CN114409916A - Nano tannin and preparation method and application thereof - Google Patents
Nano tannin and preparation method and application thereof Download PDFInfo
- Publication number
- CN114409916A CN114409916A CN202210086869.7A CN202210086869A CN114409916A CN 114409916 A CN114409916 A CN 114409916A CN 202210086869 A CN202210086869 A CN 202210086869A CN 114409916 A CN114409916 A CN 114409916A
- Authority
- CN
- China
- Prior art keywords
- tannin
- nano
- preparation
- portions
- ferrous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
- C12N1/14—Fungi; Culture media therefor
- C12N1/16—Yeasts; Culture media therefor
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Genetics & Genomics (AREA)
- Wood Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Mycology (AREA)
- Zoology (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Biotechnology (AREA)
- Botany (AREA)
- Microbiology (AREA)
- Biomedical Technology (AREA)
- Virology (AREA)
- Biochemistry (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Tropical Medicine & Parasitology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Coloring Foods And Improving Nutritive Qualities (AREA)
- General Preparation And Processing Of Foods (AREA)
Abstract
The invention provides nano tannin and a preparation method and application thereof, and relates to the technical field of chemical substance modification. The preparation method of the nano tannin comprises the following steps: according to the weight portion, 1 to 20 portions of tannin, 0.2 to 6.5 portions of surfactant, 0.01 to 0.2 portion of metal salt, 0.001 to 0.02 portion of alkaline substance and 500 portions of water are mixed and stirred evenly, thus obtaining the nano tannin. The invention adopts a soft template method to cause the coordination chemical reaction between the tannin and the metal ions to form a coordination compound, and the preparation method of the invention is adopted to prepare the nano tannin, thereby improving the specific surface area of the tannin, further increasing the probability of the tannin contacting and combining with microorganisms, and further increasing the inhibition capacity of the tannin on yeast.
Description
Technical Field
The invention relates to the technical field of chemical substance modification, and particularly relates to nano tannin as well as a preparation method and application thereof.
Background
Plant tannins are a generic term for a class of polyhydroxylated phenolic substances, which are present in terrestrial vascular plants. Plant tannins are found to have remarkable microbial toxicity and can be combined with proteins (enzymes) in a mode of synergistic action of hydrogen bond-hydrophobic action force, so that the plant tannins play a role in inhibiting the growth of microorganisms. The existing research data about tannic acid mainly focuses on the fields of pharmacy, chemical industry, food additives and the like, and the research of applying tannin to wine fermentation is basically blank.
Disclosure of Invention
The invention provides a nano tannin and a preparation method and application thereof, and aims to provide a novel tannin modification method and expand the application field of the tannin modification method.
In order to achieve the above object, the present invention provides, in a first aspect, a method for preparing nano-tannins, comprising the steps of: according to the weight portion, 1 to 20 portions of tannin, 0.2 to 6.5 portions of surfactant, 0.01 to 0.2 portion of metal salt, 0.001 to 0.02 portion of alkaline substance and 500 portions of water are mixed and stirred evenly to obtain the nano tannin.
The molecular structure of tannin is shown as a formula (I), and the molecule of tannin has a large number of ortho-phenolic hydroxyl groups which can be polymerized with metal ions through coordination reaction. The invention adopts a soft template method to cause the coordination chemical reaction between the tannin and the metal ions to form a coordination compound, and the preparation method of the invention is adopted to prepare the nano tannin, thereby improving the specific surface area of the tannin, further increasing the probability of the tannin contacting and combining with microorganisms, and further increasing the inhibition capacity of the tannin on yeast.
As a preferred embodiment of the method for preparing nano tannin of the present invention, the tannin is at least one of grape seed tannin, apple tannin, hop tannin, valonia tannin, persimmon tannin, longan tannin, myricetin and gallotannin.
Tannins are widely present in the bark, seeds, leaves, fruits of terrestrial vascular plants and can impart a "astringent" or "astringent" taste characteristic to the plants, while the degree of "astringent" and "astringent" taste of tannins is significantly related to their molecular structure. The inventor finds that the molecular weight distribution of grape seed tannin molecules is concentrated (500-. The grape skin tannin has wide molecular weight distribution (500 plus 30000Da), large average molecular weight (2000 plus 4000Da), and the three-dimensional structure of the molecule is mainly linear, rarely has a branched chain structure, has the characteristic of sharp bitter taste, and causes the wine body to have the sensory defects of bitter aftertaste and single structure. In order to further improve the sensory quality of wine, the invention combines the molecular structure characteristics of plant tannin, and selects grape seed tannin, apple tannin, hop tannin, valonia tannin, persimmon tannin, longan tannin, myricetin and gallnut tannin as the synthetic substrate of nano tannin.
In a preferred embodiment of the method for producing nano-tannins of the present invention, the surfactant is at least one of soybean lecithin, sesbania gum, sodium caseinate, sodium alginate, acetylated diglycerol fatty acid ester, lactic acid fatty acid glyceride, citric acid fatty acid glyceride, succinic acid monoglyceride, and sucrose fatty acid ester.
In the technical scheme of the invention, the surfactant is used for regulating and controlling the appearance of the polymerization reaction product of the nano tannin. The nano tannin is a result of forming a high molecular polymer based on coordination reaction of tannin-iron ions, and the method utilizes a surfactant and an alkaline substance to realize the control of coordination reaction speed and the control of the appearance of a polymerization reaction product, and finally realizes the synthesis of nano tannin particles with uniform appearance. In the limited range of the national standard 2760-.
As a preferable embodiment of the method for preparing nano tannin of the present invention, the metal salt is at least one of ferrous sulfate, ferrous gluconate, ferrous lactate, ferrous glycinate, ferric ammonium citrate, ferric orthophosphate, and ferric saccharate.
As mentioned above, the tannin-iron ion coordination reaction of the invention is the key of the synthesis of nano tannin. The inventors have found that the dissociation constant (pKa value) of iron ions is an essential prerequisite for the tannin-iron coordination reaction. The dissociation constant is too low, the tannin-iron coordination reaction is too violent, and the appearance of the nanoparticles generated by coordination is difficult to control; the dissociation constant is too high, iron ions are not easy to separate from the original ligand, and the tannin-iron coordination reaction is not easy to occur. Within the limit range of national standard 2760-. The pKa value of the substrate is between 1.5 and 3.5, and the substrate is suitable for synthesizing nano tannin particles with uniform appearance.
As a preferable embodiment of the method for preparing nano tannin of the present invention, the alkaline substance is at least one of sodium hydroxide and potassium hydroxide. Preferably, the reaction system has a pH of 3.0 to 8.0.
The coordination reaction process of tannin-iron ions is divided into two steps: (1) dissociation of tannin phenolic hydroxyl and original ligand of iron ions; (2) coordination of tannin ions and iron ions. In this reaction, dissociation of the phenolic hydroxyl group from the original ligand is a prerequisite for the reaction, and whether or not the dissociation is carried out, the degree of dissociation, is influenced by the pH of the environment. The inventor finds out through a large number of experiments that the normal proceeding of the reaction is facilitated by controlling the pH of the system within the range of 3.0-8.0, the dissociation degree is more thorough when the pH value is higher, but the coordination reaction speed is too fast and the appearance is uncontrollable when the pH value is too high (> 8.0). In the invention, within the limited range of national standard 2760--Meanwhile, the nano-tannin complex is free of any organic ligand, so that the problem that the nano-tannin is uneven in appearance caused by the fact that other organic ligands in the alkaline substance are introduced into tannin-iron coordination reaction can be solved.
As a preferable embodiment of the preparation method of the nano tannin, the mixing and stirring time is 12-24 h.
In a second aspect, the invention further provides the nano-tannin prepared by the preparation method, wherein the nano-tannin is a coordination compound of tannin-metal ions.
As a preferable embodiment of the nano tannin, the particle size of the nano tannin is 20-50 nm.
The essence of the nano tannin in the technical scheme of the invention is a coordination compound, and the particle size of the nano tannin is about 20-50 nm. The invention modifies the free vegetable tannin to obtain the nano-scale tannin, the nano-scale tannin has larger specific surface area, and the probability of the nano-scale tannin contacting and combining with microorganisms is obviously improved.
In a third aspect, the invention also provides application of the nano tannin in inhibiting yeast fermentation.
As a preferred embodiment of the application of the nano tannin in inhibiting the yeast fermentation, the application is the application of the nano tannin in inhibiting the yeast fermentation in the process of the asty nitrogen deficiency fermentation.
The invention is based on the toxic effect of the plant tannin on the yeast, and the nano tannin prepared by taking the plant tannin as the raw material is applied to the process of nitrogen deficiency fermentation of the Asttis, thereby playing the role of inhibiting the propagation of the yeast.
Compared with the prior art, the invention has the beneficial effects that:
according to the technical scheme, the coordination chemical reaction is carried out between the tannin and the metal ions by adopting a soft template method to form the coordination compound, and the nano tannin is prepared by adopting the preparation method disclosed by the invention, so that the specific surface area of the tannin is increased, the probability of the tannin contacting and combining with microorganisms is increased, and the inhibition capacity of the tannin on yeast can be increased.
Drawings
FIG. 1 is a scanning electron micrograph of a nano-tannin prepared in example 1;
FIG. 2 is an infrared spectrum of nano-tannin prepared in example 1;
FIG. 3 is a fluorescence spectrum of nano-tannin prepared in example 1;
FIG. 4 is a scanning electron micrograph of a product prepared in comparative example 1;
FIG. 5 is a scanning electron micrograph of a product prepared in comparative example 2;
fig. 6 is a scanning electron microscope photograph of the product prepared in comparative example 5.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to the following specific examples.
The preparation method of the nano tannin in the embodiment and the comparative example of the invention comprises the following steps: mixing the raw materials in proportion and stirring for 24h to obtain the nano tannin.
The raw material composition (in parts by weight) and the particle size of the nano-tannins in examples 1 to 25 and comparative examples 1 to 2 are shown in table 1 below.
TABLE 1 raw material composition and nano tannin particle size test results of examples 1-25 and comparative examples 1-2
As can be seen from Table 1, the nano-tannins prepared in examples 1 to 25 have a particle size in the range of 20 to 50 nm.
Wherein, scanning electron micrographs (A) of the nano-tannins prepared in example 1, infrared spectra (B) and fluorescence spectra (C) are shown in FIGS. 1 to 3. As can be seen from FIG. 1, the mean particle size of the nano-tannins is 35 nm. As can be seen from fig. 2, when nano-tannins, tannins and metal ions are detected by infrared spectroscopy, it can be seen that after tannins and metal ions form nano-tannins, absorption peaks of amide a, amide B, amide I, amide II and amide III bands of the tannins are significantly changed, which indicates that nano-tannins are polymerized based on coordination reaction between ortho-phenolic hydroxyl groups of tannins and metal ions. As can be seen from FIG. 3, significant fluorescence absorption peaks are observed at 280nm between tannin and metal ions, but after the tannin and the metal ions react, the fluorescence peaks are significantly quenched, the fluorescence absorption peaks are significantly reduced, the fluorescence of the tannin is from phenolic hydroxyl groups on a benzene ring, and the fluorescence quenching phenomenon after the tannin and the metal ions react further proves that the polymerization of the nano tannin is generated based on the coordination reaction between the tannin and the metal ions.
In comparison with example 1, comparative example 1 does not add a surfactant (soybean lecithin), and comparative example 1 has excessive polymerization. As can be seen from fig. 4, the product prepared in comparative example 1 is in the form of flakes, not nanoparticles.
As compared with example 1, the amount of the surfactant (soybean phospholipid) added in comparative example 2 was too low, and as can be seen from fig. 5, the product prepared in comparative example 2 was micron-sized particles and had a non-uniform morphology.
In comparative example 3, the amount of the surfactant (soybean phospholipid) added was too high compared to example 1, and the product obtained in comparative example 3 had no nanoparticles observed under a scanning electron microscope.
Compared with example 1, in comparative example 4, no alkaline substance is added, and the product obtained in comparative example 4 has no nano-particles observed under a scanning electron microscope, which indicates that no coordination reaction occurs in the reaction system of comparative example 4.
The amount of the basic substance added in comparative example 5 was higher than that in example 1, and it can be seen from fig. 6 that the product obtained in comparative example 2 was in the form of a sheet and was non-nano-particles.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The preparation method of the nano tannin is characterized by comprising the following steps: according to the weight portion, 1 to 20 portions of tannin, 0.2 to 6.5 portions of surfactant, 0.01 to 0.2 portion of metal salt, 0.001 to 0.02 portion of alkaline substance and 500 portions of water are mixed and stirred evenly to obtain the nano tannin.
2. The method of claim 1, wherein the tannin is at least one of grape seed tannin, apple tannin, hops tannin, valonia tannin, persimmon tannin, longan tannin, myricetin, and gallotannin.
3. The method according to claim 1, wherein the surfactant is at least one of soybean lecithin, sesbania gum, sodium caseinate, sodium alginate, acetylated diglycerol fatty acid ester, lactic acid fatty acid glyceride, citric acid fatty acid glyceride, succinic acid monoglyceride, and sucrose fatty acid ester.
4. The method according to claim 1, wherein the metal salt is at least one of ferrous sulfate, ferrous gluconate, ferrous lactate, ferrous glycinate, ferric ammonium citrate, ferric orthophosphate, and ferric saccharate.
5. The method according to claim 1, wherein the basic substance is at least one of sodium hydroxide and potassium hydroxide, and the reaction system has a pH of 3.0 to 8.0.
6. The nano-tannin prepared by the preparation method of any one of claims 1 to 5, wherein the nano-tannin is a coordination compound of tannin-metal ions.
7. The nano-tannin of claim 6, wherein the metal ions in the coordination compound are at least one of iron ions and ferrous ions.
8. The nano-tannin of claim 6, wherein the nano-tannin has a particle size of 20 to 50 nm.
9. Use of nano-tannins according to any one of claims 6 to 8 for inhibiting yeast fermentation.
10. Use of a nano-tannin according to any one of claims 6 to 8 for inhibiting yeast fermentation during nitrogen deficiency fermentation in astoidy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210086869.7A CN114409916B (en) | 2022-01-25 | 2022-01-25 | Nano tannin and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210086869.7A CN114409916B (en) | 2022-01-25 | 2022-01-25 | Nano tannin and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114409916A true CN114409916A (en) | 2022-04-29 |
| CN114409916B CN114409916B (en) | 2023-03-14 |
Family
ID=81277705
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210086869.7A Active CN114409916B (en) | 2022-01-25 | 2022-01-25 | Nano tannin and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114409916B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109287868A (en) * | 2018-11-28 | 2019-02-01 | 中国科学院东北地理与农业生态研究所 | A kind of preparation method of feed addictive tannin chelate iron |
| CN109545965A (en) * | 2018-11-15 | 2019-03-29 | 苏州大学 | Electric storage material based on tannic acid and iron (III) coordination compound, preparation method thereof and electric storage device |
| CN112266484A (en) * | 2020-09-17 | 2021-01-26 | 南开大学 | Preparation method and application of iron-based metal organic framework composite material capable of continuously giving electrons |
-
2022
- 2022-01-25 CN CN202210086869.7A patent/CN114409916B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109545965A (en) * | 2018-11-15 | 2019-03-29 | 苏州大学 | Electric storage material based on tannic acid and iron (III) coordination compound, preparation method thereof and electric storage device |
| CN109287868A (en) * | 2018-11-28 | 2019-02-01 | 中国科学院东北地理与农业生态研究所 | A kind of preparation method of feed addictive tannin chelate iron |
| CN112266484A (en) * | 2020-09-17 | 2021-01-26 | 南开大学 | Preparation method and application of iron-based metal organic framework composite material capable of continuously giving electrons |
Non-Patent Citations (1)
| Title |
|---|
| NURETTIN SAHINER ET AL.: "《A facile preparation of donut-like supramolecular tannic acid- Fe(III) composite as biomaterials with magnetic, conductive, and antioxidant properties》", 《JOURNAL OF COORDINATION CHEMISTRY》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114409916B (en) | 2023-03-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sharma et al. | Biotransformation of fermented black tea into bacterial nanocellulose via symbiotic interplay of microorganisms | |
| Castro-Mayorga et al. | Stabilization of antimicrobial silver nanoparticles by a polyhydroxyalkanoate obtained from mixed bacterial culture | |
| Qi et al. | A multielement compound fertilizer used polydopamine and sodium carboxymethyl starch matrices as coatings | |
| Yang et al. | Amphiphilic chitosan/carboxymethyl gellan gum composite films enriched with mustard essential oil for mango preservation | |
| Rahale et al. | Humic acid involved chelation of ZnO nanoparticles for enhancing mineral nutrition in plants | |
| CN101050136A (en) | Fertilizer of chelated zinc, and preparation method | |
| CN114409916B (en) | Nano tannin and preparation method and application thereof | |
| CN108013154B (en) | Compound marinating agent for soft bean curd | |
| KR101182364B1 (en) | Method for Preparing of Jeungpyun with Enriched Mineral | |
| CN111876364B (en) | Bacillus subtilis and method for regulating and controlling molecular weight of fermentation product gamma-polyglutamic acid | |
| KR20100042824A (en) | Method for producing high concentrated-amino acid liquid fertilizer using animal blood and product by the same | |
| JP4901372B2 (en) | Deferifericlysin high production mutant, liquid medium for siderophore production, and method for producing siderophore | |
| US4810504A (en) | Method of producing a mushroom aroma in mushroom cell masses | |
| CN114557341B (en) | Modified grafted bentonite nanoparticle loaded with gamma-polyglutamic acid and application thereof | |
| DE60009563T2 (en) | MIXING FOR ACCELERATING THE COMPOSTING | |
| Yaseen et al. | The use of phosphorus nanoparticles synthesized by rhizospheric fungus Aspergillius fumigatus as a nanofertilizer for flax plant. | |
| CN114075580B (en) | Method for improving erythritol product concentration and production conversion rate | |
| CN114958708A (en) | Method for promoting growth of microorganisms and application thereof | |
| JP2003199522A (en) | Edible seasoning | |
| JPH067785B2 (en) | Lactic acid fermented juice food | |
| CN112470837A (en) | Method for increasing vitamin C content of black-bone dish and reducing nitrite and lignin content | |
| JP2001299280A (en) | Calcium supplement including polysaccharide having carboxyl group and calcium-enriched agent | |
| Boistean et al. | Prospects for the use of agricultural waste as a substrate for acetic fermentation | |
| KR102109495B1 (en) | Cultivation of sprouts with increased sulfur using hydrogel and use thereof as food material | |
| EP4206168A1 (en) | Nano bio-carrier with plant additives coated on chemical fertilizers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |