Biomimetic synthesis of amino acid surfactant and preparation method thereof

Abstract

The present invention discloses a biomimetic synthesized amino acid surfactant and a preparation method thereof, wherein the preparation method comprises: oxidizing a catechol derivative by an oxidant, and synthesizing a quinone compound under the action of a water removing agent; and subjecting the quinone compound to a Michael addition reaction and / or a Schiff base reaction with an amino acid compound to obtain a biomimetic synthesized amino acid surfactant. The preparation method of the present invention has simple steps, high efficiency, and easy operation, and is environmentally friendly. The obtained amino acid surfactant has a special structure and good surface properties.

Description

Technical Field

[0001] The present invention relates to the technical field of amino acid surfactants, and in particular to the technical field of obtaining amino acid surfactants by using a bionic synthesis method. Background Art

[0002] Amino acid surfactants are a type of biomass raw material with a wide range of sources, low toxicity, mild performance, low irritation and good biodegradability. Currently, commonly used amino acid surfactants include: N-acyl amino acid type surfactants, N-alkyl amino acid type surfactants, N-alkyl amide type surfactants, amino acid ester type surfactants, etc., and their preparation methods all have the disadvantages of long production cycle, the need to use toxic reagents, and harsh reaction conditions. Therefore, the development of a preparation method for amino acid surfactants with high production rate, simple steps, environmental friendliness, and good surface properties of the resulting active agent is a technical problem that needs to be solved in the prior art.

[0003] In order to solve the above technical problems, the present invention proposes a green, healthy, simple and efficient method for preparing an amino acid surfactant, and the novel amino acid surfactant obtained by the method has excellent performance; the preparation method is a bionic synthesis method that simulates the melanin biosynthesis process.

[0004] The melanin biosynthesis process is as follows: in the organism, tyrosine generates dopa with a catechol structure under the catalysis of tyrosinase; dopa further generates dopaquinone under the catalysis of tyrosinase; dopaquinone, as a type of electron-deficient substance, undergoes Michael addition reaction with electron-rich nucleophilic substances containing amino and thiol groups to generate melanin. Summary of the invention

[0005] In view of the defects of the prior art, the purpose of the present invention is to propose a new method for preparing an amino acid surfactant, which has a high production rate, simple steps, and is environmentally friendly. It can obtain a new amino acid surfactant with a unique structure, and the obtained new amino acid surfactant has excellent performance.

[0006] The technical solution of the present invention is as follows:

[0007] A method for preparing a biomimetic synthetic amino acid surfactant comprises:

[0008] The catechol derivatives are oxidized by an oxidant and then, under the action of a water scavenger, quinone compounds are synthesized;

[0009] The quinone compound and the amino acid compound undergo Michael addition reaction and / or Schiff base reaction to obtain a biomimetic amino acid surfactant;

[0010] Wherein, the amino acid compound is selected from one or more of amino acids, amino acid decarboxylation derivatives, and polypeptides.

[0011] The preparation method of the present invention can realize the biomimetic synthesis of a novel amino acid surfactant by simulating the biosynthesis pathway of melanin, and specifically oxidizes the phenolic hydroxyl group of the catechol derivative to quinone by an oxidant, and then adds the amino group to the benzene ring by the reaction of the quinone compound and the amino acid acid, and reduces the quinone structure to the phenolic hydroxyl group, or combines the quinone structure to the benzene ring by a C=N bond by a Schiff base reaction. The amino acid surfactant obtained is provided with a hydrophilic part by the amino acid, and the catechol derivative is provided with a hydrophobic part.

[0012] According to some preferred embodiments of the present invention, the preparation method specifically comprises:

[0013] Obtaining an organic solution of a catechol derivative with a concentration of 1 to 600 mM and an aqueous solution of an amino acid compound with a concentration of 1 to 1000 mM;

[0014] Adding the dehydrating agent and the oxidant or the solution of the oxidant to the organic solution of the catechol derivative in sequence, reacting at 10 to 80° C., and separating a clear liquid from the system after the reaction;

[0015] The aqueous solution of the amino acid compound is added to the clear liquid, reacted at 10-80° C., and the product is extracted to obtain the biomimetic synthesized amino acid surfactant.

[0016] According to some preferred embodiments of the present invention, the molar ratio of the catechol derivative to the oxidant is 1:0.3-1.8, more preferably, the molar ratio of the catechol derivative to the oxidant is 1:0.6-0.8.

[0017] According to some preferred embodiments of the present invention, the molar ratio of the organic solution of the catechol derivative to the aqueous solution of the amino acid compound is 1:0.1-0.8; more preferably, the molar ratio of the organic solution of the catechol derivative to the aqueous solution of the amino acid compound is 1:0.25-0.5.

[0018] According to some preferred embodiments of the present invention, the preparation method further comprises: purifying the product extracted in step (3), wherein the purification comprises dissolving and drying the extracted product, and the drying temperature is 10 to 80°C.

[0019] According to some preferred embodiments of the present invention, the concentration of the organic solution of the catechol derivative is 200-300 mM; the concentration of the aqueous solution of the amino acid compound is 6-600 mM; the reaction temperature in step (2) and step (3) is 15-25°C, and the reaction time is 10-60 min.

[0020] According to some preferred embodiments of the present invention, the organic solvent used in the organic solution of the catechol derivative is selected from one or more of dioxane, acetonitrile, ethanol, acetone, ethyl acetate, chloroform, dimethyl sulfoxide, and dimethylformamide.

[0021] According to some preferred embodiments of the present invention, in step (3), the extraction is achieved by freeze-drying or rotary evaporation.

[0022] According to some preferred embodiments of the present invention, the oxidant is selected from one or more of silver oxide, sodium periodate, and ammonium cerium nitrate.

[0023] According to some preferred embodiments of the present invention, the catechol derivative is selected from one or more of ethyl 3,4-dihydroxybenzoate, ethyl caffeate, 4-methylcatechol, and 4-tert-butylcatechol.

[0024] According to some preferred embodiments of the present invention, the dehydrating agent is selected from anhydrous sodium sulfate.

[0025] According to some preferred embodiments of the present invention, the amino acid is selected from one or more of lysine, arginine, glycine, alanine, valine, leucine, isoleucine, methionine, proline, tryptophan, serine, tyrosine, cysteine, phenylalanine, aspartic acid, glutamic acid, threonine, asparagine, glutamine and histidine.

[0026] The present invention further provides a biomimetic synthesized amino acid surfactant prepared according to the above preparation method, in which the amino acid forms a hydrophilic part and the catechol derivative forms a hydrophobic part.

[0027] The surfactant has a significantly different structure from the existing amino acid surfactants, such as any of the following structural formulas:

[0028]

[0029] Wherein R1 is selected from any one of catechol derivatives: 3,4-dihydroxybenzoic acid ethyl ester, caffeic acid ethyl ester, 4-methylcatechol, 4-tert-butylcatechol; R2 is selected from any one of lysine, arginine, glycine, alanine, valine, leucine, isoleucine, methionine, proline, tryptophan, serine, tyrosine, cysteine, phenylalanine, aspartic acid, glutamic acid, threonine, asparagine, glutamine, histidine, taurine, and tripeptide. The addition site of the amino group in the amino acid and the benzene ring undergoing Michael addition reaction is at one or more of the arrow positions.

[0030] The present invention uses catechol derivatives as hydrophobic groups, generates substances with o-benzoquinone structure after oxidation by oxidants, and then uses amino acids containing amino groups as hydrophilic groups, and synthesizes novel amino acid surfactants through Michael addition reaction or Schiff base reaction. Among them, quinones are a kind of substances with extremely strong reaction activity. In addition to being easy to react with amino and sulfhydryl substances, they are also easy to undergo coupling reactions themselves, and their reactions in the body are also very complex. Different reaction paths can form different substances, such as forming eumelanin or pheomelanin respectively. The present invention can accurately obtain amino acid surfactants with superior performance by selecting specific reaction processes, specific solvents, oxidants, and further optimizing parameters such as feed ratio and reaction temperature, and effectively avoid the generation of other side reactions and by-products.

[0031] The present invention has the following beneficial effects:

[0032] (1) The preparation method of the present invention successfully achieves the simulation and biomimetic of the melanin biosynthesis pathway and provides a new synthesis idea of ​​amino acid surfactants;

[0033] (2) The structure of the amino acid surfactant synthesized by the present invention is similar to that of the melanin intermediate, and is a new type of amino acid surfactant that is significantly different from existing amino acid surfactants and has excellent performance;

[0034] (3) The preparation method of the present invention has simple steps, convenient operation, high general production efficiency, and is green and environmentally friendly. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 This is the primary mass spectrum of the product of Example 1.

[0036] Figure 2 It is the secondary mass spectrum of the product of Example 1.

[0037] Figure 3 This is the concentration surface tension diagram of the product of Example 1.

[0038] Figure 4 The foam volume of the product of Example 1 changes with time. Figure 5 This is a foam volume diagram of the product obtained by reacting the substrate 3,4-dihydroxybenzoic acid ethyl ester in Example 1 with different amino acids using dioxane as solvent after silver oxide oxidation.

[0039] Figure 6 This is a foam volume diagram of the products obtained by reacting different substrates of Examples 1 / 2 / 11 / 15 / 16 / 19 / 20 with lysine using dioxane as solvent after silver oxide oxidation.

[0040] Figure 7This is a foam volume diagram of the product obtained by reacting the substrate 3,4-dihydroxybenzoic acid ethyl ester of Example 1 / 21 / 22 / 23 / 24 with lysine in different oxidation modes using dioxane as solvent.

[0041] Figure 8 The foam volume diagram of the product obtained by reacting 3,4-dihydroxybenzoic acid ethyl ester, a substrate of Example 1 / 25 / 26 / 27 / 31, with lysine after being oxidized by silver oxide in different solvents. DETAILED DESCRIPTION

[0042] The present invention is described in detail below in conjunction with the embodiments and drawings, but it should be understood that the embodiments and drawings are only used to exemplify the present invention and do not constitute any limitation on the protection scope of the present invention. All reasonable changes and combinations within the scope of the inventive concept of the present invention fall within the protection scope of the present invention.

[0043] Example 1

[0044] A 200mM 3,4-dihydroxybenzoic acid ethyl ester solution was prepared with dioxane as solvent, and a 600mM lysine solution was prepared with deionized water as solvent. 5mL of the obtained 3,4-dihydroxybenzoic acid ethyl ester solution was placed in a reactor, and 142mg of anhydrous sodium sulfate and 139mg of silver oxide were added in sequence and placed in a 20℃ water bath for reaction for 40min, then filtered, the clear liquid was taken out and placed in a reactor, and 0.5mL of lysine solution was added, and placed in a 20℃ water bath for reaction for 1h. After the reaction time is up, it is placed in a freeze dryer for freeze drying, and the freeze-dried sample is dissolved in deionized water and filtered, and the filtered solution is placed in a drying oven at 10-80℃ for 12h. Its structure was determined by liquid chromatography-mass spectrometry analysis. At room temperature, its surface tension was measured using a BZY-1 automatic surface tension meter; and its foaming performance was measured using a Roche foam meter.

[0045] Example 2

[0046] Prepare 200mM 3,4-dihydroxybenzoic acid ethyl ester solution with dioxane as solvent, and prepare 600mM arginine solution with deionized water. Take 5mL 3,4-dihydroxybenzoic acid ethyl ester solution in a reactor, add 142mg anhydrous sodium sulfate and 139mg silver oxide in turn, and place it in a 20℃ water bath for 40min. After the reaction time is up, filter it, take out the clear liquid and place it in a reactor, add 0.5mL arginine solution, and place it in a 20℃ water bath for 1h. After the reaction time is up, place it in a freeze dryer for freeze drying, and the freeze-dried sample is dissolved in deionized water and filtered. Take the filtered solution and place it in a drying oven at 10-80℃ for 12h. The structure is determined by liquid chromatography-mass spectrometry analysis. At room temperature, the surface tension is measured using a BZY-1 automatic surface tension meter; and the foaming performance is measured using a Roche foam meter.

[0047] Example 3

[0048] Prepare 200mM 3,4-dihydroxybenzoic acid ethyl ester solution with dioxane as solvent, and prepare 600mM glycine solution with deionized water. Take 5mL 3,4-dihydroxybenzoic acid ethyl ester solution in a reactor, add 142mg anhydrous sodium sulfate and 139mg silver oxide in turn, and place it in a 20℃ water bath for 40min. After the reaction time is up, filter it, take out the clear liquid and place it in a reactor, add 0.5mL glycine solution, and place it in a 20℃ water bath for 1h. After the reaction time is up, place it in a freeze dryer for freeze drying, and the freeze-dried sample is dissolved in deionized water and filtered. Take the filtered solution and place it in a drying oven at 10-80℃ for 12h. The structure is determined by liquid chromatography-mass spectrometry analysis. At room temperature, the surface tension is measured using a BZY-1 automatic surface tension meter; and the foaming performance is measured using a Roche foam meter.

[0049] Example 4

[0050] Prepare 200mM ethyl 3,4-dihydroxybenzoate solution with dioxane as solvent, and prepare 60mM alanine solution with deionized water. Take 5mL ethyl 3,4-dihydroxybenzoate solution in a reactor, add 142mg anhydrous sodium sulfate and 139mg silver oxide in turn, and place it in a 20℃ water bath for 40min. After the reaction time is up, filter it, take out the clear liquid and place it in a reactor, add 5mL alanine solution, and place it in a 20℃ water bath for 1h. After the reaction time is up, place it in a freeze dryer for freeze drying, and the freeze-dried sample is dissolved in deionized water and filtered. Take the filtered solution and place it in a drying oven at 10-80℃ for 12h. The structure is determined by liquid chromatography-mass spectrometry analysis. At room temperature, the surface tension is measured using a BZY-1 automatic surface tension meter; and the foaming performance is measured using a Roche foam meter.

[0051] Example 5

[0052] Prepare 200mM ethyl 3,4-dihydroxybenzoate solution with dioxane as solvent, and prepare 60mM valine solution with deionized water. Take 5mL ethyl 3,4-dihydroxybenzoate solution in a reactor, add 142mg anhydrous sodium sulfate and 139mg silver oxide in turn, and place it in a 20℃ water bath for 40min. After the reaction time is up, filter it, take out the clear liquid and place it in a reactor, add 5mL valine solution, and place it in a 20℃ water bath for 1h. After the reaction time is up, place it in a freeze dryer for freeze drying, and the freeze-dried sample is dissolved in deionized water and filtered. Take the filtered solution and place it in a drying oven at 10-80℃ for 12h. The structure is determined by liquid chromatography-mass spectrometry analysis. At room temperature, the surface tension is measured using a BZY-1 automatic surface tension meter; and the foaming performance is measured using a Roche foam meter.

[0053] Example 6

[0054] Prepare 200mM ethyl 3,4-dihydroxybenzoate solution with dioxane as solvent, and prepare 100mM leucine solution with deionized water. Take 5mL ethyl 3,4-dihydroxybenzoate solution in a reactor, add 142mg anhydrous sodium sulfate and 139mg silver oxide in turn, and place it in a 20℃ water bath for 40min. After the reaction time is up, filter it, take out the clear liquid and place it in a reactor, add 3mL leucine solution, and place it in a 20℃ water bath for 1h. After the reaction time is up, place it in a freeze dryer for freeze drying, and the freeze-dried sample is dissolved in deionized water and filtered. Take the filtered solution and place it in a drying oven at 10-80℃ for 12h. The structure is determined by liquid chromatography-mass spectrometry analysis. At room temperature, the surface tension is measured using a BZY-1 automatic surface tension meter; and the foaming performance is measured using a Roche foam meter.

[0055] Example 7

[0056] Prepare 200mM ethyl 3,4-dihydroxybenzoate solution with dioxane as solvent, and prepare 100mM isoleucine solution with deionized water. Take 5mL ethyl 3,4-dihydroxybenzoate solution in a reactor, add 142mg anhydrous sodium sulfate and 139mg silver oxide in turn, and place in a 20℃ water bath to react for 40min. After the reaction time is up, filter, take out the clear liquid and place it in a reactor, add 3mL isoleucine solution, and place it in a 20℃ water bath to react for 1h. After the reaction time is up, place it in a freeze dryer for freeze drying, and the freeze-dried sample is dissolved in deionized water and filtered. Take the filtered solution and place it in a drying oven at 10-80℃ for 12h. The structure is determined by liquid chromatography-mass spectrometry analysis. At room temperature, the surface tension is measured using a BZY-1 automatic surface tension meter; and the foaming performance is measured using a Roche foam meter.

[0057] Example 8

[0058] Prepare 200mM 3,4-dihydroxybenzoic acid ethyl ester solution with dioxane as solvent, and prepare 100mM methionine solution with deionized water. Take 5mL 3,4-dihydroxybenzoic acid ethyl ester solution in a reactor, add 142mg anhydrous sodium sulfate and 139mg silver oxide in turn, and place it in a 20℃ water bath for 40min. After the reaction time is up, filter it, take out the clear liquid and place it in a reactor, add 3mL methionine solution, and place it in a 20℃ water bath for 1h. After the reaction time is up, place it in a freeze dryer for freeze drying, and the freeze-dried sample is dissolved in deionized water and filtered. Take the filtered solution and place it in a drying oven at 10-80℃ for 12h. The structure is determined by liquid chromatography-mass spectrometry analysis. At room temperature, the surface tension is measured using a BZY-1 automatic surface tension meter; and the foaming performance is measured using a Roche foam meter.

[0059] Example 9

[0060] Prepare 200mM ethyl 3,4-dihydroxybenzoate solution with dioxane as solvent, and prepare 100mM proline solution with deionized water. Take 5mL ethyl 3,4-dihydroxybenzoate solution in a reactor, add 142mg anhydrous sodium sulfate and 139mg silver oxide in turn, and place in a 20℃ water bath to react for 40min. After the reaction time is up, filter, take out the clear liquid and place it in a reactor, add 3mL proline solution, and place it in a 20℃ water bath to react for 1h. After the reaction time is up, place it in a freeze dryer for freeze drying, and the freeze-dried sample is dissolved in deionized water and filtered. Take the filtered solution and place it in a drying oven at 10-80℃ for 12h. The structure is determined by liquid chromatography-mass spectrometry analysis. At room temperature, the surface tension is measured using a BZY-1 automatic surface tension meter; and the foaming performance is measured using a Roche foam meter.

[0061] Example 10

[0062] Prepare 200mM ethyl 3,4-dihydroxybenzoate solution with dioxane as solvent, and prepare 60mM tryptophan solution with deionized water. Take 5mL ethyl 3,4-dihydroxybenzoate solution in a reactor, add 142mg anhydrous sodium sulfate and 139mg silver oxide in turn, and place it in a 20℃ water bath for 40min. After the reaction time is up, filter it, take out the clear liquid and place it in a reactor, add 5mL tryptophan solution, and place it in a 20℃ water bath for 1h. After the reaction time is up, place it in a freeze dryer for freeze drying, and the freeze-dried sample is dissolved in deionized water and filtered. Take the filtered solution and place it in a drying oven at 10-80℃ for 12h. The structure is determined by liquid chromatography-mass spectrometry analysis. At room temperature, the surface tension is measured using a BZY-1 automatic surface tension meter; and the foaming performance is measured using a Roche foam meter.

[0063] Embodiment 11

[0064] Prepare 200mM ethyl 3,4-dihydroxybenzoate solution with dioxane as solvent, and prepare 600mM serine solution with deionized water. Take 5mL ethyl 3,4-dihydroxybenzoate solution in a reactor, add 142mg anhydrous sodium sulfate and 139mg silver oxide in turn, and place it in a 20℃ water bath for 40min. After the reaction time is up, filter it, take out the clear liquid and place it in a reactor, add 0.5mL serine solution, and place it in a 20℃ water bath for 1h. After the reaction time is up, place it in a freeze dryer for freeze drying, and the freeze-dried sample is dissolved in deionized water and filtered. Take the filtered solution and place it in a drying oven at 10-80℃ for 12h. The structure is determined by liquid chromatography-mass spectrometry analysis. At room temperature, the surface tension is measured using a BZY-1 automatic surface tension meter; and the foaming performance is measured using a Roche foam meter.

[0065] Example 12

[0066] Prepare 200mM ethyl 3,4-dihydroxybenzoate solution with dioxane as solvent, and prepare 6mM tyrosine solution with deionized water. Take 5mL ethyl 3,4-dihydroxybenzoate solution in a reactor, add 142mg anhydrous sodium sulfate and 139mg silver oxide in turn, and place it in a 20℃ water bath for 40min. After the reaction time is up, filter it, take out the clear liquid and place it in a reactor, add 50mL tyrosine solution, and place it in a 20℃ water bath for 1h. After the reaction time is up, place it in a freeze dryer for freeze drying, and the freeze-dried sample is dissolved in deionized water and filtered. Take the filtered solution and place it in a drying oven at 10-80℃ for 12h. The structure is determined by liquid chromatography-mass spectrometry analysis. At room temperature, the surface tension is measured using a BZY-1 automatic surface tension meter; and the foaming performance is measured using a Roche foam meter.

[0067] Embodiment 13

[0068] Prepare 200mM 3,4-dihydroxybenzoic acid ethyl ester solution with dioxane as solvent, and prepare 60mM phenylalanine solution with deionized water. Take 5mL 3,4-dihydroxybenzoic acid ethyl ester solution in a reactor, add 142mg anhydrous sodium sulfate and 139mg silver oxide in turn, and place it in a 20℃ water bath for 40min. After the reaction time is up, filter it, take out the clear liquid and place it in a reactor, add 5mL phenylalanine solution, and place it in a 20℃ water bath for 1h. After the reaction time is up, place it in a freeze dryer for freeze drying, and the freeze-dried sample is dissolved in deionized water and filtered. Take the filtered solution and place it in a drying oven at 10-80℃ for 12h. The structure is determined by liquid chromatography-mass spectrometry analysis. At room temperature, the surface tension is measured using a BZY-1 automatic surface tension meter; and the foaming performance is measured using a Roche foam meter.

[0069] Embodiment 14

[0070] Prepare 200mM ethyl 3,4-dihydroxybenzoate solution with dioxane as solvent, and prepare 600mM aspartic acid solution with deionized water. Take 5mL ethyl 3,4-dihydroxybenzoate solution in a reactor, add 142mg anhydrous sodium sulfate and 139mg silver oxide in turn, and place it in a 20℃ water bath for 40min. After the reaction time is up, filter it, take out the clear liquid and place it in a reactor, add 0.5mL aspartic acid solution, and place it in a 20℃ water bath for 1h. After the reaction time is up, place it in a freeze dryer for freeze drying, and the freeze-dried sample is dissolved in deionized water and filtered. Take the filtered solution and place it in a drying oven at 10-80℃ for 12h. The structure is determined by liquid chromatography-mass spectrometry analysis. At room temperature, the surface tension is measured using a BZY-1 automatic surface tension meter; and the foaming performance is measured using a Roche foam meter.

[0071] Embodiment 15

[0072] Prepare 200mM 3,4-dihydroxybenzoic acid ethyl ester solution with dioxane as solvent, and prepare 60mM glutamic acid solution with deionized water. Take 5mL 3,4-dihydroxybenzoic acid ethyl ester solution in a reactor, add 142mg anhydrous sodium sulfate and 139mg silver oxide in turn, and place it in a 20℃ water bath for 40min. After the reaction time is up, filter it, take out the clear liquid and place it in a reactor, add 5mL glutamic acid solution, and place it in a 20℃ water bath for 1h. After the reaction time is up, place it in a freeze dryer for freeze drying, and the freeze-dried sample is dissolved in deionized water and filtered. Take the filtered solution and place it in a drying oven at 10-80℃ for 12h. The structure is determined by liquid chromatography-mass spectrometry analysis. At room temperature, the surface tension is measured using a BZY-1 automatic surface tension meter; and the foaming performance is measured using a Roche foam meter.

[0073] Example 16

[0074] Prepare 200mM ethyl 3,4-dihydroxybenzoate solution with dioxane as solvent, and prepare 600mM threonine solution with deionized water. Take 5mL ethyl 3,4-dihydroxybenzoate solution in a reactor, add 142mg anhydrous sodium sulfate and 139mg silver oxide in turn, and place it in a 20℃ water bath for 40min. After the reaction time is up, filter it, take out the clear liquid and place it in a reactor, add 0.5mL threonine solution, and place it in a 20℃ water bath for 1h. After the reaction time is up, place it in a freeze dryer for freeze drying, and the freeze-dried sample is dissolved in deionized water and filtered. Take the filtered solution and place it in a drying oven at 10-80℃ for 12h. The structure is determined by liquid chromatography-mass spectrometry analysis. At room temperature, the surface tension is measured using a BZY-1 automatic surface tension meter; and the foaming performance is measured using a Roche foam meter.

[0075] Embodiment 17

[0076] Prepare 200mM ethyl 3,4-dihydroxybenzoate solution with dioxane as solvent, and prepare 600mM asparagine solution with deionized water. Take 5mL ethyl 3,4-dihydroxybenzoate solution in a reactor, add 142mg anhydrous sodium sulfate and 139mg silver oxide in turn, and place in a 20℃ water bath for reaction for 40min. After the reaction time is up, filter, take the clear liquid and place it in a reactor, add 0.5mL asparagine solution, and place it in a 20℃ water bath for reaction for 1h. After the reaction time is up, place it in a freeze dryer for freeze drying, and the freeze-dried sample is dissolved in deionized water and filtered. Take the filtered solution and place it in a drying oven at 10-80℃ for 12h. The structure is determined by liquid chromatography-mass spectrometry analysis. At room temperature, the surface tension is measured using a BZY-1 automatic surface tension meter; and the foaming performance is measured using a Roche foam meter.

[0077] Embodiment 18

[0078] Prepare 200mM 3,4-dihydroxybenzoic acid ethyl ester solution with dioxane as solvent, and prepare 600mM glutamine solution with deionized water. Take 5mL 3,4-dihydroxybenzoic acid ethyl ester solution in a reactor, add 142mg anhydrous sodium sulfate and 139mg silver oxide in turn, and place it in a 20℃ water bath for 40min. After the reaction time is up, filter it, take out the clear liquid and place it in a reactor, add 0.5mL glutamine solution, and place it in a 20℃ water bath for 1h. After the reaction time is up, place it in a freeze dryer for freeze drying, and the freeze-dried sample is dissolved in deionized water and filtered. Take the filtered solution and place it in a drying oven at 10-80℃ for 12h. The structure is determined by liquid chromatography-mass spectrometry analysis. At room temperature, the surface tension is measured using a BZY-1 automatic surface tension meter; and the foaming performance is measured using a Roche foam meter.

[0079] Embodiment 19

[0080] Prepare 200mM ethyl 3,4-dihydroxybenzoate solution with dioxane as solvent, and prepare 600mM histidine solution with deionized water. Take 5mL ethyl 3,4-dihydroxybenzoate solution in a reactor, add 142mg anhydrous sodium sulfate and 139mg silver oxide in turn, and place it in a 20℃ water bath for 40min. After the reaction time is up, filter it, take out the clear liquid and place it in a reactor, add 0.5mL histidine solution, and place it in a 20℃ water bath for 1h. After the reaction time is up, place it in a freeze dryer for freeze drying, and the freeze-dried sample is dissolved in deionized water and filtered. Take the filtered solution and place it in a drying oven at 10-80℃ for 12h. The structure is determined by liquid chromatography-mass spectrometry analysis. At room temperature, the surface tension is measured using a BZY-1 automatic surface tension meter; and the foaming performance is measured using a Roche foam meter.

[0081] Embodiment 20

[0082] Prepare 200mM 3,4-dihydroxybenzoic acid ethyl ester solution with dioxane as solvent, and prepare 60mM cysteine ​​solution with deionized water. Take 5mL 3,4-dihydroxybenzoic acid ethyl ester solution in a reactor, add 142mg anhydrous sodium sulfate and 139mg silver oxide in turn, and place it in a 20℃ water bath for 40min. After the reaction time is up, filter it, take out the clear liquid and place it in a reactor, add 5mL cysteine ​​solution, and place it in a 20℃ water bath for 1h. After the reaction time is up, place it in a freeze dryer for freeze drying, and the freeze-dried sample is dissolved in deionized water and filtered. Take the filtered solution and place it in a drying oven at 10-80℃ for 12h. The structure is determined by liquid chromatography-mass spectrometry analysis. At room temperature, the surface tension is measured using a BZY-1 automatic surface tension meter; and the foaming performance is measured using a Roche foam meter.

[0083] Embodiment 21

[0084] Prepare 200mM caffeic acid ethyl ester solution with dioxane as solvent, and prepare 600mM lysine solution with deionized water. Take 5mL caffeic acid ethyl ester solution in a reactor, add 142mg anhydrous sodium sulfate and 139mg silver oxide in turn, and place it in a 20℃ water bath to react for 40min. After the reaction time is up, filter it, take out the clear liquid and place it in a reactor, add 0.5mL lysine solution, and place it in a 20℃ water bath to react for 1h. After the reaction time is up, place it in a freeze dryer for freeze drying, and the freeze-dried sample is dissolved in deionized water and filtered. Take the filtered solution and place it in a drying oven at 10-80℃ for 12h. The structure is determined by liquid chromatography-mass spectrometry analysis. At room temperature, the surface tension is measured using a BZY-1 automatic surface tension meter; and the foaming performance is measured using a Roche foam meter.

[0085] Embodiment 22

[0086] Prepare 200mM 4-methylcatechol solution with dioxane as solvent, and prepare 600mM lysine solution with deionized water. Take 5mL 4-methylcatechol solution in a reactor, add 142mg anhydrous sodium sulfate and 139mg silver oxide in turn, and place it in a 20℃ water bath for 40min. After the reaction time is up, filter it, take out the clear liquid and place it in a reactor, add 0.5mL lysine solution, and place it in a 20℃ water bath for 1h. After the reaction time is up, place it in a freeze dryer for freeze drying, and the freeze-dried sample is dissolved in deionized water and filtered. Take the filtered solution and place it in a drying oven at 10-80℃ for 12h. The structure is determined by liquid chromatography-mass spectrometry analysis. At room temperature, the surface tension is measured using a BZY-1 automatic surface tension meter; and the foaming performance is measured using a Roche foam meter.

[0087] Embodiment 23

[0088] Prepare 200mM 4-tert-butylcatechol solution with dioxane as solvent, and prepare 600mM lysine solution with deionized water. Take 5mL 4-tert-butylcatechol solution in a reactor, add 142mg anhydrous sodium sulfate and 139mg silver oxide in turn, and place it in a 20℃ water bath for 40min. After the reaction time is up, filter it, take out the clear liquid and place it in a reactor, add 0.5mL lysine solution, and place it in a 20℃ water bath for 1h. After the reaction time is up, place it in a freeze dryer for freeze drying, and the freeze-dried sample is dissolved in deionized water and filtered. Take the filtered solution and place it in a drying oven at 10-80℃ for 12h. The structure is determined by liquid chromatography-mass spectrometry analysis. At room temperature, the surface tension is measured using a BZY-1 automatic surface tension meter; and the foaming performance is measured using a Roche foam meter.

[0089] Embodiment 24

[0090] Prepare 200mM 4'-chloro-3,4-dihydroxybenzophenone solution with dioxane as solvent, and prepare 600mM lysine solution with deionized water. Take 5mL 4'-chloro-3,4-dihydroxybenzophenone solution in a reactor, add 142mg anhydrous sodium sulfate and 139mg silver oxide in turn, and place it in a 20℃ water bath for 40min. After the reaction time is up, filter it, take out the clear liquid and place it in a reactor, add 0.5mL lysine solution, and place it in a 20℃ water bath for 1h. After the reaction time is up, place it in a freeze dryer for freeze drying, and the freeze-dried sample is dissolved in deionized water and filtered. Take the filtered solution and place it in a drying oven at 10-80℃ for 12h. The structure is determined by liquid chromatography-mass spectrometry analysis. At room temperature, the surface tension is measured using a BZY-1 automatic surface tension meter; and the foaming performance is measured using a Roche foam meter.

[0091] Embodiment 25

[0092] A 200mM ethyl 3,4-dihydroxybenzoate solution was prepared with acetonitrile as solvent, and a 600mM lysine solution was prepared with deionized water. 5mL of ethyl 3,4-dihydroxybenzoate solution was placed in a reactor, and 142mg of anhydrous sodium sulfate and 139mg of silver oxide were added in sequence and placed in a 20℃ water bath for reaction for 40min. After the reaction time was up, the solution was filtered, the clear liquid was taken out and placed in a reactor, 0.5mL of lysine solution was added, and the solution was placed in a 20℃ water bath for reaction for 1h. After the reaction time was up, the solution was placed in a freeze dryer for freeze drying, and the freeze-dried sample was dissolved in deionized water and filtered. The filtered solution was placed in a drying oven at 10-80℃ for 12h. The structure was determined by LC-MS analysis. At room temperature, the surface tension was measured using a BZY-1 automatic surface tension meter, and the foaming performance was measured using a Roche foam meter.

[0093] Embodiment 26

[0094] Prepare 200mM ethyl 3,4-dihydroxybenzoate solution with ethanol as solvent, and prepare 600mM lysine solution with deionized water. Take 5mL ethyl 3,4-dihydroxybenzoate solution in a reactor, add 142mg anhydrous sodium sulfate and 139mg silver oxide in turn, and place it in a 20℃ water bath for 40min. After the reaction time is up, filter it, take out the clear liquid and place it in a reactor, add 0.5mL lysine solution, and place it in a 20℃ water bath for 1h. After the reaction time is up, place it in a freeze dryer for freeze drying, and the freeze-dried sample is dissolved in deionized water and filtered. Take the filtered solution and place it in a drying oven at 10-80℃ for 12h. The structure is determined by liquid chromatography-mass spectrometry analysis. At room temperature, the surface tension is measured using a BZY-1 automatic surface tension meter; and the foaming performance is measured using a Roche foam meter.

[0095] Embodiment 27

[0096] A 200mM ethyl 3,4-dihydroxybenzoate solution was prepared with acetone as solvent, and a 600mM lysine solution was prepared with deionized water. 5mL of ethyl 3,4-dihydroxybenzoate solution was placed in a reactor, and 142mg of anhydrous sodium sulfate and 139mg of silver oxide were added in sequence and placed in a 20℃ water bath for reaction for 40min. After the reaction time was up, the solution was filtered, the clear liquid was taken out and placed in a reactor, 0.5mL of lysine solution was added, and the solution was placed in a 20℃ water bath for reaction for 1h. After the reaction time was up, the solution was placed in a freeze dryer for freeze drying, and the freeze-dried sample was dissolved in deionized water and filtered. The filtered solution was placed in a drying oven at 10-80℃ for 12h. The structure was determined by LC-MS analysis. At room temperature, the surface tension was measured using a BZY-1 automatic surface tension meter; and the foaming performance was measured using a Roche foam meter.

[0097] Embodiment 28

[0098] Prepare 200mM ethyl 3,4-dihydroxybenzoate solution with ethyl acetate as solvent, and prepare 600mM lysine solution with deionized water. Take 5mL ethyl 3,4-dihydroxybenzoate solution in a reactor, add 142mg anhydrous sodium sulfate and 139mg silver oxide in turn, and place it in a 20℃ water bath for 40min. After the reaction time is up, filter it, take out the clear liquid and place it in a reactor, add 0.5mL lysine solution, and place it in a 20℃ water bath for 1h. After the reaction time is up, place it in a freeze dryer for freeze drying, and the freeze-dried sample is dissolved in deionized water and filtered. Take the filtered solution and place it in a drying oven at 10-80℃ for 12h. The structure is determined by liquid chromatography-mass spectrometry analysis. At room temperature, the surface tension is measured using a BZY-1 automatic surface tension meter; and the foaming performance is measured using a Roche foam meter.

[0099] Embodiment 29

[0100] Use chloroform as solvent to prepare 200mM ethyl 3,4-dihydroxybenzoate solution, and use deionized water to prepare 600mM lysine solution. Take 5mL ethyl 3,4-dihydroxybenzoate solution in a reactor, add 142mg anhydrous sodium sulfate and 139mg silver oxide in turn, and place it in a 20℃ water bath for reaction for 40min. After the reaction time is up, filter it, take out the clear liquid and place it in a reactor, add 0.5mL lysine solution, and place it in a 20℃ water bath for reaction for 1h. After the reaction time is up, place it in a freeze dryer for freeze drying, and the freeze-dried sample is dissolved in deionized water and filtered. Take the filtered solution and place it in a drying oven at 10-80℃ for 12h. The structure is determined by liquid chromatography-mass spectrometry analysis. At room temperature, the surface tension is measured using a BZY-1 automatic surface tension meter; and the foaming performance is measured using a Roche foam meter.

[0101] Embodiment 30

[0102] Prepare 200mM ethyl 3,4-dihydroxybenzoate solution with dimethyl sulfoxide as solvent, and prepare 600mM lysine solution with deionized water. Take 5mL ethyl 3,4-dihydroxybenzoate solution in a reactor, add 142mg anhydrous sodium sulfate and 139mg silver oxide in turn, and place it in a 20℃ water bath for 40min. After the reaction time is up, filter it, take out the clear liquid and place it in a reactor, add 0.5mL lysine solution, and place it in a 20℃ water bath for 1h. After the reaction time is up, place it in a freeze dryer for freeze drying, and the freeze-dried sample is dissolved in deionized water and filtered. Take the filtered solution and place it in a drying oven at 10-80℃ for 12h. The structure is determined by liquid chromatography-mass spectrometry analysis. At room temperature, the surface tension is measured using a BZY-1 automatic surface tension meter; and the foaming performance is measured using a Roche foam meter.

[0103] Embodiment 31

[0104] Prepare 200mM ethyl 3,4-dihydroxybenzoate solution with dimethylformamide as solvent, and prepare 600mM lysine solution with deionized water. Take 5mL ethyl 3,4-dihydroxybenzoate solution in a reactor, add 142mg anhydrous sodium sulfate and 139mg silver oxide in turn, and place it in a 20℃ water bath for reaction for 40min. After the reaction time is up, filter it, take out the clear liquid and place it in a reactor, add 0.5mL lysine solution, and place it in a 20℃ water bath for reaction for 1h. After the reaction time is up, place it in a freeze dryer for freeze drying, and the freeze-dried sample is dissolved in deionized water and filtered. Take the filtered solution and place it in a drying oven at 10-80℃ for 12h. The structure is determined by liquid chromatography-mass spectrometry analysis. At room temperature, the surface tension is measured using a BZY-1 automatic surface tension meter; and the foaming performance is measured using a Roche foam meter.

[0105] Embodiment 32

[0106] Prepare 200mM ethyl 3,4-dihydroxybenzoate solution with dioxane as solvent, prepare 600mM lysine solution with deionized water, and then prepare 1000mM sodium periodate solution with deionized water. Take 5mL ethyl 3,4-dihydroxybenzoate solution in a reactor, add 1mL sodium periodate solution and place it in a 20℃ water bath for reaction for 40min. After the reaction time is up, filter, take the clear liquid and place it in a reactor, add 0.5mL lysine solution, and place it in a 20℃ water bath for reaction for 1h. After the reaction time is up, place it in a freeze dryer for freeze drying, and the freeze-dried sample is dissolved in deionized water and filtered. Take the filtered solution and place it in a drying oven at 10-80℃ for 12h. The structure is determined by LC-MS analysis. At room temperature, the surface tension is measured using a BZY-1 automatic surface tension meter; and the foaming performance is measured using a Roche foam meter.

[0107] Embodiment 33

[0108] Prepare 200mM ethyl 3,4-dihydroxybenzoate solution with dioxane as solvent, prepare 600mM lysine solution with deionized water, and then prepare 1000mM ammonium cerium nitrate solution with deionized water. Take 5mL ethyl 3,4-dihydroxybenzoate solution in a reactor, add 1mL ammonium cerium nitrate solution and place it in a 20℃ water bath for reaction for 40min. After the reaction time is up, filter, take the clear liquid and place it in a reactor, add 0.5mL lysine solution, and place it in a 20℃ water bath for reaction for 1h. After the reaction time is up, place it in a freeze dryer for freeze drying, and the freeze-dried sample is dissolved in deionized water and filtered. Take the filtered solution and place it in a drying oven at 10-80℃ for 12h. The structure is determined by liquid chromatography-mass spectrometry analysis. At room temperature, the surface tension is measured using a BZY-1 automatic surface tension meter; and the foaming performance is measured using a Roche foam meter.

[0109] Embodiment 34

[0110] A 200mM 3,4-dihydroxybenzoic acid ethyl ester solution was prepared with dioxane as solvent, and a 100mM taurine solution was prepared with deionized water as solvent. 5mL of the obtained 3,4-dihydroxybenzoic acid ethyl ester solution was taken into a reactor, and 142mg of anhydrous sodium sulfate and 139mg of silver oxide were added in sequence and placed in a 20℃ water bath for reaction for 40min, then filtered, the clear liquid was taken out and placed in a reactor, and 3mL of taurine solution was added, and placed in a 20℃ water bath for reaction for 1h. After the reaction time is up, it is placed in a freeze dryer for freeze drying, and the freeze-dried sample is dissolved in deionized water and filtered, and the filtered solution is placed in a drying oven at 10-80℃ for 12h. Its structure was determined by liquid chromatography-mass spectrometry analysis. At room temperature, its surface tension was measured using a BZY-1 automatic surface tension meter; and its foaming performance was measured using a Roche foam meter.

[0111] Embodiment 35

[0112] A 200mM ethyl 3,4-dihydroxybenzoate solution was prepared with dioxane as solvent, and a 20mM tripeptide solution was prepared with deionized water as solvent. 5mL of the obtained ethyl 3,4-dihydroxybenzoate solution was placed in a reactor, and 142mg of anhydrous sodium sulfate and 139mg of silver oxide were added in sequence and placed in a 20℃ water bath for reaction for 40min, then filtered, the clear liquid was placed in a reactor and 15mL of the tripeptide solution was added, and placed in a 20℃ water bath for reaction for 1h. After the reaction time is up, it is placed in a freeze dryer for freeze drying, and the freeze-dried sample is dissolved in deionized water and filtered, and the filtered solution is placed in a drying oven at 10-80℃ for drying for 12h. Its structure was determined by liquid chromatography-mass spectrometry analysis. At room temperature, its surface tension was measured using a BZY-1 automatic surface tension meter; and its foaming performance was measured using a Roche foam meter.

[0113] The tests performed on the products of the above embodiments are as follows:

[0114] Figure 1 This is the primary mass spectrum of the product of Example 1. It was obtained by Shimadzu LCMS8040 instrument testing. A peak with a mass-to-charge ratio of +327 can be observed in the positive ion mode. This peak is consistent with the hydrogenation peak (+327) with a molecular weight of 326 of the expected Michael addition reaction product.

[0115] Figure 2 The secondary mass spectrum of the product of Example 1 was obtained by Shimadzu LCMS8040 instrument testing. In positive ion mode, a series of fragments were obtained by bombarding the peak with a mass-to-charge ratio of +327. The structure was inferred to prove that ethyl 3,4-dihydroxybenzoate and lysine underwent a Michael addition reaction to generate an amino acid surfactant.

[0116] Figure 3 The concentration surface tension diagram of the product of Example 1. At room temperature, the surface tension at different concentrations was measured using a BZY-1 automatic surface tension meter. The product can effectively reduce the surface tension of water, proving that the invention successfully synthesized a new type of amino acid surfactant.

[0117] Figure 4 The foam volume of the product of Example 1 changes with time. The foaming performance is measured by a Roche foam instrument, which proves that the product synthesized by the invention has good foaming performance and excellent foam stability.

[0118] Figure 5 The foam volume diagram of the product obtained by reacting the substrate 3,4-dihydroxybenzoic acid ethyl ester with dioxane as solvent and different amino acids after silver oxide oxidation in Example 1. The foaming performance was measured by Roche foam meter, proving that the product synthesized by the invention has good foaming performance.

[0119] Figure 6 The foam volume diagram of the products obtained by reacting different substrates of Examples 1 / 2 / 11 / 15 / 16 / 19 / 20 with lysine after silver oxide oxidation with dioxane as solvent. The foaming performance was measured by Roche foam meter, proving that the products synthesized by the invention have good foaming performance.

[0120] Figure 7 The foam volume diagram of the product obtained by reacting 3,4-dihydroxybenzoic acid ethyl ester with lysine in different oxidation modes using dioxane as solvent in Example 1 / 21 / 22 / 23 / 24. The foaming performance was measured by Roche foam meter, which proved that the product synthesized by the invention had good foaming performance.

[0121] Figure 8The foam volume diagram of the product obtained by reacting 3,4-dihydroxybenzoic acid ethyl ester, the substrate of Example 1 / 25 / 26 / 27 / 31, with lysine after being oxidized by silver oxide in different solvents. The foaming performance was measured by Roche foam meter, proving that the product synthesized by the invention has good foaming performance.

[0122] Embodiment 36

[0123] Use dioxane as solvent to prepare 100mM, 200mM, and 600mM 3,4-dihydroxybenzoic acid ethyl ester solutions, and use deionized water as solvent to prepare 200mM, 600mM, and 1200mM lysine solutions. Take 5mL of the obtained 3,4-dihydroxybenzoic acid ethyl ester solution in a reactor, add 142mg of anhydrous sodium sulfate, 69.5mg, 139mg, and 278mg of silver oxide in sequence, and place them in a water bath at 20℃, 40℃, and 60℃ for reaction for 40min, then filter, take the clear liquid and place it in a reactor and add 0.5mL of lysine solution, and place it in a water bath at 20℃ for reaction for 1h. After the reaction time is up, place it in a freeze dryer for freeze drying, and the freeze-dried sample is dissolved in deionized water and filtered. Take the filtered solution and place it in a drying oven at 10-80℃ for drying for 12h. After obtaining the sample, use a Roche foam meter to measure its foaming performance. The results are shown in the following table:

[0124]

[0125] The above embodiments are only preferred implementations of the present invention, and the protection scope of the present invention is not limited to the above embodiments. All technical solutions under the concept of the present invention belong to the protection scope of the present invention. It should be pointed out that for ordinary technicians in this technical field, improvements and modifications without departing from the principle of the present invention should also be regarded as the protection scope of the present invention.

Claims

1. A method for preparing a biomimetic synthetic amino acid surfactant, characterized in that: It includes: obtaining an organic solution of a catechol derivative having a concentration of 200 mM and an aqueous solution of an amino acid compound having a concentration of 600 mM; Adding a dehydrating agent and an oxidizing agent solution to the organic solution of the catechol derivative in sequence, reacting at 20° C. for 40 minutes, and separating a clear liquid from the system after the reaction; Adding an aqueous solution of an amino acid compound to the clear liquid, reacting at 20° C. for 60 minutes, and extracting a product by freeze-drying to obtain the biomimetic synthesized amino acid surfactant; Among them, the catechol derivative is ethyl 3,4-dihydroxybenzoate; the organic solvent used for the organic solution of the catechol derivative is dioxane; the oxidant is selected from silver oxide; the dehydrating agent is selected from anhydrous sodium sulfate; and the amino acid is selected from lysine.

2. The preparation method according to claim 1, characterized in that: in, The molar ratio of the catechol derivative to the oxidant is 1:0.3-1.8, and the molar ratio of the organic solution of the catechol derivative to the aqueous solution of the amino acid compound is 1:0.1-0.

8.

3. The preparation method according to claim 2, characterized in that: in, The molar ratio of the catechol derivative to the oxidant is 1:0.6-0.8; the molar ratio of the organic solution of the catechol derivative to the aqueous solution of the amino acid compound is 1:0.25-0.

5.

4. The preparation method according to claim 1, characterized in that: It also includes: purifying the product extracted in step (3), wherein the purification includes dissolving and drying the extracted product, and the drying temperature is 10-80°C.

5. The biomimetic synthesized amino acid surfactant prepared by the preparation method according to any one of claims 1 to 4.

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