Antibacterial fabric extracted from plants

Abstract

The invention discloses a plant extract antibacterial fabric, and relates to the technical field of fabrics, the plant extract antibacterial fabric comprises the following raw materials by weight: 60 parts of polypropylene resin, 15 parts of a plant extract, 5 parts of an activator, and 7.4 parts of an antibacterial agent; the activator is lactic acid; the plant extract is ginger polyphenol, wherein the content of 6-gingerol is not less than 80%; the antibacterial agent is prepared from 3 parts of carbon nanohorns, 1.2 parts of lanthanide doped up-conversion particles, 1 part of octadecyl glucoside and 2.2 parts of zinc oxide nanorods; the long-lasting antibacterial effect and the high antibacterial capacity can be achieved, and even the high antibacterial capacity is still achieved under the conditions of multiple times of water washing and sweat stain pH value changes.

Description

Technical Field

[0001] The present invention relates to the technical field of fabrics, and in particular to an antibacterial fabric extracted from plants. Background Art

[0002] Polypropylene fiber, commonly known as polypropylene, is made from propylene through polymerization and melt spinning. Due to its abundant raw material resources, low price, simple production process, light weight and softness, and excellent moisture-wicking and perspiration-wicking properties, it is widely used in clothing, decoration, and industrial products. It is particularly easy to blend with natural and chemical fibers to create fabrics, making it ideal for textiles that come into direct contact with the human skin, such as underwear, T-shirts, and bed sheets.

[0003] However, since the above-mentioned fabrics do not have antibacterial and skin-protecting functions, they are easily contaminated with various human secretions and various dirt in the environment when in contact with human skin, breeding bacteria or microorganisms, often causing great harm to the human body and affecting people's health.

[0004] In the prior art, antibacterial particles are often used to increase the antibacterial ability, such as metal particles containing silver, iron, and zinc. However, the interface bonding degree of metal particles in the fabric is poor, and the position of metal particles in the fabric is difficult to fix. When on the surface of the fabric, they are easy to fall off during repeated washing. When they are wrapped in the fabric, it is difficult to exert the antibacterial effect. In addition, since fabrics are often used in direct contact with human skin, they are easily exposed to sweat stains, which can easily lead to oxidation and migration of metal ions in acidic and alkaline environments, resulting in antibacterial failure. Summary of the Invention

[0005] The embodiments of the present application provide an antibacterial fabric extracted from plants, which solves the problem in the prior art that metal ion antibacterials are prone to failure of metal particles in abnormal environments during actual use, thereby achieving a long-lasting and stable antibacterial effect.

[0006] The present application provides an antibacterial fabric extracted from plants, wherein the raw materials include, by weight, 60 parts of polypropylene resin, 15 parts of plant extract, 5 parts of activator, and 7.4 parts of antibacterial agent; the activator is lactic acid; the plant extract is ginger polyphenol, wherein the content of 6-gingerol is not less than 80%; The antibacterial agent comprises 3 parts of carbon nanohorns, 1.2 parts of lanthanide-doped upconversion particles, 1 part of octadecyl glucoside, and 2.2 parts of zinc oxide nanorods.

[0007] Furthermore, the carbon nanohorn includes a carbon nanohorn quantum emitter and a carbon nanohorn photon capturer. The particle size of the carbon nanohorn photon capturer is 20nm, the particle size of the carbon nanohorn quantum emitter is 2nm, and the mass of the carbon nanohorn photon capturer is twice the mass of the carbon nanohorn quantum emitter.

[0008] Furthermore, the pretreatment method of the carbon nanohorn quantum emitter is as follows: in a sealed reactor protected by nitrogen, the carbon nanohorn quantum emitter, ZnO nanorods and a solvent of 90% ethanol are added; the reaction is carried out at 180°C and a pressure of 3MPa for 6 hours to obtain a quantum anchoring unit.

[0009] Furthermore, the pretreatment method of the carbon nanohorn photon capture body is as follows: the carbon nanohorn photon capture body is dispersed in DMF solvent, 0.5 parts of octadecyl glucoside is added as a hydrophobic template, and ultrasonic treatment is performed at 300W at 45°C for 30 minutes to obtain a photon capture unit.

[0010] Furthermore, the pretreatment method of the lanthanide-doped upconversion particles is as follows: the lanthanide-doped upconversion particles are dispersed in 50% ethanol, 0.1M 4-mercaptobenzoic acid ligand is added, and the mixture is shaken at 120 rpm for 24 hours at 25°C (pH = 6.5 ± 0.2) to obtain activated lanthanide-doped upconversion particles.

[0011] Furthermore, the preparation method of the antibacterial fabric is: The quantum anchor unit was melt-blended with polypropylene resin at 230±1°C and heated for 5000s. -1 High shear rate dispersion was performed and 0.1 wt% tripropyl borate anti-agglomeration agent was added to prepare the cortex spinning solution; Under nitrogen protection, ginger polyphenol and 3-mercaptopropionic acid were mixed in a molar ratio of 1:2 (calculated as 6-gingerol) and EDC / NHS catalyst (0.1M) was added. The mixture was reacted at 25°C for 12 hours to generate gingerol thiol derivatives. The ginger polyphenol derivatives were then reacted with 0.5 parts of octadecyl glucoside in a pH = 7.4 phosphate buffer and stirred at 50°C for 6 hours to form a ginger polyphenol complex. The complex was then melted with a photon capture unit and activated NaYF4 and polypropylene at 210 ± 1°C at a shear rate of 1000s. -1 , to obtain a core layer spinning solution; The fibers were prepared using a melt coaxial spinning method with two channels, with the outer channel extruding the sheath solution and the inner channel extruding the core solution. The flow ratio was 2:1 for the sheath:core layer, the draft ratio was 1:50, and the spinneret temperature was controlled in zones: 210±1°C for the core layer and 230±1°C for the sheath layer. The pulling speed was 3000 m / min, and the fibers were then rapidly cooled and solidified at 200°C / s. The fibers were then irradiated with a 475nm LED array (5000 lux intensity) in a 120°C hot air environment for energy level calibration. Then the plant-extracted antibacterial fabric is produced through spinning, weaving, bleaching, dyeing and shaping.

[0012] Furthermore, the shaping is performed by using a working liquid to attach to the fabric, then dipping, and finally baking at 180°C for 40 minutes. The working liquid is an acrylate polymer (low molecular weight type, 100,000-120,000 g / mol) and a ginger polyphenol auxiliary agent, with a mass ratio of 6:1.

[0013] One or more technical solutions provided in the embodiments of this application have at least the following technical effects or advantages: The combination of CNHs and NaYF4 covers the UV-NIR full spectrum activation, which solves the problem of narrow spectral response of traditional antimicrobial agents; ZnO-CNHs Z-type heterogeneity + NaYF4 upconversion inhibition e - -h + The compound extends the life of ROS and solves the problem of short life of active oxygen. The skin layer (PP / CNHs hydrophobic barrier) plus the core layer (slow-release ginger polyphenols) reduce washing loss and solve the problem of poor antibacterial persistence. Finally, the 20nm CNHs photothermal softening film and NaYF4 deep penetrating light enhance the efficiency of ROS entering the biofilm, solving the problem of difficult bacterial biofilm penetration. DETAILED DESCRIPTION

[0014] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this invention pertains; the terms used herein in the specification of the present invention are for the purpose of describing specific embodiments only and are not intended to limit the present invention; the term "and / or" used herein includes any and all combinations of one or more of the associated listed items.

[0015] Example 1: A plant-extracted antibacterial fabric, wherein the raw materials include, by weight, 60 parts of polypropylene resin, 15 parts of plant extract, 5 parts of activator, and 7.4 parts of antibacterial agent; the activator is lactic acid; the plant extract is ginger polyphenol, wherein the content of 6-gingerol is not less than 80%; The antibacterial agent includes three parts of carbon nanohorns (CNHs), lanthanide-doped upconversion particles (NaYF4:Yb 3+ / Er 3+ ) 1.2 parts, octadecyl glucoside 1 part, zinc oxide nanorods 2.2 parts (total surface area of ​​crystal plane (002): crystal plane (101) = 3:1); The carbon nanohorns include CNHs quantum emitters and CNHs photon capturers. The particle size of the CNHs photon capturer is 20nm, the particle size of the CNHs quantum emitter is 2nm, and the mass of the CNHs photon capturer is twice the mass of the CNHs quantum emitter. The pretreatment method of the antibacterial agent in the above antibacterial fabric is: In a nitrogen-protected sealed reactor, CNHs quantum emitters, ZnO nanorods, and 90% ethanol were added; the reaction was carried out at 180°C and 3 MPa pressure for 6 hours to obtain quantum anchoring units. The CNHs photon capture body was dispersed in DMF solvent and 0.5 parts of octadecyl glucoside was added as a hydrophobic template. The system was ultrasonicated at 300W for 30 minutes at 45°C to obtain a photon capture unit. NaYF4:Yb 3+ / Er 3+ Dispersed in 50% ethanol, 0.1 M 4-mercaptobenzoic acid (MPA) ligand was added, and shaken at 120 rpm at 25 °C for 24 h (pH = 6.5 ± 0.2) to obtain activated NaYF4; The preparation method of the above antibacterial fabric is: The quantum anchor unit was melt-blended with polypropylene resin at 230±1°C and heated for 5000s. -1 High shear rate dispersion was performed and 0.1 wt% tripropyl borate anti-agglomeration agent was added to prepare the cortex spinning solution; Under nitrogen protection, ginger polyphenol and 3-mercaptopropionic acid were mixed in a molar ratio of 1:2 (calculated as 6-gingerol) and EDC / NHS catalyst (0.1M) was added. The mixture was reacted at 25°C for 12 hours to generate gingerol thiol derivatives. The ginger polyphenol derivatives were then reacted with 0.5 parts of octadecyl glucoside in a pH = 7.4 phosphate buffer and stirred at 50°C for 6 hours to form a ginger polyphenol complex. The complex was then melted with a photon capture unit and activated NaYF4 and polypropylene at 210 ± 1°C at a shear rate of 1000s. -1 , to obtain a core layer spinning solution; The fibers were prepared using a melt coaxial spinning method with two channels, with the outer channel extruding the sheath solution and the inner channel extruding the core solution. The flow ratio was 2:1 for the sheath:core layer, the draft ratio was 1:50, and the spinneret temperature was controlled in zones: 210±1°C for the core layer and 230±1°C for the sheath layer. The pulling speed was 3000 m / min, and the fibers were then rapidly cooled and solidified at 200°C / s. The fibers were then irradiated with a 475nm LED array (5000 lux intensity) in a 120°C hot air environment for energy level calibration. Then, the antibacterial fabric extracted from plants is produced through spinning, weaving, bleaching, dyeing and shaping; The shaping process involves using a working liquid to attach to the fabric, then dipping it, and finally baking it at 180°C for 40 minutes. The working liquid is an acrylate polymer (low molecular weight type, 100,000-120,000 g / mol) and a ginger polyphenol auxiliary agent, with a mass ratio of 6:1.

[0016] The technical solutions in the above embodiments of the present application have at least the following technical effects or advantages: The benzene ring structure of 6-gingerol (containing phenolic hydroxyl group and β-hydroxy ketone) can bind to bacterial membrane phospholipids through hydrogen bonds or hydrophobic interactions, destroying membrane integrity; the phenolic hydroxyl group releases protons (H +) causes membrane potential imbalance and attacks bacterial proteins and DNA through oxidative stress (generating ROS); phenolic hydroxyl groups act as electron donors, quenching free radicals (such as ·OH) to enhance antioxidant properties and protect the fiber matrix; The phenolic hydroxyl groups of ginger polyphenols form an interfacial layer with the MPA ligands (-SH) on the surface of the upconversion particles through hydrogen bonds, enhancing the dispersion of the particles. The antioxidant properties of gingerol can inhibit the damage to the fibers caused by excessive ROS generated by the upconversion particles during photocatalysis. Gingerol thiol derivatives (-SH) are anchored on the surface of ZnO nanorods through covalent bonds (S-Zn), forming a "phenol-nanoro hybrid" interface and improving the efficiency of electron transfer.

[0017] Carbon nanohorns (CNHs) include quantum emitters (2nm) and photon capturers (20nm): the small size leads to quantum confinement effect, the valence band electrons are excited and then jump to the conduction band, resulting in fluorescence resonance energy transfer (FRET), enhancing near-infrared light absorption, and the large particle size provides a high specific surface area (sp 2 Carbon network), captures broad spectrum light energy through plasmon resonance (LSPR), converts it into heat energy or transfers it to quantum emitters; After absorbing light energy, the photon capturer (20 nm) transfers the energy to the quantum emitter (2 nm) through non-radiative Förster resonance energy transfer (FRET). The latter injects electrons into the ZnO conduction band (ZnO-CNHs heterojunction) through the quantum tunneling effect, promoting the separation of photogenerated electrons and holes and enhancing the antibacterial activity (ZnO+hν→e - +h + , h + oxidative bacterial membranes); sp of CNHs 2 The carbon network acts as an electron acceptor, capturing the visible light emitted by the upconversion particles, forming a "light energy relay" (NaYF4→CNHs→ZnO), and broadening the spectral response range.

[0018] Yb 3+ Absorbs 980nm infrared light and excites Er through energy transfer (ET) 3+ It emits 540nm (green light) and 660nm (red light) to penetrate bacterial biofilms. The 540nm light excites ZnO valence band electrons, and the 660nm light is absorbed by gingerol (π→π* transition), synergistically producing reactive oxygen species (ROS). The upconversion particles form a Type-II heterojunction with ZnO, and the photogenerated electrons are transferred from NaYF4 to ZnO, while the holes are retained in NaYF4, suppressing the e - -h + Compound, prolong ROS life; also with ginger polyphenols: Er 3+The 4f electrons of the molecule undergo dipole-dipole interaction with the π electron cloud of gingerol, enhancing the interface polarizability and improving the utilization rate of light energy.

[0019] The hydrophobicity of CNHs in the sheath spinning solution is highly compatible with polypropylene (PP) resin, forming a nano-barrier in the sheath to prevent bacterial attachment and delay the loss of antimicrobial agents. The 20nm CNHs / NaYF4 in the core spinning solution provides a dual photothermal and photodynamic effect, penetrating the interior of the fiber to kill latent bacteria, and utilizing its absorption of infrared light to enhance the final excitation through upconversion CNHs SPR. The antibacterial ability is improved by ginger polyphenols. The combination of CNHs and NaYF4 covers the full UV-NIR spectrum activation, solving the problem of narrow spectral response of traditional antimicrobial agents. The ZnO-CNHs Z-type heterojunction + NaYF4 upconversion inhibits e - -h + The compound extends the life of ROS and solves the problem of short life of active oxygen. The skin layer (PP / CNHs hydrophobic barrier) plus the core layer (slow-release ginger polyphenols) reduce washing loss and solve the problem of poor antibacterial persistence. Finally, the 20nm CNHs photothermal softening film and NaYF4 deep penetrating light enhance the efficiency of ROS entering the biofilm, solving the problem of difficult bacterial biofilm penetration.

[0020] In the sweat environment (pH 4.5-7.5), the phenolic hydroxyl group (-OH) of gingerol is protonated in an acidic environment to enhance its hydrophobicity, making it easier to insert into the bacterial membrane, destroying the membrane fluidity (similar to cationic antimicrobial peptides) and improving its antibacterial ability; ZnO partially dissolves to release zinc ions for direct antibacterial effect; in an alkaline environment, the generation of ·OH is inhibited, but ·O2 is promoted. - Produces (O2 + e - → O2 - ) improves the oxidative bactericidal effect, especially against Escherichia coli.

[0021] In order to verify the interaction between the components and the antibacterial ability, group experiments were conducted. The control group was a polypropylene resin fabric without added antibacterial agents and plant extracts. The experimental groups were divided into single-component groups (ginger polyphenol group, 20nm CNHs group, NaYF4 group), two-component groups (ginger polyphenol + CNHs group, ginger polyphenol + NaYF4 group, CNHs + NaYF4 group), and the whole group. At the same time, in order to verify the combined effect of CNHs with multiple particle sizes, the single particle size and combined particle size were tested. Among them, the single-component experiment is to add only a single component, the single-component group only adds the components after pretreatment of one component (CNHs photon capture body, ginger polyphenol complex, activated NaYF4), the two-component group is a combination of single components, and the full group is a combination of all three components. The particle size comparison group in the particle size control is the technical solution described in this embodiment. The single particle size group uses the same CNHs photon capture body as the full component group, and the cortex and core layers all use CNHs photon capture bodies. The experiments included antibacterial test, reactive oxygen species (ROS) test and stability test. In the antibacterial test (ISO 20743), Escherichia coli was inoculated into LB medium (37°C, 24h) and diluted to 10 5 CFU / mL: Cut fabric (5×5 cm), sterilize under UV for 30 min, add 100 μL of bacterial solution, cover with sterile film, and irradiate with simulated sunlight (xenon lamp, 400-800 nm, 1 W / cm²) for 30 min; rinse the fabric with PBS, dilute the eluate and plate (LB agar), incubate at 37°C for 24 h, count the colonies (CFU), and calculate the antibacterial rate; ;

[0022] The reactive oxygen species test was performed by flow cytometry. The fabric was cut into pieces (1×1 mm), immersed in 10 μM DCFH-DA solution (PBS, pH 7.4), incubated in the dark for 30 min, and laser irradiated at 980 nm (0.5 W / cm 2 ) irradiation for 10 min, synchronous visible light assisted (400-800 nm, 0.5 W / cm 2 ), green fluorescence (Ex / Em=488 / 525 nm) was detected by flow cytometry, 10,000 particles were analyzed, and the mean fluorescence intensity (MFI) was recorded; The stability test was a washability test. The washing method was based on AATCC TM61. The washing solution was 0.15% soap solution containing 5g steel balls, the temperature was 40°C, and each washing was for 45 minutes (equivalent to 5 home washes). After 100 washes, the antibacterial ability was tested and the antibacterial effect was retested. The stability test also included a pH stability test. The samples were immersed in pH 5.5, 7.0 (pH 7.0 was used in other experiments), and 7.4 buffer solutions for 1 hour, and then the antibacterial effect was tested. The results are shown in Table 1. Table 1 Experimental verification results

[0023] Example 2: The above example prepares an antibacterial fabric extracted from biological materials, and on this basis, the application method is improved. This example is a cleaning method thereof.

[0024] Soak the fabric in citric acid buffer solution with pH = 5.0 ± 0.2 (temperature 30℃) for 10 minutes, use protease detergent as detergent, concentration 0.5wt%, water temperature 20-25℃, flow rate less than 1m / s, time 8-10min, then use 20Hz low-frequency mechanical vibration for 3 minutes, dehydrate, and air dry. Use intermittent blue light irradiation (475nm, 500lux, 30s / 2min) during the drying process.

[0025] The technical solutions in the above embodiments of the present application have at least the following technical effects or advantages: A weak acidic environment triggers a pH-responsive switch, releasing zinc ions that bind to the edge carboxyl groups of CNHs to form a temporary protective layer (resistant to mechanical shear). Mechanical vibration is used to transmit stress waves to the 2nm CNHs to generate a piezoelectric field, driving the migration of photogenerated holes in ZnO to remove organic residues on the surface. Blue light excites the 20nm CNHs to produce LSPR, and local heating (50-60°C) accelerates the desorption of water molecules. Thermal energy simultaneously activates upconversion particles and continuously generates antibacterial free radicals.

[0026] The foregoing description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Various modifications and variations are readily apparent to those skilled in the art. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention shall be included within the scope of protection of the present invention.

Claims

1. An antibacterial fabric extracted from plants, characterized in that: The raw materials include 60 parts of polypropylene resin, 15 parts of plant extract, 5 parts of activator, and 7.4 parts of antibacterial agent by weight; the activator is lactic acid; the plant extract is ginger polyphenol, wherein the content of 6-gingerol is not less than 80%; The antibacterial agent comprises 3 parts of carbon nanohorns, 1.2 parts of lanthanide-doped upconversion particles, 1 part of octadecyl glucoside, and 2.2 parts of zinc oxide nanorods.

2. The antibacterial fabric extracted from plants according to claim 1, characterized in that: The carbon nanohorn includes a carbon nanohorn quantum emitter and a carbon nanohorn photon capturer. The particle size of the carbon nanohorn photon capturer is 20nm, the particle size of the carbon nanohorn quantum emitter is 2nm, and the mass of the carbon nanohorn photon capturer is twice the mass of the carbon nanohorn quantum emitter.

3. The antibacterial fabric extracted from plants according to claim 1, characterized in that: The pretreatment method of the carbon nanohorn quantum emitter is as follows: in a sealed reactor protected by nitrogen, the carbon nanohorn quantum emitter, ZnO nanorods and 90% ethanol solvent are added; the reaction is carried out at 180°C and 3MPa pressure for 6 hours to obtain a quantum anchoring unit.

4. The plant-extracted antibacterial fabric according to claim 1, characterized in that: The pretreatment method of the carbon nanohorn photon capture body is as follows: the carbon nanohorn photon capture body is dispersed in DMF solvent, 0.5 parts of octadecyl glucoside is added as a hydrophobic template, and ultrasonic treatment is performed at 300W at 45°C for 30 minutes to obtain a photon capture unit.

5. The plant-extracted antibacterial fabric according to claim 1, characterized in that: The pretreatment method of the lanthanide-doped upconversion particles is as follows: the lanthanide-doped upconversion particles are dispersed in 50% ethanol, 0.1 M 4-mercaptobenzoic acid ligand is added, and the mixture is shaken at 120 rpm at 25° C. for 24 hours to obtain activated lanthanide-doped upconversion particles.

6. The antibacterial fabric extracted from plants according to claim 1, characterized in that: The preparation method of antibacterial fabric is as follows: The quantum anchor unit was melt-blended with polypropylene resin at 230±1°C and heated for 5000s. -1 High shear rate dispersion was performed and 0.1 wt% tripropyl borate anti-agglomeration agent was added to prepare the cortex spinning solution; Under nitrogen protection, ginger polyphenol and 3-mercaptopropionic acid were mixed in a molar ratio of 1:2 and added with EDC / NHS catalyst, and reacted at 25 ° C for 12 hours to generate gingerol thiol derivatives; then reacted with 0.5 parts of octadecyl glucoside in pH = 7.4 phosphate buffer, stirred at 50 ° C for 6 hours to form ginger polyphenol complex, and then melted with photon capture unit and activated NaYF4 and polypropylene at 210 ± 1 ° C, with a shear rate of 1000s -1 , to obtain a core layer spinning solution; The fibers were melt-spinned using a dual-channel method. The outer channel extruded the sheath solution, while the inner channel extruded the core solution. The flow ratio was 2:1 for the sheath:core layer, and the draft ratio was 1:

50. The spinneret temperature was controlled in zones: 210±1°C for the core layer and 230±1°C for the sheath layer. The pulling speed was 3000 m / min. The fibers were then rapidly cooled and solidified at 200°C / s. The fibers were then irradiated with a 475nm LED array in a 120°C hot air environment for energy level calibration. Then the plant-extracted antibacterial fabric is produced through spinning, weaving, bleaching, dyeing and shaping.

7. The plant-extracted antibacterial fabric according to claim 1, characterized in that: The shaping process is to use a working liquid to attach to the fabric, then immerse it, and finally bake it at 180°C for 40 minutes. The working liquid is an acrylate polymer and a ginger polyphenol auxiliary agent, with a mass ratio of 6:1.

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