CN117003911A - Preparation method, product and application of natural pterostilbene grafted chitosan - Google Patents
Preparation method, product and application of natural pterostilbene grafted chitosan Download PDFInfo
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- CN117003911A CN117003911A CN202311015597.2A CN202311015597A CN117003911A CN 117003911 A CN117003911 A CN 117003911A CN 202311015597 A CN202311015597 A CN 202311015597A CN 117003911 A CN117003911 A CN 117003911A
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- pterostilbene
- natural
- chitosan
- grafted chitosan
- fabric
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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 131
- VLEUZFDZJKSGMX-ONEGZZNKSA-N pterostilbene Chemical compound COC1=CC(OC)=CC(\C=C\C=2C=CC(O)=CC=2)=C1 VLEUZFDZJKSGMX-ONEGZZNKSA-N 0.000 title claims abstract description 123
- VLEUZFDZJKSGMX-UHFFFAOYSA-N pterostilbene Natural products COC1=CC(OC)=CC(C=CC=2C=CC(O)=CC=2)=C1 VLEUZFDZJKSGMX-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000004744 fabric Substances 0.000 claims abstract description 72
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 69
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 25
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 17
- 229920002873 Polyethylenimine Polymers 0.000 claims description 15
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 13
- 230000000845 anti-microbial effect Effects 0.000 claims description 13
- 229920002866 paraformaldehyde Polymers 0.000 claims description 13
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000007598 dipping method Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- 238000007730 finishing process Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 4
- 239000003242 anti bacterial agent Substances 0.000 abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- 229920002678 cellulose Polymers 0.000 abstract description 6
- 239000001913 cellulose Substances 0.000 abstract description 6
- 238000001338 self-assembly Methods 0.000 abstract description 5
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 30
- 229920000742 Cotton Polymers 0.000 description 29
- 241000588724 Escherichia coli Species 0.000 description 14
- 241000191967 Staphylococcus aureus Species 0.000 description 13
- 230000002401 inhibitory effect Effects 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 241000894006 Bacteria Species 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229960002796 polystyrene sulfonate Drugs 0.000 description 5
- 239000011970 polystyrene sulfonate Substances 0.000 description 5
- 239000004599 antimicrobial Substances 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 238000004809 thin layer chromatography Methods 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 3
- 230000001580 bacterial effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000219146 Gossypium Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 235000003095 Vaccinium corymbosum Nutrition 0.000 description 1
- 240000000851 Vaccinium corymbosum Species 0.000 description 1
- 235000017537 Vaccinium myrtillus Nutrition 0.000 description 1
- 241000219094 Vitaceae Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000021014 blueberries Nutrition 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 235000021021 grapes Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000009988 textile finishing Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
- D06M15/03—Polysaccharides or derivatives thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
- D06M15/3566—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing sulfur
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/61—Polyamines polyimines
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Textile Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The application provides a preparation method, a product and application of natural pterostilbene grafted chitosan. The preparation method comprises the steps of grafting natural pterostilbene onto chitosan, so that the natural pterostilbene grafted chitosan with high antibacterial activity, good water solubility and good stability is prepared; the preparation method has the advantages of simple and convenient process, mild reaction conditions, energy conservation, consumption reduction, strong controllability and good reproducibility. The prepared natural pterostilbene grafted chitosan is used as an antibacterial agent to be applied to antibacterial finishing of cellulose fabrics by a layer-by-layer self-assembly method, so that finishing fabrics with excellent antibacterial performance can be obtained.
Description
Technical Field
The application belongs to the technical field of printing and dyeing auxiliary agents, and particularly relates to a preparation method, a product and application of natural pterostilbene grafted chitosan.
Background
Cellulose fabrics are popular with consumers because of their skin-friendly and soft properties, but they are extremely prone to bacterial growth. Bacterial growth can cause the problems of unpleasant smell, color change, degradation and the like of cellulose fabrics, and can also induce various human diseases. Along with the enhancement of health and environmental awareness of people, the development of ecological antibacterial fabrics is urgent. Correspondingly, development of efficient and environment-friendly antibacterial agents is an important point of research.
The natural antibacterial agent is an antibacterial active substance extracted from animals and plants, has various excellent characteristics of safety, no toxicity, good biocompatibility, wide sources and the like, and meets the development requirements of environmental protection of the antibacterial agent in the future. However, the natural antibacterial agent has weak antibacterial activity of high molecular and poor stability of small molecules. Therefore, development of a highly active and stable natural antibacterial agent is required.
Among the many natural antibacterial agents, chitosan is the most common natural polymer antibacterial agent, has good biocompatibility, safety, degradability and the like, and is widely applied to the textile industry. However, chitosan dissolves and exhibits antibacterial activity only under acidic conditions, and has weak antibacterial activity against E.coli. This greatly limits the range of applications for chitosan. In order to improve the antibacterial activity of chitosan, different types of small molecules can be introduced into the molecular structure of chitosan so as to improve the antibacterial activity and the application range of the chitosan. The small molecular antibacterial agent with high antibacterial activity and low price is found, and is introduced into a chitosan structure, so that the small molecular antibacterial agent has important significance for the development of novel natural antibacterial agents.
In addition, the traditional antibacterial finishing of the fabric often adopts the processes of dipping/padding, drying and Wen Beihong, has high energy consumption and is easy to damage the clothing performance of the fabric.
Disclosure of Invention
Pterostilbene is a natural substance extracted from blueberries, grapes and the like, contains phenolic hydroxyl groups in the structure, can damage cell membranes of bacteria, and has high-efficiency antibacterial activity. But pterostilbene has poor water solubility and thermal stability and is not suitable for being directly used for antibacterial finishing of textiles (fabrics).
In order to solve the problems in the prior art, the application provides a preparation method, a product and application of natural pterostilbene grafted chitosan, wherein the preparation method adopts high-activity small-molecule natural pterostilbene to graft and modify macromolecular chitosan, and the obtained natural pterostilbene grafted chitosan can exert the synergistic antibacterial effect of the natural pterostilbene grafted chitosan and the macromolecular chitosan, so that the broad-spectrum antibacterial performance of the chitosan is improved, and meanwhile, the water solubility and stability of the pterostilbene are also greatly improved. The prepared product is endowed with excellent broad-spectrum antibacterial property under a lower finishing process by layer-by-layer self-assembly, and the method is simple to operate, energy-saving, consumption-reducing and easy to control.
A preparation method of natural pterostilbene grafted chitosan comprises the following steps:
adding paraformaldehyde into acetic acid aqueous solution of chitosan, stirring until the paraformaldehyde is dissolved, adding pterostilbene for reaction, and after the reaction is finished, performing aftertreatment to obtain the natural pterostilbene grafted chitosan.
Preferably, the aqueous acetic acid solution of chitosan is obtained by dissolving chitosan in an aqueous acetic acid solution and stirring until complete dissolution.
Further preferably, the concentration of the aqueous acetic acid solution used is 30 to 50v/v%.
Further preferably, the dissolution temperature of chitosan in an aqueous acetic acid solution is 70 to 90 ℃.
Preferably, the concentration of chitosan in the aqueous acetic acid solution is 0.01 to 0.05mol/L. Further preferably 0.01 to 0.03mol/L.
Preferably, the molar ratio of pterostilbene to chitosan repeating structural units is (0.1 to 0.5): 1. Further preferably (0.1 to 0.3): 1.
Preferably, the molar ratio of the repeating structural units to pterostilbene in the paraformaldehyde is 1:1.
Preferably, the reaction temperature after the pterostilbene is added is 60-100 ℃. More preferably 70 to 90 ℃.
Preferably, after addition of pterostilbene, the reaction is monitored to the end point by thin layer chromatography.
Preferably, the following post-treatment is performed after the reaction is completed:
and (3) cooling the reaction liquid, adding diethyl ether for extraction to remove unreacted pterostilbene, and then removing residual diethyl ether by rotary evaporation to obtain the natural pterostilbene grafted chitosan.
The reaction process of the natural pterostilbene grafted chitosan is as follows:
the natural pterostilbene grafted chitosan is prepared by the preparation method of the natural pterostilbene grafted chitosan. The natural pterostilbene grafted chitosan has the advantages of high antibacterial activity, good water solubility, good stability and the like. The natural pterostilbene grafted chitosan is used as an antibacterial agent and applied to the antibacterial finishing of cellulose fabrics through layer-by-layer self-assembly, and the finished fabrics have excellent antibacterial performance.
Preferably, the grafting rate of the natural pterostilbene grafted chitosan is 15-20%. More preferably 16.7 to 18.3%.
An application of the natural pterostilbene grafted chitosan in the antibacterial finishing process of fabrics.
Preferably, the fabric is a cellulose fabric, including cotton, hemp, bamboo, viscose, and mixed fabrics thereof.
Preferably, the antibacterial finishing process of the fabric comprises the following steps:
(1) Immersing the fabric pretreated by alkali liquor in a Polyethyleneimine (PEI) aqueous solution, washing to remove superfluous polyethyleneimine on the surface, and drying to obtain a polyethyleneimine treated fabric I;
(2) Soaking the fabric I in a sodium polystyrene sulfonate (PSS) aqueous solution at room temperature, washing to remove unassembled sodium polystyrene sulfonate, and drying to obtain a sodium polystyrene sulfonate treated fabric II;
(3) Soaking the fabric II in a natural pterostilbene grafted chitosan finishing liquid at room temperature, washing to remove unassembled natural pterostilbene grafted chitosan, and drying to obtain an antibacterial fabric with the number of assembled layers being 1;
(4) Repeating the steps (2) and (3) for set times to obtain the antibacterial fabric with the corresponding assembly layer number.
According to the antibacterial finishing process of the fabric, the characteristics that the sodium polystyrene sulfonate has a negative charge layer and the natural pterostilbene grafted chitosan has a positive charge layer are utilized, and the sodium polystyrene sulfonate with different charges and the natural pterostilbene grafted chitosan are alternately deposited on the surface of the fabric through electrostatic action, so that the fabric has excellent antibacterial performance, is simple to operate, does not need to be baked at a high temperature, and is low in treatment cost and good in product performance.
In the step (1):
as a further preferred aspect, the alkali solution is one or a mixture of sodium hydroxide aqueous solution and potassium hydroxide aqueous solution.
Further preferably, the concentration of the alkali solution is 0.5 to 1.5mol/L.
As a further preferable mode, the bath ratio of the alkali liquor pretreatment is 1 (20-40), the pretreatment temperature is 80-100 ℃ and the pretreatment time is 20-40 min.
More preferably, the concentration of the aqueous polyethyleneimine solution is 20 to 40g/L.
More preferably, the aqueous solution of polyethyleneimine has an impregnation bath ratio of 1 (20 to 40), an impregnation temperature of 60 to 80℃and an impregnation time of 80 to 100 minutes.
In the step (2):
further preferably, the concentration of the aqueous solution of sodium polystyrene sulfonate is 5 to 15g/L.
More preferably, the aqueous solution of sodium polystyrene sulfonate has an immersion bath ratio of 1 (40 to 60) and an immersion time of 10 to 30 minutes.
In the step (3):
as a further preferred option, the natural pterostilbene grafted chitosan finishing liquid is an aqueous solution of natural pterostilbene grafted chitosan; wherein the concentration of the natural pterostilbene grafted chitosan is 10-100 g/L.
As a further preferred aspect, the impregnation bath ratio of the natural pterostilbene grafted chitosan finishing liquid is 1:
(40-60), the dipping time is 10-30 min.
Preferably, in the steps (1) to (3), the drying temperatures are each independently selected from 70 to 90 ℃.
More preferably, in the step (4), the number of repetitions is set to 1 to 4, and the number of assembled layers of the finally obtained antibacterial fabric is 2 to 5. More preferably, the number of repetitions is set to 2, and the number of assembled layers of the finally obtained antibacterial fabric is 3.
Compared with the prior art, the application has the beneficial effects that:
(1) Compared with chitosan, the antibacterial activity of the natural pterostilbene grafted chitosan disclosed by the application on escherichia coli is improved by more than about 90% (the minimum antibacterial concentration is reduced), and the antibacterial activity on staphylococcus aureus is improved by more than about 60%; the antibacterial rate of the finishing fabric to escherichia coli and staphylococcus aureus is up to 99.9%, the antibacterial rate to escherichia coli is improved by more than 80% compared with that of chitosan finishing fabric, and the antibacterial rate to staphylococcus aureus is improved by more than 50% compared with that of chitosan finishing fabric.
(2) Compared with pterostilbene, the water solubility of the natural pterostilbene grafted chitosan antibacterial agent is improved; the antibacterial activity to colibacillus is improved by more than about 40%, and the antibacterial activity to staphylococcus aureus is respectively improved by more than about 50%; the antibacterial rate of the finished fabric is improved by more than 20% compared with that of pterostilbene finished fabric, and the antibacterial rate of the finished fabric is improved by more than 30% compared with that of pterostilbene finished fabric.
According to the application, the natural pterostilbene is grafted onto chitosan, so that the natural pterostilbene grafted chitosan with high antibacterial activity, good water solubility and good stability is prepared; the preparation method has the advantages of simple and convenient process, mild reaction conditions, energy conservation, consumption reduction, strong controllability and good reproducibility. The prepared natural pterostilbene grafted chitosan is used as an antibacterial agent to be applied to antibacterial finishing of cellulose fabrics by a layer-by-layer self-assembly method, so that finishing fabrics with excellent antibacterial performance can be obtained.
Drawings
FIG. 1 is an infrared spectrum of Chitosan (CS), pterostilbene (PL) and natural pterostilbene grafted chitosan (PLCS);
FIG. 2 shows the solubility of PLCS at different pH conditions;
FIG. 3 is a comparison of bacterial growth on cotton fabric surfaces treated with different antimicrobial agents.
Detailed Description
The technical scheme of the application is further described below by combining specific embodiments. It should be understood that these examples are only for illustrating the technical scheme of the present application and are not intended to limit the scope of the present application. Various changes and modifications to the present application may be made by one skilled in the art after reading the teachings of the present application, and such equivalents fall within the scope of the application as defined in the appended claims.
Example 1: selection of pterostilbene to chitosan molar ratio
(1) 1mmol of chitosan is dissolved in 50mL of 40v/v% acetic acid water solution, and stirred at 80 ℃ until the chitosan is completely dissolved, so as to obtain 0.02mol/L chitosan solution; preparing five parts of the same chitosan solution for standby;
(2) Adding paraformaldehyde (wherein the molar weight of formaldehyde monomer is 0.1mmol, 0.2mmol, 0.5mmol, 0.75mmol and 1mmol respectively) into the five chitosan solutions, stirring until the paraformaldehyde is dissolved, then adding pterostilbene (the molar weight is 0.1mmol, 0.2mmol, 0.5mmol, 0.75mmol and 1mmol respectively) correspondingly, controlling the molar ratio of the paraformaldehyde to the pterostilbene to be 1:1, reacting at 80 ℃, and monitoring the reaction progress to an end point by using thin layer chromatography to obtain a reaction solution containing natural pterostilbene grafted chitosan;
(3) And cooling the reaction liquid, adding diethyl ether for extraction to remove unreacted pterostilbene, separating the liquid to obtain a pre-product, and removing residual diethyl ether by rotary evaporation at normal temperature to obtain five different natural pterostilbene grafted chitosan.
In order to search the grafting condition of pterostilbene on chitosan, the grafting rate calculation is carried out on the five different natural pterostilbene grafted chitosan, and the results are shown in Table 1.
TABLE 1 grafting ratio corresponding to different molar ratios of natural pterostilbene and chitosan
| Molar ratio of chitosan to pterostilbene | Grafting percentage (%) |
| 1:0.1 | 16.7 |
| 1:0.2 | 17.6 |
| 1:0.5 | 18.3 |
| 1:0.75 | 21.0 |
| 1:1 | 21.5 |
As shown in Table 1, as the amount of pterostilbene increases, the grafting rate of pterostilbene on chitosan gradually increases, and when the molar ratio of pterostilbene to chitosan exceeds 1:0.75, the increasing trend of grafting rate is obviously weakened.
FIG. 1 is an infrared spectrum of Chitosan (CS), pterostilbene (PL) and natural pterostilbene grafted chitosan (PLCS) (molar ratio of chitosan to pterostilbene 1:0.2). As can be seen from FIG. 1, the pterostilbene corresponding to the native pterostilbene grafted chitosan is 2935cm -1 、1708cm -1 、891cm -1 Three new characteristic peaks appear, demonstrating successful grafting.
The lowest antibacterial concentration of the antibacterial agent is explored by taking chitosan, pterostilbene and the five different natural pterostilbene grafted chitosan prepared by the above method as antibacterial agents, and the results are shown in Table 2. The lower the minimum inhibitory concentration, the higher the antimicrobial activity of the antimicrobial agent.
TABLE 2 minimum inhibitory concentration of different classes of antimicrobial agents
As can be seen from table 2, as the amount of pterostilbene in the natural pterostilbene grafted chitosan increases, the minimum inhibitory concentration of the natural pterostilbene grafted chitosan on staphylococcus aureus and escherichia coli decreases and then increases, and the minimum inhibitory concentration of the natural pterostilbene grafted chitosan on both bacteria is lower than the minimum inhibitory concentration of the chitosan. When the molar ratio of pterostilbene to chitosan is (0.1-0.5): 1, the lowest inhibitory concentration of natural pterostilbene grafted chitosan on two bacteria is lower; and when the molar ratio of pterostilbene to chitosan is 0.2:1, the minimum antibacterial concentration of the pterostilbene to the two bacteria is the lowest, the antibacterial activity of the chitosan to escherichia coli is obviously improved, and the minimum antibacterial concentration is reduced by about 94.8%. This shows that the grafting modification of pterostilbene on chitosan can effectively improve the antibacterial activity of chitosan, and shows excellent antibacterial performance on staphylococcus aureus and escherichia coli.
Solubility test of PLCS (native pterostilbene grafted chitosan prepared by pterostilbene to chitosan molar ratio of 0.2:1):
the antimicrobial used in textiles needs to have good solubility to facilitate finishing of the fabric, and thus the solubility of the modified PLCS antimicrobial is characterized.
The dissolution of PLCS in water and other six common solvents was tested and compared to CS and PL and the experimental results are shown in Table 1.
TABLE 3 dissolution of CS, PL and PLCS in different solvents
Note that: + means soluble, ±means slightly soluble, -means insoluble.
As can be seen from Table 3, CS is insoluble in acetone, ethanol, diethyl ether, slightly soluble in water, acetic acid, DMF, and dissolved in DMSO. PL is insoluble in water, soluble in the other six solvents; while PLCS is soluble in six solvents other than diethyl ether. In addition, the solubility of PLCS in water is greatly improved compared to CS and PL. In industrial processes, water is the most common solvent and good solubility of PLCS in water will facilitate its subsequent use in textile finishing.
In addition, in order to investigate the effect of pH on the solubility of antimicrobial agents in water, the transmittance of PLCS at different pH conditions was tested using an ultraviolet-visible spectrophotometer and the test results are shown in fig. 2. As can be seen from fig. 2, PLCS has good solubility at pH ranges of 1 to 7, but the water solubility of PLCS rapidly decreases under alkaline conditions. In agreement with the phenomenon shown in the physical diagram in the dissolved state in fig. 2, PLCS was clear and transparent in aqueous solutions at pH 2, 4 and 6, and the phenomenon of precipitation of PLCS antibacterial agent occurred in aqueous solutions at pH 8.
Example 2: selection of reaction temperature
(1) 1mmol of chitosan is dissolved in 50mL of 40v/v% acetic acid water solution, and stirred at 80 ℃ until the chitosan is completely dissolved, so as to obtain 0.02mol/L chitosan solution; preparing four identical solutions for later use;
(2) Adding paraformaldehyde with formaldehyde monomer molar weight of 0.2mmol into the four solutions respectively, stirring until the paraformaldehyde is dissolved, then adding 0.2mmol of pterostilbene, reacting at 30 ℃, 60 ℃,80 ℃, 90 ℃ and 100 ℃ respectively, and monitoring the reaction progress to an end point by using a thin layer chromatography to obtain a reaction solution containing natural pterostilbene grafted chitosan;
(3) And (3) cooling the reaction liquid, adding diethyl ether for extraction to remove unreacted pterostilbene, extracting to obtain a pre-product, and removing residual diethyl ether by rotary evaporation to obtain five different natural pterostilbene grafted chitosan.
The minimum inhibitory concentration of the natural pterostilbene grafted chitosan prepared under the different reaction temperature conditions is explored, and the results are shown in Table 3.
TABLE 3 influence of different reaction temperatures on the minimum inhibitory concentration of native pterostilbene grafted chitosan
As shown in Table 3, as the reaction temperature increases, the minimum inhibitory concentration of the natural pterostilbene grafted chitosan antibacterial agent on staphylococcus aureus and escherichia coli tends to decrease and then increase, and the minimum inhibitory concentration increases instead when the temperature is too high (more than 80 ℃). This is probably because the grafting rate increases due to the excessively high temperature, and more pterostilbene is grafted onto chitosan, but the antibacterial active site of pterostilbene cannot be completely exposed due to the steric hindrance effect, thereby reducing the antibacterial activity. This shows that in a proper temperature range, moderate temperature increase can promote the grafting modification of pterostilbene on chitosan, and then the antibacterial activity of chitosan is effectively improved, but the reaction temperature cannot be too high.
Example 3: effect of the number of assembled layers on the antimicrobial Properties of the Fabric
(1) Dissolving Chitosan (CS) with unit mole amount of 1mmol in 50mL of 40v/v% acetic acid water solution, and stirring at 80 ℃ until the Chitosan (CS) is completely dissolved to obtain 0.02mol/L chitosan solution;
(2) Adding paraformaldehyde with the molar weight of formaldehyde monomer of 0.2mmol, stirring until the paraformaldehyde is dissolved, then adding Pterostilbene (PL) with the molar weight of 0.2mmol, reacting at 80 ℃, and monitoring the reaction progress to an end point by using a thin layer chromatography to obtain a reaction solution containing natural pterostilbene grafted chitosan;
(3) Cooling the reaction liquid, adding diethyl ether for extraction to remove unreacted pterostilbene, extracting to obtain a pre-product, and removing residual diethyl ether by rotary evaporation to obtain natural pterostilbene grafted chitosan (PLCS);
(4) The cotton fabric is immersed in NaOH solution of 1mol/L, immersed for 30min at 90 ℃ according to a bath ratio of 1:30, and the NaOH solution remained on the surface is washed off, so that the pretreated cotton fabric is obtained. Immersing the pretreated cotton fabric into 30g/L Polyethyleneimine (PEI) aqueous solution, immersing for 90min at 70 ℃ according to a bath ratio of 1:30, washing to remove superfluous PEI on the surface, and drying at 80 ℃ to obtain PEI cotton fabric;
(5) Immersing the PEI cotton fabric into 10g/L sodium polystyrene sulfonate (PSS) solution, immersing for 20min at room temperature with a bath ratio of 1:50, washing to remove superfluous PSS on the surface, and drying at 80 ℃ to obtain the PSS cotton fabric;
(6) Dipping the PSS cotton fabric in PLCS finishing liquid (water is used as a solvent) of 100g/L at room temperature for 20min at a bath ratio of 1:50, washing to remove unassembled natural pterostilbene grafted chitosan, drying at 80 ℃ to obtain PLCS antibacterial cotton fabric with 1 layer of assembled layers, and preparing 5 parts of PLCS antibacterial cotton fabric with 1 layer of assembled layers;
(7) And (3) repeating the step (5) and the step (6) for 1 time, 2 times, 3 times, 4 times respectively for 4 parts of PLCS antibacterial cotton fabric with the assembly layer number of 1 layer, so as to obtain the PLCS antibacterial cotton fabric with the assembly layer number of 2 layers, 3 layers, 4 layers and 5 layers.
According to GB/T20944.3-2008, PLCS finished cotton fabrics with different assembly layers are respectively subjected to antibacterial rate tests, and the results are shown in Table 4.
TABLE 4 Effect of different number of assembled layers on the antimicrobial Rate of PLCS finished cotton
As is clear from Table 4, when the number of assembled layers was 1, the antibacterial rates of PLCS cotton fabric against Escherichia coli and Staphylococcus aureus reached 97.1% and 94.9%, respectively. As the number of self-assembled layers increases, the antimicrobial properties of PLCS cotton fabrics also gradually increase. When the number of self-assembly layers reaches 3, the antibacterial rate of the PLCS cotton fabric to escherichia coli and staphylococcus aureus reaches 99.9%; however, as the number of assembled layers continues to increase, the antimicrobial efficiency of the PLCS cotton fabric against escherichia coli and staphylococcus aureus is no longer increased, so 3 layers are the most preferred number of self-assembled layers of the antimicrobial fabric.
Fig. 3 shows the antimicrobial performance comparison (tested according to GB/T20944.3-2008) of PLCS finished cotton (number of self-assembled layers is 3), CS finished cotton (finishing process with PLCS antimicrobial finish), PL finished cotton (finishing process with PLCS antimicrobial finish) and plain cotton (untreated cotton). As shown in FIG. 3, the antibacterial rate of the cotton fabric finished by the natural pterostilbene grafted chitosan on staphylococcus aureus (shown as S. Bacteria in the figure) and escherichia coli (shown as E. Bacteria in the figure) can reach more than 99.9%, the antibacterial rate of the cotton fabric is improved by about 56.6% and 89.2% compared with the antibacterial rate of the cotton fabric finished by chitosan (the antibacterial rate on staphylococcus aureus and escherichia coli is respectively 63.8% and 52.8%), and the antibacterial rate of the cotton fabric finished by pterostilbene is improved by about 36.2% and 24.7% compared with the antibacterial rate of the cotton fabric finished by pterostilbene (the antibacterial rate on staphylococcus aureus and escherichia coli is respectively 73.3% and 80.1%). The natural pterostilbene grafted chitosan antibacterial agent has excellent antibacterial performance and has wide application prospect in antibacterial finishing of fabrics.
Claims (10)
1. The preparation method of the natural pterostilbene grafted chitosan is characterized by comprising the following steps of:
adding paraformaldehyde into acetic acid aqueous solution of chitosan, stirring until the paraformaldehyde is dissolved, adding pterostilbene for reaction, and after the reaction is finished, performing aftertreatment to obtain the natural pterostilbene grafted chitosan.
2. The method for preparing natural pterostilbene grafted chitosan according to claim 1, wherein the concentration of chitosan in acetic acid aqueous solution is 0.01-0.05 mol/L.
3. The method for preparing natural pterostilbene grafted chitosan according to claim 1, wherein the molar ratio of pterostilbene to chitosan repeating structural units is (0.1-0.5): 1;
the molar ratio of the repeating structural units to pterostilbene in the paraformaldehyde is 1:1.
4. The method for preparing natural pterostilbene grafted chitosan according to claim 1, wherein the reaction temperature after pterostilbene is 60-100 ℃.
5. A natural pterostilbene grafted chitosan, which is characterized by being prepared by the preparation method of the natural pterostilbene grafted chitosan according to any one of claims 1 to 4.
6. Use of the natural pterostilbene grafted chitosan of claim 5 in a process of antimicrobial finishing of fabrics.
7. The use according to claim 6, characterized in that the fabric antimicrobial finishing process comprises the steps of:
(1) Immersing the fabric pretreated by alkali liquor in a polyethyleneimine aqueous solution, washing to remove superfluous polyethyleneimine on the surface, and drying to obtain a polyethyleneimine treated fabric I;
(2) Soaking the fabric I in a sodium polystyrene sulfonate aqueous solution at room temperature, washing to remove unassembled sodium polystyrene sulfonate, and drying to obtain a sodium polystyrene sulfonate treated fabric II;
(3) Soaking the fabric II in a natural pterostilbene grafted chitosan finishing liquid at room temperature, washing to remove unassembled natural pterostilbene grafted chitosan, and drying to obtain an antibacterial fabric with the number of assembled layers being 1;
(4) Repeating the steps (2) and (3) for set times to obtain the antibacterial fabric with the corresponding assembly layer number.
8. The use according to claim 7, wherein in step (1) the concentration of the aqueous polyethyleneimine solution is between 20 and 40g/L;
the dipping bath ratio is 1 (20-40), the dipping temperature is 60-80 ℃, and the dipping time is 80-100 min;
in the step (2), the concentration of the sodium polystyrene sulfonate aqueous solution is 5-15 g/L;
the dipping bath ratio is 1 (40-60), and the dipping time is 10-30 min.
9. The use according to claim 7, wherein in step (3), the natural pterostilbene grafted chitosan finishing liquor is an aqueous solution of natural pterostilbene grafted chitosan; wherein the concentration of the natural pterostilbene grafted chitosan is 10-100 g/L;
the dipping bath ratio is 1 (40-60), and the dipping time is 10-30 min.
10. The use according to claim 7, wherein in step (4), the number of repetitions is set to 1 to 4, and the number of assembled layers of the finally obtained antibacterial fabric is set to 2 to 5.
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