CN111270520A - A flexible fabric capable of efficiently luminescent detection of bacteria and its preparation method and application - Google Patents

Abstract

The invention discloses a flexible fabric capable of efficiently emitting light to detect bacteria, and a preparation method and application thereof. Grafting hybrid luminescent nanoparticles on the surface of a fabric through a covalent bond, wherein the hybrid luminescent nanoparticles are obtained by embedding a metal ion complex with high-efficiency luminescent property by using natural biological polyelectrolyte with negative charges, such as heparin sodium, sodium hyaluronate, chondroitin sulfate and the like; after the luminous fabric is co-cultured with escherichia coli (e.coli) and staphylococcus aureus (s.aureus) for 12-24 hours, the existence of bacteria can be detected through the quenching of the fluorescence signal of the luminous fabric.

Description

A flexible fabric capable of efficiently luminescent detection of bacteria and its preparation method and application

technical field

The invention relates to a flexible fabric capable of efficiently detecting bacteria by luminescence, and a preparation method and application thereof.

Background technique

The fabric has the advantages of high strength, soft hand feeling and strong skin affinity, so it is widely used in daily life. However, fabrics are susceptible to damage by bacteria. Bacteria can live on fabrics and spread disease. The mechanical properties and certain functions of the fabric may be impaired. Bacterial infections are becoming increasingly difficult to treat due to rising antibiotic resistance and stalled antibiotic development and approval. It is very urgent to develop a functional fabric in order to detect the presence of bacteria as early as possible.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide a flexible fabric capable of efficiently detecting bacteria by luminescence, and a preparation method and application thereof. After co-culturing the luminescent fabric with Escherichia coli (E.coli) and Staphylococcus aureus (S. aureus) for 12-24 hours, the presence of bacteria can be detected by quenching the fluorescent signal of the luminescent fabric itself. In the present invention, the hybrid luminescent nanoparticles are grafted on the surface of the fabric through covalent bond. Hybrid luminescent nanoparticles are obtained by embedding metal ion complexes with highly efficient luminescent properties with negatively charged natural biopolyelectrolytes such as sodium heparin, sodium hyaluronate, and chondroitin sulfate.

A preparation method of a flexible fabric capable of efficiently detecting bacteria by luminescence, comprising the following steps:

(1) Prepare solution: configure polyelectrolyte solution with acetic acid-sodium acetate buffer solution of 0.1M pH= ₅ ; configure EuCl solution, tta solution and phen solution with ethanol;

( ₂ ) Preparation of hybrid luminescent nanoparticles: add tta solution dropwise to the EuCl solution, adjust the pH of the reaction solution to be 6-8 after stirring with a magnetic stirrer for 1-2 hours, add phen solution dropwise to it, stir for 1- After 5 hours, the negatively charged polyelectrolyte solution was added thereto, and the hybrid luminescent nanoparticles were obtained after stirring for 1-5 hours;

(3) Preparation of flexible luminescent cotton fabric: at room temperature to 90°C, the fabric is treated in the reaction solution for 2-10 hours, and then the prepared hybrid luminescent nanoparticles are added to it to maintain the temperature from room temperature to 90°C, and treated for 2 -10 hours to obtain the flexible fabric; the reaction solution consists of a non-formaldehyde crosslinking agent and a penetrating agent.

In the preparation method, the concentration of EuCl ₃ ethanol solution is 0.01mol/L; the concentration of tta ethanol solution is 0.03mol/L; the concentration of phen ethanol solution is 0.01mol/L.

In the preparation method, the ratio of EuCl ₃ , tta and phen substances is EuCl ₃ :tta:phen=1:3:1.

In the preparation method, the polyelectrolyte solution is a substance consisting of one or two of natural biological polyelectrolytes including sodium heparin, sodium hyaluronate and chondroitin sulfate.

In the preparation method, when stirring on a magnetic stirrer, the stirring speed is 800rpm-1500rpm.

In the preparation method, the fabrics are polyester-cotton fabrics, pure cotton fabrics or viscose fabrics; for pure cotton fabrics, before the reaction solution treatment in step (3), the pure cotton fabrics are first put into NaOH solution, and then JFC is added dropwise to infiltrate The mixture is heated to boiling and kept boiling for 30 minutes; the treated cotton fabric is taken out, washed several times with hot water, and finally washed with cold water until neutral; the concentration of JFC penetrant is 1g/L; NaOH The solution concentration is 10g/L.

In the preparation method, the non-formaldehyde crosslinking agent is 1,2,3,4-butanetetracarboxylic acid (BTCA), citric acid (CA), pentaerythritol (PER), maleic acid (MA), itaconic acid (IA) one; penetrant is one of F-121, T99, JFC.

In the preparation method, the bath ratio of the fabric to the reaction solution in the reaction process is 1:50; the concentration of the penetrant in the reaction process is 1 g/L.

The flexible fabric capable of efficiently detecting bacteria by luminescence prepared according to any one of the preparation methods.

The application of the flexible fabric for bacterial detection: at room temperature to 40° C., the flexible light-emitting fabric is co-cultured with Escherichia coli (E.coli) and Staphylococcus aureus (S.aureus) for 12-24 hours, respectively, The fluorescence spectra of the flexible light-emitting fabrics before and after bacterial culture were tested, and the presence of bacteria was detected by the quenching of the fluorescence signal of the light-emitting fabric itself.

By testing the fluorescence spectrum of the flexible light-emitting fabric before and after bacterial culture, the fluorescence quenching of the flexible light-emitting fabric itself can be found. Therefore, the flexible light-emitting fabric can detect the presence of Escherichia coli and Staphylococcus aureus through efficient light emission, and can be widely used in medical and daily environments.

Description of drawings

FIG. 1 is the excitation and emission spectra of hybrid luminescent nanoparticles.

Figure 2 shows the fluorescence emission spectrum of the flexible light-emitting fabric before and after co-cultivation with Escherichia coli (E.coli) for 12-24 hours.

Figure 3 shows the fluorescence emission spectra of the flexible light-emitting fabric before and after co-culturing with Staphylococcus aureus (S. aureus) for 12-24 hours.

Figure 4 is a flow chart of the preparation of a flexible fabric capable of efficiently detecting bacteria by luminescence.

Detailed ways

The present invention will be described in detail below with reference to specific embodiments.

Example 1

To 1 mL of 0.01 mol/L EuCl ₃ ethanol solution, add 1 mL of 0.03 mol/L tta ethanol solution, and stir at room temperature for 1.5 hours. Adjust the pH of the reaction solution to 7-8, then add 1 mL of 0.01 mol/L phen ethanol solution to the reaction solution, and stir for 3 hours to obtain a europium complex solution.

Take 4 mL of 10 mg/mL sodium hyaluronate solution (prepared from 0.1 mol/L, pH=5 acetic acid-sodium acetate buffer solution as solvent), add 4 mL of the above-obtained europium complex solution, and stir at room temperature After 4 hours, the hybrid luminescent nanoparticles were obtained (shown in Figure 1, the excitation and emission spectra of the hybrid luminescent nanoparticles).

The cotton fabric was placed in a beaker with NaOH solution (10 g/L), then JFC penetrant (1 g/L) was added dropwise and mixed well. Heat the mixture to a boil and keep it boiling for 30 minutes. The treated cotton fabric was taken out, washed several times with hot water, and finally washed with cold water until neutral, to avoid the influence of residual NaOH on subsequent experiments.

The reaction solution was composed of a mixed solution of 61.6 mL of pentaerythritol (PER) aqueous solution (10 g/L) and 5 drops of JFC penetrant (1 g/L) heated to 60 °C, into which 1.232 g of the above cotton fabric was immersed (the bath ratio was 50: 1), to carry out grafting pretreatment on the surface of cotton fabric, after stirring for 4 hours, add 40 mL of hybrid luminescent nanoparticles into it, and continue to treat at 60 ° C for 4 hours to graft the hybrid luminescent particles to cotton fabric on the fiber. The treated cotton fabric is removed and washed several times in hot water, then several times in cold water. The cotton fabric was taken out and dried to constant weight to obtain a flexible luminous cotton fabric.

From room temperature to 40°C, the flexible light-emitting cotton fabrics were co-cultured with Escherichia coli (E.coli) and Staphylococcus aureus (S. aureus) for 12-24 hours, and the fluorescence spectra of the flexible light-emitting cotton fabrics before and after bacterial culture were tested. (Fig. 2 is the fluorescence emission spectrum of the flexible light-emitting fabric before and after co-cultivation with Escherichia coli (E.coli) for 12-24 hours, Fig. 3 is the co-culture of the flexible light-emitting fabric with Staphylococcus aureus (S. aureus) Before and after 12-24 hours, the fluorescence emission spectrum of the flexible light-emitting fabric is shown), and the presence of bacteria can be detected by quenching the fluorescence signal of the light-emitting cotton fabric itself.

Example 2

To 1 mL of 0.01 mol/L EuCl ₃ ethanol solution, add 1 mL of 0.03 mol/L tta ethanol solution, and stir at room temperature for 1.5 hours. Adjust the pH of the reaction solution to 7-8, then add 1 mL of 0.01 mol/L phen ethanol solution to the reaction solution, and stir for 3 hours to obtain a europium complex solution.

Take 4 mL of 10 mg/mL heparin sodium solution (prepared from 0.1 mol/L, pH=5 acetic acid-sodium acetate buffer solution as solvent), add 4 mL of the above-obtained europium complex solution, and stir at room temperature for 4 hours , to obtain hybrid luminescent nanoparticles.

The reaction solution consisted of a mixed solution of 31.4 mL of 1,2,3,4-butanetetracarboxylic acid (BTCA) aqueous solution (10g/L) heated to 60°C and 2 drops of F-121 penetrant (1g/L) , immersed 0.627g viscose fabric in it (the bath ratio is 50:1) to pretr Under treatment for 4 hours, to graft the hybrid luminescent particles onto viscose fabric fibers. The treated viscose fabric is removed and washed several times in hot water, then several times in cold water. The viscose fabric was taken out and dried to constant weight to obtain a flexible luminous viscose fabric. After co-culturing the flexible light-emitting viscose fabric with Escherichia coli (E.coli) and Staphylococcus aureus (S. aureus), the presence of bacteria can be detected by quenching the fluorescence signal of the light-emitting viscose fabric itself.

Example 3

To 1 mL of 0.01 mol/L EuCl ₃ ethanol solution, add 1 mL of 0.03 mol/L tta ethanol solution, and stir at room temperature for 1.5 hours. Adjust the pH of the reaction solution to 7-8, then add 1 mL of 0.01 mol/L phen ethanol solution to the reaction solution, and stir for 3 hours to obtain a europium complex solution.

Take 4 mL of 10 mg/mL sodium hyaluronate solution (prepared from 0.1 mol/L, pH=5 acetic acid-sodium acetate buffer solution as solvent), add 4 mL of the above-obtained europium complex solution, and stir at room temperature After 4 hours, hybrid luminescent nanoparticles were obtained.

The reaction solution was a mixed solution of 41.2 mL of 1,2,3,4-butanetetracarboxylic acid (BTCA) aqueous solution (10g/L) heated to 80°C and 4 drops of F-121 penetrant (1g/L) composition, 0.824g of viscose fabric was immersed in it (the bath ratio was 50:1) to pretreat the surface of the viscose fabric by grafting, after stirring for 4 hours, 25mL of hybrid luminescent nanoparticles were added into it, and continued in Treated at 80°C for 4 hours, the hybrid luminescent particles were grafted onto viscose fabric fibers. The treated viscose fabric is removed and washed several times in hot water, then several times in cold water. The viscose fabric was taken out and dried to constant weight to obtain a flexible luminous viscose fabric. After co-culturing the flexible light-emitting viscose fabric with Escherichia coli (E.coli) and Staphylococcus aureus (S. aureus), the presence of bacteria can be detected by quenching the fluorescence signal of the light-emitting viscose fabric itself.

Example 4

To 1 mL of 0.01 mol/L EuCl ₃ ethanol solution, add 1 mL of 0.03 mol/L tta ethanol solution, and stir at room temperature for 1.5 hours. Adjust the pH of the reaction solution to 7-8, then add 1 mL of 0.01 mol/L phen ethanol solution to the reaction solution, and stir for 3 hours to obtain a europium complex solution.

Take 4 mL of 10 mg/mL chondroitin sulfate solution (prepared from 0.1 mol/L, pH=5 acetic acid-sodium acetate buffer solution as solvent), add it to the above-obtained europium complex solution, and stir at room temperature for 4 hours, the hybrid luminescent nanoparticles were obtained.

The reaction solution is composed of a mixed solution of 42.6 mL of citric acid (CA) aqueous solution (10 g/L) and 4 drops of F-121 penetrant (1 g/L) heated to 60 ° C, and 0.852 g of polyester cotton cloth is immersed in it (bath). The ratio of 50:1) was used to pretreat the surface of polyester-cotton fabric by grafting. After stirring for 4 hours, 28 mL of hybrid luminescent nanoparticles were added to it, and the treatment was continued at 60 °C for 4 hours. Grafted onto polyester-cotton fabric fibers. Take out the treated polyester-cotton cloth and wash it several times in hot water, then several times in cold water. Take out the polyester-cotton cloth and dry to constant weight to obtain a flexible luminous polyester-cotton cloth. After co-culturing the flexible light-emitting polyester-cotton fabric with Escherichia coli (E.coli) and Staphylococcus aureus (S. aureus), the presence of bacteria can be detected by quenching the fluorescence signal of the light-emitting polyester-cotton fabric itself.

Example 5

To 1 mL of 0.01 mol/L EuCl ₃ ethanol solution, add 1 mL of 0.03 mol/L tta ethanol solution, and stir at room temperature for 1.5 hours. Adjust the pH of the reaction solution to 7-8, then add 1 mL of 0.01 mol/L phen ethanol solution to the reaction solution, and stir for 3 hours to obtain a europium complex solution.

Take 4 mL of 10 mg/mL sodium hyaluronate solution (prepared from 0.1 mol/L, pH=5 acetic acid-sodium acetate buffer solution as solvent), add 4 mL of the above-obtained europium complex solution, and stir at room temperature After 4 hours, hybrid luminescent nanoparticles were obtained.

The cotton fabric was placed in a beaker with NaOH solution (10 g/L), then JFC penetrant (1 g/L) was added dropwise and mixed well. Heat the mixture to a boil and keep it boiling for 30 minutes. The treated cotton fabric is removed and washed several times in hot water and finally in cold water until neutral.

The reaction solution was a mixed solution of 53.7 mL of 1,2,3,4-butanetetracarboxylic acid (BTCA) aqueous solution (10g/L) heated to 80°C and 5 drops of F-121 penetrant (1g/L) composition, 1.074g of cotton fabric was immersed in it (the bath ratio was 50:1) to pre-treat the surface of the cotton fabric by grafting, after stirring for 4 hours, 35mL of hybrid luminescent nanoparticles were added into it, and the temperature was continued at 80 °C. Treated for 4 hours to graft the hybrid luminescent particles onto cotton fabric fibers. The treated cotton fabric is removed and washed several times in hot water, then several times in cold water. The cotton fabric was taken out and dried to constant weight to obtain a flexible luminous cotton fabric. After co-culturing the flexible luminescent viscose fabric with Escherichia coli (E.coli) and Staphylococcus aureus (S. aureus), the presence of bacteria can be detected by quenching the fluorescent signal of the luminescent cotton fabric itself.

It should be understood that, for those skilled in the art, improvements or changes can be made according to the above description, and all these improvements and changes should fall within the protection scope of the appended claims of the present invention.

Claims (10)

1. a preparation method of a flexible fabric capable of efficiently luminescent detection bacteria, is characterized in that, comprises the following steps: (1) prepare solution: configure polyelectrolyte solution with acetic acid _- sodium acetate buffer solution; configure EuCl solution with ethanol, tta solution and phen solution; ( ₂ ) Preparation of hybrid luminescent nanoparticles: add tta solution dropwise to the EuCl solution, adjust the pH of the reaction solution to be 6-8 after stirring with a magnetic stirrer for 1-2 hours, add phen solution dropwise to it, stir for 1- After 5 hours, the negatively charged polyelectrolyte solution was added thereto, and the hybrid luminescent nanoparticles were obtained after stirring for 1-5 hours; (3) Preparation of flexible luminescent cotton fabric: at room temperature to 90°C, the fabric is treated in the reaction solution for 2-10 hours, and then the prepared hybrid luminescent nanoparticles are added to it to maintain the temperature from room temperature to 90°C, and treated for 2 -10 hours to obtain the flexible fabric; the reaction solution consists of a non-formaldehyde crosslinking agent and a penetrating agent. 2. preparation method according to claim ₁ is characterized in that, EuCl ethanolic solution concentration is 0.01mol/L; tta ethanolic solution concentration is 0.03mol/L; phen ethanolic solution concentration is 0.01mol/L. 3 . The preparation method according to claim 1 , wherein the ratio of the amounts of EuCl ₃ , tta and phen is EuCl ₃ : tta:phen=1:3:1. 4 . 4 . The preparation method according to claim 1 , wherein the polyelectrolyte solution is a substance composed of one or two of natural biological polyelectrolytes including sodium heparin, sodium hyaluronate, and chondroitin sulfate. 5 . 5. The preparation method according to claim 1, wherein when stirring on a magnetic stirrer, the stirring rate is 800rpm-1500rpm. 6. preparation method according to claim 1, is characterized in that, fabric is polyester-cotton cloth, pure cotton fabric or viscose fabric; For pure cotton fabric, before step (3) carries out reaction solution processing, first pure cotton fabric Put in NaOH solution, then add JFC penetrant dropwise and mix well; heat the mixture to boiling and keep it boiling for 30 minutes; take out the treated cotton fabric, wash it with hot water several times, and finally wash it with cold water until it is neutral; The concentration of JFC penetrant is 1g/L; the concentration of NaOH solution is 10g/L. 7. preparation method according to claim 1 is characterized in that, non-formaldehyde crosslinking agent is 1,2,3,4-butane tetracarboxylic acid (BTCA), citric acid (CA), pentaerythritol (PER), Maleic acid (MA), one of itaconic acid (IA); penetrant is F-121, T99, one of JFC. 8. preparation method according to claim 1 is characterized in that, in the reaction process, the bath ratio of the fabric and the reaction solution is 1:50; in the reaction process, the concentration of the penetrant is 1 g/L. 9 . The flexible fabric capable of efficiently detecting bacteria by luminescence prepared according to the preparation method of any one of claims 1 to 8 . 10. The application of the flexible fabric according to claim 9, characterized in that it is used for bacterial detection: at room temperature to 40° C., the flexible light-emitting fabric is separately treated with Escherichia coli (E.coli), Staphylococcus aureus (S.aureus) ) After co-cultivation for 12-24 hours, the fluorescence spectrum of the flexible light-emitting fabric before and after bacterial culture was tested, and the presence of bacteria was detected by quenching the fluorescence signal of the light-emitting fabric itself.

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