CN111518146B - Novel large-scale synthesis and preparation method of compound arginine fructoside-AF - Google Patents
Novel large-scale synthesis and preparation method of compound arginine fructoside-AF Download PDFInfo
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Abstract
Arginine Fructoside (AF), also known as arginine monoglycoside, is present in various plants in the nature, is also a Maillard Reaction product generated during the process of processing fresh ginseng into red ginseng and sun-dried ginseng, and is a marked component for ginseng processing. Pharmacological studies now show that: AF has a variety of pharmacological activities. The invention belongs to the technical field of compound synthesis and preparation, and provides a novel method for large-scale synthesis and preparation of a compound arginine fructoside-AF. The method can greatly improve the crude synthesis rate of the product, is simple to operate, reduces the production cost of AF, has no pungent smell of the composition, belongs to a green environment-friendly synthesis method, and can be completely suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of compound synthesis and preparation, and particularly relates to a novel large-scale synthesis and preparation method and application of a specific product of red ginseng processing, namely compound argininol-AF, and particularly relates to a method for synthesizing argininol AF by taking a mixed solution of propylene glycol and ethanol as a solvent.
Background
Arginine fructoside, molecular weight 337.3, chemical name 1- (arginine-N alpha base) -1-deoxy-D fructose. The purified AF monomer is a white powder, is hardly soluble in organic solvents such as methanol and ethanol, has hygroscopicity, and is unstable to heat. The AF content in nature is very low, but researches show that the AF content is higher and can reach 2.51 percent when the ginseng is processed into sun-dried ginseng and red ginseng[1,2]. During the process of processing the fresh ginseng into the red ginseng, the glucose and the arginine have carbonyl condensation reaction, and AF is generated through Amadori rearrangement. Zhang YAN SONG adopts repeated FR-980 biological electrophoresis image analysis system to analyze AF content in radix Panacis Quinquefolii, and the result is 0.237%[3]. Yukio Suzuki et al established the relationship between browning generation and AF in red ginseng processing, and the results show that the increase of arginine and sugar can accelerate the browning degree[4,5]. Zhao Jing et al studied the effect of different heating times on AF and AFG content in red ginseng and pointed out: as the preheating time is prolonged, the contents of AF and AFG show rising trend[6]. AF exists in natural plants, but the steps are complicated, the time is long and the content is low when a pure AF monomer is obtained from the natural plants. Therefore, chemical synthesis provides a convenient way to obtain large amounts of AF products.
The chemical synthesis method reported in the past is as follows: glacial acetic acid or glycerol is taken as a medium to obtain the AF crude composition, but the product has strong irritant sour taste, poor product stability, easy moisture absorption, large arginine residual quantity, large viscosity of the synthetic liquid, poor liquidity and difficult subsequent anhydrous acetone precipitation and washing. Therefore, it is necessary to find a synthetic method which has high product synthesis rate, high purity, low arginine residue, no pungent smell, low production cost, environmental protection, and simple and easy operation.
At present, the prior art for the preparation of the compound is as follows:
CN201610172045.6 discloses a preparation method of AF, arginine and glucose are put into glycerol, sodium sulfite or vitamin C serving as a Maillard reaction inhibitor is added, and a total reactant is obtained after reaction for 120-200 min; the total composition was concentrated at low pressure and freeze dried to yield AF of about 63%.
As can be seen from the existing AF synthesis process, the existing synthesis process has the following characteristics and main defects:
(1) longer reaction time, low efficiency and low yield. (2) The synthesis method of AF usually takes glycerol as a reaction medium, the glycerol has high viscosity and poor fluidity, the subsequent acetone precipitation and washing times are increased, the cost is increased, and the product is not easy to separate; (3) the glycerol has strong water absorption and is easy to absorb moisture, and a little glycerol residue in the product can accelerate the moisture absorption of the product and reduce the stability. (4) The defects of using sodium sulfite or vitamin C as a catalyst and a reaction medium are obvious, the sodium sulfite is decomposed by high heat to generate toxic sulfide smoke, and the vitamin C has poor stability and is easy to oxidize.
The invention surprisingly discovers that the defects of the existing synthesis method can be fully overcome by using citric acid as a catalyst and using a mixed solution of propylene glycol and ethanol as a reaction medium, and in addition, the reaction solvent propylene glycol has the characteristics of low viscosity, strong fluidity, better stability than glycerol and the like.
Disclosure of Invention
In view of the problems in the prior art, the invention provides a novel method for preparing the compound arginine fructoside-AF in a large-scale synthesis way and application thereof: arginine, glucose and propylene glycol ethanol mixed solution are used as reaction media, citric acid is used as a catalyst, AF is synthesized under the conditions of heating and uniform mixing, and in addition, as AF is a substance which is easy to deteriorate, the post-treatment after the reaction is also very important for obtaining products with high yield and high purity. The method has the characteristics of simple operation, high crude synthesis rate of the product, low arginine residue of the compound, low cost, low irritation of the product, high stability and the like.
Specifically, the invention is realized by the following technical scheme:
the new method for synthesizing and preparing the compound arginine fructoside-AF in a large scale comprises the following steps:
and (3) synthesizing AF by taking a mixed solution of propylene glycol and ethanol as a reaction medium: putting arginine, glucose and citric acid into a mixed solution of propylene glycol and ethanol according to a certain proportion, uniformly mixing, and heating to generate AF, wherein the specific method comprises the following steps:
putting arginine and glucose into 10-20 times (by mass of arginine, g/mL) of propylene glycol and ethanol mixed solution according to the weight ratio of 1 (1-3), adding citric acid as a catalyst, heating at 20-100 ℃ for 30-150 min, precipitating and washing an organic reagent, carrying out vacuum filtration, and drying at low temperature to obtain AF.
As a preferred embodiment of the present invention, the ratio of arginine: maltose: adding citric acid into the propylene glycol ethanol mixed solution according to the weight ratio of 1:1:0.75 for reaction.
As a preferable technical scheme of the invention, the volume ratio of the ethanol in the propylene glycol and ethanol mixed solution is 5-20%.
In a preferred embodiment of the present invention, the amount of the mixture of propylene glycol and ethanol is preferably 100mL, when measured at 10.0g for arginine, 10.0g for maltose and 7.5g for citric acid.
As a preferred technical scheme of the invention, the heating temperature is 80 ℃, and the time is 100-120 min.
In a preferred embodiment of the present invention, the organic reagent is selected from acetone, wherein the volume ratio of the propylene glycol and ethanol mixed solution to acetone is 1: (10-15).
A large number of experimental researches show that AF can generate precipitation with high-concentration organic reagents to obtain precipitates. In particular, acetone and the reaction solution can be well mutually dissolved, and the target product AF can perform reversible reaction in various solvents, preferably trial acetone.
In a preferred embodiment of the present invention, the washing is performed 2 to 3 times, and propylene glycol can be washed.
In a preferred embodiment of the present invention, the propylene glycol is selected from 1, 2-propylene glycol or 1, 3-propylene glycol, and the ethanol is absolute ethanol.
As a preferred technical scheme of the invention, the propylene glycol is food grade.
The beneficial effects of the invention compared with the prior art comprise:
according to the method for synthesizing AF by using the propylene glycol and ethanol mixed solution as the reaction medium for the first time, the crude synthesis rate can reach more than 75%, the AF purity reaches 80-83%, the production cost of AF is reduced, the crude synthesis product has no pungent smell, and citric acid used in the reaction is a common food additive, so that the method is safe and reliable.
The method has the advantages that the propylene glycol and ethanol mixed solution is used as a reaction medium, the arginine residue in the preparation is less, the propylene glycol viscosity is small, the fluidity is good, the subsequent precipitation and the elution times are easy to reduce, the crude synthesis rate of the product is greatly improved, the production cost is reduced, the water absorption of the propylene glycol is weaker than that of glycerol, and the stability of the product is improved.
More importantly, the propylene glycol is a common lubricant in cosmetics, toothpaste and perfumed soap, is common in the pharmaceutical industry, has no harm to human bodies, has good volatility of ethanol, cannot be remained in products, increases the use safety of the AF crude compound, and accelerates the application of the AF crude compound in industrial production. The propylene glycol is preferably food grade 1, 2-propylene glycol or 1, 3-propylene glycol, and the reaction rate of the propylene glycol and the 1, 2-propylene glycol is equivalent.
Description of the drawings:
FIG. 1: schematic diagram of Maillard reaction scheme;
FIG. 2 is a drawing: a schematic diagram of AF content determination in a reaction group of a mixed solution of propylene glycol and ethanol.
Reference to the literature
[1]Ha KS,Jo SH,Kang BH,Apostolidis E,Lee MS,Jang HD,et al.In vitro and in vivo antihyperglycemic effect of 2amadori rearrangement compounds,arginyl-fructose and arginyl-fructosyl-glucose[J].J Food Sci.2011；76:188–93.doi:10.1111/j.1750-3841.2011.02361.x.
[2]Joo KM,Park CW,Jeong HJ,Lee SJ,Chang IS.Simultaneous determination of two Amadori compounds in Korean red ginseng(Panax ginseng)extracts and rat plasma by high-performance anion-exchange chromatography with pulsed amperometric detection[J].J Chromatography B.2008；865:159–66.doi:10.1016/j.jchromb.2008.02.012.
[3] Research on the relationship between Zhanyansong and synthetic arginine derivatives and related factors A quantitative analysis of AFG and AF in Panax plants [ D ]. Jilin agricultural university, 2003.
[4]Yukio Suzuki,Kang-Ju Choi,Kei Uchida,et al.Effects of the Preheating Treatments of Raw Ginseng in the Model System on the Synthesis of the Maillard Type-Browning Reaction Products of Red Ginseng[J].J Ginseng Res,2004,3(28):136～142.
[5]Yukio Suzuki,Kang-Ju Choi,Kei Uchida,et al.Arginyl-fructosyl-glucose and Arginyl-fructose,Compounds Related to Browning Reaction in the Model System of Steaming and Heat-drying Processes for the Preparation of Red Ginseng[J].J Ginseng Res,2004,3(28):143～148.
[6] The influence of different preheating times on the AF and AFG contents in red ginseng [ J ] modern agricultural science 2010(08):364+366.
Detailed Description
The present invention will be experimentally explained in the following manner with reference to the accompanying drawings, but the present invention is not limited thereto.
Experimental example I Effect of the reaction Medium propylene glycol to ethanol ratio on AF Synthesis
Effect of propylene glycol to ethanol ratio on AF preparation
1.1 arginine by ratio: glucose: the citric acid is put into reaction media (propylene glycol and ethanol mixed solution) with different proportions according to the weight of 1:1:0.75 for reaction, a composition is obtained by regulating and controlling the proportion of the propylene glycol and the ethanol, the crude yield is weighed and calculated, and the AF purity is detected by a sugar derivation method.
1.2 precisely weighing 5 parts (10.g arginine +10.0g glucose +7.5g citric acid), respectively placing the 5 parts in 100mL of reaction medium of propylene glycol and ethanol mixed solution (wherein the using amount of ethanol is respectively 0mL, 5mL, 10mL, 15mL and 20mL, heating to 80 ℃ in sequence under the condition of uniform mixing, reacting for 120min, washing, filtering and drying the reaction solution at low temperature to obtain the product, and weighing and calculating the crude yield and detecting the AF purity by a sugar derivative method.
Experimental example II Effect of acetone washing on AF Synthesis
Influence of acetone washing times and dosage on synthesis of AF
2.1 arginine by ratio: glucose: adding citric acid into 10 times (by mass of arginine, g/mL) of propylene glycol and ethanol mixed solution (ethanol accounts for 10%) by weight of 1:1:0.75 for reaction for 120min, regulating and controlling the washing times and the dosage of acetone to obtain a compound, weighing and calculating the crude yield, and detecting the AF purity by a sugar derivation method.
2.2 precisely weighing 5 parts (10.g arginine +10.0g glucose +7.5g citric acid), placing the 5 parts in 100mL propylene glycol and ethanol mixed liquor (ethanol accounts for 10%), sequentially eluting with acetone for 1 time, 2 times, 3 times, 4 times and 5 times under the condition of uniform mixing, wherein each time is 300mL, filtering the reaction solution, drying at low temperature to obtain the product, and weighing to calculate the crude yield and detecting the AF purity by a sugar derivative method.
Experimental example III, optimum technological conditions for synthesizing AF from propylene glycol ethanol mixed solution
Effect of AF preparation on Synthesis temperature and time
3.1 arginine by ratio: glucose: adding citric acid into 10 times (by mass of arginine, g/mL) of propylene glycol ethanol mixed solution (ethanol accounts for 10%) by weight of 1:1:0.75 for reaction, regulating and controlling temperature and time to obtain a compound, weighing and calculating crude yield, and detecting AF purity by a sugar derivation method.
3.2 precisely weighing 5 parts (10.g arginine +10.0g glucose +7.5g citric acid), placing the 5 parts in 100mL of propylene glycol and ethanol mixed solution (ethanol accounts for 10%), mixing the solution uniformly, heating the solution to 20 ℃, 40 ℃, 60 ℃, 80 ℃ and 100 ℃ in sequence, reacting for 30min, washing, filtering and drying the reaction solution at low temperature to obtain the product, and weighing and calculating the crude yield and detecting the AF purity by a sugar derivative method.
3.3 precisely weighing 7 parts (10.g arginine +10.0g glucose +7.5g citric acid), placing the 7 parts in 100mL propylene glycol ethanol mixed solution (ethanol accounts for 10%), sequentially reacting for 20min, 40min, 60min, 80min, 100min, 120min and 150min under the condition of uniform mixing, heating to the reaction temperature of 80 ℃, washing, filtering and drying the reaction solution at low temperature to obtain the product, wherein the crude yield is weighed and the AF purity is detected by a sugar derivation method.
Detection of arginine in crude Synthesis of AF
4.1 detection method: and detecting the residual quantity of arginine in the crude compositions of 1.1, 1.2 and 1.3 by using a pre-column derivatization high performance liquid chromatography.
4.2 arginine standard preparation: accurately weighing 10.0mg of analytical grade arginine, adding chromatographic grade methanol to fix the volume to 10mL, namely the concentration is 1 mg/mL; and (5) standby.
4.3 sample preparation: each group was precisely weighed at 50.0mg, and derivatization was performed according to the amino acid derivatization method.
4.4 chromatographic conditions: venusil- -AA amino acid column (5 μm, 4.6 mm. times.250 mm). Mobile phase a sodium acetate buffer solution-acetonitrile solution (pH 6.5); and the mobile phase B comprises an acetonitrile aqueous solution V (acetonitrile), and V (water) is 4: 1.0 min, 0% B; 4min, 3% B; 16min, 10% B; 17min, 20% B; 32min, 34% B; 30 min; the flow rate is 1.0 mL/min; the detection wavelength is 254 nm; a column temperature of 40; the amount of the sample was 20. mu.L.
Example 1
Accurately weighing 10.0g of arginine, 10.0g of glucose and 7.5g of citric acid, placing all the materials in 100mL of anhydrous propylene glycol as a reaction medium, uniformly mixing the materials, placing the mixture in a constant-temperature water bath shaking table at 80 ℃, reacting for 120min, washing a reaction solution for 3 times by using acetone, performing suction filtration on 300mL of the reaction solution each time, drying a crude compound at a low temperature, weighing, and repeating the test for 3 times, wherein the yield of an average product is 56 percent, and the AF purity is 68.1 percent.
Example 2
Accurately weighing 10.0g of arginine, 10.0g of glucose and 7.5g of citric acid, placing the arginine, the glucose and the citric acid into 100mL of reaction medium (5mL of mixed solution of ethanol and 95mL of propylene glycol), uniformly mixing, placing the mixture into a constant-temperature water bath shaking table at 80 ℃, reacting for 120min, washing the reaction solution with acetone for 3 times, each time obtaining 300mL, performing suction filtration, drying the crude compound at low temperature, weighing, repeating the test for 3 times, wherein the yield of the average product is 76.2%, and the AF purity is 72.5%.
Example 3
Accurately weighing 10.0g of arginine, 10.0g of glucose and 7.5g of citric acid, placing the arginine, the glucose and the citric acid into 100mL of reaction medium (10mL of mixed solution of ethanol and 90mL of propylene glycol), uniformly mixing, placing the mixture into a constant-temperature water bath shaking table at 80 ℃, reacting for 120min, washing the reaction solution with acetone for 3 times (300 mL each time), performing suction filtration, drying the crude compound at low temperature, weighing, repeating the test for 3 times, wherein the yield of the average product is 77.7%, and the AF purity is 82.4%.
Example 4
Accurately weighing 10.0g of arginine, 10.0g of glucose and 7.5g of citric acid, placing the arginine, the glucose and the citric acid into 100mL of reaction medium (15mL of mixed solution of ethanol and 85mL of propylene glycol), uniformly mixing, placing the mixture into a constant-temperature water bath shaking table at 80 ℃, reacting for 120min, washing the reaction solution with acetone for 3 times (300 mL each time), performing suction filtration, drying the crude compound at low temperature, weighing, repeating the test for 3 times, wherein the yield of the average product is 72.0%, and the AF purity is 73.6%.
Example 5
Accurately weighing 10.0g of arginine, 10.0g of glucose and 7.5g of citric acid, placing the arginine, the glucose and the citric acid into 100mL of reaction medium (20mL of mixed solution of ethanol and 80mL of propylene glycol), uniformly mixing, placing the mixture into a constant-temperature water bath shaking table at 80 ℃, reacting for 120min, washing the reaction solution with acetone for 3 times (300 mL each time), performing suction filtration, drying the crude compound at low temperature, weighing, repeating the test for 3 times, wherein the yield of the average product is 72.3%, and the AF purity is 70.5%.
Example 6
Accurately weighing 10.0g of arginine, 10.0g of glucose and 7.5g of citric acid, placing the arginine, the glucose and the citric acid into 100mL of reaction medium (propylene glycol solution containing 10% ethanol by volume), uniformly mixing, placing the mixture into a constant-temperature water bath shaking table at 80 ℃, reacting for 120min, washing the reaction solution with acetone for 1 time, each time washing 300mL, performing suction filtration, drying the crude compound at low temperature, weighing, repeating the test for 3 times, wherein the yield of the average product is 70.3%, and the AF purity is 79.5%.
Example 7
Accurately weighing 10.0g of arginine, 10.0g of glucose and 7.5g of citric acid, placing the arginine, the glucose and the citric acid into 100mL of reaction medium (propylene glycol solution containing 10% ethanol by volume), uniformly mixing, placing the mixture into a constant-temperature water bath shaking table at 80 ℃, reacting for 120min, washing the reaction solution with acetone for 2 times, each time obtaining 300mL, performing suction filtration, drying the crude compound at low temperature, weighing, repeating the test for 3 times, wherein the yield of the average product is 76.8%, and the AF purity is 82.1%.
Example 8
Accurately weighing 10.0g of arginine, 10.0g of glucose and 7.5g of citric acid, placing the arginine, the glucose and the citric acid into 100mL of reaction medium (propylene glycol solution containing 10% ethanol by volume), uniformly mixing, placing the mixture into a constant-temperature water bath shaking table at 80 ℃, reacting for 120min, washing the reaction solution with acetone for 3 times, each time obtaining 300mL, performing suction filtration, drying the crude compound at low temperature, weighing, repeating the test for 3 times, wherein the yield of the average product is 77.6 percent, and the AF purity is 82.5 percent. The reaction scheme is shown in FIG. 1, and the HPLC spectrum of AF is shown in FIG. 2.
Example 9
Accurately weighing 10.0g of arginine, 10.0g of glucose and 7.5g of citric acid, placing the arginine, the glucose and the citric acid into 100mL of reaction medium (propylene glycol solution containing 10% ethanol by volume), uniformly mixing, placing the mixture into a constant-temperature water bath shaking table at 80 ℃, reacting for 120min, washing the reaction solution with acetone for 4 times, each time obtaining 300mL, performing suction filtration, drying the crude compound at low temperature, weighing, repeating the test for 3 times, wherein the yield of the average product is 74.9%, and the AF purity is 82.3%.
Example 10
Accurately weighing 10.0g of arginine, 10.0g of glucose and 7.5g of citric acid, placing the arginine, the glucose and the citric acid into 100mL of reaction medium (propylene glycol solution containing 10% ethanol by volume), uniformly mixing, placing the mixture into a constant-temperature water bath shaking table at 80 ℃, reacting for 120min, washing the reaction solution with acetone for 5 times, each time washing 300mL, performing suction filtration, drying the crude compound at low temperature, weighing, repeating the test for 3 times, wherein the yield of the average product is 74.5%, and the AF purity is 82.5%.
Example 11
Accurately weighing 10.0g of arginine, 10.0g of glucose and 7.5g of citric acid, placing the arginine, the glucose and the citric acid into 100mL of reaction medium (propylene glycol solution containing 10% ethanol by volume), uniformly mixing, placing the mixture into a constant-temperature water bath shaking table at 20 ℃, reacting for 30min, drying the crude compound at low temperature, weighing, and repeating the test for 3 times, wherein the yield of the average product is 10.2% and the AF purity is 6.2%.
Example 12
Accurately weighing 10.0g of arginine, 10.0g of glucose and 7.5g of citric acid, placing the arginine, the glucose and the citric acid into 100mL of reaction medium (propylene glycol solution containing 10% ethanol by volume), uniformly mixing, placing the mixture into a constant-temperature water bath shaking table at 40 ℃, reacting for 30min, drying the crude compound at low temperature, weighing, and repeating the test for 3 times, wherein the average yield is 25.4% and the AF purity is 15.3%.
Example 13
Accurately weighing 10.0g of arginine, 10.0g of glucose and 7.5g of citric acid, placing the arginine, the glucose and the citric acid into 100mL of reaction medium (propylene glycol solution containing 10% ethanol by volume), uniformly mixing, placing the mixture into a constant-temperature water bath shaking table at 60 ℃, reacting for 30min, drying the crude compound at low temperature, weighing, and repeating the test for 3 times, wherein the average yield is 50.2% and the AF purity is 19.2%.
Example 14
Accurately weighing 10.0g of arginine, 10.0g of glucose and 7.5g of citric acid, placing the arginine, the glucose and the citric acid into 100mL of reaction medium (propylene glycol solution containing 10% ethanol by volume), uniformly mixing, placing the mixture into a constant-temperature water bath shaking table at 80 ℃, reacting for 30min, drying the crude compound at low temperature, weighing, and repeating the test for 3 times, wherein the average yield is 62.0% and the AF purity is 35.4%.
Example 15
Accurately weighing 10.0g of arginine, 10.0g of glucose and 7.5g of citric acid, placing the arginine, the glucose and the citric acid into 100mL of reaction medium (propylene glycol solution containing 10% ethanol by volume), uniformly mixing, placing the mixture into a 100 ℃ constant-temperature water bath shaking table, reacting for 30min, drying the crude compound at low temperature, weighing, and repeating the test for 3 times, wherein the average yield is 68.4% and the AF purity is 37.0%.
Example 16
Accurately weighing 10.0g of arginine, 10.0g of glucose and 7.5g of citric acid, placing the arginine, the glucose and the citric acid into 100mL of reaction medium (propylene glycol solution containing 10% ethanol by volume), uniformly mixing, placing the mixture into a constant-temperature water bath shaking table at 80 ℃, reacting for 20min, drying the crude compound at low temperature, weighing, and repeating the test for 3 times, wherein the average yield is 17.4% and the AF purity is 30.0%.
Example 17
Accurately weighing 10.0g of arginine, 10.0g of glucose and 7.5g of citric acid, placing the arginine, the glucose and the citric acid into 100mL of reaction medium (propylene glycol solution containing 10% ethanol by volume), uniformly mixing, placing the mixture into a constant-temperature water bath shaking table at 80 ℃, reacting for 40min, drying the crude compound at low temperature, weighing, and repeating the test for 3 times, wherein the average yield is 44.3% and the AF purity is 50.6%.
Example 18
Accurately weighing 10.0g of arginine, 10.0g of glucose and 7.5g of citric acid, placing the arginine, the glucose and the citric acid into 100mL of reaction medium (propylene glycol solution containing 10% ethanol by volume), uniformly mixing, placing the mixture into a constant-temperature water bath shaking table at 80 ℃, reacting for 60min, drying the crude compound at low temperature, weighing, and repeating the test for 3 times, wherein the average yield is 63.8% and the AF purity is 65.0%.
Example 19
Accurately weighing 10.0g of arginine, 10.0g of glucose and 7.5g of citric acid, placing the arginine, the glucose and the citric acid into 100mL of reaction medium (propylene glycol solution containing 10% ethanol by volume), uniformly mixing, placing the mixture into a constant-temperature water bath shaking table at 80 ℃, reacting for 80min, drying the crude compound at low temperature, weighing, and repeating the test for 3 times, wherein the average yield is 71.7% and the AF purity is 74.6%.
Example 20
Accurately weighing 10.0g of arginine, 10.0g of glucose and 7.5g of citric acid, placing the arginine, the glucose and the citric acid into 100mL of reaction medium (propylene glycol solution containing 10% ethanol by volume), uniformly mixing, placing the mixture into a constant-temperature water bath shaking table at 80 ℃, reacting for 100min, drying the crude compound at low temperature, weighing, and repeating the test for 3 times, wherein the average yield is 76.3%, and the AF purity is 82.5%.
Example 21
Accurately weighing 10.0g of arginine, 10.0g of glucose and 7.5g of citric acid, placing the arginine, the glucose and the citric acid into 100mL of reaction medium (propylene glycol solution containing 10% ethanol by volume), uniformly mixing, placing the mixture into a constant-temperature water bath shaking table at 80 ℃, reacting for 120min, drying the crude compound at low temperature, weighing, and repeating the test for 3 times, wherein the average yield is 76.2% and the AF purity is 82.6%.
Example 22
Accurately weighing 10.0g of arginine, 10.0g of glucose and 7.5g of citric acid, placing the arginine, the glucose and the citric acid into 100mL of reaction medium (propylene glycol solution containing 10% ethanol by volume), uniformly mixing, placing the mixture into a constant-temperature water bath shaking table at 80 ℃, reacting for 150min, drying the crude compound at low temperature, weighing, and repeating the test for 3 times, wherein the average yield is 72.4% and the AF purity is 78.7%.
The results, according to the above example, can be seen from table 1: AF is synthesized by regulating and controlling the proportion of the reaction medium propylene glycol and ethanol, and experimental results show that the yield and purity of the product can reach the optimal state when the reaction medium proportion is 10 percent propylene glycol solution.
TABLE 1 statistical table of different ratios of propylene glycol to ethanol for influencing AF synthesis
As shown in Table 1, the yield and purity were the highest when 10% ethanol was reacted.
The results, according to the above example, can be seen from table 2: the washing times of the acetone for synthesizing AF can be 3 times by controlling the washing times and the dosage of the acetone.
TABLE 2 statistical Table of the effects of different acetone washes on AF synthesis
As can be seen from Table 2, the optimum acetone washing frequency for obtaining AF was 2 to 3 times by controlling the number and amount of acetone washing.
The results, according to the above examples, are seen in table 3: AF is synthesized by regulating and controlling time and temperature, and experimental results show that when the temperature is 80 ℃, the time is 100min, the yield of the synthesized product is highest, and the purity of AF reaches the maximum.
TABLE 3 statistical tables of different time and temperature pairs affecting AF synthesis
As can be seen from Table 3, the optimum synthesis temperature for AF was 80 ℃ and the optimum synthesis time was 100min, which were obtained by controlling the time and temperature by the variable control method.
Comparative Experimental example I Synthesis of AF
Synthesis of AF Using different media according to the preferred preparation conditions described above
D1.1 arginine by proportion: glucose: citric acid was mixed in a ratio of 1:1: and (3) putting 0.75 weight of the obtained product into a medium in an amount which is 10 times that of the obtained product to react, precipitating the reaction solution by using acetone, washing for 2-3 times, drying at low temperature to obtain a compound, and weighing and calculating the crude yield and the AF purity.
D1.1.1 weighing arginine 10.0g, glucose 10.0g and citric acid 7.5g accurately according to the above proportion, placing in 100mL glacial acetic acid, heating to 80 deg.C under mixing condition, reacting for 100min, precipitating and eluting the reaction solution with acetone, filtering, drying at low temperature to obtain crude compound, repeating the test for 3 times, and calculating the yield and AF purity.
D1.1.2 weighing 10.0g arginine, 10.0g glucose and 7.5g citric acid accurately, placing in 100mL anhydrous glycerol, heating to 80 ℃ under the condition of mixing uniformly, reacting for 100min, precipitating and eluting the reaction solution by acetone, filtering, drying at low temperature to obtain a crude compound, repeating the test for 3 times, and calculating the average yield of the product and the AF purity.
D1.1.3 arginine 10.0g, glucose 10.0g and citric acid 7.5g are precisely weighed, placed in 100mL mixed solution (propylene glycol: ethanol 9:1), heated to 80 ℃ under the condition of uniform mixing, reacted for 100min, the reaction solution is precipitated and eluted by acetone, filtered, dried at low temperature to obtain crude compound, the test is repeated for 3 times, and the average yield and AF purity of the product are calculated.
D1.1.4 weighing 10.0g arginine, 10.0g glucose and 7.5g citric acid accurately, placing in 100mL anhydrous propylene glycol, heating to 80 ℃ under the condition of mixing uniformly, reacting for 100min, precipitating and eluting the reaction solution by acetone, filtering, drying at low temperature to obtain a crude compound, repeating the test for 3 times, and calculating the average yield of the product and the AF purity.
D1.1.5 weighing 10.0g arginine, 10.0g glucose and 7.5g citric acid accurately, placing in 100mL propanol, heating to 80 deg.C under mixing condition, reacting for 100min, precipitating and eluting the reaction solution with acetone, filtering, drying at low temperature to obtain crude compound, repeating the experiment for 3 times, and calculating the average yield and AF purity of the product.
The results are shown in Table 4: the ratio of the glacial acetic acid group to the glycerol group to the propylene glycol group has lower product yield and lower AF purity; and the arginine residue of the glacial acetic acid group and the glycerol group is obviously higher than that of the propylene glycol group, and the propanol group does not generate precipitate in the reaction and can not react.
The influence and the advantages and the disadvantages of different reaction media on the yield of the synthetic AF and the residual quantity of AR can be summarized by combining the test results and the test process.
TABLE 4 comparison of the characteristics of AF synthesis processes using different media
It can be concluded from table 4 that the reaction of glucose and arginine can be greatly promoted under specific reaction conditions by using the mixed solution of propylene glycol and ethanol as the reaction medium, so that the yield and the AF purity of the product are improved, the residual amount of arginine is effectively reduced, the reaction difficulty is reduced, the amount of acetone used in elution is effectively reduced, and the stability of the product is increased. The propanol is used as a reaction solvent, and because the boiling point of the propanol is close to the reaction temperature, the propanol is volatile during the reaction, cannot complete the reaction, and does not generate precipitates.
The above embodiments are preferred and preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be regarded as equivalent replacements within the protection scope of the present invention.
Claims (4)
1. A method for synthesizing and preparing a compound arginine fructoside-AF is characterized by comprising the following steps:
putting arginine and glucose into a mixed solution of propylene glycol and ethanol, wherein the volume ratio of the ethanol in the mixed solution of propylene glycol and ethanol is 5-20%, and adding citric acid as a catalyst, wherein the weight ratio of arginine: glucose: the weight ratio of the citric acid is 1:1:0.75, when the arginine is counted according to 10.0g, the maltose is counted according to 10.0g and the citric acid is counted according to 7.5g, the using amount of a propylene glycol and ethanol mixed solution is 100mL, the heating temperature is 80 ℃, the time is 120min, the organic reagent is precipitated and washed, the organic reagent is selected from acetone, the washing times are 2-3 times, and the AF is obtained through vacuum filtration and low-temperature drying.
2. The method according to claim 1, wherein the volume ratio of the propylene glycol-ethanol mixture to the acetone is 1: (10-15).
3. The method according to claim 1, wherein the propylene glycol is selected from 1, 2-propylene glycol and 1, 3-propylene glycol, and the ethanol is anhydrous ethanol.
4. The method of claim 1, wherein the propylene glycol is food grade.
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