阅读说明：本技术 一种可用于健康监测的新型水凝胶电极贴片及其制备方法 (Novel hydrogel electrode patch for health monitoring and preparation method thereof ) 是由 惠俊峰 刘婉 范代娣 郑晓燕 于 2021-09-12 设计创作，主要内容包括：本发明公开了一种可用于健康监测的新型水凝胶电极贴片及其制备方法,具体制备方法包括：将甘油、明胶、聚乙烯醇和植酸溶于水,在70～100℃的环境使上述混合物转变为澄清的透明溶液,再将该透明溶液倒入模具中进行冷冻处理,即得到一种可用于健康监测的新型水凝胶电极贴片。本发明新型水凝胶电极贴片无色透明,具有良好的空间稳定性、锁水性、导电性、抗菌性、黏附性和易完整剥离性,在人机交互医疗监控设备方面具有良好应用前景。(The invention discloses a novel hydrogel electrode patch for health monitoring and a preparation method thereof, and the preparation method comprises the following steps: dissolving glycerol, gelatin, polyvinyl alcohol and phytic acid in water, converting the mixture into a clear transparent solution at the temperature of 70-100 ℃, and pouring the transparent solution into a mould for freezing treatment to obtain the novel hydrogel electrode patch for health monitoring. The novel hydrogel electrode patch is colorless and transparent, has good space stability, water locking property, conductivity, antibacterial property, adhesiveness and easy complete stripping property, and has good application prospect in the aspect of human-computer interaction medical monitoring equipment.)

1. A novel hydrogel electrode patch for health monitoring is characterized by comprising the following components: the weight ratio of the components is 5-50 wt% of glycerol aqueous solution to 30-80 wt% of phytic acid aqueous solution, wherein the weight ratio of the components is (5-25): (0.1-2): 1-10): 10-50).

2. The novel hydrogel electrode patch useful for health monitoring as claimed in claim 1, wherein: the molecular weight of the polyvinyl alcohol is 16000-200000Da, and the molecular weight of the gelatin is 20000-150000 Da.

3. The method for preparing a novel hydrogel electrode patch useful for health monitoring as claimed in claim 1, wherein: uniformly mixing the glycerol aqueous solution with the gelatin, the polyvinyl alcohol and the phytic acid aqueous solution to obtain a transparent solution, pouring the transparent solution into a mould, and freezing and crosslinking to obtain the novel hydrogel electrode patch for health monitoring.

4. The method for preparing a novel hydrogel electrode patch for health monitoring according to claim 3, wherein the method comprises the following steps: the mass percentage of the glycerol in the glycerol aqueous solution is 5-50 wt%; the mass percentage of the phytic acid in the phytic acid aqueous solution is 30-80 wt%; the molecular weight of the polyvinyl alcohol is 16000-200000Da, and the molecular weight of the gelatin is 20000-150000 Da.

5. The method for preparing a novel hydrogel electrode patch for health monitoring according to claim 3, wherein the method comprises the following steps: the mass ratio of the glycerin aqueous solution, gelatin, polyvinyl alcohol and phytic acid aqueous solution is (5-25): (0.1-2): 1-10): 10-50.

6. The method for preparing a novel hydrogel electrode patch for health monitoring according to claim 3, wherein the method comprises the following steps: the temperature of the solution mixing process is 30-100 ℃.

7. The method for preparing a novel hydrogel electrode patch for health monitoring according to claim 6, wherein the method comprises the following steps: the temperature of the solution mixing process is 70-100 ℃.

8. The method for preparing a novel hydrogel electrode patch for health monitoring according to claim 3, wherein the method comprises the following steps: the solution is mixed by stirring at a rotation speed of 400-1500 r/min.

9. The method for preparing a novel hydrogel electrode patch for health monitoring according to claim 3, wherein the method comprises the following steps: the temperature of the crosslinking reaction is 4 to-50 ℃.

10. The method for preparing a novel hydrogel electrode patch for health monitoring according to claim 3, wherein the method comprises the following steps: the crosslinking reaction is kept for 15 to 72 hours.

Technical Field

The invention belongs to the technical field of hydrogel preparation, and particularly relates to a preparation method and application of a novel hydrogel electrode patch for health monitoring.

Background

With the rapid development of artificial intelligence, the wearable flexible electronic equipment can realize the real-time monitoring of human motion information and physiological information (such as myoelectricity, electrocardio and electroencephalogram), and has important application in the fields of health detection, human-computer interaction and the like. The hydrogel is constructed by 3D microstructure network macromolecules, and the material is soft and elastic, and has good biocompatibility and skin fitting property, so that the development of the conductive hydrogel with a sensing function becomes a hot spot of current research. In order to obtain accurate physiological signals and reduce the interference of human body movement to the signals, a good adhesion effect is required between a conductive hydrogel material applied to wearable equipment and the skin, so that a great deal of research focuses on improving the conductivity and the adhesion of the hydrogel, and neglecting the peeling problem of the material and the skin, so that after the device is used, the psychological discomfort of a user is easily caused by residues caused by incomplete peeling from the skin, the service life of the device is short, and the skin is even damaged due to excessive adhesion with the skin. Although reversible adhesion between interfaces is achieved by biomimetic studies (e.g. octopus chucks, gecko feet, burdock seeds, etc.), they are mostly suitable for rough flat substrates and are not ideal for use on free-form and soft surfaces (e.g. skin). Therefore, the development of the conductive hydrogel material patch with controllable adhesion/peeling for health monitoring is undoubtedly of great significance in the fields of flexible electronic wearable, medical monitoring, biological electronic apparatus and the like.

Disclosure of Invention

The invention aims to provide a novel hydrogel electrode patch for health monitoring and a preparation method thereof.

The invention is realized by the following processes:

a novel hydrogel electrode patch for health monitoring comprises the following components: the weight ratio of the components is 5-50 wt% of glycerol aqueous solution to 30-80 wt% of phytic acid aqueous solution, wherein the weight ratio of the components is (5-25): (0.1-2): 1-10): 10-50).

The molecular weight of the polyvinyl alcohol is 16000-200000Da, and the molecular weight of the gelatin is 20000-150000 Da.

A preparation method of a novel hydrogel electrode patch for health monitoring comprises the following steps: uniformly mixing the glycerol aqueous solution with the gelatin, the polyvinyl alcohol and the phytic acid aqueous solution to obtain a transparent solution, pouring the transparent solution into a mould, and freezing and crosslinking to obtain the novel hydrogel electrode patch for health monitoring.

The mass percentage of the glycerol in the glycerol aqueous solution is 5-50 wt%; the mass percentage of the phytic acid in the phytic acid aqueous solution is 30-80 wt%; the molecular weight of the polyvinyl alcohol is 16000-200000Da, and the molecular weight of the gelatin is 20000-150000 Da. The mass ratio of the glycerin aqueous solution, gelatin, polyvinyl alcohol and phytic acid aqueous solution is (5-25): (0.1-2): 1-10): 10-50.

The temperature of the solution in the mixing process is 30-100 ℃, and preferably 70-100 ℃.

The solution is mixed and stirred at a rotation speed of 400-1500 r/min.

The temperature of the crosslinking reaction is 4 to-50 ℃, and the holding time is 15 to 72 hours.

The novel hydrogel electrode patch obtained by the method is colorless and transparent, and has good space stability, water locking property, conductivity, antibacterial property, adhesiveness and complete stripping property.

The forming mechanism of the novel hydrogel electrode patch for health monitoring is as follows: polyvinyl alcohol is a one-dimensional polyhydroxy polymer, gelatin is a high polymer product obtained after collagen hydrolysis, which contains abundant amino, carboxyl, hydroxyl and other functional groups, phytic acid is also called phytic acid, each molecule of phytic acid contains six phosphate ions, and the phytic acid is easy to form an ionic bond with amino and form a hydrogen bond with hydroxyl, so that the phytic acid can be bonded with related functional groups on molecular chains of polyvinyl alcohol and gelatin to form an intermolecular three-dimensional network cross-linked structure. The stability of a hydration film at the periphery of a linear molecular chain is greatly reduced due to the strong anchoring effect of glycerin on water molecules in a glycerin water solution, the molecules stretch and interlace, and a large amount of intermolecular hydrogen bonds are easily formed when side chain groups are fully exposed and interacted. The hydrogen bond energy is very low, the hydrogen bond can not exist at high temperature, but when the polyvinyl alcohol, gelatin and phytic acid compound which forms the intermolecular three-dimensional network cross-linking structure is placed in a low-temperature environment, under the promotion action of glycerol, strong hydrogen bonds can be formed among all functional groups in the three-dimensional network, and finally, the novel hydrogel electrode patch which has good spatial stability, water locking property, conductivity, antibacterial property, adhesiveness and complete stripping property and can be used for health monitoring is obtained.

The invention has the advantages that: (1) the novel hydrogel electrode patch for health monitoring fully utilizes the ionic bond crosslinking and hydrogen ion ionization effects of phytic acid in a polyvinyl alcohol and gelatin polymer network and the strong and weak reversibility of hydrogen bonds in a high-temperature and low-temperature range, and realizes the stability of the electrode patch and the temperature controllability of viscosity. (2) The novel hydrogel electrode patch for health monitoring can be obtained by only one-time freezing on the basis of not introducing a chemical cross-linking agent, so that the time is greatly saved and the cost is reduced on the basis of ensuring the safety and the non-toxicity of the obtained material, and the electrode patch has good light transmittance and flexibility, is more easily accepted by users on the aspects of attractiveness and comfort level, and is convenient to popularize and apply. (3) The novel hydrogel electrode patch for health monitoring has good antibacterial property, good adhesion and self-adaptability to skin, can be effectively attached to the skin even in a motion state, can effectively collect body electrical signal changes by utilizing the conductivity and current resistance changes generated by stretching and bending, and has good application prospect in the aspect of human-computer interaction medical monitoring equipment.

Drawings

FIG. 1 is a photograph of a novel hydrogel electrode patch in real life;

figure 2 is a fourier infrared image of the novel hydrogel electrode patch;

FIG. 3 is a graph of the rheological properties of the novel hydrogel electrode patch;

FIG. 4 is a photograph of the adhesion of the novel hydrogel electrode patch to different substrates;

figure 5 is a photograph of the adaptation of the novel hydrogel electrode patch to the skin;

FIG. 6 is a photograph of a peel-away of the novel hydrogel electrode patch from the skin;

figure 7 photograph of conductivity test of the novel hydrogel electrode patch;

figure 8 photograph of the antibacterial performance of the novel hydrogel electrode patch.

Detailed Description

The objects and aspects of the invention will be further illustrated with reference to specific examples of the invention, all of which are commercially available.

Example 1 preparation of a novel hydrogel electrode patch for health monitoring

Adding 0.06g of gelatin, 0.54g of polyvinyl alcohol and 3 g of a 50 wt% phytic acid aqueous solution into 1.5 g of a 20 wt% glycerol aqueous solution, placing the mixture in a water bath kettle at 85 ℃ for magnetic stirring at 800 r/min for 30 minutes to obtain a clear and transparent mixed solution, pouring the mixed solution into a mould, and then placing the mould in a refrigerator at-20 ℃ for freezing for 48 hours to obtain the novel hydrogel electrode patch for health monitoring.

The physicochemical properties of the novel hydrogel electrode patch prepared in this example are characterized, and fig. 1 is an appearance photograph of the hydrogel electrode patch prepared in example 1, which shows that the hydrogel electrode patch is colorless and transparent in appearance, and the text covered by the hydrogel electrode patch can be clearly seen through the electrode patch, which indicates that the hydrogel has good light transmittance; FIG. 2 is a Fourier infrared spectrum of the hydrogel electrode patch prepared in example 1 at 995 cm^-1And 1044 cm^-1Characteristic peaks respectively corresponding to P-O bonds and C-N bonds appear, which indicates that the electrode patch prepared in example 1 contains phytic acid and gelatin in a range of 3210-3370 cm^-1The broad band of (A) shows that the material contains a large amount of-OH, and that there are a large number of hydrogen bonds in the hydrogel electrode patch compared with polyvinyl alcohol, and therefore the-OH position occurs to the rightMoving; fig. 3 is a rheological property of the hydrogel electrode patch prepared in example 1, illustrating that the storage modulus rapidly decreases the viscosity of the electrode patch increases with increasing temperature, whereas the viscosity decreases.

Example 2 preparation of a novel hydrogel electrode Patch for health monitoring

Adding 0.06g of gelatin, 0.54g of polyvinyl alcohol and 3 g of a 50 wt% phytic acid aqueous solution into 1.5 g of a 20 wt% glycerol aqueous solution, placing the mixture into a water bath kettle at 85 ℃ for magnetic stirring at 800 r/min for 30 minutes to obtain a clear and transparent mixed solution, pouring the mixed solution into a mold, and then placing the mold into a refrigerator at-40 ℃ for freezing for 24 hours to obtain the novel hydrogel electrode patch for health monitoring, wherein the physical and chemical properties of the novel hydrogel electrode patch are similar to those of the embodiment 1.

Example 3 preparation of a novel hydrogel electrode Patch for health monitoring

Adding 1g of gelatin, 5g of polyvinyl alcohol and 10 g of 30 wt% phytic acid aqueous solution into 5g of 10 wt% glycerol aqueous solution, placing the mixture into a water bath kettle at 85 ℃ and magnetically stirring the mixture for 30 minutes at 800 r/min to obtain a clear and transparent mixed solution, pouring the mixed solution into a mold, and then placing the mold into a refrigerator at-20 ℃ to freeze the mixed solution for 48 hours to obtain the novel hydrogel electrode patch for health monitoring, wherein the physical and chemical properties of the novel hydrogel electrode patch are similar to those of the novel hydrogel electrode patch in example 1.

Example 4 preparation of a novel hydrogel electrode Patch for health monitoring

Adding 0.06g of gelatin, 0.54g of polyvinyl alcohol and 2.5 g of a 50 wt% phytic acid aqueous solution into 2 g of a 20 wt% glycerol aqueous solution, placing the mixture into a water bath kettle at 85 ℃, magnetically stirring the mixture for 30 minutes at 800 r/min to obtain a clear and transparent mixed solution, pouring the mixed solution into a mold, and then placing the mold into a refrigerator at 4 ℃ to freeze the mixed solution for 60 hours to obtain the novel hydrogel electrode patch for health monitoring, wherein the physical and chemical properties of the novel hydrogel electrode patch are similar to those of example 1.

Example 5 novel hydrogel electrode Patch Performance testing for health monitoring

The novel hydrogel electrode patch for health monitoring used in this example was obtained from example 1. The specific tests are as follows:

(1) novel hydrogel electrode patch adhesion and adaptivity test

After the novel hydrogel electrode patch is pretreated at 50 ℃ for 3 minutes, the novel hydrogel electrode patch is attached to objects made of different materials, and the result is shown in fig. 4. Fig. 4 shows photographs showing that the novel hydrogel electrode patch of the present invention shows good adhesion to animal tissues (kidney, liver, skin, lung, spleen) and different substrates (stainless steel, plastic, glass, rubber, copper sheet).

The novel hydrogel electrode patch is pre-treated at 50 ℃ for 3 minutes and then attached to the wrist, and the hydrogel can still be well adhered to the wrist and the gap after the wrist is stretched or bent without the falling-off sign, as shown in fig. 5. The novel hydrogel electrode patch has good adhesion to human skin, has good adaptability to dynamic skin, and can be used as an adhesive patch.

(2) Novel hydrogel electrode patch peeling experiment

It is important for the user to peel the electrode patch from the skin without pain and residue. One side of the hydrogel electrode patch in example 1 is covered with plastic paper, and after pretreatment at 50 ℃, the electrode patch can be well adhered to the back of a hand; then applying ice compress, the viscosity of the electrode patch is reduced. Fig. 6 shows that the novel hydrogel electrode patch can be peeled off from the skin without residue and causing secondary damage to the skin after ice compress.

(3) Novel hydrogel electrode patch conductivity test

Fig. 7 shows that the novel hydrogel electrode patch of example 1 is placed in a 6V circuit with an LED bulb, and the LED bulb in the circuit can normally emit light after being powered on, indicating that the novel hydrogel electrode patch has good conductivity.

(4) Novel hydrogel electrode patch antibacterial property test

The hydrogel in a moist environment is easy to breed bacteria, and the hydrogel patch has antibacterial capacity and can effectively prevent the skin from being infected by the bacteria when being used as a gel patch which is in long-time contact with the skin. The antibacterial ability of the novel hydrogel electrode patch described in example 1 was studied by using gram-positive bacteria (staphylococcus aureus) and gram-negative bacteria (escherichia coli) as model bacteria. And punching a circular hole with the diameter of 8 mm in the center of the flat plate, and respectively placing the hydrogel electrode patches, wherein the diameters of inhibition zones of the hydrogel electrode patches on escherichia coli and staphylococcus aureus are respectively 4.5 cm and 3.8 cm, which shows that the novel hydrogel electrode patch has excellent inhibition capacity.

Finally, it should be noted that while the present invention has been described above with reference to embodiments, the present invention is not limited to the above embodiments and application fields, and the above embodiments are only for illustrative and instructional purposes, and are not restrictive. Those skilled in the art, having the benefit of this disclosure, may effect numerous modifications thereto and changes may be made without departing from the scope of the invention as defined by the appended claims.