 3
A method for synthesizing propyl gallate by tannic acid biocatalysis comprises the following steps:
1) preparing a tannic acid solution with the mass concentration of 80% in tannic acid solution water, and performing ultrasonic dispersion with sodium carboxymethylcellulose-immobilized tannase at the power of 100W for 5 min;
2) Adding n-butanol into the product obtained in the step 1), performing ultrasonic dispersion for 10min under the condition of 100W of power, heating to 45 ℃, performing heat preservation reaction for 20h, and filtering to recover the catalyst;
3) transferring the filtrate into a microwave kettle, performing microwave irradiation treatment for 5min under the condition of 260W, recovering n-propanol by reduced pressure distillation, cooling for crystallization, and vacuum drying to obtain propyl gallate;
the propyl gallate is prepared from the reaction monomers, the organic solvent and the catalyst in a mass ratio of 1: 5: 1.3;
the preparation method of the sodium carboxymethylcellulose-immobilized tannase comprises the following steps: mixing the tannase solution and sodium carboxymethylcellulose at a constant temperature of 35 ℃ and oscillating;
the volume mass ratio of the tannase solution in the sodium carboxymethylcellulose solidified tannase to the sodium carboxymethylcellulose is 1: 0.6;
the tannase solution is prepared by preparing commercially available tannase and water into a solution with the mass concentration of 70%, and then adjusting the pH value to be 6.7 by using a citric acid-sodium citrate solution, wherein the concentration of the tannase solution is 3000U/mL.
Example 4
A method for synthesizing propyl gallate by tannic acid biocatalysis comprises the following steps:
1) preparing a tannic acid solution with the mass concentration of 63% in tannic acid solution water, and performing ultrasonic dispersion on the tannic acid solution and sodium carboxymethyl cellulose-cured tannase for 9min under the condition that the power is 80W;
2) Adding n-butanol into the product obtained in the step 1), performing ultrasonic dispersion for 11min under the condition of 80W of power, heating to 44 ℃, performing heat preservation reaction for 17h, and filtering to recover the catalyst;
3) transferring the filtrate into a microwave kettle, performing microwave irradiation treatment for 4min under the condition of 250W, recovering n-propanol by reduced pressure distillation, cooling for crystallization, and vacuum drying to obtain propyl gallate;
the propyl gallate is prepared from the reaction monomers, the organic solvent and the catalyst in a mass ratio of 1: 4: 0.9;
the preparation method of the sodium carboxymethylcellulose-immobilized tannase comprises the following steps: mixing the tannase solution and sodium carboxymethylcellulose at a constant temperature of 32 ℃ and oscillating;
the volume mass ratio of the tannase solution in the sodium carboxymethylcellulose solidified tannase to the sodium carboxymethylcellulose is 1: 0.4;
the tannase solution is prepared by preparing a solution with a mass concentration of 67% by using commercially available tannase and water, and then adjusting the pH value to be 6.6 by using a citric acid-sodium citrate solution, wherein the concentration of the tannase solution is 2500U/mL.
Test example 1 the performance of the immobilized tannase of the present invention was examined;
first part test method
Test group 1: immobilized tannase was prepared using the method of example 1;
Test group 2: the sodium carboxymethylcellulose in example 1 was replaced with chitosan;
test group 3: the sodium carboxymethylcellulose in example 1 was replaced with β -cyclodextrin;
test group 4: replacing the sodium carboxymethylcellulose in example 1 with a stilbene/acrylate based macroporous adsorbent resin;
test group 5: the sodium carboxymethylcellulose in example 1 was replaced by cellulose.
The second part of the detection method comprises the following steps:
1. determination of enzyme activity and recovery rate of enzyme activity
At 40 deg.C, 1mL of free tannase solution or 1g of immobilized tannase per minute reduced the absorbance of PG solution at a wavelength of 270nm by 0.001, defined as 1 enzyme activity unit (U), and the enzyme activity was calculated according to the formula (1)
Formula (1) X ═ a × n/(0.001 × t); wherein X is the enzyme activity/(U/mL) (or U/g) of the sample; a is the absorbance of the sample at a wavelength of 270 nm; t is the reaction time/min of the sample; and n is the dilution multiple of the enzyme solution.
The recovery rate of enzyme activity/%, namely 100 x total activity of immobilized enzyme/(total activity of enzyme liquid-activity of residual enzyme liquid); in the formula: total activity (U) of immobilized enzyme is immobilized enzyme activity (U/g) x immobilized enzyme mass (g); total enzyme activity (U) ═ enzyme activity (U/mL) × enzyme volume (mL); activity of residual enzyme solution (U) × activity of enzyme solution (U/mL) × volume of residual enzyme solution (mL) after the immobilized enzyme was filtered out.
2. Storage stability of immobilized tannase
And (3) preserving each group of immobilized tannase at 4 ℃ for 45d, then carrying out enzyme activity determination, and investigating the activity residual rate of the immobilized tannase.
Residual rate of enzyme activity/% (100 × total activity of enzyme solution after preservation for 45 d)/total activity of initial enzyme solution
3. Number of times of recycling of immobilized tannase
And (3) hydrolyzing 50mL of PG standard solution for 20min by using 0.2g of immobilized tannase, filtering the immobilized tannase after each hydrolysis, cleaning, measuring the enzyme activity, and then putting the PG standard solution into the PG standard solution for the next hydrolysis until the enzyme activity is reduced to 70% of the initial enzyme activity, so as to investigate the recycling times of the immobilized tannase.
4. Data processing
Each experiment was performed in 3 replicates and the results are expressed as "mean ± standard deviation". Data fitting, model construction and regression analysis were performed with SAS 9.4(SAS institute inc, Cary, NC, USA) software.
Third part of the analysis
1. The results of the enzyme activity recovery measurement are shown in Table 1:
TABLE 1
2. The results of the enzyme preservation stability assay are shown in table 2:
TABLE 2
3. The results of the number of cycles of immobilized tannase are shown in Table 3:
TABLE 3
| Item | Test group 1 | Test group 2 | Test group 3 | Test group 4 | Test group 5 |
| Number of times | 10 | 5 | 7 | 4 | 5 |
The above data show that: the solidified tannase prepared by the method has better stability and cyclic utilization rate.
Test example 2 measurement of propyl gallate content
First part of the Experimental methods
Test groups 1-4: example 1-example 4;
test group 5: on the basis of example 4, sodium carboxymethylcellulose immobilized tannase was replaced with tannase;
test group 6: on the basis of the example 2, the step 1) and the step 2) are not subjected to ultrasonic dispersion;
test group 7: in the technology of the embodiment 3, the temperature of the heat preservation in the step 2) is 47 ℃;
test group 8: on the basis of example 1, step 3) was not subjected to microwave treatment;
second part detection method
1. Propyl gallate yield detection
Detecting propyl gallate by high performance liquid chromatography. The detection conditions were as follows: c18 column, mobile phase methanol-0.5% acetic acid water buffer solution (65: 35), flow rate of 0.8mL/min, column temperature of 30 deg.C, detection wavelength of 280nm, and sample amount of 10 μ L. Taking a proper amount of propyl gallate or a sample, preparing a 0.01mg/mL standard solution or sample solution by using a buffer solution as a solvent, and calculating the yield of propyl gallate according to the formula (2) after detection:
(ii) formula (2) propyl gallate yield/% (100 × C × V × D/m); in the formula: c is the mass concentration of propyl gallate/(mg/mL); d is the dilution multiple of the solution to be detected; v is the volume/L of the liquid to be detected; and m is the mass of the tannic acid/mg in the sample.
DPPH radical scavenging ability
Weighing 0.0197g of DPPH, and fixing the volume to 100mL by using methanol, wherein the concentration is 500 mu mol/L; 10mL of the solution was taken, and the volume was adjusted to 100mL with methanol, and 0.1mL of an antioxidant and 3.9mL of DPPH solution were added and reacted at 37 ℃ for 30 min. The absorbance value was measured at a wavelength of 517 nm. Absorbance was measured against 0.1mL of methanol +3.9mL of DPPH. The concentration of the sample solution was 8. mu. mol/L. The DPPH free radical scavenging ability is calculated as formula (3);
formula (3): DPPH radical scavenging ability/% (A) 100 × (Sample (I)-AControl)/AControl(ii) a In the formula: a. theSample (I)Represents the absorbance value of the sample set at a wavelength of 517 nm; a. theControlRepresenting the absorbance value of the control group at a wavelength of 517 nm;
ABTS radical scavenging ability
And (3) carrying out isometric reaction on the 7mmol/L ABTS stock solution and the 2.45mmol/L potassium persulfate stock solution for 16h at room temperature in a dark place to obtain the ABTS stock solution. Diluting the stock solution with 95% ethanol or deionized water, maintaining the temperature at 30 deg.C for 6min, measuring absorbance at wavelength of 734nm to obtain ABTS working solution with absorbance value of 0.7 + -0.02, and recording the absorbance value of blank group. 3mL of ABTS working solution was mixed with 20. mu.L of sample solution (8. mu. mol/L), and reacted at 30 ℃ for 6min to obtain a sample solution. 3mL of ABTS working solution is mixed with 20 mu L of ethanol with the volume fraction of 95 percent, and the mixture reacts for 6min at the temperature of 30 ℃ to obtain blank solution. The absorbance value was measured at a wavelength of 734 nm. The scavenging ability of ABTS free radicals is shown in formula (4);
Formula (4): ABST free radical scavenging rate/% (A) 100 × (E-AB)/AB(ii) a In the formula: a. theERepresents the absorbance value of the sample set at the wavelength of 734 nm; a. theBRepresents the absorbance value of the blank at a wavelength of 734 nm;
third part result analysis
1. The results of the propyl gallate yield for each group are shown in table 4:
TABLE 4
Thus illustrating that: the method of the invention has better yield, which can promote the forward movement of esterification because the sodium carboxymethyl cellulose has hygroscopicity, and can saturate the reaction by using microwave treatment, and when the temperature is higher than 45 ℃, the catalytic capability is reduced because of the heat intolerance of enzyme.
2. The DPPH radical scavenging ability of each group of propyl gallate is shown in table 5:
TABLE 5
| Item | Test group 1 | Test group 2 | Test group 3 | Test group 4 |
| Clearance rate/%) | 92.3 | 90.9 | 91.5 | 92.1 |
| Item | Test group 5 | Test group 6 | Test group 7 | Test group 8 |
| Clearance rate/%) | 75.9 | 79.5 | 64.6 | 70.6 |
3. The ABST free radical scavenging ability of each group of propyl gallate is shown in table 6:
TABLE 6
| Item | Test group 1 | Test group 2 | Test group 3 | Test group 4 |
| Clearance rate/%) | 95.2 | 93.4 | 92.3 | 92.6 |
| Item | Test group 5 | Test group 6 | Test group 7 | Test group 8 |
| Clearance rate/%) | 76.7 | 85.3 | 62.1 | 72.8 |
It can be seen from this that: the propyl gallate of the invention has stronger oxidation resistance.
Claims (9)
1. A method for synthesizing propyl gallate by tannic acid biocatalysis is characterized in that tannic acid is used as a reaction monomer, sodium carboxymethylcellulose-immobilized tannase is used as a catalyst, and the reaction is catalyzed in an organic solvent by cooperating with microwaves, and then the propyl gallate is obtained by reduced pressure distillation, cooling crystallization and vacuum drying.
2. The method for synthesizing propyl gallate by using tannic acid through biocatalysis as claimed in claim 1, wherein the mass ratio of the reaction monomer, the organic solvent and the catalyst in the synthesis process of propyl gallate is 1: (2-5): (0.8-1.3).
3. The method for the biocatalytic synthesis of propyl gallate with tannic acid of claim 1, wherein the organic solvent is n-butanol.
4. The method for the biocatalytic synthesis of propyl gallate with tannic acid of claim 1, wherein the sodium carboxymethyl cellulose immobilized tannase is prepared by: mixing the tannase solution and sodium carboxymethylcellulose at constant temperature of 25-35 deg.C, and shaking.
5. The method for synthesizing propyl gallate through tannic acid biocatalysis as claimed in claim 4, wherein the ratio of the tannase solution in the sodium carboxymethyl cellulose immobilized tannase to the sodium carboxymethyl cellulose is 1: (0.3-0.6).
6. The method for the biocatalytic synthesis of propyl gallate with tannic acid as claimed in claim 5, wherein the tannase solution is prepared by mixing commercially available tannase with water to a mass concentration of 50-70%, and adjusting the pH value to 6.3-6.7 with citric acid-sodium citrate solution.
7. The method for the biocatalytic synthesis of propyl gallate with tannic acid of claim 8, wherein the concentration of the tannase solution is 2000-.
8. The method for the biocatalytic synthesis of propyl gallate with tannic acid of claim 1, comprising the steps of:
1) preparing a tannic acid solution with the mass concentration of 60-80% in water, and performing ultrasonic dispersion with a catalyst for 5-10 min;
2) adding an organic solvent into the product obtained in the step 1), performing ultrasonic dispersion for 10-15min, heating to 40-45 ℃, performing heat preservation reaction for 16-20h, and filtering to recover the catalyst;
3) transferring the filtrate into a microwave kettle, performing microwave irradiation treatment for 3-5min under the condition of 120-260W, performing reduced pressure distillation to recover n-propanol, cooling, crystallizing, and vacuum drying to obtain propyl gallate.
9. The method for the biocatalytic synthesis of propyl gallate with tannic acid of claim 8, wherein the ultrasonic dispersion is at a power of 50-100W.
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| CN1635127A (en) * | 2004-11-10 | 2005-07-06 | 浙江大学 | Process for synthesizing propyl gallate in organic phase by microbiological method |
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| 单爱琴等主编: "《环境微生物学》", 30 November 2014, 中国矿业大学出版社 * |
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