Phycocyanobilin hydrogel sensor as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of flexible sensor materials, and particularly relates to a phycocyanobilin hydrogel sensor as well as a preparation method and application thereof, and the phycocyanobilin hydrogel sensor is prepared from the following raw materials in parts by mass: 2-7 parts of phycocyanobilin, 10-13 parts of polyvinyl alcohol, 35-55 parts of ethylene glycol, 10-15 parts of sodium malate and 100 parts of water. The phycocyanobilin hydrogel sensor disclosed by the invention can bear a heavy object of 3.3 Kg without being snapped; the composite material has strong stress, strain and conductivity, and also has the advantages of good drying resistance, freezing resistance, cell compatibility and the like.

Description

Technical Field

[0001] The present invention relates to the technical field of flexible sensor materials, and in particular to a phycocyanin hydrogel sensor and a preparation method and application thereof. Background Art

[0002] Hydrogel flexible sensors are new flexible sensors developed in recent years. They can convert various motion information of humans and machines into electrical signals and are widely used in bionic skin, wearable devices, soft robots and other fields. Phycocyanin is an extract extracted from natural algae such as cyanobacteria. It has antioxidant, anti-inflammatory and anti-apoptotic properties. It is widely used in the fields of food, medicine and cosmetics. In 2013, it was approved by the US Food and Drug Administration (FDA) as a food colorant. According to literature research, no products based on phycocyanin hydrogel sensors have been reported. Moreover, pure phycocyanin aqueous solution cannot form hydrogel products even after repeated freezing treatment, heating treatment or traditional chemical cross-linking reaction. Pure phycocyanin aqueous solution still maintains a solution state. And the existing physical cross-linking method for preparing hydrogels is often difficult to withstand external mechanical stress. Summary of the invention

[0003] In view of the above-mentioned shortcomings, the present invention provides a phycocyanin hydrogel sensor and a preparation method and application thereof. The phycocyanin hydrogel sensor of the present invention can carry a weight of 3.3 kg without being broken; it has strong stress, strain and conductivity, and also has the advantages of good anti-drying, anti-freezing and cell compatibility.

[0004] In order to achieve the above-mentioned object, the present invention provides a phycocyanin hydrogel sensor. The raw materials of the phycocyanin hydrogel sensor are as follows, calculated by weight: 2 to 7 parts of phycocyanin, 10 to 13 parts of polyvinyl alcohol, 35 to 55 parts of ethylene glycol, 10 to 15 parts of sodium malate, and 100 parts of water.

[0005] According to one aspect of the present invention, the weight average molecular weight of the polyvinyl alcohol is 140,000-180,000, and the alcoholysis degree is 99%.

[0006] According to one aspect of the present invention, the phycocyanin hydrogel sensor comprises a long flexible sensor body, both ends of the flexible sensor body in the length direction are respectively covered with copper foil connecting strips, and the copper foil connecting strips are connected to the wires.

[0007] Based on the same inventive concept, the present invention also provides a method for preparing the above-mentioned phycocyanin hydrogel sensor, comprising the following steps:

[0008] S1. Mix 2 to 7 parts of phycocyanin, 10 to 13 parts of polyvinyl alcohol, 35 to 55 parts of ethylene glycol, 10 to 15 parts of sodium malate and 100 parts of deionized water, disperse and mix them evenly, and stir them at 90 to 100° C. for 1 to 4 hours to obtain a mixed solution;

[0009] S2. Pour the mixed solution into a mold and place it at room temperature for 4 to 48 hours to obtain a finished flexible sensor.

[0010] According to one aspect of the present invention, in step S1, the stirring speed is 1000-1800 r / min.

[0011] According to one aspect of the present invention, the mold is any one of a standard dumbbell-shaped mold and a plastic tube mold.

[0012] According to one aspect of the present invention, the inner diameter of the plastic tube mold is 1.5 to 2 cm and the length is 4 to 5 cm.

[0013] Based on the same inventive concept, the present invention also provides the application of the above-mentioned phycocyanin hydrogel sensor in wearable flexible materials.

[0014] Based on the same inventive concept, the present invention also provides the application of the above-mentioned phycocyanin hydrogel sensor in conductive materials.

[0015] Based on the same inventive concept, the present invention also provides the application of the above-mentioned phycocyanin hydrogel sensor in smart screen touch screen materials.

[0016] Beneficial effects of the present invention:

[0017] (1) Compared with the existing pure phycocyanin aqueous solution, which cannot form a hydrogel product even after repeated freezing treatment, heating treatment or traditional chemical cross-linking reaction, the present invention uses the hydroxyl groups in the molecular structure of polyvinyl alcohol and ethylene glycol, the hydroxyl / carboxyl groups on the sodium malate molecules and the hydroxyl groups on the phycocyanin molecules to form hydrogen bonds, accelerate the formation of phycocyanin hydrogel, shorten the preparation time, simplify the preparation process and make it green, and significantly enhance its mechanical properties.

[0018] (2) The phycocyanin, polyvinyl alcohol, ethylene glycol, sodium malate and water molecules of the present invention form a super hydrogen bond network, which is used to further reduce the freezing point of the hydrogel and inhibit the evaporation of water in the hydrogel, thereby significantly improving the antifreeze and anti-drying abilities of the phycocyanin-based hydrogel, and ultimately achieving an effective fusion of multiple advantages including strong mechanical properties, strong antifreeze ability, strong anti-drying ability and cell compatibility, thereby overcoming the defects of traditional flexible sensors that have only one good performance but poor other performances.

[0019] (3) The phycocyanin hydrogel sensor of the present invention can carry a weight of 3.3 kg without being broken; it has strong stress, strain and conductivity, and also has the advantages of good anti-drying, anti-freezing and cell compatibility. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 The flexibility of the flexible sensor prepared in Example 4 of the present invention after being in an open environment for 3 months;

[0021] Figure 2 This is the flexibility of the flexible sensor prepared in Example 5 of the present invention after being placed at -55°C for 10 hours. DETAILED DESCRIPTION

[0022] To make the present invention easier to understand, the present invention is further described below in conjunction with specific examples. It should be understood that these examples are only used to illustrate the present invention and are not used to limit the scope of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments in the present invention, all other embodiments obtained by ordinary technicians in the field without making creative work are within the scope of protection of the present invention. Unless otherwise defined, the professional terms used below are consistent with the meanings understood by professional and technical personnel in the field; unless otherwise specified, the raw materials and reagents involved in this article can be purchased from the market or prepared by known methods.

[0023] Example 1

[0024] A method for preparing a phycocyanin hydrogel (phycocyanin / polyvinyl alcohol / sodium malate / ethylene glycol) sensor comprises the following steps:

[0025] (1) According to the weight percentage (based on the weight of water), the concentration of phycocyanin is 5%, the concentration of polyvinyl alcohol is 11%, the concentration of ethylene glycol is 45%, and the concentration of sodium malate is 15%. Weigh 2.5 g of phycocyanin, 5.5 g of polyvinyl alcohol, 22.5 g of ethylene glycol, and 7.5 g of sodium malate, add 55 g of deionized water, and stir at 90° C. for 4 h to obtain a phycocyanin / polyvinyl alcohol / sodium malate / ethylene glycol mixed solution for later use;

[0026] (2) pouring the phycocyanin / polyvinyl alcohol / sodium malate / ethylene glycol mixed solution prepared in step (1) into a standard dumbbell-shaped mold at room temperature;

[0027] (3) placing the mold containing the mixed solution in step (2) at room temperature for 10 hours to obtain a finished flexible sensor.

[0028] It was determined that the stress of the finished flexible sensor obtained in this embodiment was 1.3 MPa, the strain was 540%, and the conductivity was 16 S / m. See Table 1 for details.

[0029] Example 2

[0030] A method for preparing a phycocyanin hydrogel (phycocyanin / polyvinyl alcohol / sodium malate / ethylene glycol) sensor comprises the following steps:

[0031] (1) According to the weight percentage (based on the weight of water), the concentration of phycocyanin is 5%, the concentration of polyvinyl alcohol is 6%, the concentration of ethylene glycol is 45%, and the concentration of sodium malate is 15%. Weigh 2.5 g of phycocyanin, 3 g of polyvinyl alcohol, 22.5 g of ethylene glycol, and 7.5 g of sodium malate, add 55 g of deionized water, and stir at 90° C. for 4 h to obtain a phycocyanin / polyvinyl alcohol / sodium malate / ethylene glycol mixed solution for later use;

[0032] (2) pouring the phycocyanin / polyvinyl alcohol / sodium malate / ethylene glycol mixed solution prepared in step (1) into a standard dumbbell-shaped mold at room temperature;

[0033] (3) placing the mold containing the mixed solution in step (2) at room temperature for 10 hours to obtain a finished flexible sensor.

[0034] It was determined that the stress of the finished flexible sensor obtained in this embodiment was 0.8 MPa, the strain was 560%, and the conductivity was 16 S / m. See Table 1 for details.

[0035] Example 3

[0036] A method for preparing a phycocyanin hydrogel (phycocyanin / polyvinyl alcohol / sodium malate / ethylene glycol) sensor comprises the following steps:

[0037] (1) According to the weight percentage (based on the weight of water), the concentration of phycocyanin is 5%, the concentration of polyvinyl alcohol is 11%, the concentration of ethylene glycol is 36%, and the concentration of sodium malate is 10%. Weigh 2.5 g of phycocyanin, 5.5 g of polyvinyl alcohol, 36 g of ethylene glycol, and 5 g of sodium malate, add 64 g of deionized water, and stir at 95° C. for 4 h to obtain a phycocyanin / polyvinyl alcohol / sodium malate / ethylene glycol mixed solution for later use;

[0038] (2) pouring the phycocyanin / polyvinyl alcohol / sodium malate / ethylene glycol mixed solution prepared in step (1) into a standard dumbbell-shaped mold at room temperature;

[0039] (3) placing the mold containing the mixed solution in step (2) at room temperature for 24 hours to obtain a finished flexible sensor.

[0040] It was determined that the stress of the finished flexible sensor obtained in this embodiment was 0.7 MPa, the strain was 570%, and the electric current was 16 S / m. See Table 1 for details.

[0041] Example 4

[0042] A method for preparing a phycocyanin hydrogel (phycocyanin / polyvinyl alcohol / sodium malate / ethylene glycol) sensor comprises the following steps:

[0043] (1) According to the weight percentage (based on the weight of water), the concentration of phycocyanin is 5%, the concentration of polyvinyl alcohol is 11%, the concentration of ethylene glycol is 45%, and the concentration of sodium malate is 15%. Weigh 2.5 g of phycocyanin, 5.5 g of polyvinyl alcohol, 22.5 g of ethylene glycol, and 7.5 g of sodium malate, add 55 g of deionized water, and stir at 90° C. for 4 h to obtain a phycocyanin / polyvinyl alcohol / sodium malate / ethylene glycol mixed solution for later use;

[0044] (2) pouring the phycocyanin / polyvinyl alcohol / sodium malate / ethylene glycol mixed solution prepared in step (1) into a standard dumbbell-shaped mold at room temperature;

[0045] (3) placing the mold containing the mixed solution in step (2) at room temperature for 10 hours to obtain a finished flexible sensor.

[0046] It was determined that the stress of the finished flexible sensor obtained in this embodiment was 1.3 MPa, the strain was 540%, and the conductivity was 16 S / m. See Table 1 for details.

[0047] Example 5

[0048] A method for preparing a phycocyanin hydrogel (phycocyanin / polyvinyl alcohol / sodium malate / ethylene glycol) sensor comprises the following steps:

[0049] (1) According to the weight percentage (based on the weight of water), the concentration of phycocyanin is 5%, the concentration of polyvinyl alcohol is 11%, the concentration of ethylene glycol is 45%, and the concentration of sodium malate is 10%. Weigh 2.5 g of phycocyanin, 5.5 g of polyvinyl alcohol, 45 g of ethylene glycol, and 5 g of sodium malate, add 55 g of deionized water, and stir at 95° C. for 4 h to obtain a phycocyanin / polyvinyl alcohol / sodium malate / ethylene glycol mixed solution for later use;

[0050] (2) pouring the phycocyanin / polyvinyl alcohol / sodium malate / ethylene glycol mixed solution prepared in step (1) into a standard dumbbell-shaped mold at room temperature;

[0051] (3) placing the mold containing the mixed solution in step (2) at room temperature for 24 hours to obtain a finished flexible sensor.

[0052] Example 6

[0053] A method for preparing a phycocyanin hydrogel (phycocyanin / polyvinyl alcohol / sodium malate / ethylene glycol) sensor comprises the following steps:

[0054] (1) According to the weight percentage (based on the weight of water), the concentration of phycocyanin is 5%, the concentration of polyvinyl alcohol is 11%, the concentration of ethylene glycol is 36%, and the concentration of sodium malate is 10%. Weigh 2.5 g of phycocyanin, 5.5 g of polyvinyl alcohol, 36 g of ethylene glycol, and 5 g of sodium malate, add 64 g of deionized water, and stir at 95° C. for 4 h to obtain a phycocyanin / polyvinyl alcohol / sodium malate / ethylene glycol mixed solution for later use;

[0055] (2) pouring the phycocyanin / polyvinyl alcohol / sodium malate / ethylene glycol mixed solution prepared in step (1) into a standard dumbbell-shaped mold at room temperature;

[0056] (3) placing the mold containing the mixed solution in step (2) at room temperature for 24 hours to obtain a finished flexible sensor.

[0057] Comparative Example 1

[0058] The difference between this comparative example and Example 1 is that polyvinyl alcohol is replaced by sodium alginate, and the other steps and parameters are the same as Example 1. This comparative example cannot form a hydrogel in the end.

[0059] Comparative Example 2

[0060] The difference between this comparative example and Example 3 is that ethylene glycol is replaced by DMSO, and the other steps and parameters are the same as those in Example 3.

[0061] It was determined that the stress of the finished flexible sensor obtained in this embodiment was 0.11 MPa, the strain was 510%, and the conductivity was 16 S / m.

[0062] Comparative Example 3

[0063] The difference between this comparative example and Example 3 is that sodium malate is replaced by sodium chloride, and the other steps and parameters are the same as those in Example 3.

[0064] It was measured that the stress of the finished flexible sensor obtained in this embodiment was 0.3 MPa, the strain was 531%, and the electric current was 15.8 S / m.

[0065] Performance testing and result analysis:

[0066] The stress, strain and conductivity of the finished flexible sensors prepared in Examples 1 to 4 and Comparative Examples 2 to 3 of the present application are shown in Table 1 below.

[0067] Table 1:

[0068] Stress / MPa strain / % Conductivity / S / m Example 1 1.3 540 16 Example 2 0.8 560 16 Example 3 0.7 570 16 Example 4 1.3 540 16 Comparative Example 2 0.11 510 16 Comparative Example 3 0.3 531 15.8

[0069] (1) Strong mechanical properties test

[0070] The flexible sensor prepared by Example 4 of the present invention was used to test the mechanical properties: the flexible sensor could bear a weight of 3.3 kg without being broken, which proved that the flexible sensor could withstand external mechanical stress. The flexible sensors of Comparative Examples 2-3 could not bear a weight of 1 kg.

[0071] (2) Drying resistance test

[0072] The flexible sensor prepared in Example 4 of the present invention was tested for its dryness resistance: after being placed in an open environment for 3 months, the flexible sensor had good flexibility ( Figure 1 ), was not dried into a solid, proving that it has a strong ability to resist drying.

[0073] (3) Antifreeze ability test

[0074] The flexible sensor prepared in Example 5 of the present invention was tested for its antifreeze ability: the flexible sensor still had good flexibility after being placed at -55°C for 10 hours ( Figure 2 ).

[0075] (4) Cytocompatibility test

[0076] The flexible sensor prepared in Example 6 of the present invention was subjected to a cell compatibility test: the MTT cytotoxicity test was used to analyze the effect of the flexible sensor on human renal epithelial 293T cells. The cell survival rate after 24 hours was as high as 97.5%, indicating strong cell compatibility.

[0077] The above is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by any technician familiar with the art within the technical scope disclosed in the present invention should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention shall be based on the protection scope of the claims.

Claims

1. A phycocyanin hydrogel sensor, characterized in that: The raw materials of the phycocyanin hydrogel sensor are as follows, calculated by weight: 2-7 parts of phycocyanin, 10-13 parts of polyvinyl alcohol, 35-55 parts of ethylene glycol, 10-15 parts of sodium malate, and 100 parts of water.

2. The phycocyanin hydrogel sensor according to claim 1, characterized in that: The weight average molecular weight of the polyvinyl alcohol is 140,000-180,000, and the alcoholysis degree is 99%.

3. The phycocyanin hydrogel sensor according to claim 1, characterized in that: The phycocyanin hydrogel sensor comprises a long flexible sensor body, both ends of the flexible sensor body in the length direction are respectively covered with copper foil connecting strips, and the copper foil connecting strips are connected to the wires.

4. The method for preparing the phycocyanin hydrogel sensor according to any one of claims 1 to 3, characterized in that: The following steps are involved: S1. Mix 2 to 7 parts of phycocyanin, 10 to 13 parts of polyvinyl alcohol, 35 to 55 parts of ethylene glycol, 10 to 15 parts of sodium malate and 100 parts of deionized water, disperse and mix them evenly, and stir them at 90 to 100° C. for 1 to 4 hours to obtain a mixed solution; S2. Pour the mixed solution into a mold and place it at room temperature for 4 to 48 hours to obtain a finished flexible sensor.

5. The method for preparing the phycocyanin hydrogel sensor according to claim 4, characterized in that: In step S1, the stirring speed is 1000-1800 r / min.

6. The method for preparing the phycocyanin hydrogel sensor according to claim 4, characterized in that: The mold is any one of a standard dumbbell-shaped mold and a plastic tube mold.

7. The method for preparing the phycocyanin hydrogel sensor according to claim 5, characterized in that: The inner diameter of the plastic tube mold is 1.5 to 2 cm, and the length is 4 to 5 cm.

8. Application of the phycocyanin hydrogel sensor according to any one of claims 1 to 3 or the phycocyanin hydrogel sensor prepared by the preparation method according to any one of claims 4 to 7 in wearable flexible materials.

9. Use of the phycocyanin hydrogel sensor according to any one of claims 1 to 3 or the phycocyanin hydrogel sensor prepared by the preparation method according to any one of claims 4 to 7 in conductive materials.

10. Use of the phycocyanin hydrogel sensor according to any one of claims 1 to 3 or the phycocyanin hydrogel sensor prepared by the preparation method according to any one of claims 4 to 7 in smart screen touch screen materials.

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