Polyurethane fluorescent material applicable to bacterial detection and preparation method thereof

Abstract

The application belongs to the technical field of functional polyurethane materials, and more particularly relates to a polyurethane fluorescent material applicable to bacterial detection and a preparation method thereof. The polyurethane pre-polymer is obtained by pre-polymerization of a hydrophobic polyether monomer, isocyanate, a catalyst and a hydrophilic solvent; a chain extender is added to the pre-polymer for chain extension reaction, and then a capping agent is added for capping reaction, and after curing, a polyurethane elastomer is obtained; the polyurethane elastomer is mixed with an ethanol solution, curcumin is added, and stirred uniformly to obtain a fluorescent polyurethane solution, and curing obtains a polyurethane-based fluorescent material. The polyurethane fluorescent material applicable to bacterial detection is designed through a polyurethane segment, ensures solid-state light emission of curcumin, does not cause fluorescence quenching, ensures activity of a heat-sensitive base material at room temperature, and the fluorescent color is different under different bacterial concentrations, and the response is sensitive.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of functional polyurethane materials, and more particularly relates to a polyurethane fluorescent material applicable to bacterial detection and a preparation method thereof. BACKGROUND

[0002] Fluorescent functional materials have great application potential in the fields of biosensing, intelligent packaging, wearable health monitoring and anti-counterfeiting identification. At present, common strategies to realize the fluorescent properties of materials mainly include: incorporating inorganic fluorescent powder or synthesizing organic fluorescent dye. However, inorganic fluorescent powder often faces problems such as poor compatibility with polymer matrix, uneven dispersion, easy agglomeration and sedimentation, which leads to the decrease of material transmittance, the deterioration of mechanical properties and the attenuation of fluorescent efficiency; while traditional organic dyes generally have poor light stability, are easy to be photobleached, have potential biological toxicity and have single function (usually only have light emitting property) and other limitations.

[0003] In addition, giving materials specific biological recognition function (such as bacterial detection) often needs additional complex surface modification or introduction of other probe molecules, which increases the preparation difficulty and cost, and may affect the uniformity and stability of the material. Therefore, developing a multifunctional integrated flexible fluorescent material with excellent fluorescent performance, good processability and direct response to the presence of bacteria has become a technical problem to be solved. SUMMARY

[0004] The purpose of the present application is to provide a polyurethane fluorescent material applicable to bacterial detection and a preparation method thereof, in order to solve the problems existing in the prior art.

[0005] To achieve the above purpose, the present application provides the following solutions.

[0006] One of the technical solutions of the present application provides a preparation method of a polyurethane fluorescent material applicable to bacterial detection, comprising the following steps:

[0007] After the hydrophobic polyether monomer is dehydrated, it is mixed with isocyanate, catalyst and hydrophilic solvent, and a polyurethane prepolymer is obtained through prepolymerization;

[0008] A chain extender is added to the prepolymer to perform chain extension reaction, and then a blocking agent is added to perform blocking reaction, to obtain a polyurethane solution;

[0009] After the polyurethane solution is cured, a polyurethane elastomer is obtained;

[0010] The polyurethane elastomer is mixed with an ethanol solution, curcumin is added and stirred uniformly to obtain a fluorescent polyurethane solution;

[0011] The fluorescent polyurethane solution is cured to obtain the polyurethane-based fluorescent material.

[0012] The chain extender defined in the application can enhance the network structure, and the formed polyurethane material does not cause aggregation quenching of curcumin;

[0013] The application has a milder curing condition, and does not cause fluorescence quenching after curing, solves the problem that curcumin cannot emit light in solid state, and has universality.

[0014] Further, the dehydration temperature is 50-160℃, and the time is 1-6h.

[0015] Further, the temperature of the prepolymerization is 50-160℃, and the time is 6-10h.

[0016] Further, the temperature of the chain extension reaction is 50-160℃, and the time is 1-3h.

[0017] Further, the temperature of the end-capping reaction is 50-160℃, and the time is 1-3h.

[0018] Further, the solid content of the polyurethane solution is 10-80wt%.

[0019] Further, the curing temperature for preparing the polyurethane elastomer is 70-100℃, and the time is 4-10h.

[0020] Further, the curing temperature for preparing the polyurethane-based fluorescent material is room temperature, and the time is 10-30min, preferably 20min.

[0021] Further, the hydrophobic polyether monomer includes polytetrahydrofuran (MW=2000) and / or polyvinyl alcohol (MW=2000).

[0022] Further, the isocyanate includes at least one of PDI, TDI, MDI and IPDI.

[0023] Further, the catalyst includes at least one of triethylamine, triethylenediamine, dibutyltin dilaurate, iron octoate, zinc naphthenate and titanium acid tetraisobutyl ester.

[0024] Further, the hydrophilic solvent includes at least one of N,N-dimethylacetamide, N,N-dimethylformamide and dimethyl sulfoxide.

[0025] Further, the chain extender includes adipic acid dihydrazide and 4,4'-diaminodiphenyl disulfide, and the molar ratio is 4:1.

[0026] The network structure formed under the action of the chain extender can wrap curcumin, so that curcumin cannot aggregate to induce light emission.

[0027] Further, the end-capping agent includes ethylene glycol.

[0028] Further, the use ratio of the hydrophobic polyether monomer, the hydrophilic solvent, the isocyanate, the catalyst, the chain extender and the end-capping agent is 5g:(10-15)mL:(1.5-1.8)g:(10-20)uL:(0.2-0.4)g:(0.01-0.05)g, preferably 5g:10mL:1.67g:20uL:0.285g:0.023g.

[0029] Further, the mass fraction of the ethanol solution is 70-80%, preferably 75%.

[0030] Further, the mass ratio of the polyurethane elastomer, the curcumin and the ethanol solution is 10:(0.01-0.013):(12-18), preferably 10:0.0125:15.

[0031] The present application realizes efficient luminescence of the polyurethane by adding curcumin particles to the polyurethane solution and combining with the room temperature curing process, and the obtained product is suitable for bacterial detection.

[0032] The second technical scheme of the present application provides a polyurethane fluorescent material applicable to bacterial detection, which is prepared by the above preparation method.

[0033] The third technical scheme of the present application provides an application of the above polyurethane fluorescent material applicable to bacterial detection in the field of bacterial detection.

[0034] The present application discloses the following technical effects:

[0035] The present application provides a polyurethane fluorescent material applicable to bacterial detection, which has excellent fluorescent performance and bacterial responsiveness, and the preparation process is simple and easy to implement.

[0036] In the polyurethane fluorescent material applicable to bacterial detection, the design of the polyurethane chain segment ensures the solid-state luminescence of curcumin without causing fluorescence quenching, ensures the activity of the heat-sensitive base material (curcumin) under room temperature curing, and the fluorescence color is different under different bacterial concentrations, and the response is sensitive. BRIEF DESCRIPTION OF DRAWINGS

[0037] The drawings constituting a part of the present application are used to provide further understanding of the present application, the schematic embodiments of the present application and the description thereof are used to explain the present application, and do not constitute improper limitation on the present application. In the drawings:

[0038] Figure 1 From left to right, they are the pictures of the polyurethane solution, the polyurethane elastomer, the fluorescent polyurethane solution under normal light irradiation and the fluorescent polyurethane solution under ultraviolet irradiation in Example 1.

[0039] Figure 2 Pictures of the polyurethane-based fluorescent material under UV irradiation and under natural light for Example 1, left picture under UV irradiation, right picture under natural light.

[0040] Figure 3 Graph of the change in fluorescent color of the polyurethane-based fluorescent material for different bacterial concentrations.

[0041] Figure 4 Fluorometer results for different bacterial numbers.

[0042] Figure 5 Change in fluorescent color for different bacterial concentrations in real samples. DETAILED DESCRIPTION

[0043] Various example embodiments of the present application will now be described in detail with reference to the drawings. Such description, however, is to be considered in all respects only as illustrative, and not restrictive.

[0044] It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the present application. In addition, where particular ranges of values are given, understand that each intervening value, to the upper or lower limit of the ranges is also specifically included. Each smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in that stated range is also encompassed. The upper and lower limits of these smaller ranges can independently be included or excluded in the range, and are also encompassed within the application, subject to any specifically excluded limit in the stated

[0045] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. Although preferred methods and materials are described, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present application. All documents mentioned herein are incorporated by reference to disclose and describe the methods and / or materials in connection with which the documents are cited. In case of conflict, the present specification will control.

[0046] Various modifications and changes can be made to the specific embodiments of the present application described herein without departing from the scope or spirit of the application. Other embodiments of the application will be apparent to those of ordinary skill in the art from the description and examples presented herein. The description and examples are illustrative of the application and are not intended to limit the scope of the application.

[0047] As used herein, the terms "comprise", "comprising", "include", "including", "have", "having" and the like are open-ended and do not exclude additional elements or steps.

[0048] Unless otherwise specified, all raw materials and reagents involved in the embodiments of the present application are commercially available products.

[0049] Unless otherwise specified, room temperature and normal temperature in the embodiments of the present application both refer to 20-30℃.

[0050] It should be noted that the details not described in the present application are all conventional operating means in the art and are not the focus of the present application.

[0051] Unless otherwise specified, all raw materials and reagents involved in the embodiments of the present application are commercially available products.

[0052] Unless otherwise specified, room temperature and normal temperature in the embodiments of the present application both refer to 20-30℃.

[0053] It should be noted that the details not described in the present application are all conventional operating means in the art and are not the focus of the present application.

[0054] Example 1

[0055] The preparation steps of the polyurethane fluorescent material applicable to bacterial detection include:

[0056] S1, 5g of polytetrahydrofuran ether (MW=2000) was placed in a container and placed in a heating oil bath, the temperature was set to 120℃, and at the same time, a vacuum pump was used for vacuumizing, and dehydrating for 3 hours, then 1.67g of isocyanate (IPDI) was added into a three-necked flask at the same time, and a catalyst (dibutyltin dilaurate 20μL) and a hydrophilic solvent (N,N-dimethylacetamide 10mL) were added, and the oil bath was used for heating and stirring at 80℃ for 5 hours to obtain a polyurethane prepolymer;

[0057] S2, a chain extender (0.21g of adipic acid dihydrazide and 0.075g of 4,4'-diaminodiphenyl disulfide, the molar ratio is about 4:1) was added to the polyurethane prepolymer, and the oil bath was used for heating and stirring at 80℃ for 2 hours, then 0.023g of ethylene glycol was added for end-capping, and the reaction was continued for 1 hour to obtain a polyurethane solution with a solid content of 40%;

[0058] S3, the polyurethane solution was poured into a polytetrafluoroethylene mold and cured in an 80℃ oven for 6h to obtain a polyurethane elastomer;

[0059] S4, 10g of the polyurethane elastomer was mixed with 15g of 75% ethanol solution, 0.0125g of curcumin was added, and the mixture was stirred uniformly to obtain a fluorescent polyurethane solution;

[0060] S5, the fluorescent polyurethane solution was cured at room temperature for 20 minutes to obtain a polyurethane-based fluorescent material.

[0061] Test Example

[0062] Figure 1 From left to right, the pictures are polyurethane solution, polyurethane elastomer, fluorescent polyurethane solution under normal light and fluorescent polyurethane solution under UV light in Example 1.

[0063] Figure 2 The pictures are under UV light and natural light for polyurethane-based fluorescent material in Example 1. The left picture is under UV light and the right picture is under natural light.

[0064] Bacteria detection test: the fluorescent polyurethane solution is cured at room temperature on a plastic wrap to obtain a polyurethane-based fluorescent material (film). The material is placed in different concentrations of E. coli culture dishes to observe the change of fluorescent color. The presence of bacteria is detected by the change of fluorescent color, as shown in Figure 3

[0065] Figure 3 The pictures are the change of fluorescent color of polyurethane-based fluorescent material under different concentrations of bacteria.

[0066] Figure 4 The pictures are the results of fluorescence photometer under different amounts of bacteria.

[0067] Figure 5 The pictures are the change of fluorescent color under different concentrations of bacteria in actual samples.

[0068] The various embodiments in the specification are described in a progressive manner, and each embodiment focuses on the difference from other embodiments. The same or similar parts between the embodiments can be referred to each other.

[0069] The above description of disclosed embodiments enables those skilled in the art to carry out or use the present application. Various modifications to these embodiments will be apparent to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present application. Therefore, the present application will not be limited to these embodiments shown herein, but will conform to the widest scope consistent with the principles and novel features disclosed herein.​

Claims

1. A method for preparing a polyurethane fluorescent material applicable to bacterial detection, characterized in that the steps include... include: After dehydration, the hydrophobic polyether monomer is mixed with isocyanate, catalyst and hydrophilic solvent, and then subjected to a prepolymerization reaction to obtain a polyurethane prepolymer. A chain extender is added to the prepolymer to carry out a chain extension reaction, followed by the addition of a capping agent to carry out a capping reaction, resulting in a polyurethane solution. After curing the polyurethane solution, a polyurethane elastomer is obtained; The polyurethane elastomer was mixed with an ethanol solution, curcumin was added, and the mixture was stirred until homogeneous to obtain a fluorescent polyurethane solution. The fluorescent polyurethane solution is cured to obtain the polyurethane fluorescent material; The chain extender comprises adipic acid dihydrazide and 4,4'-diaminodiphenyl disulfide in a molar ratio of 4:1; The capping agent includes ethylene glycol.

2. The preparation method according to claim 1, characterized in that, The dehydration temperature is 50-160 ℃, and the time is 1-6 h; And / or, the temperature of the prepolymerization reaction is 50-160 °C and the time is 6-10 h.

3. The preparation method according to claim 1, characterized in that, The chain extension reaction is carried out at a temperature of 50-160 ℃ for 1-3 h. And / or, the end-capping reaction is carried out at a temperature of 50-160 °C for a time of 1-3 h; And / or, the solid content of the polyurethane solution is 10-80 wt%.

4. The preparation method according to claim 1, characterized in that, The curing temperature for preparing the polyurethane elastomer is 70-100 ℃, and the curing time is 4-10 h. And / or, the curing temperature for preparing the polyurethane fluorescent material is room temperature, and the curing time is 20 min.

5. The preparation method according to claim 1, characterized in that, The hydrophobic polyether monomers include polytetrahydrofuran and / or polyvinyl alcohol; And / or, the isocyanate includes at least one of PDI, TDI, MDI and IPDI; And / or, the catalyst comprises at least one of triethylamine, triethylenediamine, dibutyltin dilaurate, ferric octanoate, zinc naphthenate, and tetraisobutyl titanate; And / or, the hydrophilic solvent includes at least one of N,N-dimethylacetamide, N,N-dimethylformamide, and dimethyl sulfoxide.

6. The preparation method according to claim 1, characterized in that, The ratio of the hydrophobic polyether monomer, hydrophilic solvent, isocyanate, catalyst, chain extender and capping agent is 5g:(10-15)mL:(1.5-1.8)g:(10-20)μL:(0.2-0.4)g:(0.01-0.05)g.

7. The preparation method according to claim 1, characterized in that, The ethanol solution has a mass fraction of 70-80%; And / or, the mass ratio of the polyurethane elastomer, curcumin and ethanol solution is 10:(0.01-0.013):(12-18).

8. A polyurethane fluorescent material applicable to bacterial detection, characterized in that, The polyurethane fluorescent material applicable to bacterial detection is prepared by the preparation method according to any one of claims 1-7.

9. The application of the polyurethane fluorescent material of claim 8, applicable to bacterial detection, in the field of bacterial detection, wherein the application is for the purpose of non-disease diagnosis and treatment.

Images