CN116102666A - 2-quaternary ammonium salt modified ethyl cellulose derivative and preparation method and application thereof - Google Patents
2-quaternary ammonium salt modified ethyl cellulose derivative and preparation method and application thereof Download PDFInfo
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- CN116102666A CN116102666A CN202310124017.7A CN202310124017A CN116102666A CN 116102666 A CN116102666 A CN 116102666A CN 202310124017 A CN202310124017 A CN 202310124017A CN 116102666 A CN116102666 A CN 116102666A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- -1 nitrogen-containing compound Chemical class 0.000 claims abstract description 11
- 241000588724 Escherichia coli Species 0.000 claims abstract description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 17
- 230000000844 anti-bacterial effect Effects 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 229940126214 compound 3 Drugs 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- LSTRKXWIZZZYAS-UHFFFAOYSA-N 2-bromoacetyl bromide Chemical compound BrCC(Br)=O LSTRKXWIZZZYAS-UHFFFAOYSA-N 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 229940125904 compound 1 Drugs 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 150000007530 organic bases Chemical class 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 2
- 230000000845 anti-microbial effect Effects 0.000 claims 2
- 239000001856 Ethyl cellulose Substances 0.000 abstract description 19
- 229920001249 ethyl cellulose Polymers 0.000 abstract description 19
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 abstract description 15
- 235000019325 ethyl cellulose Nutrition 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 5
- 229920002678 cellulose Polymers 0.000 abstract description 4
- 239000001913 cellulose Substances 0.000 abstract description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 abstract description 4
- 150000001262 acyl bromides Chemical class 0.000 abstract description 3
- KDPAWGWELVVRCH-UHFFFAOYSA-N bromoacetic acid Chemical group OC(=O)CBr KDPAWGWELVVRCH-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- 230000007515 enzymatic degradation Effects 0.000 abstract description 2
- 230000005764 inhibitory process Effects 0.000 abstract description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 239000000523 sample Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000012512 characterization method Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 108090000790 Enzymes Proteins 0.000 description 7
- 102000004190 Enzymes Human genes 0.000 description 7
- 229940088598 enzyme Drugs 0.000 description 7
- 239000006228 supernatant Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- DQXKOHDUMJLXKH-PHEQNACWSA-N (e)-n-[2-[2-[[(e)-oct-2-enoyl]amino]ethyldisulfanyl]ethyl]oct-2-enamide Chemical compound CCCCC\C=C\C(=O)NCCSSCCNC(=O)\C=C\CCCCC DQXKOHDUMJLXKH-PHEQNACWSA-N 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 230000003385 bacteriostatic effect Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 2
- 108010089807 chitosanase Proteins 0.000 description 2
- 239000012045 crude solution Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- CBMPTFJVXNIWHP-UHFFFAOYSA-L disodium;hydrogen phosphate;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound [Na+].[Na+].OP([O-])([O-])=O.OC(=O)CC(O)(C(O)=O)CC(O)=O CBMPTFJVXNIWHP-UHFFFAOYSA-L 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- PFZPMLROUDTELO-UHFFFAOYSA-N 1-methyl-1h-imidazol-1-ium;acetate Chemical compound CC(O)=O.CN1C=CN=C1 PFZPMLROUDTELO-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 108010059892 Cellulase Proteins 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
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- 239000007853 buffer solution Substances 0.000 description 1
- 239000008366 buffered solution Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 229940106157 cellulase Drugs 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000007071 enzymatic hydrolysis Effects 0.000 description 1
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- VSPPONOIKZXUBJ-UHFFFAOYSA-N n,n-diethylethanamine;oxolane Chemical compound C1CCOC1.CCN(CC)CC VSPPONOIKZXUBJ-UHFFFAOYSA-N 0.000 description 1
- JXDNGTCNFHAVIO-UHFFFAOYSA-N n,n-dimethylmethanamine;oxolane Chemical compound CN(C)C.C1CCOC1 JXDNGTCNFHAVIO-UHFFFAOYSA-N 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 230000001954 sterilising effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
- C08B11/20—Post-etherification treatments of chemical or physical type, e.g. mixed etherification in two steps, including purification
-
- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
- A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
-
- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
-
- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
-
- 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
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The invention relates to a 2-quaternary ammonium salt modified ethyl cellulose derivative, and a preparation method and application thereof. The invention synthesizes cellulose containing bromoacetate structure by adopting the reaction of high activity acyl bromide reagent and 2-hydroxyl of ethyl cellulose under alkaline condition, and then builds quaternary ammonium salt by utilizing nucleophilicity of nitrogen-containing compound. The ethyl cellulose derivative modified by the quaternary ammonium salt has good escherichia coli inhibition activity after being subjected to enzymatic degradation, and has the advantages of high yield and simple operation.
Description
Technical Field
The invention relates to the technical field of antibacterial materials, in particular to a 2-quaternary ammonium salt modified ethylcellulose derivative, a preparation method and application thereof.
Background
Antibacterial materials are widely used in natural environments and daily life of human beings, and are functional materials with sterilizing or bacteriostasis capability. Antibacterial materials can be classified into inorganic and organic antibacterial materials, and can be classified into natural antibacterial materials and synthetic antibacterial materials from the viewpoint of artificial synthesis. At present, the research and development of novel antibacterial materials with environmental protection, durability, broad spectrum and high efficiency are uniformly accepted by all communities, and become a popular research direction of the industry.
Cellulose is natural polysaccharide formed by polymers from glucose, and has the advantages of environmental protection, being degradable by enzymes and the like. Glucose has better water solubility when the polymerization degree is lower, has a certain antibacterial property, is used as a good nutrient substance at the same time, and is beneficial to the growth of bacteria at a higher concentration. The ethylcellulose has certain fat solubility, overcomes the defect of insufficient fat solubility when the polymerization degree of glucose is low, has the advantage of being degraded by enzyme, and is more beneficial to penetrating through cell walls after being degraded by enzyme. Based on the advantages, the ethyl cellulose is widely used as a bacteriostatic raw material at present, but the ethyl cellulose is mostly used as a matrix or film forming material, and the bacteriostatic effect of the ethyl cellulose is further improved by not directly carrying out chemical modification on the ethyl cellulose. The application document with publication number of CN11358178A discloses an alkyl glycoside biological bacteriostat and a preparation process thereof, wherein ethyl cellulose is used as a film forming material to be matched with a bacteriostasis component and other auxiliary agents to be a bacteriostat, and water is required to be added for swelling when the ethyl cellulose is used, so that the preparation process is complex.
Disclosure of Invention
The invention provides a 2-quaternary ammonium salt modified ethyl cellulose derivative, a preparation method and application thereof, wherein a high-activity acyl bromide reagent is adopted to react with 2-hydroxyl of ethyl cellulose to construct cellulose containing bromoacetate structure under alkaline condition, and then nucleophilic property of a nitrogen-containing compound is utilized to construct quaternary ammonium salt. The ethyl cellulose derivative modified by the quaternary ammonium salt has good escherichia coli inhibition activity after being subjected to enzymatic degradation, and has the advantages of high yield and simple operation.
The scheme for solving the technical problems is as follows: a2-quaternary ammonium salt modified ethyl cellulose derivative has a structural formula as follows:
wherein r=n + (CH 3 ) 3 Br - ,N + (CH 2 CH 3 ) 3 Br - ,
n=40-50. The synthetic route of the above 2-quaternary ammonium salt modified ethylcellulose derivative is as follows: />
Wherein r=n + (CH 3 ) 3 Br - ,N + (CH 2 CH 3 ) 3 Br - ,
n＝40-50；
The synthesis steps are as follows:
a) Compound 1 is dissolved in a first solvent, organic base is added, stirring is carried out for 4-6 hours at room temperature, and cooling is carried out to 0-5 ℃. Bromoacetyl bromide is added dropwise, the reaction is carried out for half an hour at 0-5 ℃, the temperature is restored to room temperature, the mixture obtained after stirring for 24-36 hours is poured into a large amount of cold water, white solid is separated out, the white solid is filtered, and the compound 3 is obtained after the solid is dried.
b) Dissolving the compound 3 in a second solvent, adding a nitrogen-containing compound at room temperature, stirring for 24-36 hours at 25-100 ℃, cooling to room temperature, pouring the obtained mixture into cold water, precipitating a pale yellow solid, filtering, and drying to obtain the compound I.
Preferably, the molar ratio of compound 1 to bromoacetyl bromide in step a) is 1:1.2-1.5. Preferably, in the step a), the first solvent is one or a mixture of a plurality of anhydrous tetrahydrofuran and dichloromethane.
Preferably, in the step a), the organic base is one of triethylamine and pyridine.
The process for the preparation of a 2-quaternary ammonium salt modified ethylcellulose derivative as claimed in claim 2 wherein said step b) is carried out in a molar ratio of compound 3 to nitrogen-containing compound of from 1:1.1 to 1.5.
Preferably, in the step b), the second solvent is one or a mixture of a plurality of anhydrous tetrahydrofuran and dichloromethane.
Preferably, the nitrogen-containing compound in the step b) is one of trimethylamine, triethylamine, 1-methylimidazole and pyridine.
The application of the ethyl cellulose derivative modified by the 2-quaternary ammonium salt in antibacterial materials is disclosed.
Preferably, the antibacterial material has a bacteriostasis rate of 40-81%, more preferably 80-81% to Escherichia coli.
The beneficial effects of the invention are as follows: the invention adopts the acyl bromide reagent with high activity to react with the 2-hydroxyl of the ethyl cellulose to construct cellulose containing bromoacetate structure under alkaline condition, and then utilizes the nucleophilicity of the nitrogen-containing compound to construct quaternary ammonium salt modified ethyl cellulose. The reaction operation is simple, the reaction condition is mild, and the yield is high; the prepared ethyl cellulose derivative modified by the 2-quaternary ammonium salt has good escherichia coli resistance after being degraded by cellulase.
The foregoing description is only an overview of the present invention, and is intended to provide a better understanding of the present invention, as it is embodied in the following description, with reference to the preferred embodiments of the present invention and the accompanying drawings. Specific embodiments of the present invention are given in detail by the following examples and the accompanying drawings.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, illustrate embodiments of the invention and together with the description serve to explain the invention and do not constitute a limitation on the invention. In the drawings:
FIG. 1 is a structural formula diagram of a 2-quaternary ammonium salt modified ethylcellulose derivative provided by the invention;
fig. 2 is a synthetic circuit diagram of the 2-quaternary ammonium salt modified ethylcellulose derivative provided by the invention.
Detailed Description
The principles and features of the present invention are described below with reference to the drawings, the examples are illustrated for the purpose of illustrating the invention and are not to be construed as limiting the scope of the invention.
Example 1
The synthetic scheme for compound I-1 is shown below:
the synthesis steps are as follows:
a) Preparation of compound 3 (2-bromoacetate-ethylcellulose): 10g of Compound 1 (ethylcellulose) was dispersed in 120mL of anhydrous tetrahydrofuran, and 8.63mL of pyridine was added to the reaction solution under ice-water bath conditions. 7.42mL of bromoacetyl bromide was dissolved in 10mL of tetrahydrofuran and slowly added dropwise to the reaction system. The reaction system was poured into a large amount of water, and a white solid was precipitated, filtered, and dried to give compound 3 (12.0696 g, yield: 79.6%).
b) Preparation of compound I-1 (2- (1-N, N, N-trimethylacetate) -ethylcellulose): compound 3 (3.552 g,10 mmol) was weighed out, anhydrous tetrahydrofuran was added under nitrogen protection, and the mixture was stirred and dispersed at room temperature. At room temperature, 15mmol of 1M/L trimethylamine tetrahydrofuran solution is dripped into the reaction system, and stirring is continued for about 24 hours. After the reaction, the mixture was diluted with methylene chloride or diethyl ether and centrifuged. The supernatant was poured into a large amount of water to precipitate a white solid, which was filtered under reduced pressure and dried under vacuum to give solid compound I-1 (3.629 g, yield: 87.6%).
Compound I-1 was taken for characterization and the results were as follows:
FTIR characterization: 2977cm -1 ,2931cm -1 ,2861cm -1 (saturated CH), 1747cm -1 (C＝O),1261cm -1 (C-N),1081cm -1 (C-O-C),1049cm -1 (C-O-C on sugar ring).
1H NMR(400MHz,CDCl 3 )δ5.09-2.71(O-CH 2 and N-CH 3 ，22H)，1.17(CH 3 ，CH 3 CH 2 ，9H).
Example 2
The synthetic scheme for compound I-2 is shown below:
the synthesis steps are as follows:
a) Preparation of compound 3 (2-bromoacetate-ethylcellulose): the specific operation is the same as in step a) in example 1.
b) Preparation of Compound I-2 (2- (1-N, N, N-triethylacetate) -ethylcellulose): compound 3 (3.552 g,10 mmol) was weighed out, anhydrous tetrahydrofuran was added under nitrogen protection, and the mixture was stirred and dispersed at room temperature. At room temperature, 15mmol of 1M/L triethylamine tetrahydrofuran solution was added dropwise to the reaction system, and stirring was continued for about 24 hours. After the reaction, the mixture was diluted with methylene chloride or diethyl ether and centrifuged. The supernatant was poured into a large amount of water to precipitate a white solid, which was filtered under reduced pressure and dried under vacuum to give solid compound I-2 (3.017 g, yield: 66.1%).
Compound I-2 was taken for characterization and the results were as follows:
FTIR characterization: 2972cm -1 ,2917cm -1 ,2875cm -1 (saturated CH), 1747cm -1 (C＝O),1278cm -1 (C-N),1081cm -1 (C-O-C),1049cm -1 (C-O-C on sugar ring).
1 H NMR(400MHz,CDCl 3 )δ5.08-2.97(O-CH 2 and N-CH 3 ，19H)，1.16(CH 3 ，CH 3 CH 2 N and CH 3 CH 2 O，15H).
Example 3
The synthetic scheme for compound I-3 is shown below:
a) Preparation of compound 3 (2-bromoacetate-ethylcellulose): the specific operation is the same as in step a) in example 1.
b) Preparation of compound I-3 (2- (1-methyl-1H-imidazolium acetate) -ethylcellulose): compound 3 (3.552 g,10 mmol) was weighed out, anhydrous tetrahydrofuran was added under nitrogen protection, and the mixture was stirred and dispersed at room temperature. At room temperature, 15mmol of 1M/L1-methylimidazole in tetrahydrofuran was added dropwise to the reaction system, and the mixture was heated to 60℃and stirred for 36 hours. Cooled to room temperature, diluted with dichloromethane or diethyl ether and centrifuged. The supernatant was poured into a large amount of water to precipitate a white solid, which was filtered under reduced pressure and dried under vacuum to give solid compound I-3 (1.557 g, yield: 35.6%).
Compound I-3 was taken for characterization and the results were as follows:
FTIR characterization: 2871cm -1 ,2866cm -1 (saturated CH), 1768cm -1 (C＝O),1629cm -1 (C＝C),1378cm -1 (CH 3 ),1107cm -1 (C-O-C),1048cm -1 (C-O-C on sugar ring), 923cm -1 (imidazole ring C-H flexural vibration).
1 H NMR(400MHz,CDCl 3 )δ7.48(s,H,imidazole-H),7.05(s,H,imidazole-H),6.90(s,H,imidazole-H),4.79-3.03(O-CH 2 and N-CH 3 ，16H)，1.27-1.14(CH 3 ，CH 3 CH 2 O，6H).
Example 4
The synthetic scheme for compound I-4 is shown below:
a) Preparation of compound 3 (2-bromoacetate-ethylcellulose): the specific operation is the same as in step a) in example 1.
b) Preparation of compound I-4 (2- (1-pyridinylacetate) -ethylcellulose): compound 3 (3.552 g,10 mmol) was weighed out, anhydrous tetrahydrofuran was added under nitrogen protection, and the mixture was stirred and dispersed at room temperature. 15mmol of pyridine in tetrahydrofuran was added dropwise to the reaction system at room temperature, and the mixture was stirred at 60℃for 24 hours. Cooled to room temperature, diluted with dichloromethane or diethyl ether and centrifuged. The supernatant was poured into a large amount of water to precipitate an orange-yellow solid, which was filtered under reduced pressure and dried under vacuum to give solid compound I-4 (1.212 g, yield: 34.2%).
Compound I-4 was taken for characterization and the results were as follows:
FTIR characterization: 2972cm -1 ,2863cm -1 (saturated CH) 1760cm -1 (C＝O)1637cm -1 (pyridine ring c=c), 1374cm -1 (CH 3 ),1343cm -1 (C-N),1111cm -1 (primary alcohol C-O), 1054cm -1 (C-O-C on sugar ring).
1 H NMR(400MHz,CDCl 3 )δ9.36(s,H,pyridine-H),8.52(s,H,pyridine-H),8.09(s,H,pyridine-H),4.98-3.02(O-CH 2 and CH，13H)，1.17-1.15(CH 3 ，CH 3 CH 2 O，6H).
Example 5 determination of bacteriostatic Activity
1) Preparation of crude solution of chitosan enzyme
30g of a powdery enzyme sample (chitosanase content: 68%) was weighed, dissolved in 70mL of distilled water, stirred and left to stand, and sufficiently soaked for 3 hours. Centrifuging with a centrifuge at 4000r/min for 20min to obtain yellow supernatant. The enzyme-containing supernatant was packaged and stored in a refrigerator at 4 ℃.
2) Enzymolysis of Compound I-1-I-4
The solid sample compounds I-1-I-4 prepared in examples 1-6 were weighed out using an analytical balance and dissolved in 1mL of a buffered solution of citric acid-disodium hydrogen phosphate at pH 4.8, respectively. The corresponding 20mmol/L concentration sample I-1-I-4 is prepared, 2mL of activated chitosanase crude solution is added, and after hydrolysis for about 100 minutes at 50 ℃, the temperature is heated to 100 ℃ to inactivate enzymes in the degradation sample I-1-I-4. Then, the sample I-1-I-4 was subjected to centrifugation (rotation speed 4000r/min, time 5-10 min). After centrifugation, the supernatant was taken, the degraded sample solution I-1-I-4 was added to the LB medium with E.coli, 1mL of a buffer solution of citric acid-disodium hydrogen phosphate having a pH of 4.8 was added to the LB medium with E.coli, the mixture was set as a blank, and the blank and the sample solution I-1-I-4 were cultured in a constant temperature incubator for 24 hours (culture temperature: 37 ℃ C.), and the antibacterial ratio was calculated, and the results were shown in Table 1.
Calculating the bacteriostasis rate: antibacterial ratio (%) = [ (sample outer diameter-sample inner diameter) - (blank outer diameter-blank inner diameter) ]/(sample outer diameter-sample inner diameter) = [ (sample outer diameter-blank outer diameter) ]/(sample outer diameter-sample inner diameter) ]×100%.
Antibacterial Activity of Compounds I-1-I-4 after enzymatic hydrolysis
When the substituent r=nme 3 (Compound I-1), NEt 3 (compound I-2), the chain hydrocarbon substituent is superior to the heterocyclic ring I-3 and I-4 substituent, so that the antibacterial activity is higher, and the antibacterial rate of the compound I-3 is superior to that of the compound I-4 related to the amphiphilicity of the imidazolyl.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention in any way; those skilled in the art will readily appreciate that the present invention may be implemented as shown in the drawings and described above; however, those skilled in the art will appreciate that many modifications, adaptations, and variations of the present invention are possible in light of the above teachings without departing from the scope of the invention; meanwhile, any equivalent changes, modifications and evolution of the above embodiments according to the essential technology of the present invention still fall within the scope of the present invention.
Claims (10)
1. A 2-quaternary ammonium salt modified ethylcellulose derivative, which is characterized in that the structural formula is as follows:
wherein r=n + (CH 3 ) 3 Br - ,N + (CH 2 CH 3 ) 3 Br - ,
n＝40-50。
2. The preparation of a 2-quaternary ammonium salt modified ethylcellulose derivative as claimed in claim 1 wherein the synthetic route is as follows:
wherein r=n + (CH 3 ) 3 Br - ,N + (CH 2 CH 3 ) 3 Br - ,
n＝40-50；
The synthesis steps are as follows:
a) Dissolving the compound 1 in a first solvent, adding an organic base, stirring at room temperature, dropwise adding bromoacetyl bromide under the condition of ice bath external bath, continuously reacting, recovering to room temperature, stirring for 24-36 hours, pouring the obtained mixture into a large amount of cold water, precipitating a solid, filtering, and drying the solid to obtain a compound 3;
b) And (3) dissolving the compound 3 in a second solvent, adding a nitrogen-containing compound at room temperature, stirring for reaction for 24-36 hours, cooling to room temperature, pouring the obtained mixture into cold water, precipitating a solid, filtering, and drying to obtain the compound I.
3. The method for preparing a 2-quaternary ammonium salt modified ethylcellulose derivative as claimed in claim 2 wherein said step a) is performed in a molar ratio of 1:1.2-1.5 of compound 1 to bromoacetyl bromide.
4. The method for preparing a 2-quaternary ammonium salt modified ethylcellulose derivative as claimed in claim 2 wherein said step a) is performed by using a first solvent selected from the group consisting of anhydrous tetrahydrofuran and dichloromethane.
5. The method for preparing a 2-quaternary ammonium salt modified ethylcellulose derivative as claimed in claim 2 wherein said organic base in said step a) is one of triethylamine and pyridine.
6. The process for the preparation of a 2-quaternary ammonium salt modified ethylcellulose derivative as claimed in claim 2 wherein said step b) is carried out in a molar ratio of compound 3 to nitrogen-containing compound of from 1:1.1 to 1.5.
7. The method for preparing a 2-quaternary ammonium salt modified ethylcellulose derivative as claimed in claim 2 wherein said second solvent in said step b) is one or a mixture of two of anhydrous tetrahydrofuran and dichloromethane.
8. The method for preparing a 2-quaternary ammonium salt modified ethylcellulose derivative as claimed in claim 2, wherein said nitrogen-containing compound in said step b) is one of trimethylamine, triethylamine, 1-methylimidazole and pyridine.
9. Use of a 2-quaternary ammonium salt modified ethylcellulose derivative as claimed in claim 1 in the preparation of an antibacterial material.
10. The use of a 2-quaternary ammonium salt modified ethylcellulose derivative as claimed in claim 9 in said antimicrobial material, wherein said antimicrobial material has a bacteriostasis rate of 40-81% for escherichia coli.
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| US4035457A (en) * | 1975-05-01 | 1977-07-12 | Chemical Systems Incorporated | Nonbiodegradable polymers |
| KR20070078172A (en) * | 2006-01-26 | 2007-07-31 | 코오롱생명과학 주식회사 | Process for preparing quaternary nitrogen-containing cellulose ether |
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| US4035457A (en) * | 1975-05-01 | 1977-07-12 | Chemical Systems Incorporated | Nonbiodegradable polymers |
| KR20070078172A (en) * | 2006-01-26 | 2007-07-31 | 코오롱생명과학 주식회사 | Process for preparing quaternary nitrogen-containing cellulose ether |
| CN101812140A (en) * | 2010-01-21 | 2010-08-25 | 清华大学 | Cyclodextrin-bonded comb-shaped copolymer and preparation method thereof |
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