CN112889835B - Novel food preservative and preparation method and application thereof - Google Patents
Novel food preservative and preparation method and application thereof Download PDFInfo
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- CN112889835B CN112889835B CN202110409498.7A CN202110409498A CN112889835B CN 112889835 B CN112889835 B CN 112889835B CN 202110409498 A CN202110409498 A CN 202110409498A CN 112889835 B CN112889835 B CN 112889835B
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
- A01N47/42—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=CX2 groups, e.g. isothiourea
- A01N47/44—Guanidine; Derivatives thereof
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
- A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
- A23L3/3454—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
- A23L3/3463—Organic compounds; Microorganisms; Enzymes
- A23L3/3526—Organic compounds containing nitrogen
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
- A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
- A23L3/3454—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
- A23L3/3463—Organic compounds; Microorganisms; Enzymes
- A23L3/3544—Organic compounds containing hetero rings
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- C07—ORGANIC CHEMISTRY
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- C07C277/00—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
- C07C277/08—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups of substituted guanidines
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- C07C279/00—Derivatives of guanidine, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
- C07C279/04—Derivatives of guanidine, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of guanidine groups bound to acyclic carbon atoms of a carbon skeleton
- C07C279/14—Derivatives of guanidine, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of guanidine groups bound to acyclic carbon atoms of a carbon skeleton being further substituted by carboxyl groups
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
- C07C55/02—Dicarboxylic acids
- C07C55/06—Oxalic acid
- C07C55/07—Salts thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/235—Saturated compounds containing more than one carboxyl group
- C07C59/245—Saturated compounds containing more than one carboxyl group containing hydroxy or O-metal groups
- C07C59/255—Tartaric acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/80—Acids; Esters in position 3
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/90—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in food processing or handling, e.g. food conservation
Abstract
The invention provides a food preservative comprising lauroyl arginine ethyl ester (LAE) ion pair derivatives. The invention also provides a method for preparing the preservative. The food preservative has the characteristics of being natural, non-toxic, high-efficiency, bacteriostatic, easy to degrade and environment-friendly.
Description
The application is a divisional application of Chinese invention patent application with the application date of 2019, 6 and 24 months and the application number of 201910549117.8, and the invention name of the invention is 'novel food preservative and a preparation method and application thereof'.
Technical Field
The invention relates to a food preservative, in particular to a food preservative containing lauroyl arginine ethyl ester derivatives (ion pair compounds), wherein the lauroyl arginine ethyl ester ion pair has an antibacterial effect, can prevent putrefaction and deterioration caused by microorganisms and can prolong the shelf life of food.
Background
The food preservative is an additive capable of preventing spoilage caused by microorganisms and prolonging the shelf life of food. It is also called antimicrobial (antimicrobial) because it has the function of preventing food poisoning caused by microorganism reproduction. Its main function is to inhibit the reproduction of microorganisms in food.
Food preservatives approved in China include benzoic acid \ sodium benzoate, sorbic acid \ potassium sorbate, calcium propionate, sodium propionate, ethyl p-antelope benzoate, butyl p-antelope benzoate, dehydroacetic acid, sodium diacetate, dimethyl fumarate, nisin, carbon dioxide, hydrogen peroxide and moroxydine. Among them, sodium benzoate, potassium sorbate and the like are most commonly used. Sodium benzoate is more toxic than potassium sorbate and at the same acidity value, the bacteriostatic efficacy is only 1/3 of sorbic acid, so potassium sorbate is increasingly used in many countries. But the sodium benzoate is low in price, so that the sodium benzoate is still commonly used in China and is mainly used for carbonated beverages and fruit juice beverages. The potassium sorbate has strong antibacterial power and low toxicity, and can participate in normal metabolism of human body and convert into CO2 and water. From the development trend of the preservative, the biological preservative prepared by biological fermentation will become the development trend in the future.
With the increase of health preservation and healthy diet awareness of modern people, the development of natural nontoxic preservatives becomes a research hotspot in a plurality of fields including cosmetics and foods.
Lauroyl arginine Ethyl ester (LAE) is an organic matter formed by condensing fatty acid and dibasic amino acid, is a white hygroscopic solid, is stable in chemical property within the range of pH 3-7, has a melting point of 50-58 ℃, can be dispersed in 1kg of water at the temperature of 247g, has a distribution coefficient of more than 10 in water and oil, and is mainly in a water phase. Researches find that the lauroyl arginine ethyl ester LAE has the characteristics of strong antibacterial capability, low biological toxicity, good in vivo metabolism effect and high environmental compatibility. The most representative characteristic is that no residue is left in the metabolism of lauroyl arginine ethyl ester, and related researches show that the lauroyl arginine ethyl ester can be rapidly and naturally metabolized in human bodies and animal bodies to generate lauric acid and arginine which are further metabolized into ornithine, urea, carbon dioxide and water. All primary metabolites and final metabolites produced during the metabolism of lauroyl arginine ethyl ester are non-toxic and harmless, and are the same as the metabolites of food ingested daily by humans and animals in the body.
In 2005, LAE was approved by FDA as a GRAS (generally recognized as safe) food additive in the united states, approved by European Food Safety Administration (EFSA) for safe food certification in 2007, and listed as a standard of food additive general law by 2011 international committee on food code, and is approved as a preservative for 20 kinds of foods and fresh agricultural products.
Chinese patent invention 200980104596.7, "use of cationic surfactants to protect against dental erosion" discloses the use of LAE as a cationic surfactant in the form of a composition for oral use, such as a dry powder mixture of a dessert, candy, tablet, lozenge, lollipop, nougat, jelly, gum, drops or drink powder intended for dissolution, wherein the LAE compound is present in the composition at a concentration of 0.001% to 5% by weight, preferably 0.001% to 2% by weight. In the composition, the presence of LAE produces a microbial effect and provides a source of neutralizing plaque acids, which is highly effective.
Chinese patent 201480081262.3 entitled mouthwash composition containing peroxide source and N-acetyl-L-arginine alkyl ester salt discloses LAE and its salt and hydrogen peroxide (H)2O2) Proportioned mouthwash wherein the LAE and salts thereof are present in the composition in a concentration of 0.05 to 0.4% by weight, preferably 0.1 to 0.3% by weightIt is possible to have a dual effect of effective whitening activity and antimicrobial activity, and this effect can maintain the whitening activity and the antimicrobial activity over time.
However, the research on the invention of food preservatives involving LAE and its salts has mainly focused on the foreign applicants. Facing the largest food market all over the world, China needs a new efficient, nontoxic and stable food preservative.
Disclosure of Invention
One principle of the invention is that according to the characteristics that lauroyl arginine ethyl ester LAE has strong antibacterial ability, low biological toxicity, good in vivo metabolism effect, high environmental compatibility and no reaction with other compounds at normal temperature, the LAE is further improved to obtain a novel derivative, namely, LAE and organic acid salt are subjected to condensation reaction, so that the LAE ion pair compound is obtained. The ion pair compound is used as a bacteriostatic agent and a preservative component in cosmetics, and has the advantages of better bacteriostatic effect and lower dosage compared with LAE, thereby being more beneficial to preparing natural, non-toxic and environment-friendly food preservatives.
Accordingly, a first object of the present invention is to provide the use of a LAE ion pair compound as a food preservative, wherein the LAE ion pair compound has a formula as shown in formula (III):
wherein, the RCOO-The organic acid or salt is selected from salicylic acid, formic acid, ammonium formate, calcium formate, acetic acid, sodium diacetate, propionic acid, ammonium propionate, sodium propionate, calcium propionate, butyric acid, sodium butyrate, lactic acid, benzoic acid, sodium benzoate, sorbic acid, sodium sorbate, potassium sorbate, fumaric acid, citric acid, potassium citrate, sodium citrate, calcium citrate, tartaric acid, malic acid, phosphoric acid, sodium carbonate, oxalic acid or carbonic acid having antibacterial activity. In a preferred embodiment, the organic acid is selected from the group consisting of nicotinic acid, tartaric acid, oxalic acid, salicylic acid.
In any of the above embodiments, the food product is a solid food product, a liquid food product, a powder food product, or the like.
Wherein the LAE ion pair compound is 0.001-1% by mass in the food; preferably 0.001-0.01%, 0.01-0.05%, 0.05-0.1%, 0.1-0.5%, 0.5-1%, more preferably 0.01-0.05%, 0.05-0.1%.
It is a third object of the present invention to provide a method for preparing a preservative containing the above LAE ion pair compound, comprising the steps of:
(1) heating and dissolving the compound shown in the formula (II), and then adding an organic acid salt solution;
(2) fully stirring and uniformly mixing, and reacting to generate the LAE ionic compound under the condition of heating, wherein the reaction is shown as the following reaction formula:
wherein the RCOO-organic acid or salt is selected from salicylic acid, formic acid, ammonium formate, calcium formate, acetic acid, sodium diacetate, propionic acid, ammonium propionate, sodium propionate, calcium propionate, butyric acid, sodium butyrate, lactic acid, benzoic acid, sodium benzoate, sorbic acid, sodium sorbate, potassium sorbate, fumaric acid, citric acid, potassium citrate, sodium citrate, calcium citrate, tartaric acid, malic acid, phosphoric acid, sodium carbonate, oxalic acid or carbonic acid, which have antibacterial activity. In a preferred embodiment, the organic acid is selected from the group consisting of nicotinic acid, tartaric acid, oxalic acid, salicylic acid.
(3) After full reaction, cooling to room temperature, purifying and then drying in vacuum to prepare the lauroyl arginine ethyl ester organic acid ion pair compound shown in the formula (III);
(4) dissolving the LAE ion pair compound in an organic solvent in a container to obtain an ion pair compound mother solution;
(5) adding the mother liquor into a preservative matrix at room temperature, and fully stirring to obtain the preservative.
In the step (1), the heating and dissolving temperature is 50-100 ℃; preferably, it is 90 ℃.
In the step (2), the reaction temperature is 50-100 ℃; preferably, it is 90 ℃.
In the step (2), the reaction time is 50-100 ℃; preferably, it is 90 ℃.
In the step (3), the vacuum drying condition is 50-100 ℃; preferably, it is 60 ℃.
In the step (4), the container is preferably made of stainless steel or inert material.
In the step (4), the organic solvent is methanol, ethanol or the like.
In one embodiment, wherein the RCOO-organic acid or salt is selected from salicylic acid, formic acid, ammonium formate, calcium formate, acetic acid, sodium diacetate, propionic acid, ammonium propionate, sodium propionate, calcium propionate, butyric acid, sodium butyrate, lactic acid, benzoic acid, sodium benzoate, sorbic acid, sodium sorbate, potassium sorbate, fumaric acid, citric acid, potassium citrate, sodium citrate, calcium citrate, tartaric acid, malic acid, phosphoric acid, sodium carbonate, oxalic acid, or carbonic acid, having antibacterial activity. In a preferred embodiment, the organic acid is selected from the group consisting of nicotinic acid, tartaric acid, oxalic acid, salicylic acid.
In another embodiment, the RCOO-The preparation method of the organic acid salt comprises the following steps: adding the organic acid into a methanol solution, adding a proper amount of NaOH, stirring at room temperature until a white solid is separated out, carrying out suction filtration, and washing with methanol to obtain the organic acid salt.
It is a fourth object of the present invention to provide a preservative comprising the above LAE ion pair compound or prepared by the above method.
Terms and definitions
Lauroyl arginine Ethyl ester (LAE) is an organic matter formed by condensing fatty acid and dibasic amino acid, is a white hygroscopic solid, is stable in chemical property within the range of pH 3-7, has a melting point of 50-58 ℃, can be dispersed in 1kg of water at the temperature of 247g, has a distribution coefficient of more than 10 in water and oil, and is mainly in a water phase. Researches find that the lauroyl arginine ethyl ester LAE has the characteristics of strong antibacterial capability, low biological toxicity, good in vivo metabolism effect and high environmental compatibility. The most representative characteristic is that no residue is left in the metabolism of lauroyl arginine ethyl ester, and related researches show that the lauroyl arginine ethyl ester can be rapidly and naturally metabolized in human bodies and animal bodies to generate lauric acid and arginine which are further metabolized into ornithine, urea, carbon dioxide and water. All primary metabolites and final metabolites produced during the metabolism of lauroyl arginine ethyl ester are non-toxic and harmless, and are the same as the metabolites of food ingested daily by humans and animals in the body.
The invention improves the derivatives of the LAE, breaks through the traditional thought of the development of the derivatives, namely, the traditional thought is not limited to selecting the proper forms of acid, alkali and salt/ester which are traditionally suitable for the LAE or processing the LEA with acid, alkali, salt or esterification groups, but creatively selects an acid radical group which can enhance the bacteriostatic synergistic effect of the LAE and combines the acid radical group and the acid radical group with the salt or the esterification group through strong intermolecular ionic bonds to form a new derivative, namely an ion pair compound, thereby obviously improving the application of the LAE derivative in food preservatives.
Technical effects
The cosmetic composition of the invention has the advantages that:
the LAE ion pair compound is creatively used to replace bacteriostatic agents and preservatives in food, and the food preservative has the advantages of low cost, simple preparation process and good stability of the traditional food preservative, and also has the advantages of obvious bacteriostatic effect, single component, simple preparation, no harm to human bodies, easy catabolism, easy long-term storage and the like.
Drawings
FIG. 1: ESI mass spectrum of cation B + molecular ion peak of LAE ion pair compound;
FIG. 2: ESI mass spectrum of anion A-molecular ion peak of LAE nicotinic acid ion pair compound;
FIG. 3: peak shape and chemical shift pattern of 1H-NMR of LAE;
FIG. 4: peak shape and chemical shift pattern by 1H-NMR of nicotinic acid;
FIG. 5: peak shape and chemical shift pattern by 1H-NMR of LAE nicotinic acid ion pair;
FIG. 6: ESI mass spectrum of LAE tartrate ion on the anion A-molecule ion peak of the compound.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples and drawings, and the present invention is not limited to the following examples. Variations and advantages that may occur to those skilled in the art are intended to be included within the invention without departing from the spirit and scope of the inventive concept, and the scope of the invention is to be determined by the appended claims. The procedures, conditions, reagents, experimental methods and the like for carrying out the present invention are general knowledge and common general knowledge in the art except for the contents specifically mentioned below, and the present invention is not particularly limited.
The first embodiment is as follows: preparation method of ion pair compound synthesized from lauroyl arginine ethyl ester hydrochloride and nicotinic acid
Dissolving 2.0g of sodium nicotinate (purchased from Taishiai (Shanghai) chemical industry development Co., Ltd.) in 50mL of water to prepare a sodium nicotinate saline solution (A); dissolving lauroyl arginine ethyl ester hydrochloride 6.8g in 40mL of water, heating to 90 ℃ until the lauroyl arginine ethyl ester hydrochloride is completely dissolved to prepare lauroyl arginine ethyl ester hydrochloride aqueous solution (B); slowly adding the sodium nicotinate aqueous solution (A) into the lauroyl arginine ethyl ester hydrochloride aqueous solution (B) at 90 ℃, continuously stirring, reacting for 2 hours, cooling to room temperature, filtering, fully washing the precipitate with purified water, and performing vacuum drying on the precipitate at 60 ℃ to obtain 7.6g of the nicotinic acid ion pair compound.
Example analysis of molecular formula and molecular weight of dilauroyl arginine ethyl ester nicotinic acid ion pair compound
By mass spectrometry,1H-NMR、13The compound obtained by C-NMR spectroscopy has the formula:
1. mass Spectrometry (ESI) analysis
Cation B+The molecular ion peak has m/z 385.3, see fig. 1;
anion A-The molecular ion peak has m/z of 122.1, see fig. 2.
The theoretical calculation of the niacin ion for the cation in the compound was 507.4, and the observed value coincided with the theoretical value.
NMR analysis
Mixing lauroyl arginine ethyl ester hydrochloride (see figure 3), nicotinic acid1H-NMR (see FIG. 4) and of LAE Niacin ion-pair Compounds1H-NMR (see FIG. 5). In the salt forming process of the LAE ion pair compound, the peak shape and chemical shift of lauroyl arginine ethyl ester in the ion pair compound are not changed greatly, but all hydrogen on nicotinic acid has shift change, and the spectral characteristics of the acid and base part are closer to the space distance compared with the original inorganic acid salt (namely LAE hydrochloride), so that the influence is generated, and the corresponding change is generated compared with the original LAE and the hydrochloride thereof, the simple superposition of the acid and base parts is not generated, for example, the solubility is changed when purified water is used for washing and precipitating, which shows that strong interaction is generated between all hydrogen nuclei of the lauroyl arginine ethyl ester and the nicotinic acid, and a stable single compound structure is formed through strong ionic bonds.
Example three: preparation method of ion pair compound synthesized by lauroyl arginine ethyl ester hydrochloride and tartaric acid
2.0g of tartaric acid (purchased from Chiese chemical industry Co., Ltd.) was dissolved in 50mL of methanol, and an equivalent amount of NaOH was added thereto, and the mixture was stirred at room temperature until a white solid was precipitated, and then the solution was filtered under suction and washed with 30mL of methanol three times to obtain a tartaric acid sodium salt. Dissolving sodium tartrate salt in 50mL of water to prepare a sodium tartrate salt aqueous solution (A); dissolving 5.6g of lauroyl arginine ethyl ester hydrochloride in 40mL of water, heating to 90 ℃ until the lauroyl arginine ethyl ester hydrochloride is completely dissolved to prepare lauroyl arginine ethyl ester hydrochloride aqueous solution (B); slowly adding the tartaric acid sodium salt aqueous solution (A) into the lauroyl arginine ethyl ester hydrochloride aqueous solution (B) at 90 ℃, continuously stirring, reacting for 2 hours, cooling to room temperature, filtering, fully washing the precipitate with purified water, and performing vacuum drying on the precipitate at 60 ℃ to obtain 6.3g of the tartaric acid ion pair compound.
Examples analysis of molecular weight of Compound by Tetralauroyl arginine Ethyl ester tartrate ion
Mass Spectrometry (ESI) analysis of cation B+Molecular ionPeak m/z 385.3 (see FIG. 1)
Anion a-molecular ion peak m/z 149.0 (see fig. 6)
The theoretical calculation of the niacin ion for the cation in the compound was 534.3, and the observed value coincided with the theoretical value.
Example five: preparation method for synthesizing ion pair compound by using lauroyl arginine ethyl ester hydrochloride and oxalic acid
Oxalic acid (purchased from research Co., Ltd.) 1.0g was dissolved in 50mL of methanol, and an equivalent amount of NaOH was added thereto, and the mixture was stirred at room temperature until a white solid precipitated, filtered under suction and washed with 30mL of methanol three times to obtain an oxalic acid sodium salt. Dissolving sodium oxalate in 50mL of water to prepare sodium oxalate aqueous solution (A); dissolving 4.7g of lauroyl arginine ethyl ester hydrochloride in 40mL of water, heating to 90 ℃ until the lauroyl arginine ethyl ester hydrochloride is completely dissolved to prepare lauroyl arginine ethyl ester hydrochloride aqueous solution (B); slowly adding the sodium oxalate salt aqueous solution (A) into the lauroyl arginine ethyl ester hydrochloride aqueous solution (B) at 90 ℃, continuously stirring, reacting for 2 hours, cooling to room temperature, filtering, fully washing the precipitate with purified water, and drying the precipitate in vacuum at 60 ℃ to obtain 5.0g of the oxalate ion pair compound.
The results of NMR and ESI analyses performed according to the method of example two show that the ion pair compound is not a simple superposition of two acid and base portions, which are closely spaced and affect the spectral characteristics, and the spectral data of the ion pair compound is changed compared with the original LAE and its hydrochloride, for example, the solubility is changed when the precipitate is washed with purified water, which indicates that all hydrogen nuclei of lauroyl arginine ethyl ester have strong interactions with oxalic acid and form a stable single compound structure through strong ionic bonds.
Example six: preparation method of ion pair compound synthesized by lauroyl arginine ethyl ester hydrochloride and carbonic acid
1.0g of sodium carbonate (purchased from research Co., Ltd.) was dissolved in 50mL of water to prepare an aqueous sodium carbonate solution (A); dissolving 4.0g of lauroyl arginine ethyl ester hydrochloride in 40mL of water, heating to 90 ℃ until the lauroyl arginine ethyl ester hydrochloride is completely dissolved to prepare lauroyl arginine ethyl ester hydrochloride aqueous solution (B); slowly adding the sodium carbonate aqueous solution (A) into the lauroyl arginine ethyl ester hydrochloride aqueous solution (B) at 90 ℃, continuously stirring, reacting for 2 hours, cooling to room temperature, filtering, fully washing the precipitate with purified water, and drying the precipitate in vacuum at 60 ℃ to obtain 4.0g of the carbonate ion pair compound.
The results of NMR and ESI analyses performed according to the method of example two show that the ion pair compound does not have a simple superposition of two acid and base portions, the two acid and base portions are close in space distance and have an influence, and the spectral data of the ion pair compound is changed correspondingly compared with the original LAE and hydrochloride thereof, which indicates that all hydrogen nuclei of the lauroyl arginine ethyl ester have strong interaction with carbonic acid and form a stable single compound structure through strong ionic bonds.
Example seven: determination of lauroyl arginine ethyl ester ion pair compound Minimum Inhibitory Concentration (MIC) in vitro
The principle and the purpose are as follows: according to the microbubult dilution method specified by CLSI, the minimum drug concentration at which bacterial growth is inhibited after 24h of co-incubation of the drug with bacteria in a 96-well plate is the minimum inhibitory concentration of the drug.
The method comprises the following steps: lauroyl arginine ethyl ester hydrochloride (LAE) and the pair of lauroyl arginine ethyl ester organic acid ions prepared above are respectively diluted to different concentrations by Trypticase Soy Broth (TSB), the medicine and the bacteria are mixed and incubated in a 96-well plate, and a blank control culture medium CK1 without bacteria, a culture medium CK2 added with LAE (1000 mu g/ml) and a normal growth control culture medium CK3 without medicine are additionally arranged. The absorbance at 625nm of each well was measured after incubating the 96-well plate in a 37 ℃ incubator for 24 hours. OD with blank control625Wells with consistent values were considered to have no significant growth of bacteria. The lowest concentration of drug at which bacteria do not significantly grow is the minimum Inhibitory concentration mic (minimum inhibition concentration) of LAE to bacteria.
The results of comparing the antibacterial activities of various LAE derivatives (ion pair compounds) prepared with respect to the original LAE compound are shown in table 1 below, wherein the percentage values in the bracket () represent the mass percentage of each additive in the reaction system.
TABLE 1 in vitro antibacterial Effect of LAE and its ion-pair Compounds on two bacteria
| Comparison | Escherichia coli | Staphylococcus aureus |
| LAE | 16(0.0016％) | 8(0.0008％) |
| LAE nicotinic acid ion pair | 16(0.0016％) | 4(0.0004％) |
| LAE tartrate ion pair | 16(0.0016％) | 8(0.0008％) |
| LAE oxalate ion pair | 8(0.0008％) | 8(0.0008％) |
| LAE carbonate ion pair | 16(0.0016％) | 16(0.0016％) |
And (4) analyzing results:
(1) most of the LAE ion pair compound keeps the same antibacterial activity to escherichia coli, and especially the antibacterial activity of the LAE oxalic acid ion pair compound is improved;
(2) most of the LAE ion pair compounds keep the same antibacterial activity to staphylococcus aureus, the antibacterial activity of the LAE carbonate ion pair compounds is reduced, and the antibacterial activity of the LAE nicotinic acid ion pair compounds is obviously improved;
and (4) conclusion: ion pair compounds of LAE derivatives do not inhibit the antibacterial activity of the original LAE in a single component, but are beneficial to the antibacterial activity. Wherein, the nicotinic acid ion pair compound has obvious bacteriostatic effect on staphylococcus aureus.
Example eight: determination of inhibitory Activity of lauroyl arginine Ethyl ester ion pair Compound on food-borne mildew microorganisms
The principle and the purpose are as follows:
the inhibition effect of the preservative film of the lauroyl arginine ethyl ester (LAE) ion on the penicillium and aspergillus is detected by the bacteriostatic circle method for the experiment, so that the mildew-proof effect of the lauroyl arginine ethyl ester ion pair is evaluated.
The inhibition effect of lauroyl arginine ethyl ester (LAE) ions on penicillium and aspergillus of the compound is detected by the inhibition zone method for the experiment, so that the mildew-proof effect of the lauroyl arginine ethyl ester ions on penicillium and aspergillus is evaluated.
The method comprises the following steps: respectively putting penicillium or aspergillus spores into an LB liquid culture medium, selecting fungi single colonies, putting the fungi single colonies into a PDB liquid culture medium, culturing for 24 hours at room temperature, and uniformly coating the amplified bacterial liquid on the surface of the LB solid culture medium. The medium was punched with a 0.8mm punch, and about 100. mu.l of each well of lauroyl arginine ethyl ester ion pair or sodium methyl paraben, a positive fruit preservative, was added to the wells, which were covered with a lid, and incubated in an incubator at 37 ℃ for 48 hours. And measuring and counting the diameter of the inhibition zone of each hole.
And (4) analyzing results: tables 2 and 3 show the inhibition zones of the LAE ion pair compounds for Penicillium and Aspergillus, respectively. Both LAE and LAE ion pair can inhibit the growth of Penicillium, LAE-formate ion pair, and LAE-salicylate ion pair have inhibitory effect at concentration of 256 μ g/ml or more, and LAE-nicotinic acid ion pair inhibits the growth of Microbacterium at concentration of 512 μ g/ml or more. Both LAE and LAE ion pair can inhibit the growth of Aspergillus, LAE-formate ion pair, LAE-salicylate ion pair have inhibitory effect at a concentration of 128 μ g/ml or more, and LAE-nicotinic acid ion pair inhibit the growth of Microbacterium at a concentration of 256 μ g/ml or more.
And (4) conclusion: the LAE can inhibit the growth of mildew-causing microorganisms, the ability of LAE ion pairs to inhibit the mildew-causing microorganisms is not lost, and the inhibition effect of LAE-nicotinic acid ion pairs on penicillium and aspergillus is strongest.
TABLE 2 LAE and its ion pair Compounds results for the zone of inhibition of Penicillium
TABLE 3 LAE and its results for zone of inhibition of Aspergillus by ion-pair compounds
Although the 0.2% dose group showed the highest bacteriostatic effect among the above-mentioned several groups of experiments, and from the in vitro cell test data of the applicant's previously filed patent application (title of the invention: "use of lauroyl arginine ethyl ester derivative as an antibacterial agent for animals", application No. 201810648982.3), the 0.0032% concentration produced the bacteriostatic effect, and the addition of a dose of LAE or its derivative in a certain range could improve the bacteriostatic effect, but the bacteriostatic effect was not significantly improved relative to the 0.1% dose group, indicating that the 0.02% -0.1% dose range had satisfied the production requirements.
If the addition amount of the LAE and the derivatives thereof is increased, although the bacteriostatic rate is correspondingly increased, the excessively high bacteriostatic rate means more residues and is not beneficial to human health. Even so, because the bacteriostatic agent components of the LAE and the derivatives thereof belong to natural environment-friendly and nontoxic components, the bacteriostatic agent has the advantage of being friendly to human bodies when being added and used in high dosage compared with the traditional chemical bacteriostatic agent.
Therefore, in consideration of the production cost and the actual production requirement, the LAE and the ion thereof can effectively prevent and treat the bacterial or fungal hazards when the mass percentage concentration of the LAE and the ion thereof to the active ingredients of the antimicrobial composition is 0.001-0.01% or 0.01-0.05%, 0.05-0.1% or 0.1-0.5%, and the production requirement is met.
Claims (8)
- Use of a LAE ion pair compound for the preparation of a food preservative, wherein the LAE ion pair compound is prepared by the reaction:(1) dissolving the compound shown in the formula (II) in water, heating to 90 ℃ until the compound is completely dissolved, and then slowly adding sodium tartrate, sodium carbonate or sodium oxalate at the temperature of 90 ℃;
(2) fully stirring and uniformly mixing, and reacting under the condition of heating to 90 ℃ to obtain an LAE ion pair compound;(3) after sufficient reaction, the reaction mixture is cooled to room temperature, and is fully washed and purified by purified water and then dried in vacuum, thereby preparing the purified LAE ion pair compound. - 2. Use according to claim 1, wherein the organic acid salt is selected from sodium oxalate.
- 3. Use according to claim 1, wherein the food preservative is a solid food, a liquid food, a powdered food.
- 4. The use of claim 1, wherein the LAE ion pair compound is present in the food product at a concentration of 0.001 to 1% by weight.
- 5. The use of claim 4, wherein the LAE ion pair compound is present in the food product at a concentration of 0.001-0.01%, 0.01-0.05%, 0.05-0.1%, 0.1-0.5%, 0.5-1% by weight.
- 6. A preparation method of a food preservative is characterized by comprising the following steps:(1) dissolving the compound shown in the formula (II) in water, heating to 90 ℃ until the compound is completely dissolved, and slowly adding sodium tartrate, sodium carbonate or sodium oxalate at 90 ℃;
(2) fully stirring and uniformly mixing, and reacting under the condition of heating to 90 ℃ to generate an LAE ion pair compound;(3) after full reaction, cooling to room temperature, fully washing and purifying with purified water, and then drying in vacuum to prepare a purified LAE ion pair compound;(4) dissolving the LAE ion pair compound in an organic solvent in a container to obtain a LAE ion pair compound mother liquor;(5) adding the LAE ion pair compound mother liquor into a food preservative matrix at room temperature, and fully stirring to obtain the food preservative. - 7. The method of claim 6, wherein the organic acid salt is selected from sodium oxalate.
- 8. A food preservative prepared by the method of any one of claims 6 to 7.
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