CN116556069A - Photo-thermal antibacterial modified cotton cloth based on ZIF-67 nano-particle in-situ synthesis and preparation method and application thereof - Google Patents
Photo-thermal antibacterial modified cotton cloth based on ZIF-67 nano-particle in-situ synthesis and preparation method and application thereof Download PDFInfo
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- 229920000742 Cotton Polymers 0.000 title claims abstract description 162
- 239000004744 fabric Substances 0.000 title claims abstract description 148
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 48
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 39
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 36
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000001308 synthesis method Methods 0.000 title description 2
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 29
- 239000003814 drug Substances 0.000 claims abstract description 15
- 229940079593 drug Drugs 0.000 claims abstract description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- SLCITEBLLYNBTQ-UHFFFAOYSA-N CO.CC=1NC=CN1 Chemical compound CO.CC=1NC=CN1 SLCITEBLLYNBTQ-UHFFFAOYSA-N 0.000 claims description 9
- 241000588724 Escherichia coli Species 0.000 claims description 7
- RJQXTJLFIWVMTO-TYNCELHUSA-N Methicillin Chemical compound COC1=CC=CC(OC)=C1C(=O)N[C@@H]1C(=O)N2[C@@H](C(O)=O)C(C)(C)S[C@@H]21 RJQXTJLFIWVMTO-TYNCELHUSA-N 0.000 claims description 7
- 206010041925 Staphylococcal infections Diseases 0.000 claims description 7
- 241000191967 Staphylococcus aureus Species 0.000 claims description 7
- 208000015688 methicillin-resistant staphylococcus aureus infectious disease Diseases 0.000 claims description 7
- 229960003085 meticillin Drugs 0.000 claims description 7
- ISDKBADJUSXAFO-UHFFFAOYSA-L CO.[Co](Cl)Cl Chemical compound CO.[Co](Cl)Cl ISDKBADJUSXAFO-UHFFFAOYSA-L 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 4
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 230000002209 hydrophobic effect Effects 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 2
- 241000894007 species Species 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 241000894006 Bacteria Species 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 8
- 239000002086 nanomaterial Substances 0.000 abstract description 7
- 239000004753 textile Substances 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 17
- 239000000835 fiber Substances 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 7
- 230000001580 bacterial effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 4
- 230000004083 survival effect Effects 0.000 description 4
- 239000003242 anti bacterial agent Substances 0.000 description 3
- 229940088710 antibiotic agent Drugs 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 3
- 230000003115 biocidal effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000012258 culturing Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- 229910020676 Co—N Inorganic materials 0.000 description 1
- 241000192125 Firmicutes Species 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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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
- 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
- D06M15/687—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing atoms other than phosphorus, silicon, sulfur, nitrogen, oxygen or carbon in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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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
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention relates to the technical field of nano material in-situ synthesis and textile modification, in particular to photo-thermal antibacterial modified cotton cloth based on ZIF-67 nano particle in-situ synthesis, and a preparation method and application thereof. According to the preparation method, ZIF-67 nano particles are synthesized on cotton cloth in situ, and photo-thermal antibacterial modified cotton cloth based on ZIF-67 nano particles in situ synthesis is obtained. The preparation method provided by the invention has the advantages of simple process and low production cost; the temperature of the prepared modified cotton cloth can reach 120 ℃ in 30s under the irradiation of Near Infrared (NIR) and the surface of the modified cotton cloth is killed by 99.99% of drug-resistant bacteria after the irradiation of NIR for 3min.
Description
Technical Field
The invention relates to the technical field of nano material in-situ synthesis and textile modification, in particular to photo-thermal antibacterial modified cotton cloth based on ZIF-67 nano particle in-situ synthesis, and a preparation method and application thereof.
Background
The increasing antibiotic resistance has a serious influence in various fields of public health, clinical treatment and the like, namely, the use of antibiotics is required to be continuously limited in medical and health, and the use of antibiotics is gradually forbidden in livestock breeding. On the other hand, the high cost and long period necessary for developing new antibiotics have resulted in a growth rate that is difficult to rival the development rate of antibiotic resistance.
The photo-thermal characteristics of the metal related nano material have general killing capability on drug-resistant bacteria. The part of nano material can efficiently convert light with specific wavelength into heat energy, thereby achieving the aim of killing surface bacteria with specific area height Wen Yongyi. Wherein the zeolite-like imidazole framework material (Zeolitic Imidazolate Frameworks, ZIFs) is a metal nanomaterial formed by self-assembly of different kinds of metal ions and organic ligands, and the ZIF-67 is specifically cobalt ions (Co 2+ ) The ZIFs nano material which is complexed with the 2-methylimidazole has the advantages of low synthesis cost, good biocompatibility, larger specific surface area and certain photo-thermal property, and is widely applied to the fields of catalysis, biological medicine and the like.
The modified textile with photothermal antibacterial capability can be obtained by selecting proper nano materials to combine with textile fibers, so that pathogenic bacteria contacting and contaminating the surface can be killed. Most of the existing antibacterial textiles are complex in synthesis process, more in intermediate products, high in toxicity, complex in equipment, high in cost and difficult to produce in a large scale, and in addition, the nano particles on the surface of the prepared antibacterial textiles are unevenly and infirm in load.
Cotton cloth has good flexibility and high mechanical property, is a natural fiber material widely used by textile industry, and has abundant binding sites for binding and reacting with nano particles.
Therefore, developing a modified cotton cloth with photo-thermal antibacterial capability is an urgent goal for researchers in the technical field.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides photo-thermal antibacterial modified cotton cloth based on ZIF-67 nano-particle in-situ synthesis, and a preparation method and application thereof. The preparation method has the advantages of simple process and low production cost; the temperature of the prepared modified cotton cloth can reach 120 ℃ in 30s under the irradiation of Near Infrared (NIR) and the surface of the modified cotton cloth is killed by 99.99% of drug-resistant bacteria after the irradiation of NIR for 3min.
The technical scheme provided by the invention is as follows:
a preparation method of photo-thermal antibacterial modified cotton cloth based on ZIF-67 nano-particle in-situ synthesis comprises the following steps: and synthesizing ZIF-67 nano particles on the cotton cloth in situ to obtain the photo-thermal antibacterial modified cotton cloth based on the ZIF-67 nano particles in situ synthesis.
Based on the technical scheme, the ZIF-67 nano particles can be directly synthesized in situ on cotton cloth by combining with the synthesis of ZIF-67. The ZIF-67 nano particles are well combined with cotton cloth, are uniformly distributed and have strong circulation stability, and can not cause physical or chemical damage to cotton cloth fibers in the process. The obtained material has new photo-thermal antibacterial capability, and basically maintains the original state and performance of cotton cloth fiber.
Specifically, the cotton cloth is raw cotton fiber cotton cloth or modified cotton cloth which is not subjected to hydrophobic treatment.
The preparation method has wide applicability to cotton cloth materials. Raw cotton cloth, such as common cotton cloth obtained by commercialization, including but not limited to plain cloth, twill cloth, etc.; it is not subjected to any special treatment, and can also be recycled cotton cloth recovered after use. In addition, the method can be also suitable for other modified cotton cloth which is not subjected to hydrophobic treatment, such as various cotton cloth which is subjected to concentrated alkali treatment.
Specifically, the cotton cloth is raw cotton fiber cotton cloth, the radial yarn is cotton cloth yarn, and the weft direction is cotton cloth yarn; the infrared characteristic peak value thereof comprises 2901.55cm -1 Where 3332.52cm -1 Where 1426.35cm -1 Department and 1029.22cm -1 Where it is located.
The preparation method of the photo-thermal antibacterial modified cotton cloth based on ZIF-67 nano-particle in-situ synthesis specifically comprises the following steps:
1) Preparation of cobalt chloride methanol solution: dissolving cobalt chloride hexahydrate in methanol, and uniformly dispersing by ultrasonic to form cobalt chloride methanol solution with the concentration of 180-220 mM;
2) Adding cotton cloth into the solution obtained in the step 1), and stirring at room temperature;
3) Preparation of 2-methylimidazole methanol solution: dissolving 2-methylimidazole in methanol, and uniformly dispersing by ultrasonic to form a 2-methylimidazole methanol solution with the concentration of 1800-2200 mM;
4) Adding the 2-methylimidazole methanol solution obtained in the step 3) into the solution obtained in the step 2) according to the volume ratio of 1:1, and continuing stirring at room temperature;
5) Taking out cotton cloth from the solution obtained in the step 4), and drying the cotton cloth in an oven overnight to obtain the photo-thermal antibacterial modified cotton cloth based on ZIF-67 nano-particle in-situ synthesis.
The invention also provides photo-thermal antibacterial modified cotton cloth based on ZIF-67 nano-particle in-situ synthesis, which is prepared by the preparation method.
Specifically, the photo-thermal antibacterial modified cotton cloth synthesized in situ based on ZIF-67 nano particles has an infrared characteristic peak value of 755.63cm -1 Where 1577.72cm -1 Where 2901.55cm -1 Where 3332.52cm -1 Where 1426.35cm -1 Department and 1029.22cm -1 Where it is located.
As can be seen by comparing with the infrared data of the raw cotton cloth, the preparation method successfully synthesizes the ZIF-67 nano particles in situ under the condition of not chemically damaging the raw cotton cloth.
Specifically, the loading of ZIF-67 nano particles on cotton cloth is 1.6+/-0.1 mg/cm 2 。
Based on the technical scheme, the light-heat performance is low due to the fact that the load is lower than the load, and the temperature required by sterilization cannot be reached after NIR irradiation; above this loading, the properties of the cotton fibers themselves are significantly affected, and the original properties of the cotton fibers are partially lost.
The invention also provides application of the photo-thermal antibacterial modified cotton cloth based on ZIF-67 nano-particle in-situ synthesis, which is used for preparing photo-thermal antibacterial materials.
The photo-thermal antibacterial modified cotton cloth provided by the invention not only has new photo-thermal antibacterial performance, but also maintains the state and performance of the original cotton cloth, so that the photo-thermal antibacterial modified cotton cloth can be applied to the scene which is originally suitable for the cotton cloth, and the photo-thermal antibacterial capability can be further realized under the condition. The temperature rising speed is high, and the temperature is maintained well.
Specifically, the photo-thermal antibacterial modified cotton cloth is subjected to antibacterial under the following illumination conditions: near infrared light with the wavelength of 808nm is adopted; the laser power density was 10.5W/cm 2 。
Specifically, the species inhibited include, but are not limited to: drug resistant escherichia coli (Drug Resistant Escherichia coli, DREC) and methicillin resistant staphylococcus aureus (Methicillin Resistant Staphylococcus aureus, MRSA).
For each strain, the photo-thermal antibacterial modified cotton cloth provided by the invention has antibacterial capacity of up to 99.99%.
Drawings
Fig. 1 is a physical and electronic microscope morphology diagram, which comprises a common cotton cloth physical diagram (a), a common cotton cloth scanning electronic microscope diagram (b, c, d, e), a modified cotton cloth physical diagram (f) and a modified cotton cloth scanning electronic microscope diagram (g, h, i, j).
FIG. 2 shows the IR spectrum of common cotton cloth and modified cotton cloth.
FIG. 3 shows that the common cotton cloth and the modified cotton cloth are at 10.5W/cm 2 Temperature profile of 808nm NIR irradiation for 5min over time.
FIG. 4 shows a modified cotton cloth at 10.5W/cm 2 Temperature profile over time for 5 consecutive cycles of 5min of NIR irradiation at 808nm of (F).
FIG. 5 shows the survival rate of DREC on the surface of modified cotton cloth or common cotton cloth after 3min NIR or light shielding treatment.
FIG. 6 shows survival rate of MRSA on the surface of modified cotton cloth or common cotton cloth after treatment with NIR for 3min or in the dark.
Detailed Description
The principles and features of the present invention are described below with examples only to illustrate the present invention and not to limit the scope of the present invention.
Testing method and material
Photo-thermal performance test:
the prepared modified cotton cloth is placed on a glass plate in sequence, NIR light is used for irradiation, the distance between the laser and the modified cotton cloth is 20cm, and a thermal imager is used for recording temperature change every 30 seconds.
Antibacterial ability test based on photo-thermal properties:
selecting single colony of drug-resistant Escherichia coli in LB liquid medium and single colony of methicillin-resistant Staphylococcus aureus in MH liquid medium, culturing to logarithmic phase, diluting with sterile PBS, testing OD value of bacteria with ultraviolet-visible spectrophotometer, adjusting OD600 of bacterial solution to 1.40, and at the same time, corresponding bacterial concentration of 4.00×10 9 CFU/mL. And 1 mu L of the bacterial suspension is respectively dripped on the modified cotton cloth obtained in the step 5) and the common cotton cloth selected in the step 2), the light group is treated by using NIR for 3min, the bacterial droplets are in the light spot area, and the light-shielding control group is kept still in the dark for 3min. The treated samples were transferred to sterile centrifuge tubes and 2mL of PBS was added. Bacteria on the surface of the sample were eluted with PBS, and then 20. Mu.L of each of the eluate was aspirated for dilution coating, and the kill rate was calculated.
The cotton cloth is common cotton cloth obtained by commercialization, no special treatment is carried out, the radial yarn is cotton cloth yarn, and the weft direction is cotton cloth yarn. The average diameter of the cotton cloth fiber is 10.53 mu m plus or minus 1.68 mu m, and the average pore size of the cotton cloth is 25.58 plus or minus 3.81 mu m.
Drug resistant escherichia coli (Drug Resistant Escherichia coli, DREC) and methicillin resistant staphylococcus aureus (Methicillin Resistant Staphylococcus aureus, MRSA), both supplied by third people hospitals in the martial arts.
Example 1:
the preparation method of the photo-thermal antibacterial modified cotton cloth based on ZIF-67 nano-particle in-situ synthesis comprises the following steps:
1) Preparation of cobalt chloride methanol solution: 1.19g of cobalt chloride hexahydrate was dissolved in 25mL of methanol and dispersed uniformly by ultrasound to form a cobalt chloride methanol solution having a concentration of 200 mM;
2) Adding 1cm multiplied by 1cm common cotton cloth into the solution obtained in the step 1), and stirring at room temperature for 1h;
3) Preparation of 2-methylimidazole methanol solution: dissolving 4.11g of 2-methylimidazole in 25mL of methanol, and uniformly dispersing by ultrasonic to form a 2-methylimidazole methanol solution with a concentration of 2000 mM;
4) Adding the 2-methylimidazole methanol solution obtained in the step 3) into the solution obtained in the step 2), and continuously stirring at room temperature for 1h;
5) And 4) taking out cotton cloth from the solution obtained in the step 4), and drying the cotton cloth in an oven at 60 ℃ overnight to obtain the modified cotton cloth synthesized in situ based on ZIF-67 nano particles.
Example 2:
the modified cotton obtained in example 1 was used, and ordinary cotton was used as a control. Photographing an object; and then carrying out platinum spraying treatment on the surface, and observing the morphology of the surface under a field emission scanning electron microscope. The results are shown in FIG. 1.
In fig. 1, the cotton cloth scanning electron microscope comprises a common cotton cloth physical image (a), a common cotton cloth scanning electron microscope image (b, c, d, e), a modified cotton cloth physical image (f) and a modified cotton cloth scanning electron microscope image (g, h, i, j). Therefore, the cotton cloth substrate is commercially available common cotton cloth, no special treatment is performed, the radial yarns are cotton cloth yarns, and the weft directions are cotton cloth yarns; the average diameter of the cotton cloth fiber is 10.53 mu m plus or minus 1.68 mu m, and the average pore size of the cotton cloth is 25.58 plus or minus 3.81 mu m.
After in-situ synthesis of ZIF-67, the obtained modified cotton cloth has dark blue color, the average diameter of cotton cloth fiber is about 10.62+/-1.05 mu m, the average pore diameter of cotton cloth is 22.31+/-4.40 mu m, and the particle size of ZIF-67 nano particles on the surface is 346.10+/-86.55 nm. After ZIF-67 nano particles are synthesized in situ, the diameter and the pore diameter of the modified cotton cloth fiber are not changed much compared with those of common cotton cloth fibers, so that the characteristics of the cotton cloth fiber are basically maintained, and the fact that the in situ synthesis does not cause physical damage to the cotton cloth fiber is shown.
Example 3:
the modified cotton obtained in example 1 was used and characterized by infrared spectrum using ordinary cotton as a control. The results are shown in FIG. 2.
FIG. 2 is an infrared spectrum of plain cotton and modified cotton. Common cottonThe characteristic peak of the cloth comprises 2901.55cm -1 Where 3332.52cm -1 Where 1426.35cm -1 Department and 1029.22cm -1 Where the modified cotton cloth comprises 755.63cm -1 Where 1577.72cm -1 Where 2901.55cm -1 Where 3332.52cm -1 Where 1426.35cm -1 Department and 1029.22cm -1 Where it is located. Wherein 3332.52cm of common cotton cloth -1 The peak value is the absorption peak of the hydroxy (O-H) stretching vibration, 2901.55cm -1 Peak at methylene (-CH) 2 ) Absorption peak of telescopic vibration 1426.35cm -1 The peak value is the absorption peak of hydroxyl (O-H) flexural vibration, 1029.22cm -1 The peak value is C-O telescopic vibration absorption peak, 1100-1400 cm -1 The absorption peak of the stretching vibration of the ether bond (C-O-C) is arranged in the interval. 755.63cm from modified cotton -1 The peak value is the absorption peak of Co-N bond stretching vibration, 1577.72cm -1 The peak is the absorption peak of the c=n bond in the imidazole ring. These two characteristic peaks are unique to ZIF-67 nanoparticles, which in turn demonstrate that ZIF-67 nanoparticles are grown on the modified cotton cloth. In addition, the original peaks of the cotton cloth are detected on the modified cotton cloth, which indicates that the in-situ synthesis does not cause chemical damage to the cotton cloth.
Example 4:
the modified cotton obtained in example 1 was used, and ordinary cotton was used as a control.
Photo-thermal performance test: and 5) sequentially placing the modified cotton cloth obtained in the step 5) on a glass plate, irradiating with NIR light, keeping the distance between the laser and the modified cotton cloth at 20cm, and recording temperature change every 30s by using a thermal imager.
The NIR wavelength used was 808nm and the laser power density was 10.5W/cm 2 。
FIG. 3 is a graph showing the temperature of common cotton cloth and modified cotton cloth irradiated with NIR for 5min as a function of time. This shows that the modified cotton cloth is excellent in photo-thermal properties, can reach 120℃within 30 seconds, and can maintain this temperature in 5 minutes of irradiation.
FIG. 4 is a graph of temperature versus time for a modified cotton cloth continuously cycled 5 times for 5 minutes under NIR irradiation. After 5 cycles of heating and cooling, the highest temperature reached by the modified cotton cloth after NIR irradiation is kept stable, which shows that the photo-thermal characteristics of the modified cotton cloth are kept stable for a long time and a certain cycle times.
Example 5:
the modified cotton obtained in example 1 was used, and ordinary cotton was used as a control. And antibacterial ability test was performed according to the photo-thermal properties obtained in example 4.
Antibacterial ability test based on photo-thermal properties: respectively picking DREC single colony in LB liquid medium and MARS and placing them in MH liquid medium, culturing to logarithmic phase, diluting with sterile PBS for use, testing OD value of bacteria with ultraviolet-visible spectrophotometer, regulating OD600 of bacteria liquid to 1.40, and at this time, the corresponding bacterial concentrations are all 4.00×10 9 CFU/mL. And 1 mu L of the bacterial suspension is respectively dripped on the modified cotton cloth obtained in the step 5) and the common cotton cloth selected in the step 2), the light group is treated by using NIR for 3min, the bacterial droplets are in the light spot area, and the light-shielding control group is kept still in the dark for 3min. The treated samples were transferred to sterile centrifuge tubes and 2mL of PBS was added. The bacteria on the surface of the sample were eluted with PBS, and then 20. Mu.L of each of the eluate was diluted and coated, and the number of colonies grown by counting was counted for 24 hours, thereby calculating the kill rate.
The NIR wavelength used was 808nm and the laser power density was 10.5W/cm 2 。
Fig. 5 shows the survival rate of the modified cotton cloth and the DREC on the surface of the common cotton cloth after being treated by 3min NIR or light-shielding, and fig. 6 shows the survival rate of the modified cotton cloth and the MRSA on the surface of the common cotton cloth after being treated by 3min NIR or light-shielding, so that the modified cotton cloth can kill 99.997% of the DREC and 99.993% of the MRSA after being irradiated by 3min NIR. DREC is representative of drug-resistant gram-negative bacteria, MRSA is representative of drug-resistant gram-positive bacteria, and the modified cotton cloth has a killing capacity of more than 99.99% on the drug-resistant gram-negative bacteria.
In conclusion, the results of the examples show that the method has simple process, the modified cotton cloth has excellent and stable photo-thermal characteristics, and 99.99% of drug-resistant bacteria on the surface can be effectively killed, so that the method has wide application prospects in the production of antibacterial medical equipment and household antibacterial fabrics.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (10)
1. The preparation method of the photo-thermal antibacterial modified cotton cloth based on ZIF-67 nano-particle in-situ synthesis is characterized by comprising the following steps: and synthesizing ZIF-67 nano particles on the cotton cloth in situ to obtain the photo-thermal antibacterial modified cotton cloth based on the ZIF-67 nano particles in situ synthesis.
2. The preparation method of the photo-thermal antibacterial modified cotton cloth based on ZIF-67 nanoparticle in-situ synthesis as claimed in claim 1, which is characterized by comprising the following steps: the cotton cloth is raw cotton fiber cotton cloth or non-hydrophobic modified cotton fiber cotton cloth.
3. The preparation method of the photo-thermal antibacterial modified cotton cloth based on ZIF-67 nanoparticle in-situ synthesis as claimed in claim 2, which is characterized by comprising the following steps: the cotton cloth is raw cotton fiber cotton cloth, the radial yarn is cotton cloth yarn, and the weft direction is cotton cloth yarn; the infrared characteristic peak value thereof comprises 2901.55cm -1 Where 3332.52cm -1 Where 1426.35cm -1 Department and 1029.22cm -1 Where it is located.
4. The preparation method of the photo-thermal antibacterial modified cotton cloth based on ZIF-67 nanoparticle in-situ synthesis according to any one of claims 1 to 3, which is characterized by comprising the following steps:
1) Preparation of cobalt chloride methanol solution: dissolving cobalt chloride hexahydrate in methanol, and uniformly dispersing by ultrasonic to form cobalt chloride methanol solution with the concentration of 180-220 mM;
2) Adding cotton cloth into the solution obtained in the step 1), and stirring at room temperature;
3) Preparation of 2-methylimidazole methanol solution: dissolving 2-methylimidazole in methanol, and uniformly dispersing by ultrasonic to form a 2-methylimidazole methanol solution with the concentration of 1800-2200 mM;
4) Adding the 2-methylimidazole methanol solution obtained in the step 3) into the solution obtained in the step 2) according to the volume ratio of 1:1, and continuing stirring at room temperature;
5) Taking out cotton cloth from the solution obtained in the step 4), and drying the cotton cloth in an oven overnight to obtain the photo-thermal antibacterial modified cotton cloth based on ZIF-67 nano-particle in-situ synthesis.
5. A photo-thermal antibacterial modified cotton cloth based on ZIF-67 nanoparticle in-situ synthesis prepared by the preparation method according to any one of claims 1 to 4.
6. The photo-thermal antibacterial modified cotton cloth based on ZIF-67 nanoparticle in-situ synthesis according to claim 5, wherein the photo-thermal antibacterial modified cotton cloth is characterized in that: the infrared characteristic peak value thereof comprises 755.63cm -1 Where 1577.72cm -1 Where 2901.55cm -1 Where 3332.52cm -1 Where 1426.35cm -1 Department and 1029.22cm -1 Where it is located.
7. The photo-thermal antibacterial modified cotton cloth based on ZIF-67 nanoparticle in-situ synthesis according to claim 5, wherein the photo-thermal antibacterial modified cotton cloth is characterized in that: the loading of ZIF-67 nano particles on cotton cloth is 1.6+/-0.1 mg/cm 2 。
8. Use of a photo-thermal antibacterial modified cotton cloth based on ZIF-67 nanoparticle in situ synthesis according to any one of claims 5 to 7, characterized in that: is used for preparing photothermal antibacterial materials.
9. The use according to claim 8, characterized in that: the photo-thermal antibacterial modified cotton cloth is subjected to antibacterial under the following illumination conditions: near infrared light with the wavelength of 808nm is adopted; the laser power density was 10.5W/cm 2 。
10. The use according to claim 8, wherein the suppressed species include, but are not limited to: drug resistant escherichia coli (Drug Resistant Escherichia coli, DREC) and methicillin resistant staphylococcus aureus (Methicillin Resistant Staphylococcus aureus, MRSA).
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| CN202310255055.6A CN116556069A (en) | 2023-03-16 | 2023-03-16 | Photo-thermal antibacterial modified cotton cloth based on ZIF-67 nano-particle in-situ synthesis and preparation method and application thereof |
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| CN202310255055.6A CN116556069A (en) | 2023-03-16 | 2023-03-16 | Photo-thermal antibacterial modified cotton cloth based on ZIF-67 nano-particle in-situ synthesis and preparation method and application thereof |
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