阅读说明：本技术 一种功能化纸张的制备方法和扩散驱动纸张功能化装置 (Preparation method of functionalized paper and diffusion-driven paper functionalization device ) 是由 杨丹丹 汤书华 周艳聪 王岩 马茜 王硕朋 于 2021-09-27 设计创作，主要内容包括：本发明提供了一种功能化纸张的制备方法和扩散驱动纸张功能化装置,涉及新材料技术领域。本发明将功能化修饰试剂第一反应液和第二反应液通过纸张隔离后进行扩散界面反应,得到功能化纸张。本发明提供的制备方法,以分子扩散为驱动力,无需提供额外的能量,反应条件温和,操作简便、节能、环保。与化学键合一般只能对纸张表面的羟基和纤维素环的还原端进行反应修饰相比,本发明提供的制备方法能够制备得到多种含有不同的活性物质的功能化纸张,具有普适性；而且,本发明提供的制备方法不会破坏纸张表面结构,对于推动功能化纸基分析平台在分析检测中的应用具有重要的意义。本发明采用的装置简单,能够实现多种功能化纸张的制备。(The invention provides a preparation method of functionalized paper and a diffusion-driven paper functionalization device, and relates to the technical field of new materials. According to the invention, the first reaction solution and the second reaction solution of the functional modification reagent are separated by paper and then subjected to diffusion interface reaction to obtain the functional paper. The preparation method provided by the invention takes molecular diffusion as a driving force, does not need to provide additional energy, has mild reaction conditions, is simple and convenient to operate, saves energy and is environment-friendly. Compared with the chemical bonding which can only carry out reaction modification on the hydroxyl on the surface of the paper and the reducing end of the cellulose ring, the preparation method provided by the invention can prepare a plurality of functional papers containing different active substances and has universality; moreover, the preparation method provided by the invention does not damage the surface structure of the paper, and has important significance for promoting the application of the functionalized paper-based analysis platform in analysis and detection. The device adopted by the invention is simple, and can realize the preparation of various functional papers.)

1. A preparation method of functionalized paper is characterized by comprising the following steps:

isolating the first reaction solution and the second reaction solution through paper, and performing diffusion interface reaction on the surface of the paper to obtain functionalized paper;

the first reaction solution comprises one or more of a disodium terephthalate aqueous solution, a sodium alginate solution and a sodium alginate solution containing rare earth nanoparticles;

the second reaction solution comprises a rare earth salt aqueous solution and/or a calcium ion solution.

2. The method according to claim 1, wherein the molar ratio of the first reaction solution to the second reaction solution is 3 to 20:1, based on the rare earth metal ion and the disodium terephthalate, respectively.

3. The method of claim 1 or 2, wherein the rare earth metal ions in the aqueous rare earth salt solution comprise lanthanum, terbium and europium; the total concentration of rare earth metal ions in the rare earth salt water solution is 1-10 mmol/L.

4. The method according to claim 1 or 2, wherein the concentration of the aqueous disodium terephthalate solution is 3 to 150 mmol/L.

5. The preparation method according to claim 1 or 2, wherein the temperature of the diffusion interface reaction is room temperature and the time is 1-180 min.

6. The production method according to claim 1 or 2, wherein the first reaction solution and the second reaction solution are separated by paper, and a diffusion interface reaction is performed on the surface of the paper, specifically:

isolating part of the first reaction solution and part of the second reaction solution through paper, and performing pre-diffusion interface reaction on the surface of the paper to obtain a functional paper precursor; the part of the first reaction liquid accounts for 10-30% of the total amount of the first reaction liquid; the part of the second reaction liquid accounts for 40-90% of the total amount of the second reaction liquid;

separating the residual second reaction liquid and the residual first reaction liquid through a functional paper precursor, and performing re-diffusion interface reaction on the surface of the functional paper precursor to obtain functional paper;

the contact surface of the residual second reaction liquid and part of the first reaction liquid with the paper is the same, and the contact surface of the residual first reaction liquid and part of the second reaction liquid with the paper is the same.

7. A functionalized paper obtained by the production method according to any one of claims 1 to 6.

8. Use of the functionalized paper of claim 7 in analytical testing.

9. The diffusion-driven paper functionalization device adopted by the preparation method according to any one of claims 1 to 6, comprising an open container B and an open container A which are detachably connected; an opening is formed in the bottom surface of the open container A, and paper is fixed at the opening;

the inner bottom surface of the open container B is in contact with the open container A.

Technical Field

The invention relates to the technical field of new materials, in particular to a preparation method of functionalized paper and a diffusion-driven paper functionalization device.

Background

The paper is a widely used material prepared by utilizing plant cellulose, and has the advantages of low price, good biocompatibility, good portability, recoverability, reutilization, easy cutting, easy degradation and the like. Has important application in the fields of printing, food, medical treatment and environment. A multifunctional analysis platform is constructed by paper, so that toxic substances in food can be detected, and the food safety is guaranteed; the biological markers in the blood can be detected in real time, the obtained detection data can provide basis for disease diagnosis and treatment, and people can monitor the self health condition in real time by combining big data analysis, and certain guidance and suggestion can be obtained through a data analysis platform. Particularly, the paper-based analysis platforms can be prepared into miniature portable devices, and are convenient to popularize and apply. The basis of the construction of these paper-based analytical platforms is the substance with analytical detection function on the surface modification of the paper.

At present, the methods for functionalizing the surface of paper mainly include electrostatic adsorption, covalent bond modification, embedding, and the like. These methods generally require the introduction of functional groups that are charged or chemically reactive on the surface of the paper and then introduce molecules with detection functions on the surface of the paper by electrostatic interaction or chemical bonding. However, the above method is complicated.

Disclosure of Invention

In view of the above, the present invention provides a method for preparing functionalized paper and a diffusion-driven paper functionalizing apparatus, and the preparation method provided by the present invention is simple in operation.

In order to achieve the above object, the present invention provides the following technical solutions:

the invention provides a preparation method of functional paper, which comprises the following steps:

isolating the first reaction solution and the second reaction solution through paper, and performing diffusion interface reaction on the surface of the paper to obtain functionalized paper;

the first reaction solution comprises one or more of a disodium terephthalate aqueous solution, a sodium alginate solution and a sodium alginate solution containing rare earth nanoparticles;

the second reaction solution comprises a rare earth salt aqueous solution and/or a calcium ion solution.

Preferably, the molar ratio of the first reaction solution to the second reaction solution is 3-20: 1, respectively calculated on the basis of rare earth metal ions and disodium terephthalate.

Preferably, the rare earth metal ions in the rare earth salt aqueous solution comprise lanthanum, terbium and europium; the total concentration of rare earth metal ions in the rare earth salt water solution is 1-10 mmol/L.

Preferably, the concentration of the disodium terephthalate aqueous solution is 3-150 mmol/L.

Preferably, the temperature of the diffusion interface reaction is room temperature, and the time is 1-180 min.

Preferably, the first reaction solution and the second reaction solution are isolated by paper, and a diffusion interface reaction is performed on the surface of the paper, specifically:

isolating part of the first reaction solution and part of the second reaction solution through paper, and performing pre-diffusion interface reaction on the surface of the paper to obtain a functional paper precursor; the part of the first reaction liquid accounts for 10-30% of the total amount of the first reaction liquid; the part of the second reaction liquid accounts for 40-90% of the total amount of the second reaction liquid;

separating the residual second reaction liquid and the residual first reaction liquid through a functional paper precursor, and performing re-diffusion interface reaction on the surface of the functional paper precursor to obtain functional paper;

the contact surface of the residual second reaction liquid and part of the first reaction liquid with the paper is the same, and the contact surface of the residual first reaction liquid and part of the second reaction liquid with the paper is the same.

The invention provides the functional paper obtained by the preparation method in the technical scheme.

The invention provides application of the functional paper in the technical scheme in analysis and detection.

The invention also provides a diffusion driving paper functionalization device adopted by the preparation method in the technical scheme, which comprises an open container B and an open container A which are detachably connected; an opening is formed in the bottom surface of the open container A, and paper is fixed at the opening;

the inner bottom surface of the open container B is in contact with the open container A.

The invention provides a preparation method of functional paper, which comprises the following steps: isolating the first reaction solution and the second reaction solution through paper, and performing diffusion interface reaction on the surface of the paper to obtain functionalized paper; the first reaction solution comprises a disodium terephthalate aqueous solution, a sodium alginate solution or a sodium alginate solution containing rare earth nanoparticles; the second reaction solution comprises a rare earth salt aqueous solution or a calcium ion solution. The preparation method provided by the invention is a diffusion driving modification method, a functional modification reagent is divided into a first reaction solution and a second reaction solution, the first reaction solution and the second reaction solution are separated by paper to be modified, the solute concentration in the two reaction solutions is higher than that of the substance in a surface solution, the substance can spontaneously migrate from a high-concentration area to a low-concentration area, the first reaction solution and the second reaction solution are further diffused towards the opposite surface, and the reaction solutions in the two parts of a paper medium undergo a diffusion interface reaction, so that a reaction product is fixed on the paper. The preparation method provided by the invention takes molecular diffusion as a driving force, does not need to provide additional energy, has mild reaction conditions, is simple and convenient to operate, saves energy and is environment-friendly. Compared with the chemical bonding which can only carry out reaction modification on the hydroxyl on the surface of the paper and the reducing end of the cellulose ring, the preparation method provided by the invention can prepare a plurality of functional papers containing different active substances and has universality; moreover, the preparation method provided by the invention does not damage the surface structure of the paper, has important significance for promoting the application of the functionalized paper-based analysis platform in analysis and detection, and provides more resources for the construction of the paper-based analysis platform.

The invention provides the functional paper obtained by the preparation method in the technical scheme. The functionalized paper provided by the invention has high strength and good application prospect in analysis and detection.

The invention provides a diffusion-driven paper functionalization device adopted by the preparation method, which comprises an open container B and an open container A which are detachably connected; an opening is formed in the bottom surface of the open container A, and paper is fixed at the opening; the inner bottom surface of the open container B is in contact with the open container A. The diffusion-driven paper functionalization device provided by the invention is simple and can realize preparation of various functionalized papers.

Drawings

FIG. 1 is a block diagram of a diffusion driven paper functionalization apparatus;

FIG. 2 is a process flow diagram for making a functionalized paper using a build diffusion driven paper functionalization apparatus;

FIG. 3 is a physical diagram of a diffusion-driven paper-functionalizing device constructed in example 1;

FIG. 4 is a scanning electron micrograph of the functionalized paper prepared in example 1;

FIG. 5 is a graph of fluorescence spectra of blank paper and functionalized paper under 320nm excitation;

fig. 6 is a standard work curve of sunset yellow standard.

Detailed Description

The invention provides a preparation method of functional paper, which comprises the following steps:

and (3) isolating the first reaction solution and the second reaction solution through paper, and performing diffusion interface reaction on the surface of the paper to obtain the functionalized paper.

In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.

In the present invention, the second reaction solution includes a rare earth salt aqueous solution or a calcium ion solution; the rare earth metal ions in the rare earth salt water solution preferably comprise lanthanum, terbium and europium, and the rare earth salt preferably comprises lanthanum nitrate, terbium nitrate and europium nitrate; the total concentration of the rare earth metal ions in the rare earth salt water solution is preferably 1-10 mmol/L, more preferably 2-8 mmol/L, and further preferably 3-5 mmol/L. In the embodiment of the present invention, the rare earth salt aqueous solution is preferably obtained by mixing lanthanum nitrate, terbium nitrate, europium nitrate and distilled water until the solid is completely dissolved.

In the invention, the first reaction solution comprises a disodium terephthalate aqueous solution, a sodium alginate solution or a sodium alginate solution containing rare earth nanoparticles; the concentration of the disodium terephthalate aqueous solution is preferably 3 to 140mmol/L, more preferably 20 to 120mmol/L, and further preferably 50 to 90 mmol/L. In the present invention, the aqueous solution of disodium terephthalate is preferably ready for use; the preparation method of the disodium terephthalate aqueous solution comprises the following steps: terephthalic acid, sodium hydroxide and water are mixed for acid-base neutralization reaction, and then the mixture is filtered to obtain a disodium terephthalate aqueous solution. In the present invention, the molar ratio of terephthalic acid to sodium hydroxide is preferably 1: 2; the water is preferably distilled water. In the present invention, the mixing is preferably performed by stirring, and the stirring is preferably performed by a magnetic stirrer. In the invention, the acid-base neutralization reaction is preferably carried out under stirring, and the time of the acid-base neutralization reaction is preferably 10-20 min, and more preferably 15 min. In the present invention, the filtration is preferably suction filtration, and the suction filtration is preferably performed using a vacuum pump.

In the present invention, the molar ratio of the first reaction solution to the second reaction solution is preferably 3 to 20:1, more preferably 8 to 20:1, and even more preferably 13 to 20:1, based on the rare earth metal ion and the disodium terephthalate, respectively.

In the present invention, the paper is preferably filter paper. In the invention, the temperature of the diffusion interface reaction is preferably room temperature, and the time is preferably 1-180 min, and more preferably 5-100 min. In the present invention, taking rare earth salt aqueous solution and disodium terephthalate aqueous solution as examples, rare earth ions and disodium terephthalate form metal-organic coordination polymer through coordination during the diffusion interface reaction.

In the present invention, the first reaction solution and the second reaction solution are separated by paper, and a diffusion interface reaction is performed on the surface of the paper, and preferably specifically: isolating part of the first reaction solution and part of the second reaction solution through paper, and performing pre-diffusion interface reaction on the surface of the paper to obtain a functional paper precursor; and separating the residual second reaction liquid from the residual first reaction liquid through a functional paper precursor, and performing re-diffusion interface reaction on the surface of the functional paper precursor to obtain the functional paper. In the invention, the part of the first reaction liquid preferably accounts for 10-30% of the total amount of the first reaction liquid, more preferably 15-30%, and even more preferably 20-25%; the part of the second reaction solution accounts for 40-90% of the total amount of the second reaction solution, preferably 60-90%, and more preferably 70-80%. In the present invention, the contact surface between the remaining second reaction solution and the paper is the same as the contact surface between part of the first reaction solution and the paper, and the contact surface between the remaining first reaction solution and the paper is the same as the contact surface between part of the second reaction solution and the paper. In the invention, the temperature of the pre-diffusion interface reaction is preferably room temperature, the time is preferably 1-180 min, and more preferably 5-100 min; after the pre-diffusion interface reaction, the invention preferably further comprises washing the paper after the pre-diffusion interface to obtain a functional paper precursor. In the invention, the temperature of the re-diffusion interface reaction is preferably room temperature, the time is preferably 1-180 min, and more preferably 5-100 min; after the re-diffusion interface reaction, the invention preferably further comprises washing the paper after the re-diffusion interface reaction with water and then drying to obtain the functionalized paper; the drying mode is preferably natural airing.

The invention provides the functional paper obtained by the preparation method in the technical scheme.

The invention provides application of the functional paper in the technical scheme in analysis and detection.

The invention also provides a diffusion driving paper functionalization device adopted by the preparation method in the technical scheme, which comprises an open container B and an open container A which are detachably connected; an opening is formed in the bottom surface of the open container A, and paper is fixed at the opening; the inner bottom surface of the open container B is in contact with the open container A. The material of the open container A is not particularly limited, and the open container A is not required to react with the first reaction liquid and the second reaction liquid, specifically, the open container A is made of plastic, and the plastic is preferably food-grade plastic; in the present invention, the open container a is preferably derived from a food grade plastic sealed bottle. The material of the open container B is not particularly limited, and the open container B is not required to be reacted with a first reaction liquid and a second reaction liquid, such as glass or plastic; in an embodiment of the present invention, the open container B is preferably a petri dish.

When the open container A is derived from a food-grade plastic sealed bottle and the open container B is used as a culture dish, the construction method of the diffusion-driven paper functionalization device (shown in figure 1) preferably comprises the following steps: cutting a large-diameter plastic bottle, reserving a bottle cap and a part of a bottle body, perforating the bottle cap, flatly paving paper in the bottle cap, and screwing the bottle cap and the bottle body tightly to obtain an open container A; and placing the bottle cap part of the open container A on the inner bottom surface of the open container B to obtain the diffusion drive paper functionalization device. In the invention, the aperture of the large-aperture plastic bottle is preferably 3-10 cm; the length of the part of the bottle body is preferably 1-10 cm, and more preferably 2-9 cm; the diameter of the through hole is preferably 0.5-1.5 cm smaller than the inner diameter of the bottle cap; the paper is preferably circular, and the diameter of the paper is preferably the same as the inner diameter of the bottle cap; the paper is preferably cut. The invention has no special limitation on the smooth paving, and can ensure that paper is flatly paved on the inner surface of the bottle cap, and the outer diameter of the paper is tightly attached to the inner diameter of the bottle cap. The diffusion-driven paper functionalization device provided by the invention fixes paper in the bottle cap by utilizing the occlusion effect between the bottle cap and the bottle mouth, at the moment, the paper seals the end of the bottle cap of the open container A to form a paper sealing end, and the paper sealing end is downwards placed on the inner surface of the open container B to form the diffusion-driven paper functionalization device. The construction method of the diffusion driving paper functionalization device is easy to construct, the required raw materials are convenient to obtain, and the cost is low.

The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

The diffusion-driven paper functionalization device is constructed according to the construction method flow chart of fig. 1, and the functionalized paper is prepared according to the functionalized paper preparation flow chart shown in fig. 2, and the specific steps are as follows:

(1) cutting off the mouth of a food-grade plastic sealed bottle with threads, the diameter of the bottle is 6.5cm, the height of the bottle is 15cm, and the height of the bottle body is kept to be 5 cm; the bottle mouth is unscrewed, and a circular hole with the diameter of about 5.5cm is dug in the center of the bottle cap; taking a piece of quantitative filter paper, cutting the filter paper into a circle, and enabling the outer diameter of the filter paper to be tightly attached to the inner diameter of the bottle cap; screwing the bottle mouth and the bottle cap again, and fixing the filter paper placed in the bottle cap to obtain an open container A; taking a culture dish with the diameter of about 9cm as an open container B, and placing the filter paper sealing end of the open container A on the surface of the culture dish to obtain the diffusion driving reaction device, wherein a material object diagram of the diffusion driving reaction device is shown in FIG. 3;

(2) putting terephthalic acid and sodium hydroxide into a 100mL small beaker, adding 50mL distilled water, adding a small magnet, stirring for 15min on a magnetic stirrer to generate disodium terephthalate, pouring into a filter flask, performing suction filtration by using a vacuum pump, pouring the solution after the suction filtration into the beaker to obtain a first reaction solution, wherein the molar ratio of the terephthalic acid to the sodium hydroxide is 1:2, and the concentration of the disodium terephthalate in the first reaction solution is 70 mmol/L;

putting lanthanum nitrate, terbium nitrate and europium nitrate into a 100mL small beaker, adding 50mL of distilled water, slightly shaking and uniformly stirring to completely dissolve solids to obtain a second reaction solution, wherein the concentration of lanthanum ions is 4mmol/L, the concentration of terbium ions is 0.3mmol/L, and the concentration of europium is 0.1 mmol/L;

(3) filling 10mL of first reaction liquid into an open container A sealed by filter paper, filling 40mL of second reaction liquid into an open container B, putting the open container A into the open container B, removing bubbles between the filter paper and the open container B, carrying out pre-diffusion interfacial reaction for 10min under the condition of room temperature and standing, taking out the open container A, removing residual reaction liquid in the open container A and the open container B, and washing two sides of the filter paper, the open container A and the open container B by distilled water to wash away residual reaction liquid;

(4) and (3) filling 40mL of first reaction liquid into an open container B, filling 10mL of second reaction liquid into an open container A, removing bubbles between the functional paper precursor and the open container B, carrying out diffusion interface reaction for 10min under the conditions of room temperature and standing, taking out the open container A, removing the residual reaction liquid in the open container A and the open container B, cleaning two sides of the functional paper precursor with distilled water, and naturally airing to obtain the functional paper.

Fig. 4 is a scanning electron microscope image of the functionalized paper prepared in this example, and it can be seen from fig. 4 that the functionalized nanoparticles are loaded on the surface of the paper.

FIG. 5 is a graph showing fluorescence spectra of blank paper (filter paper) and functionalized paper under 320nm excitation, wherein fluorescence emission at 487nm and 544nm is terbium ion⁵D₄→⁷F₆And⁵D₄→⁷F₅fluorescence generated by energy level transition, wherein the fluorescence emission at 616nm is europium ion⁵D₀→⁷F₂Fluorescence generated by energy level transition. As can be seen from fig. 5, the functionalized rare earth material imparts unique fluorescence properties to the paper and can be used for analytical detection.

Test example

(1) Standard working curve

The sunset yellow standard substance is dissolved in distilled water to prepare a series of standard solutions with the concentrations of 10 mug/mL, 25 mug/mL, 50 mug/mL, 100 mug/mL and 150 mug/mL respectively. The functionalized paper prepared in example 1 was cut into small pieces (size)1 x 2cm), respectively immersing the cut small pieces of functional paper in a blank solution and a series of standard solutions for 30s, then measuring the fluorescence spectrum of the functional paper under the excitation of 320nm by using a fluorescence spectrometer, taking the concentration of sunset yellow as an ordinate, and taking the ratio of fluorescence intensity at 487nm to 616nm (I)₄₈₇/I₆₁₆) The standard work curve of sunset yellow is plotted on the abscissa, the result is shown in FIG. 6, the obtained work curve equation is that y is-4036.30303 x +385.46071, the linear range is 10-150 mug/mL, R²＝0.99561。

(2) Taking a commercial Fenda beverage containing sunset yellow as an analysis object, diluting Fenda with water by one time, adjusting the pH value to 7 by using sodium hydroxide to obtain a beverage solution to be detected, immersing the functional paper in the beverage solution to be detected for 30s, measuring the fluorescence intensity of the functional paper, and calculating the content of the sunset yellow in Fenda to be 39.6 mu g/mL by using a standard working curve.

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.