CN115340682B - High-bioactivity lignin and preparation method thereof - Google Patents
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Abstract
The invention provides a method for preparing aminated modified lignin with high biological activity by taking nano Lignin (LNP) as a raw material. 10 to 50 parts of nano lignin, 10 to 50 parts of amino compound, 10 to 50 parts of aldehyde compound and titanium dioxide (TiO 2 ) 0.1-2 parts. The method comprises mixing lignin and amino compound at a certain ratio, magnetically stirring at normal temperature, and mixing aldehyde compound with TiO 2 Uniformly mixing water dispersion in a dropwise adding mode, and carrying out Mannich reaction under the conditions of 60-100 ℃ and inert gas protection; the method has simple process, short preparation period and high yield. Compared with commercial antioxidants, the aminated modified high-activity lignin prepared by using lignin has obviously improved free radical scavenging performance, excellent synergistic ultraviolet shielding performance and antibacterial activity, and can be applied to the fields of cosmetics, personal care products, biopharmaceuticals, polymer composites and the like.
Description
Technical Field
The invention belongs to the field of environment-friendly natural polymer materials, and relates to lignin with high antioxidation, broad-spectrum antibiosis and ultraviolet resistance and a preparation method thereof.
Background
With the improvement of life quality, antioxidants play an increasingly important role in human dietary life. The addition of antioxidant functional substances such as dibutyl hydroxy toluene (BHT) and tert-butyl p-hydroxy anisole (BHA) can delay aging speed of human body and promote health. Medical research shows that the primary generation of human chronic diseases is caused by the robbery of cell electrons, and free radicals easily rob cell electrons after entering human bodies, so that the resistance of cells is reduced, and the human bodies are easily infected by bacteria and even form cancerogenic substances. Therefore, the oxidation resistance and free radical removal are all research hot spots at home and abroad.
With the increasing health awareness, the use of some natural antioxidants is gradually replacing commercial antioxidants, which is of great importance for reducing costs and for efficient use of antioxidants. Lignin is a natural polyphenol with a three-dimensional network structure, and the properties of lignin are quite diversified: such as antioxidation, antibiosis, innocuity, ultraviolet resistance and the like. However, most lignin is currently disposed of as industrial waste or fuel; and when lignin is used as a natural antioxidant, the lignin has low antioxidant and antibacterial activities and insufficient ultraviolet shielding efficiency. Therefore, improving the comprehensive biological activity of lignin has great significance for expanding the application of lignin and promoting the sustainable utilization of resources. Literature Ind.crops prod.2019,128,177-185, ACS Sustainable chem.eng.2018,6 (2), 2591-2595 and Ind.crops prod.2017,95,512-520 respectively depolymerize by hydrothermal method, mold and modify ionic liquid to improve the oxidation resistance of lignin, but the ultraviolet shielding performance and antibacterial activity are not substantially improved; the literature Green chem 2020,22,6357-6371 reports grafting arginine, histidine and lysine to the lignin surface, improving the antibacterial activity of lignin, the modified lignin product, while having a selective antibacterial effect on gram positive and negative bacteria, does not have a broad spectrum antibacterial function, and the antioxidant and ultraviolet shielding capabilities of lignin are not substantially improved.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a novel method for preparing lignin with excellent antioxidant, antibacterial and anti-ultraviolet functions by using a lignin two-step method. The invention can increase the specific surface area of lignin and increase antioxidant active groups. The prepared antioxidant nano lignin has excellent antioxidant, synergistic broad-spectrum antibacterial, ultraviolet shielding and other functions. The method has the advantages of simple synthesis process, readily available raw materials and environmental protection.
In order to achieve the above purpose, the present invention is realized by the following technical scheme:
the first object of the invention is a modified lignin and a preparation method thereof, which is characterized in that the modified lignin is prepared from the following raw materials:
in one embodiment of the invention, the components in the modification process are mixed according to parts by weight and comprise 50-100 parts of nano lignin, 10-50 parts of amino compound, 10-50 parts of aldehyde compound and TiO 2 0.1-2 parts.
In one embodiment of the invention, the modified lignin and the preparation method thereof uniformly mix 0.1-5 w/v% nano lignin dispersion liquid and amino compound according to a certain proportion, and then add aldehyde compound and TiO 2 And (3) uniformly mixing the dispersion liquid, reacting under the protection of inert gas, and dialyzing after the reaction is finished to obtain the modified lignin.
In one embodiment of the invention, the nano lignin is one or more of alkali lignin, organic solvent lignin, lignosulfonate and sulfate lignin.
In one embodiment of the present invention, the aldehyde is one of formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, furfural, dialdehyde, and unsaturated aldehyde.
In one embodiment of the present invention, the linear or branched alkylamine has a carbon number of 1 to 8.
In one embodiment of the present invention, the amine is one of a linear or branched alkyl amine, a cyclic amine, a polyamine, a hydroxyalkyl amine, and an amino acid.
In one embodiment of the invention, the aldehyde compound and the TiO are slowly added dropwise at 60-100 DEG C 2 And (3) a dispersion.
In one embodiment of the invention, the nano lignin dispersion and TiO 2 The solvent of the dispersion is water. In one embodiment of the invention, the TiO 2 The dosage is 0.1 to 2 parts
In one embodiment of the present invention, the dialysis time is 1 to 12 hours.
In one embodiment of the invention, nanolignin and an amine-based compound are added to a bottle, N 2 As protective gas, slowly dripping aldehyde compound and TiO at 60-100 DEG C 2 The Mannich reaction is carried out in a compounding way, and the reaction is finished for 1 to 12 hoursAnd then dialyzing to obtain the aminated modified lignin. The obtained product has excellent antioxidant, antibacterial and ultraviolet shielding functions
In one embodiment of the invention, the mannich reaction is carried out under heating, preferably in the absence of water at 50 to 100 ℃.
In one embodiment of the present invention, the amount of aldehyde and amine substances required is 1:0.4 to 2.5 in terms of CHO to NH molar ratio.
In one embodiment of the present invention, the aldehyde may be, but is not limited to, formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, furfural, dialdehydes (e.g., glutaraldehyde, glyoxal, etc.), unsaturated aldehydes (e.g., acrolein, crotonaldehyde, etc.), and the like.
In one embodiment of the present invention, the amine is one of a linear or branched alkyl amine, a cyclic amine, a polyamine (e.g., ethylenediamine, hexamethylenediamine, diethylenetriamine, triethyltetramine, tetraethylpentamine, etc.), a hydroxyalkyl amine (e.g., hydroxyethylamine, diethylenetriamine, triethyleneamine, aminoethylethanolamine, etc.), an amino acid (e.g., lysine, creatine, glycine, iminodiacetic acid, tyrosine, aspartic acid, etc.).
In one embodiment of the present invention, the solvent may be at least one of water, acetone, dimethylformamide (DMF), dimethylacetamide (DMAC), tetrahydrofuran (THF), dioxane.
The invention further provides a modified lignin by using the method.
A second object of the present invention is to provide the use of the modified lignin described above in the fields of cosmetics, personal care products, biopharmaceuticals, paints, polymer composites.
Compared with the prior art, the invention has the following advantages:
1. the lignin raw material has wide sources, is renewable, has environmental friendliness and biodegradability and is low in cost. Meanwhile, the nano lignin has high surface activity, and compared with a commercial antioxidant, the aminated modified nano lignin has better environmental friendliness; and has excellent oxidation resistance, the capability of scavenging diphenyl picrylphenylhydrazine (DPPH) free radical after 6 hours reaches 98.0 percent, and the effect is better than that of commercial antioxidant dibutyl hydroxy toluene (BHT).
2. The aminated lignin disclosed by the invention is safe and nontoxic, has excellent antibacterial performance, wherein the antibacterial efficiency of gram-positive bacteria and gram-negative bacteria exceeds 50%, and exceeds the antibacterial efficiency of lignin per se (< 20%).
3. Compared with lignin, the T-LNP has more excellent ultraviolet shielding function, and the ultraviolet shielding performance is improved by more than 35%.
4. The modified T-LNP can be used in the fields of cosmetics, personal care products, biopharmaceuticals, polymer composites and the like.
Detailed Description
Although the present invention has been described in detail, the present invention is not limited thereto, and those skilled in the art can make modifications according to the principles of the present invention, and thus, all modifications made according to the principles of the present invention should be construed as falling within the scope of the present invention.
Antioxidant Activity test: preparing a sample to be tested into 0.01g/mL of aqueous solution, mixing 2.0mL of 0.01g/mL of solution with 2.0mL of 50mg/L DPPH solution, detecting and fitting the peak area at 517nm through an ultraviolet spectrophotometer after the free radical capturing reaction for 1, 3 and 6 hours, and calculating to obtain the strength of free radical removal, wherein the peak area of a blank sample at 517nm is 22.5.
Antibacterial activity test: preparing lignin sample into 1.0g/L concentration, mixing 10 μL with 180 μL bacterial suspension, coating the mixture on agar plate of culture medium, irradiating with ultraviolet light at 37deg.C for 3 hr, culturing in culture medium for 24 hr, observing and counting bacterial colony number, and respectively obtaining 1.5X10 g gram positive bacteria (Staphylococcus aureus) and gram negative bacteria (Escherichia coli) bacteria without lignin blank 7 CFU/mL and 1.3X10 7 CFU/mL。
Ultraviolet shielding performance test: and (3) fully mixing the obtained lignin sample with PVA (polyvinyl alcohol) to obtain an aqueous solution, pouring the aqueous solution into a film, wherein the lignin content is 1.0%, the film thickness is 200 microns, and testing the transparency (500 nm) and the ultraviolet shielding performance (320 nm) of the PVA composite material film by an ultraviolet spectrophotometer, wherein the light transmittance of the pure PVA film at 500nm and 320nm is 92% and 85%, respectively.
With respect to TiO 2 Dispersion liquid: 1.0g of TiO is taken 2 Dispersing into 100mL of water to prepare 0.01g/mL TiO 2 The dispersion was taken in 1.0mL portions.
Regarding the ZnO dispersion: 1.0g of ZnO was dispersed in 100mL of water to prepare a ZnO dispersion of 0.01g/mL, and 1.0mL of the ZnO dispersion was used as a single portion.
Example 1:
adding nano lignin (100 parts by mass, 0.01g as one part) and ethylenediamine (10 parts) into a reaction flask, N 2 As a protective gas, formaldehyde (10 parts) and TiO were slowly added dropwise at 60 DEG C 2 The dispersion (0.1 part) is subjected to Mannich reaction, and dialysis is carried out after the reaction is finished for 10 hours, so that aminated modified lignin can be obtained, the product is simply referred to as T-LNP1, the antioxidant activity is shown in Table 1, the antibacterial activity is shown in Table 2, and the ultraviolet shielding performance is shown in Table 3.
Example 2:
nano lignin (100 parts) and ethylenediamine (50 parts) were added to a reaction flask, N 2 As a protective gas, formaldehyde (50 parts) and TiO were slowly added dropwise at 100 DEG C 2 The dispersion (0.5 part) was subjected to Mannich reaction, and after 1 hour of reaction, dialysis was performed to obtain aminated modified lignin, the product was abbreviated as T-LNP2, the antioxidant activity was shown in Table 1, the antibacterial activity was shown in Table 2, and the ultraviolet shielding performance was shown in Table 3.
Example 3:
nano lignin (100 parts) and dihydroxyethylamine (50 parts) were added to a reaction flask, N 2 Glutaraldehyde (50 parts) and TiO were slowly added dropwise as a shielding gas at 100deg.C 2 The dispersion (2 parts) is subjected to Mannich reaction, and dialysis is carried out after 1 hour of reaction is finished, so that aminated modified lignin is obtained, the product is called T-LNP3 for short, the antioxidant activity is shown in table 1, the antibacterial activity is shown in table 2, and the ultraviolet is generatedThe line shielding properties are shown in table 3.
Example 4:
nano lignin (100 parts) and lysine (10 parts) were added to a reaction flask, N 2 As a protective gas, formaldehyde (10 parts) and TiO were slowly added dropwise at 60 DEG C 2 The dispersion (0.5 part) is subjected to Mannich reaction, and dialysis is carried out after the reaction is finished for 12 hours, so that aminated modified lignin is obtained, the product is called T-LNP4 for short, the antioxidant activity is shown in table 1, the antibacterial activity is shown in table 2, and the ultraviolet shielding performance is shown in table 3.
Example 5:
nano lignin (80 parts) and hexamethylenediamine (20 parts) were added to a reaction flask, N 2 Furfural (20 parts) and TiO are slowly added dropwise as protective gas at 70 DEG C 2 And (3) performing Mannich reaction on the dispersion liquid (1 part), and dialyzing after the 8-hour reaction is finished to obtain aminated modified lignin, wherein the product is called T-LNP5 for short, the antioxidant activity is shown in a table 1, the antibacterial activity is shown in a table 2, and the ultraviolet shielding performance is shown in a table 3.
Example 6:
nano lignin (50 parts) and aspartic acid (50 parts) were added to a reaction flask, N 2 As a shielding gas, acrolein (50 parts) and TiO were slowly added dropwise at 100 ℃ 2 And (3) performing Mannich reaction on the dispersion liquid (2 parts), and dialyzing after the reaction is finished for 6 hours to obtain aminated modified lignin, wherein the product is called as T-LNP6 for short, the antioxidant activity is shown in a table 1, the antibacterial activity is shown in a table 2, and the ultraviolet shielding performance is shown in a table 3.
Example 7:
nano lignin (100 parts) and aspartic acid (25 parts) were added to a reaction flask, N 2 As a shielding gas, acrolein (25 parts) and TiO were slowly added dropwise at 65 ℃ 2 And (3) performing Mannich reaction on the dispersion liquid (1 part), and dialyzing after the reaction is finished for 12 hours to obtain aminated modified lignin, wherein the product is called as T-LNP7 for short, the antioxidant activity is shown in a table 1, the antibacterial activity is shown in a table 2, and the ultraviolet shielding performance is shown in a table 3.
Example 8:
nano lignin (100 parts) and tyrosol acid (25 parts) were added to a reaction flask, N 2 As a shielding gas, at 100℃slowFormaldehyde (25 parts) and TiO were added dropwise 2 The dispersion (1.5 parts) is subjected to Mannich reaction, and dialysis is carried out after 2 hours of reaction is finished, so that aminated modified lignin is obtained, the product is called T-LNP8 for short, the antioxidant activity is shown in table 1, the antibacterial activity is shown in table 2, and the ultraviolet shielding performance is shown in table 3.
Comparative example 1:
100 parts of common lignin is taken, acidolysis nanocrystallization and amination modification treatment are not carried out, and the lignin is only micron lignin obtained by grinding raw materials and passing through a 120-mesh screen, wherein the antioxidant activity is shown in table 1, the antibacterial activity is shown in table 2, and the ultraviolet shielding performance is shown in table 3.
Comparative example 2:
adding nano lignin (100 parts by mass of 0.01g as one part) into a reaction bottle, slowly dripping TiO at 60 DEG C 2 The dispersion (0.1 part) was dialyzed after completion to prepare comparative sample 2, whose antioxidant activity is shown in Table 1, antibacterial activity is shown in Table 2, and ultraviolet shielding property is shown in Table 3.
Comparative example 3:
referring to comparative example 2, tiO 2 The dispersion was replaced with an equivalent amount of ZnO dispersion, and the other was unchanged, to prepare comparative sample 3, whose antioxidant activity is shown in table 1, bacteriostatic activity is shown in table 2, and uv-shielding property is shown in table 3.
Comparative example 4:
100 parts of commercial antioxidant BHT (dibutyl hydroxy toluene) purchased from Michelin corporation was taken as comparative sample 4, the antioxidant activity is shown in Table 1, the antibacterial activity is shown in Table 2, and the ultraviolet shielding performance is shown in Table 3.
Comparative example 5:
100 parts of common lignin is taken, aminated modified lignin is prepared by referring to the conditions of example 1, so that aminated modified lignin is obtained, and comparative sample 5 is prepared, wherein the antioxidant activity is shown in Table 1, the antibacterial activity is shown in Table 2, and the ultraviolet shielding performance is shown in Table 3.
Comparative example 6:
referring to example 1, tiO 2 The dispersion liquid is replaced by equivalent ZnO dispersion liquid, the rest conditions are unchanged, a comparative sample 6 is prepared, the antioxidant activity of the prepared aminated modified lignin is shown in table 1, the antibacterial activity is shown in table 2, and the purple is shown in the table 2The external shielding properties are shown in Table 3.
Comparative example 7:
with reference to example 1, no TiO was added 2 An aminated modified lignin comparative sample 7 was prepared, the antioxidant activity of which is shown in Table 1, the antibacterial activity of which is shown in Table 2, and the ultraviolet shielding performance of which is shown in Table 3.
Table 1 shows the antioxidant Activity of samples
Description: antioxidant efficiency Q 1 = (22.5-x)/22.5, x represents the fitting area at 517nm of the uv spectrophotometer at different times;
according to the test results: examples 1 to 8 have significantly improved oxidation resistance over comparative examples 1 and 2 for different time periods; compared with comparative example 3, examples 1 to 8 have higher antioxidant capacity than commercial antioxidant BHT even after 3 hours of radical trapping reaction, because the phenolic hydroxyl content of lignin can be increased by Mannich reaction, and the generated amino groups enable lignin to form more stable phenoxy radicals, hydrogen protons are easier to separate to react with DPPH radicals, and the antioxidant activity is improved; nano lignin has higher activity than micro lignin because the specific surface area of small-sized lignin is increased and more phenolic hydroxyl groups are exposed. In contrast, in comparative example 4, lignin is not treated, so that the specific surface area is small, the amination reaction degree is low, and the antioxidant activity cannot reach the effect of the commercial antioxidant BHT.
Table 2 comparison table of antibacterial effect of each sample
Description: antibacterial efficiency Q 2 = (a-y)/a or= (b-y)/b, where a=1.5×10 7 CFU/mL;b=1.3×10 7 CFU/mL, y represents the bacterial numbers of the different samples;
according to the test results: compared with comparative examples 1, 2, 3 and 4, the antibacterial efficiency of the examples 1 to 8 is obviously improved by more than 30 percent; compared with comparative example 1, the antibacterial efficiency of the nano lignin in comparative example 2 is slightly improved, the antibacterial efficiency of staphylococcus aureus is 20.0%, the antibacterial efficiency of escherichia coli bacteria is 13.8%, the mechanisms of lignin antibacterial and antioxidation are similar, namely, the antioxidation performance is improved, the general antibacterial activity is also improved to a certain extent, the nano lignin with small particle size can inhibit the bacterial growth more effectively, the BHT (example 3) also has a certain antibacterial performance, the antibacterial efficiency of staphylococcus aureus is 24.0%, and the antibacterial efficiency of escherichia coli bacteria is 16.9%. Compared with comparative example 1, the antibacterial efficiency of the aminated modified lignin of comparative example 4 is obviously improved, but the antibacterial efficiency is still at a lower level, because the lignin used in comparative example 4 is large in size and small in specific surface area, so that more amino groups cannot be grafted on the lignin in the amination reaction.
Meanwhile, in various embodiments, as TiO 2 The content is increased, and the antibacterial effect of each group of samples is obviously improved after ultraviolet irradiation, and the principle is that titanium dioxide is decomposed under the photocatalytic effect to achieve the antibacterial effect, and aminated lignin and titanium dioxide show synergistic antibacterial effect, for example, in the embodiment 6, the antibacterial efficiency of staphylococcus aureus of the prepared modified lignin reaches 93.3%, the antibacterial efficiency of escherichia coli bacteria reaches 93.1%, and the antibacterial efficiency of all other samples is exceeded. Experimental results show that by combining with TiO 2 The product obtained by the Mannich reaction after the compounding shows the ultraviolet light catalysis synergistic broad-spectrum antibacterial effect.
TABLE 3 ultraviolet and visible light transmittance of PVA composite films of the Components
Sample preparation | Light transmittance at 320nm (%) | 500nm transmittance (%) |
Example 1 | 6.5 | 70.4 |
Example 2 | 3.6 | 70.8 |
Example 3 | 1.5 | 73.5 |
Example 4 | 4.6 | 65.6 |
Example 5 | 2.5 | 69.2 |
Example 6 | 1.0 | 71.5 |
Example 7 | 3.4 | 68.2 |
Example 8 | 2.4 | 72.1 |
Comparative example 1 | 30.2 | 82.4 |
Comparative example 2 | 10.4 | 83.1 |
Comparative example 3 | 78.3 | 84.6 |
Comparative example 4 | 80.4 | 92.0 |
Comparative example 5 | 20.6 | 60.4 |
Comparative example 6 | 77.4 | 88.3 |
Comparative example 7 | 15.8 | 66.6 |
According to the test results: examples 1 to 8 have significantly improved uv shielding properties compared to comparative examples 1, 2, 3, 4, but at the same time have sacrificed some transparency; meanwhile, in each of examples and comparative example 5, as TiO 2 The content is increased, the light transparency is improved, and the ultraviolet shielding performance is further improved. The ultraviolet shielding ability of the nano lignin of comparative example 2 is higher than that of comparative example 1 because the nano lignin of small particle size can be uniformly distributed in PVA, and the ultraviolet shielding performance is improved; meanwhile, BHT is colorless and transparent after being dissolved in water, so that the ultraviolet resistance of the PVA film is not improved; comparative example 4 the ultraviolet transmittance of the aminated modified lignin was reduced to 20.6%, but after the amination reactionThe visible light transmittance is reduced to 60.4 percent; by combining with TiO 2 The ultraviolet shielding capability of the product obtained by Mannich amination modification after compounding is further improved, in the embodiment 6, the ultraviolet shielding performance at 320nm reaches 99.0%, the light transparency at 500nm is kept at a level of 72.1%, and the product has higher optical transparency and excellent ultraviolet shielding function, and compared with the embodiment, the ultraviolet shielding performance is improved by more than 35%.
In conclusion, the lignin with high oxidation resistance, antibacterial property and ultraviolet resistance prepared by the method can be used in the fields of cosmetics, personal care products, biological pharmacy, polymer matrix composite materials and the like.
Claims (5)
1. A method for preparing modified lignin is characterized by comprising an amino compound, an aldehyde compound and TiO 2 Modifying nano lignin;
the components in the modification process are mixed according to parts by weight and comprise 50 parts of nano lignin, 50 parts of amino compounds, 50 parts of aldehyde compounds and 2 parts of TiO 2 A dispersion;
the method comprises the steps of uniformly mixing 0.1-5 w/v% nano lignin dispersion liquid and an amino compound, and then adding aldehyde compound and TiO 2 Uniformly mixing the dispersion liquid, reacting under the protection of inert gas, and dialyzing after the reaction is finished to obtain modified lignin;
the concentration of the TiO2 dispersion liquid is 0.01g/mL;
the amino compound is aspartic acid;
the aldehyde compound is acrolein.
2. The method of claim 1, wherein the nanolignin is one or more of alkali lignin, organosolv lignin, lignosulfonate, kraft lignin.
3. The method according to claim 1, wherein the aldehyde compound and TiO are slowly added dropwise at 60-100 DEG C 2 And (3) a dispersion.
4. A modified lignin produced by the method of any one of claims 1-3.
5. Use of a modified lignin according to claim 4 in the fields of cosmetics, personal care products, biopharmaceuticals, paints, polymer composites.
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Title |
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《Enhancing the Radical Scavenging Activity and UV Resistance of Lignin Nanoparticles via Surface Mannich Amination toward a Biobased Antioxidant》;Yang Weijun;《Biomacromolecules》;20210602;第22卷;第2693-2699页 * |
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