CN113152091A - Polysaccharide-based hydrogel-based fabric for visually detecting escherichia coli and pH response and preparation method thereof - Google Patents
Polysaccharide-based hydrogel-based fabric for visually detecting escherichia coli and pH response and preparation method thereof Download PDFInfo
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- CN113152091A CN113152091A CN202110430207.2A CN202110430207A CN113152091A CN 113152091 A CN113152091 A CN 113152091A CN 202110430207 A CN202110430207 A CN 202110430207A CN 113152091 A CN113152091 A CN 113152091A
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- fabric
- modified
- polysaccharide
- konjac glucomannan
- reaction
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- D06N2201/00—Chemical constitution of the fibres, threads or yarns
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Abstract
The invention relates to a polysaccharide-based hydrogel-based fabric for visually detecting escherichia coli and pH response and a preparation method thereof. The method comprises the following steps: the preparation method comprises the steps of preparing modified konjac glucomannan, preparing modified chitosan, preparing modified fabric and preparing polysaccharide-based hydrogel-based fabric. The method is simple and easy for industrial production, and the prepared polysaccharide-based hydrogel-based fabric has good antibacterial property and washing resistance, can visually detect escherichia coli, and has pH-responsive discoloration property and reversibility.
Description
Technical Field
The invention belongs to the technical field of biomedical materials, and particularly relates to a polysaccharide-based hydrogel-based fabric for visually detecting escherichia coli and pH response and a preparation method thereof.
Background
The hydrogel is a three-dimensional cross-linked network structure composed of polymer segments, can absorb a solvent with a volume several times of that of the hydrogel, and contains more hydrophilic functional groups such as carboxyl (-COOH), hydroxyl (-OH) and amino (-NH)2) And sulfonic acid (-SO)3H) And hydrogen bonds can be formed, so that the hydrogel can absorb water and swell, and the water is locked and not lost. Due to the characteristics of high water content, softness and good biocompatibility, the nano-composite material is popular in the field of biomedical materials (such as sanitary products, tissue engineering, drug delivery, wound dressings and the like).
Konjac Glucomannan (KGM) is a renewable natural high-molecular polysaccharide, mainly comes from tubers of perennial herb konjak of the Araceae konjak, and is a natural healthy food which is confirmed in China. The konjac glucomannan has excellent physicochemical properties such as gel behavior, water retention property and the like, is low in price and cost, is suitable for industrial production, and has wide application prospects in the fields of food industry, biomedicine, functional materials and the like. Chitosan is a natural aminopolysaccharide and has good biodegradability and biocompatibility, but the application is influenced by the low solubility in aqueous solution.
Coli is one of the most common food-borne pathogenicity, and poses great threat to human health and water quality environment, for example, bacterial wound infection can cause the delay and even stop of normal wound healing, and can cause the formation of chronic non-healing wounds; foods and products contaminated by bacteria can affect human health or life safety after being used, so that microbial detection is of great importance; efficient and rapid differentiation of bacterial species facilitates rapid decision-making and targeted therapy. Common clinical microorganism detection methods include a plate method, a maximum possible number tube method, a direct determination microbiological method, a cell component analysis method and the like, but are not suitable for non-laboratory environment detection in families, outdoors and the like. Most pathogenic bacteria secrete bacterial enzymes, high concentrations of which represent a highly productive result of the bacteria, and chromogenic/fluorescent compounds are used as substrates to allow visual detection of microorganisms through enzymatic lysis reactions. The color/fluorescence intensity produced by the enzyme-substrate interaction is positively correlated with the concentration of bacteria in the test environment, and the detection of enzymes using established substrate techniques is robust and cost-effective. The pH is an important index reflecting pathological conditions and body health, for example, urine pH detection is a routine physical examination item in a hospital, and the alkalinity (pH) of uric acid is increased and is found in metabolic acidosis or renal tubular acidosis; uric acid alkalinity (pH) decrease, seen in alkalosis, tubular alkalosis, urinary tract infection, diabetic ketoacidosis, etc.; the pH and the bacterial state are also important detection items in water quality and food.
The commonly used antibacterial materials are mainly prepared by adding the antibacterial agent in a physical blending manner or introducing the antibacterial agent in a chemical grafting reaction manner. The quaternary ammonium salt antibacterial agent of the organic antibacterial agent is widely used for industrial production due to low price and high sterilization speed.
Disclosure of Invention
The invention aims to solve the technical problem of providing a polysaccharide-based hydrogel-based fabric for visually detecting escherichia coli and pH response and a preparation method thereof, so as to fill the blank in the prior art.
The invention provides a polysaccharide-based hydrogel-based fabric for visually detecting escherichia coli and pH response, which is prepared by putting the fabric into an organic silicon quaternary ammonium salt solution for reaction to obtain a modified fabric, coating the modified konjac glucomannan solution and the modified chitosan solution on the modified fabric, and carrying out Schiff base reaction and in-situ gelling;
the modified konjac glucomannan is obtained by adding an oxidant into a konjac glucomannan monomer solution for reaction, and reacting the obtained oxidized konjac glucomannan monomer containing aldehyde groups with a pH indicator;
the modified chitosan is obtained by activating color development/fluorescence compound solution by EDC and NHS, adjusting pH, adding chitosan with adjusted pH, adjusting pH and reacting.
Preferably, in the polysaccharide-based hydrogel-based fabric, the fabric comprises one of a polyester cotton fabric, a pure cotton fabric and a viscose fabric.
Preferably, in the above-mentioned polysaccharide-based hydrogel-based fabric, the oxidizing agent comprises one of hydrogen peroxide, potassium permanganate, and sodium periodate.
Preferably, in the above polysaccharide-based hydrogel base fabric, the pH indicator includes one or more of congo red, neutral red and litmus.
Preferably, in the above-mentioned polysaccharide-based hydrogel base fabric, the chromogenic/fluorescent compound comprises one or more of 6-chloro-3-indolyl-D-galactopyranoside Red-Gal, 4-nitrophenyl- β -D-glucuronide PNPG, 6-chloro-3-indolyl- β -D-galactopyranoside X-Gluc, 4-methylumbelliferone- β -D-glucuronide MUG.
Preferably, in the polysaccharide-based hydrogel base fabric, the organosilicon quaternary ammonium salt is obtained by dissolving long carbon chain tertiary amine and a silane coupling agent in an organic solvent and reacting under the nitrogen condition.
Preferably, in the polysaccharide-based hydrogel-based fabric, the polysaccharide-based hydrogel-based fabric comprises the following raw materials in parts by weight: 12-24 parts of konjac glucomannan polymerizable monomer, 6-12 parts of chitosan polymerizable monomer, 10-20 parts of organic silicon quaternary ammonium salt, 1.8-3.6 parts of color development/fluorescence compound, 1.8-3.6 parts of pH indicator, 10000-40000 parts of deionized water and a plurality of fabrics.
The invention also provides a preparation method of the polysaccharide-based hydrogel-based fabric for visually detecting escherichia coli and pH response, which comprises the following steps:
(1) dissolving konjac glucomannan monomer in water, adding an oxidant for reaction, dialyzing (dialyzing in deionized water to remove small molecular impurities), centrifuging, drying, dissolving the obtained oxidized konjac glucomannan monomer containing aldehyde groups in water, adding a pH indicator for reaction, dialyzing (removing unreacted substances), and freeze-drying to obtain modified konjac glucomannan; wherein the mass ratio of the konjac glucomannan monomer to the oxidant is 1: 0.2-1: 1, and the mass ratio of the oxidized aldehyde group-containing konjac glucomannan monomer to the pH indicator is 1: 0.005-1: 0.001;
(2) dissolving a color development/fluorescence compound in water, adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride EDC and N-hydroxysuccinimide NHS for activation, adjusting the pH to acidity, dissolving chitosan in an acid solution, adjusting the pH to acidity, adding the solution into the activated color development/fluorescence compound solution, adjusting the pH to acidity for reaction, dialyzing, and freeze-drying to obtain modified chitosan, wherein the mass ratio of the color development/fluorescence compound, EDC, NHS to chitosan is 0.020-0.075: 0.48-1.0: 0.30-0.65: 1;
(3) mixing long carbon chain tertiary amine and silane coupling agent in a molar ratio of 1: 1-1: 2, dissolving in an organic solvent, reacting under the condition of nitrogen, filtering (removing impurities), distilling under reduced pressure (removing the solvent and unreacted substances), recrystallizing, filtering, and drying to obtain the organosilicon quaternary ammonium salt, wherein the ratio of the long-carbon-chain tertiary amine to the organic solvent is 20-40 g: 10-30 mL;
(4) dissolving the organic silicon quaternary ammonium salt in the step (3) in water, adding the fabric, stirring for reaction, taking out the fabric, washing and drying to obtain the modified fabric, wherein the mass ratio of the organic silicon quaternary ammonium salt to the water is 1: 100 to 1000;
(5) dissolving the modified konjac glucomannan in the step (1) in water, dissolving the modified chitosan in the step (2) in water, coating the obtained modified konjac glucomannan solution and the obtained modified chitosan solution on the modified fabric in the step (4) in a volume ratio of 1: 1-5: 1, and carrying out Schiff base reaction to carry out in-situ gelling to obtain the polysaccharide-based hydrogel base fabric.
Preferably, in the above method, the step (1) of adding an oxidizing agent comprises: and carrying out dark reaction at room temperature for 8-20 h.
Preferably, in the above method, the adding of the pH indicator in step (1) reacts as follows: reacting for 0.2-1 h at room temperature.
Preferably, in the method, the pH value is adjusted to 4-6 in the step (2).
Preferably, in the method, the activation time in the step (2) is 3-6 h; the reaction time is 4-8 h.
Preferably, in the above method, the acid solution in the step (2) is a 0.5% (w/v) acetic acid solution.
Preferably, in the above method, the dialysis in step (2) is dialysis in deionized water, so as to remove small molecule impurities.
Preferably, in the above method, the number of carbons of the long carbon chain tertiary amine in the step (3) is 10 to 18.
Preferably, in the above method, the silane coupling agent in step (3) is a chloropropyltrichlorosilane coupling agent.
Preferably, in the above method, the organic solvent in the step (3) comprises methanol.
Preferably, in the method, the reaction temperature in the step (3) is 70-100 ℃, and the reaction time is 6-24 hours.
Preferably, in the above method, the recrystallization in the step (3) is a recrystallization purification in an organic solvent at a low temperature of-8 to 0 ℃.
Preferably, in the above method, the stirring reaction temperature in the step (4) is room temperature, and the stirring reaction time is 8-12 hours.
Preferably, in the method, the modified konjac glucomannan mass fraction in the modified konjac glucomannan solution in the step (5) is 6-12%; the mass fraction of the modified chitosan in the modified chitosan solution is 3-6%.
Preferably, in the method, the reaction temperature of the Schiff base in the step (5) is 20-30 ℃ and the time is 10 s-30 min.
The invention also provides application of the polysaccharide-based hydrogel-based fabric in detection of escherichia coli and pH.
The hydrogel prepared from the polysaccharide monomer is combined with the antibacterial fabric for use, the polysaccharide hydrogel is degradable, and the antibacterial fabric can be repeatedly used by washing and provides strength, thereby being beneficial to sustainable development. The siloxane-containing quaternary ammonium salt is synthesized by long-carbon-chain tertiary amine and chloropropyl trichlorosilane coupling agent, has the effects of high temperature resistance and durability, and avoids the defects of poor chemical stability, easy elution and the like commonly existing in micromolecule quaternary ammonium salts.
In the preparation of polysaccharide-based hydrogel base fabric for detecting escherichia coli and pH response, konjac glucomannan is introduced into aldehyde groups through oxidation reaction, part of the aldehyde groups are grafted with amino groups of a pH indicator through Schiff base reaction, and part of the aldehyde groups react with the amino groups on chitosan to form a hydrogel network; the chitosan contains a large amount of amino groups, and part of the amino groups are grafted with carboxyl groups on the chromophoric/fluorescent compound through an amide reaction; the surface of the fabric contains a large amount of hydroxyl, and the hydroxyl is subjected to hydrolysis reaction with organosilicon quaternary ammonium salt to obtain the modified antibacterial fabric.
The konjac glucomannan and the chitosan are modified, the modified chitosan is grafted with a color development/fluorescence compound through an amide reaction, the modified chitosan is cut by bacterial enzyme secreted by escherichia coli, a color development or fluorescence group is released within 30 minutes at the fastest speed, the color development is visible under natural light, and the fluorescence is visible under ultraviolet light; the pH indicator is chemically grafted on the oxidized konjac glucomannan through Schiff base, the original pH response color change performance and reversibility are unchanged, and dye molecules are fixed in the hydrogel and are not lost due to the influence of the inlet and outlet or flow of a solvent, so that the pH indicator has extremely high stability. The Schiff base forms hydrogel, the reaction is mild, and the Schiff base is biodegradable; the fabric is chemically grafted with the organic silicon quaternary ammonium salt, so that the antibacterial property is improved, the washing resistance is improved, the fabric can be recycled, and the sustainable development requirement is met; the method can be used for the field of sanitary materials, can be used for detecting urine, milk, body fluid and the like, and detecting microorganisms, health and monitoring products in non-laboratory environments such as families, outdoors and the like, and has the advantages of low raw material price, simple and safe synthesis steps, mild reaction and easy industrial production.
The invention uses bacterial enzyme enzymatic cracking reaction to lead the chromophoric/fluorescent compound to change color or emit fluorescence within 30 minutes at the fastest, the bacterial enzyme can be secreted by 98 percent of known bacteria such as escherichia coli, and the detection limit of polysaccharide hydrogel cotton fabric to the escherichia coli is 102CFU/mL; the color development state and pH response range of the hydrogel base are determined by the pH indicator used, the color development state and pH response range are the color development range and state of neutral red, the response time is not more than 30 minutes, namely the hydrogel is red when the pH is less than or equal to 4.5The color is that the hydrogel is orange when the pH value is more than 4.5 and less than or equal to 8.3, and the hydrogel is yellow when the pH value is more than 8.3; it should be noted here that references to pH indicators in the present invention include, but are not limited to, neutral Red.
Advantageous effects
(1) The konjac glucomannan and chitosan monomer are adopted to synthesize the hydrogel, and the hydrogel is obtained from natural healthy plants and animals, has high safety and good biocompatibility, and can be biodegraded;
(2) the polysaccharide-based hydrogel base fabric for visually detecting escherichia coli and pH response uses a chromophoric/fluorescent compound sensitive to escherichia coli and pH, is cut by bacterial enzyme to release a color change or fluorescent group, is visible by naked eyes or ultraviolet light irradiation within 30 minutes, and is simple to operate, convenient to carry and short in detection time in non-laboratory environments such as families and outdoors;
(3) according to the polysaccharide-based hydrogel base fabric for visually detecting escherichia coli and pH response, the pH indicator is covalently fixed on the oxidized konjac glucomannan, so that the stability is strong, leakage in the using process is avoided, and the reversible pH discoloration property is good; the hydrogel changes color from the contact with the solvent, and the response time is not more than 30 min;
(4) the siloxane-containing quaternary ammonium salt used in the invention has low cost and good sterilization effect, is high temperature resistant and more durable than common organic quaternary ammonium salt, is chemically grafted on the surface of fabric, has water washing resistance and can be repeatedly used for antibacterial fabric.
Drawings
FIG. 1 is a process for preparing Oxidized Konjac Glucomannan (OKGM) containing aldehyde groups in polysaccharide-based hydrogel-based fabric for visual detection of Escherichia coli and pH response according to the present invention;
FIG. 2 is a process for preparing modified konjac glucomannan (OKGM-NR) in the polysaccharide-based hydrogel-based fabric for visual detection of Escherichia coli and pH response according to the present invention;
FIG. 3 is a process for preparing modified chitosan (CS-MUG) in polysaccharide-based hydrogel-based fabric for visual detection of E.coli and pH response according to the present invention;
FIG. 4 is a process for preparing quaternary ammonium salts in polysaccharide-based hydrogel-based fabrics for visual detection of E.coli and pH response in accordance with the present invention;
FIG. 5 is a schematic of the synthesis of a polysaccharide-based hydrogel-based fabric for visual detection of E.coli and pH response according to the present invention;
FIG. 6 is the results of the antibacterial test of the modified cotton fabric and the polysaccharide hydrogel-based fabric in example 1 of the present invention;
FIG. 7 is the result of pH response of the polysaccharide hydrogel-based fabric in example 1 of the present invention;
FIG. 8 is the results of the detection of Escherichia coli by the polysaccharide hydrogel-based fabric in example 1 of the present invention;
FIG. 9 is a fluorescence spectrum of fluorescence emitted when the polysaccharide hydrogel-based fabric in example 1 of the present invention was detected for Escherichia coli.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
In the embodiment, the wavelength of an ultraviolet lamp is 365nm, and the preparation mode of escherichia coli liquid is prepared according to the requirement of GB/T20944.3-2008; performing water washing resistance characterization according to GB/T20944.3-2008 and GB/T3921-2008; antibacterial experiment the quantitative antibacterial experiment is carried out according to GB/T20944.3-2008, escherichia coli and staphylococcus aureus are taken as experimental strains, and the bacteriostasis of the sample is calculated according to the following formula:
in the formula: y is the bacteriostasis rate of the sample; wtThe average value of viable bacteria concentration in the flask after the control sample is in contact with the control sample for 24 hours in a vibration mode; qtThe average value of viable bacteria concentration in the flask after 24h shaking contact of the antibacterial sample is shown.
Example 1
The embodiment provides a polysaccharide-based hydrogel-based fabric for visually detecting escherichia coli and pH response, which is prepared by the following specific steps:
step 1: preparation of modified konjac glucomannan and modified chitosan
a. Preparing modified konjac glucomannan:
dissolving 1g konjac glucomannan (formula 1 in figure 1) in 100mL water, stirring for 10min to dissolve it uniformly, dripping 0.4g sodium periodate, reacting for 12h in dark at room temperature, adding 5mL ethylene glycol to stop the reaction, dialyzing with deionized water for 72h, centrifuging, collecting supernatant, and drying to obtain oxidized konjac glucomannan (formula 2 in figure 1); dissolving 1g of oxidized konjac glucomannan monomer in 20mL of water, adding 0.003g of neutral red (structural formula 3 in figure 3), reacting at 25 ℃ for 1h, dialyzing for 72h to remove unreacted substances, and freeze-drying to obtain the modified konjac glucomannan (structural formula 4 in figure 2). b. Preparing modified chitosan:
dissolving 0.068g of 4-methylumbelliferone-beta-D-glucuronide (MUG) (structural formula 6 in the figure) in 10mL of water, adding 0.970g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) and 0.621g of N-hydroxysuccinimide (NHS), adjusting the pH value to be within the range of 4-6, and activating for 4 hours; meanwhile, 1g of chitosan (structural formula 5 in fig. 3) was dissolved in 100mL of 0.5% (w/v) acetic acid solution, pH was adjusted to 5, and then added to the activated chromophoric/fluorescent compound aqueous solution; adjusting the pH value to 5 and reacting for 6 h; after the reaction is finished, dialyzing in deionized water for 72h to remove small molecular impurities, and freeze-drying to obtain the modified chitosan (structural formula 7 in figure 3).
Step 2: preparing organosilicon quaternary ammonium salt:
25.608g of dodecyl dimethyl tertiary amine (structural formula 8 in figure 4) and 19.872g of chloropropyl trichlorosilane coupling agent (structural formula 9 in figure 4) are dissolved in 15mL of anhydrous methanol, the temperature is 80 ℃, the reaction is carried out for 21h under the condition of nitrogen, the reduced pressure distillation is carried out for 4h to remove the solvent and unreacted substances, the recrystallization is carried out in acetone at the temperature of-8 ℃ to 0 ℃, and the organic silicon quaternary ammonium salt (structural formula 10 in figure 4) which is the target product is obtained after the filtration and the drying at the temperature of 40 ℃ to 50 ℃;
and step 3: preparation of polysaccharide hydrogel-based portable fabric tablets for visual detection of escherichia coli and pH response:
dissolving 0.02g of organosilicon quaternary ammonium salt in 10mL of deionized water, adding 1g of washed and dried cotton fabric (3cm multiplied by 1cm), reacting for 8h at room temperature, taking out, fully washing and drying to obtain modified cotton fabric; dissolving the modified konjac glucomannan in water to obtain a modified konjac glucomannan aqueous solution with the mass fraction of 6%, dissolving the modified chitosan in water to obtain a modified chitosan aqueous solution with the mass fraction of 3%, wherein the modified konjac glucomannan aqueous solution comprises the following components in parts by mass: the modified chitosan aqueous solution is prepared by mixing the following components in a volume ratio of 1:1, uniformly coating the modified fabric, and reacting with Schiff base at 25 ℃ for 15s to form gel in situ to form the polysaccharide hydrogel-based fabric.
The antibacterial test result of the modified cotton fabric is shown in fig. 6, and the antibacterial rates of the modified cotton fabric on escherichia coli and staphylococcus aureus can respectively reach 99.98% and 99.99% according to the formula; after washing for 20 times, calculating the antibacterial rate of 99.77 percent and 99.9 percent to escherichia coli and staphylococcus aureus according to a formula; the antibacterial rate of the polysaccharide hydrogel base fabric to escherichia coli and staphylococcus aureus is 99.97% and 99.99%; all have better antibacterial effect.
The pH response results of the polysaccharide hydrogel-based fabric are shown in fig. 7, which is obtained by soaking the fabric in PBS buffer solution with pH 4,7, and 9 for 20min, respectively, which is purple red, orange, and yellow.
The result of detecting escherichia coli by the polysaccharide hydrogel-based fabric is shown in fig. 8, and fig. 8(a) is the polysaccharide hydrogel-based fabric under natural light; FIG. 8(b) shows on the left the polysaccharide hydrogel-based fabric without grafted MUG under UV light (prepared as in example 1 except that no MUG was grafted), and on the right of FIG. 8(b) the polysaccharide hydrogel-based fabric with grafted MUG (example) soaked in a suspension of E.coli (concentration 10%8CFU/mL) for 30min, the right side had visually intense blue fluorescence under UV illumination, the fluorescence intensity was 530000, and no fluorescence was observed on the left side. At the same time, the polysaccharide hydrogel-based fabric was soaked in an E.coli suspension (10 concentration)2CFU/mL) for 8h, as shown in FIG. 8(c), under UV irradiation, the same polysaccharide hydrogel-based fabric (except that MUG was not grafted) was used as in example 1Prepared as the same procedure), the polysaccharide hydrogel-based fabric grafted with MUG on the right (example) showed a clear blue fluorescence, no fluorescence on the left, fluorescence intensity of 20900. The fluorescence spectrum is shown in FIG. 9.
Example 2
The example provides a polysaccharide-based hydrogel-based fabric for visually detecting escherichia coli and pH response, and the specific preparation steps are as in example 1, wherein 0.4g of sodium periodate in example 1 is changed into 0.6g, and the rest is the same as in example 1, so that the polysaccharide-based hydrogel-based fabric is obtained.
pH responsive discoloration results (test procedure same as example 1): after the polysaccharide hydrogel base fabric is soaked in PBS (phosphate buffer solution) with the pH of 4,7 and 9 for 20min, the colors of the polysaccharide hydrogel base fabric correspond to purple, orange and yellow in sequence.
Coli assay results (procedure same as in example 1): the polysaccharide hydrogel-based fabric was soaked in a suspension of E.coli (10 concentration)8CFU/mL) for 30min, the fluorescence intensity was 515000; soaking in 102The fluorescence intensity of the CFU/mL Escherichia coli liquid after 8h was 18000.
Example 3
The example provides a polysaccharide-based hydrogel-based fabric for visually detecting escherichia coli and pH response, and the specific preparation steps are as in example 1, wherein 0.4g of sodium periodate in example 1 is changed into 0.8g, and the rest is the same as in example 1, so that the polysaccharide-based hydrogel-based fabric is obtained.
pH responsive color change results: soaking the polysaccharide hydrogel base fabric in PBS buffer solution with pH of 4,7 and 9 for 20min, wherein the colors are respectively purple red, orange and yellow.
And E, detection results of Escherichia coli: the polysaccharide hydrogel-based fabric was soaked in a suspension of E.coli (10 concentration)8CFU/mL) for 30min, the fluorescence intensity is 510000; soaking in 102After 8h, the fluorescence intensity of the CFU/mL Escherichia coli liquid is 21500.
Example 4
The embodiment provides a polysaccharide-based hydrogel-based fabric for visually detecting escherichia coli and pH response, which is prepared by the following specific steps of according to embodiment 1, wherein the mass of sodium periodate is 0.6g, and the volume ratio of a modified konjac glucomannan aqueous solution to a modified chitosan aqueous solution is 2: 1 was uniformly coated on the modified fabric, and the rest was the same as in example 1, to obtain a polysaccharide-based hydrogel-based fabric.
pH responsive color change results: soaking the polysaccharide hydrogel base fabric in PBS buffer solution with pH of 4,7 and 9 for 20min, wherein the colors are respectively purple red, orange and yellow.
And E, detection results of Escherichia coli: the polysaccharide hydrogel-based fabric was soaked in a suspension of E.coli (10 concentration)8CFU/mL) for 30min, the fluorescence intensity is 529000; soaking in 102After 8h, the fluorescence intensity of the CFU/mL Escherichia coli liquid is 22000.
Example 5
The example provides a polysaccharide-based hydrogel-based fabric for visually detecting escherichia coli and pH response, and the specific preparation steps are as in example 1, wherein the mass of sodium periodate is 0.6g, the mass of neutral red is 0.004g, and the rest is the same as that in example 1, so that the polysaccharide-based hydrogel-based fabric is obtained.
pH responsive color change results: the polysaccharide hydrogel was soaked in PBS buffer solution with pH 4,7, and 9 for 30min, and the color was purple red, orange, and yellow.
And E, detection results of Escherichia coli: the polysaccharide hydrogel-based fabric was soaked in a suspension of E.coli (10 concentration)8CFU/mL) for 30min, the fluorescence intensity is 527500; soaking in 102After 8h, the fluorescence intensity of the CFU/mL Escherichia coli liquid is 19600.
Example 6
This example provides a polysaccharide-based hydrogel based fabric for visual detection of e.coli and pH response, prepared according to example 1, sodium periodate 0.6g, 4-methylumbelliferyl- β -D-glucuronide (MUG) 0.034g, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) 0.485g, N-hydroxysuccinimide (NHS) 0.310g, and the rest the same as example 1, to yield a polysaccharide-based hydrogel based fabric.
pH responsive color change results: the polysaccharide hydrogel is soaked in PBS buffer solution with pH 4,7, and 9 for 20min, and the color is respectively purple red, orange, and yellow.
And E, detection results of Escherichia coli: the polysaccharide hydrogel-based fabric was soaked in a suspension of E.coli (10 concentration)8CFU/mL) for 30min, the fluorescence intensity is 543000; soaking in 102And after 8h, the fluorescence intensity of the CFU/mL escherichia coli liquid is 20100.
Example 7
The embodiment provides a polysaccharide-based hydrogel base fabric for visually detecting escherichia coli and pH response, which is prepared by the specific steps of dissolving 22.242g of decaalkyldimethyl tertiary amine and 19.872g of chloropropyltrichlorosilane coupling agent (structural formula 9 in figure 4) in 15mL of anhydrous methanol at 80 ℃, reacting for 21h under the condition of nitrogen, distilling under reduced pressure for 4h to remove solvent and unreacted substances, recrystallizing in acetone at-8-0 ℃, filtering, drying at 40-50 ℃ to obtain a target product, namely organosilicon quaternary ammonium salt, and obtaining the polysaccharide-based hydrogel base fabric in the same manner as in example 1 except for the steps.
The antibacterial quantitative result of the modified cotton fabric is as follows: the antibacterial rate to escherichia coli is 99.5%, and the antibacterial rate to staphylococcus aureus is 99.7%; after being washed by water for 20 times, the antibacterial rate to escherichia coli is 99.45%, the antibacterial rate to staphylococcus aureus is 99.6%, and the antibacterial agent has certain antibacterial performance. The antibacterial quantification results of the polysaccharide hydrogel-based fabric were: the antibacterial rate to escherichia coli is 99.55%, and the antibacterial result to staphylococcus aureus is 99.76%.
And E, detection results of Escherichia coli: the polysaccharide hydrogel-based fabric was soaked in a suspension of E.coli (10 concentration)8CFU/mL) for 30min, the fluorescence intensity is 506000; soaking in 102The fluorescence intensity of the CFU/mL Escherichia coli liquid after 8h was 19900.
Example 8
The embodiment provides a polysaccharide-based hydrogel base fabric for visually detecting escherichia coli and pH response, which is prepared by the specific steps of dissolving 32.221g of hexadecyl dimethyl tertiary amine and 19.872g of chloropropyl trichlorosilane coupling agent in 15mL of anhydrous methanol at 80 ℃ for 21h under the condition of nitrogen according to example 1, distilling under reduced pressure for 4h to remove the solvent and unreacted substances, recrystallizing in acetone at-8-0 ℃, filtering, drying at 40-50 ℃ to obtain a target product, namely organosilicon quaternary ammonium salt, and the balance of the steps are the same as in example 1 to obtain the polysaccharide-based hydrogel base fabric.
The antibacterial quantitative result of the modified cotton fabric is as follows: the antibacterial rate to escherichia coli is 99.99%, and the antibacterial rate to staphylococcus aureus is 99.999%; after being washed by water for 20 times, the antibacterial rate to escherichia coli is 99.985%, the antibacterial rate to staphylococcus aureus is 99.99%, and the antibacterial agent has certain antibacterial performance. The antibacterial quantification results of the polysaccharide hydrogel-based fabric were: the antibacterial rate to escherichia coli is 99.95%, and the antibacterial result to staphylococcus aureus is 99.99%.
And E, detection results of Escherichia coli: the polysaccharide hydrogel-based fabric was soaked in a suspension of E.coli (10 concentration)8CFU/mL) for 30min, the fluorescence intensity is 551000; soaking in 102After 8h, the fluorescence intensity of the CFU/mL escherichia coli liquid is 22100.
Claims (10)
1. A polysaccharide-based hydrogel-based fabric is characterized in that the fabric is put into an organic silicon quaternary ammonium salt solution to react to obtain a modified fabric, a modified konjac glucomannan solution and a modified chitosan solution are coated on the modified fabric, and the modified fabric is subjected to Schiff base reaction and in-situ gelling to obtain the polysaccharide-based hydrogel-based fabric;
the modified konjac glucomannan is obtained by adding an oxidant into a konjac glucomannan monomer solution for reaction, and reacting the obtained oxidized konjac glucomannan monomer containing aldehyde groups with a pH indicator;
the modified chitosan is obtained by activating color development/fluorescence compound solution by EDC and NHS, adjusting pH, adding chitosan with adjusted pH, adjusting pH and reacting.
2. The polysaccharide-based hydrogel-based fabric of claim 1, wherein the fabric comprises one of a polyester cotton fabric, a pure cotton fabric, a viscose fabric; the oxidant comprises one of hydrogen peroxide, potassium permanganate and sodium periodate; the pH indicator comprises one or more of Congo red, neutral red and litmus.
3. The polysaccharide-based hydrogel-based fabric of claim 1, wherein the chromogenic/fluorescent compound comprises one or more of 6-chloro-3-indolyl-D-galactopyranoside Red-Gal, 4-nitrophenyl- β -D-glucuronide PNPG, 6-chloro-3-indolyl- β -D-galactopyranoside X-Gluc, 4-methylumbelliferone- β -D-glucuronide MUG.
4. A method of preparing a polysaccharide-based hydrogel-based fabric, comprising:
(1) dissolving konjac glucomannan monomer in water, adding an oxidant for reaction, dialyzing, centrifuging, drying, dissolving the obtained oxidized konjac glucomannan monomer containing aldehyde in water, adding a pH indicator for reaction, dialyzing, and freeze-drying to obtain modified konjac glucomannan; wherein the mass ratio of the konjac glucomannan monomer to the oxidant is 1: 0.2-1: 1, and the mass ratio of the oxidized aldehyde group-containing konjac glucomannan monomer to the pH indicator is 1: 0.005-1: 0.001;
(2) dissolving a color development/fluorescence compound in water, adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride EDC and N-hydroxysuccinimide NHS for activation, adjusting the pH to acidity, dissolving chitosan in an acid solution, adjusting the pH to acidity, adding the solution into the activated color development/fluorescence compound solution, adjusting the pH to acidity for reaction, dialyzing, and freeze-drying to obtain modified chitosan, wherein the mass ratio of the color development/fluorescence compound, EDC, NHS to chitosan is 0.020-0.075: 0.48-1.0: 0.30-0.65: 1;
(3) mixing long carbon chain tertiary amine and silane coupling agent in a molar ratio of 1: 1-1: 2, dissolving in an organic solvent, reacting under the condition of nitrogen, filtering, distilling under reduced pressure, recrystallizing, filtering, and drying to obtain the organosilicon quaternary ammonium salt, wherein the ratio of the long-carbon-chain tertiary amine to the organic solvent is 20-40 g: 10-30 mL;
(4) dissolving the organic silicon quaternary ammonium salt in the step (3) in water, adding the fabric, stirring for reaction, taking out the fabric, washing and drying to obtain the modified fabric, wherein the mass ratio of the organic silicon quaternary ammonium salt to the water is 1: 100 to 1000;
(5) dissolving the modified konjac glucomannan in the step (1) in water, dissolving the modified chitosan in the step (2) in water, coating the obtained modified konjac glucomannan solution and the obtained modified chitosan solution on the modified fabric in the step (4) in a volume ratio of 1: 1-5: 1, and carrying out Schiff base reaction to carry out in-situ gelling to obtain the polysaccharide-based hydrogel base fabric.
5. The method according to claim 4, wherein the step (1) of adding the oxidant comprises the following reaction steps: carrying out dark reaction at room temperature for 8-20 h; adding a pH indicator to react: reacting for 0.2-1 h at room temperature.
6. The method according to claim 4, wherein the pH is adjusted to 4-6 in the step (2); the activation time is 3-6 h; the reaction time is 4-8 h.
7. The method according to claim 4, wherein the number of carbons of the long-carbon-chain tertiary amine in the step (3) is 10 to 18; the silane coupling agent is chloropropyl trichlorosilane coupling agent; the organic solvent comprises methanol; the reaction temperature is 70-100 ℃, and the reaction time is 6-24 h.
8. The method according to claim 4, wherein the stirring reaction temperature in the step (4) is room temperature, and the stirring reaction time is 8-12 h.
9. The method as claimed in claim 4, wherein the modified konjac glucomannan mass fraction in the modified konjac glucomannan solution in the step (5) is 6-12%; the mass fraction of the modified chitosan in the modified chitosan solution is 3-6 percent; the reaction temperature of the Schiff base is 20-30 ℃, and the reaction time is 10 s-30 min.
10. Use of the polysaccharide-based hydrogel-based fabric of claim 1 for detecting e.
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