A silk fiber-based flexible wearable hydrogen peroxide sensor and its construction method
By depositing Prussian blue in situ on silk fibers, the problem of poor fitting and large errors in traditional sensors is solved, and high sensitivity and stability detection of hydrogen peroxide is achieved, which is suitable for health signal detection and medical monitoring.
Patent Information
- Application Number
- CN202310471155.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2023-04-27
- Publication Date
- 2025-08-19
- Estimated Expiration
- 2043-04-27
AI Technical Summary
Most of the existing hydrogen peroxide sensors are composite film substrates, with poor bonding and large errors, making it difficult to achieve real-time and accurate monitoring of hydrogen peroxide concentration, and traditional enzyme detection methods lack flexibility and wearability.
Using silk fibers as the base, flexible wearable sensors are prepared by in-situ deposition of Prussian blue (PB). The specific steps include activation of silk fibers, treatment of potassium ferriccyanide and ammonium ferric citrate solution and ultraviolet irradiation to form a PB@ASF fiber bundle and fixed on the working electrode.
It realizes high sensitivity, stability, cycle and repeatability detection of hydrogen peroxide, has good anti-interference and water washing resistance, and is suitable for wearable applications in the textile and clothing field.
Smart Images
Figure CN116660330B_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the field of health signal detection and medical monitoring, and specifically relates to a method for constructing a flexible wearable hydrogen peroxide sensor using silk fibers as a substrate and in-situ deposition synthesis of Prussian blue. Background Art
[0002] Proactive health is a medical model that enhances human function through real-time monitoring, analysis, evaluation, and prevention of human health signals. It maintains the body in a controllable, unstable, "far-from-equilibrium" state, thereby stimulating its self-organizing capacity to eliminate disease and promote health. In living systems, H2O2 is produced by aerobic respiration, acting as a messenger in various signal transduction pathways and a key indicator in molecular diagnostics. However, H2O2 is a metabolite of oxidases in biological tissue cells. A normal H2O2 concentration is crucial for maintaining normal cellular physiological activity; however, excessive H2O2 concentrations can be toxic and may cause central nervous system disorders, cardiovascular disease, diabetes, and even cancer. Previously reported hydrogen peroxide sensors are mostly based on composite membranes, which result in poor adhesion and large errors. Therefore, to accurately monitor H2O2 concentrations in real time, this patent design utilizes silk fibers as a flexible substrate and Prussian blue as a functional deposition material to detect hydrogen peroxide concentrations. Summary of the Invention
[0003] The present invention aims to address the defects of enzyme sensors for detecting hydrogen peroxide and people's functional needs for textile clothing. It provides a flexible wearable sensor with silk fiber as the substrate and Prussian blue as the functional deposition material. The sensor can detect the concentration of hydrogen peroxide to meet people's needs for stable and anti-interference detection, flexibility, and wearability. It gets rid of the defects of catalase in detecting hydrogen peroxide. The PB@ASF fiber sensor has good responsiveness to hydrogen peroxide. At the same time, the PB@ASF fiber sensor has strong mechanical properties, is washable, and is combined with traditional textile technology.
[0004] In order to solve the above problems, the present invention adopts the following technical solutions:
[0005] A method for constructing a silk fiber-based flexible wearable hydrogen peroxide sensor comprises the following steps:
[0006] S1: soaking the degummed silk fiber bundle in a weak acid aqueous solution at a certain temperature for a period of time, and then repeatedly rinsing with deionized water to remove excess electrolytes to obtain a surface-activated silk fiber bundle;
[0007] S2: soaking the surface-activated silk fiber bundle obtained in S1 in a potassium ferricyanide solution of a certain concentration for a period of time at a certain temperature, and then rinsing with deionized water to obtain a silk fiber bundle adsorbing ferrocyanide ions for later use;
[0008] S3: Protect from light, soak the silk fiber bundle adsorbing ferrocyanide ions obtained in S2 in a certain concentration of ammonium ferric citrate solution at a certain temperature, irradiate with a UV lamp of a certain power for a period of time, take out and rinse with deionized water to obtain the silk fiber bundle PB@ASF with in situ deposition of Prussian blue;
[0009] S4: Repeat steps S2 and S3 with the silk fiber bundle PB@ASF obtained in S3 to obtain PB@ASF fiber bundles with different deposition times;
[0010] S5: The PB@ASF fiber bundle obtained in S4 was fixed on the working electrode to obtain silk fiber-based flexible wearable hydrogen peroxide sensors of different morphologies that responded well to hydrogen peroxide.
[0011] Furthermore, in S1, the degummed silk fiber bundle is immersed in a weak acid aqueous solution at 30-45° C. for 5-20 minutes.
[0012] Furthermore, the pH of the weak acid aqueous solution in S1 is 3, and the weak acid aqueous solution is carbonic acid, acetic acid or phosphoric acid.
[0013] Further, in S2, the activated silk fiber bundle is immersed in a potassium ferricyanide solution with a concentration of 50-1000 mg / L, a bath ratio of 1:(10-200), a soaking temperature of 30-45°C, a soaking time of 5-20 min, and after soaking, it is rinsed with deionized water 2-3 times for standby use.
[0014] Furthermore, in S3, the silk fiber bundle adsorbing ferrocyanide ions was immersed in a 50~1000 mg / L ammonium ferric citrate solution with a bath ratio of 1:(10-200), a soaking temperature of 30~45℃, a soaking time of 5~35 min, an ultraviolet lamp with a power of 30~85W, and an irradiation time of 5~35 min. After being taken out, it was rinsed with deionized water three times to obtain a silk fiber bundle PB@ASF with in situ Prussian blue deposition.
[0015] Furthermore, in S4, the obtained PB@ASF fiber bundle is subjected to steps S2 and S3 for 1 to 9 times to obtain PB@ASF fiber bundles with different deposition times. Finally, the prepared PB@ASF fiber bundle is dried at room temperature and stored in a vacuum dryer for later use.
[0016] Furthermore, in S5, the PB@ASF fibers were fixed on the working electrode in a horizontal, spiral or vertical arrangement to obtain PB@ASF fiber sensors with different structures, namely, silk fiber-based flexible wearable hydrogen peroxide sensors.
[0017] The silk fiber-based flexible wearable hydrogen peroxide sensor obtained by the construction method of the present invention has a sensitivity of 21.82 μA·mM -1 cm -2 The stability, cyclicity and repeatability of hydrogen peroxide detection can reach up to 96.12%, 98.60% and 96.50% respectively, and the highest anti-interference ability is 27.41%.
[0018] The method of the present invention is combined with traditional textile technology to produce PB@ASF strands, ribbons, and flexible sensor fabrics. It should be noted that the preparation method of the present invention only modifies the surface of the silk, ensuring the flexibility of the silk fiber itself.
[0019] The silk fiber-based flexible wearable hydrogen peroxide sensor prepared by the preparation method of the present invention has a sensitivity of 21.82 μA·mM -1 cm -2 This fiber sensor uses natural silk fibers as a flexible substrate, potassium ferrocyanide and ammonium ferric citrate as sensitizers, and through 1 to 9 in-situ deposition cycles, the resulting Prussian blue particles range in diameter from 1.80 to 46.54 nm. The fiber obtained after the ninth in-situ deposition cycle exhibited a strength of 123.89 MPa (breaking strength) and 89.15% (breaking elongation). Its surface was smooth and uniform, and the resulting PB@ASF fiber sensor exhibited transient hydrophobicity. Increasing the number of in-situ deposition cycles further improved the fiber sensor's mechanical properties and sensitivity for hydrogen peroxide detection.
[0020] The present invention has the following beneficial effects: To meet various needs for flexible wearable sensors to detect hydrogen peroxide concentrations, the present invention utilizes an in-situ deposition process to synthesize Prussian blue particles on silk fibers. The silk material exhibits excellent biocompatibility and is non-irritating to the skin. The PB@ASF fiber sensor exhibits significant electrochemical responsiveness to hydrogen peroxide, with excellent stability, cyclability, and repeatability, and exhibits specific selectivity for hydrogen peroxide in the presence of interfering molecules. The silk fiber-based flexible wearable hydrogen peroxide sensor fabricated using the in-situ deposition process is convenient to operate, simple to manufacture, and low-cost, and has great potential in the textile and apparel industry. It overcomes the shortcomings of catalase-based hydrogen peroxide detection and exhibits excellent responsiveness to hydrogen peroxide. Furthermore, the PB@ASF fiber sensor exhibits strong mechanical properties, is washable, and integrates with traditional textile technologies. Compared to traditional methods for detecting hydrogen peroxide, the silk fiber-based flexible hydrogen peroxide sensor boasts ultrahigh sensitivity, excellent stability, cyclability, repeatability, and anti-interference properties, making it suitable for detection in human body fluid environments and promising a broad market prospect. BRIEF DESCRIPTION OF THE DRAWINGS
[0021] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.
[0022] Figure 1 This is a morphology picture of the silk fiber after activation in Example 4.
[0023] Figure 2 This is a morphology diagram of the activated silk fiber after in-situ deposition of Prussian blue in Example 4.
[0024] Figure 3 This is the in-situ deposition flow chart of the present invention.
[0025] Figure 4 This is a diagram of the in-situ deposition mechanism of the present invention.
[0026] Figure 5 Example 4 Mechanical properties of PB@ASF fiber bundles deposited 9 times.
[0027] Figure 6 Example 4: Electrical conductivity of the PB@ASF fiber bundle deposited 9 times.
[0028] Figure 7 Water resistance performance of the PB@ASF fiber sensor prepared in Example 4.
[0029] Figure 8 Anti-interference performance of the PB@ASF fiber sensor prepared in Example 4.
[0030] Figure 9 This is a physical picture of the PB@ASF fiber prepared in Example 4.
[0031] Figure 10 This is the PB@ASF fiber electrode sensor prepared in Example 4.
[0032] Figure 11 This is the morphology of the activated silk fiber after in-situ deposition of Prussian blue in Comparative Example 1. DETAILED DESCRIPTION
[0033] Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiments are only used to illustrate the present invention and are not used in limiting the scope of the present invention.In addition, should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall equally within the scope limited by the appended claims of the application.
[0034] Example 1
[0035] The construction method of the silk fiber-based flexible wearable hydrogen peroxide sensor of this embodiment is as follows:
[0036] (1) The degummed silk fiber bundles were immersed in 250 mL of 30°C carbonate aqueous solution (pH = 3) and treated at room temperature for 5 min. The degummed silk fiber bundles were then repeatedly rinsed with deionized water to obtain surface-activated silk fiber bundles.
[0037] (2) Soak the activated silk fiber bundle in potassium ferricyanide solution (bath ratio: 1:10, 100 mg / L, 30°C) for 5 min, then rinse with deionized water 2 to 3 times and set aside.
[0038] (3) Under the premise of protecting from light, the silk fiber bundles adsorbed with ferricyanide ions were placed in ammonium ferric citrate solution (bath ratio: 1:10, 200 mg / L, 30°C) and irradiated with a 70W ultraviolet lamp for 20 min. After being taken out, they were rinsed with deionized water three times to obtain silk fiber bundles with in situ deposition of Prussian blue (PB@ASF) for later use.
[0039] (4) Repeat steps S2 and S3 twice with the obtained PB@ASF fiber bundle to obtain a PB@ASF fiber bundle deposited twice. Finally, the prepared PB@ASF fiber bundle is dried at room temperature and stored in a vacuum desiccator for later use.
[0040] (5) The PB@ASF fibers were fixed on the working electrode in a transverse arrangement to obtain a PB@ASF fiber sensor with a transverse structure.
[0041] The sensitivity, stability, cyclicity, repeatability and anti-interference performance of the PB@ASF fiber sensor for detecting hydrogen peroxide were tested, and the results are shown in Table 1.
[0042] Example 2
[0043] The construction method of the silk fiber-based flexible wearable hydrogen peroxide sensor of this embodiment is as follows:
[0044] (1) The degummed silk fiber bundles were immersed in 250 mL of 35°C acetic acid aqueous solution (pH = 3) and treated at room temperature for 10 min. The degummed silk fiber bundles were then repeatedly rinsed with deionized water to obtain surface-activated silk fiber bundles.
[0045] (2) Soak the activated silk fiber bundle in potassium ferricyanide solution (bath ratio: 1:50, 400 mg / L, 35°C) for 10 min, then rinse with deionized water 2 to 3 times and set aside.
[0046] (3) Under the premise of protecting from light, the silk fiber bundle adsorbed with ferricyanide ions was placed in ammonium ferric citrate solution (bath ratio: 1:50, 800 mg / L, 35°C) and irradiated with a 75W ultraviolet lamp for 25 min. After being taken out, it was rinsed with deionized water three times to obtain the silk fiber bundle PB@ASF with in situ deposition of Prussian blue for later use.
[0047] (4) Repeat steps S2 and S3 for 5 times to obtain the PB@ASF fiber bundles deposited 5 times. Finally, the prepared PB@ASF fiber bundles were dried at room temperature and stored in a vacuum dryer for later use.
[0048] (5) The PB@ASF fibers were fixed on the working electrode in a vertical arrangement to obtain a PB@ASF fiber sensor with a vertical structure.
[0049] The sensitivity, stability, cyclicity, repeatability and anti-interference performance of the PB@ASF fiber sensor for detecting hydrogen peroxide were tested, and the results are shown in Table 1.
[0050] Example 3
[0051] The construction method of the silk fiber-based flexible wearable hydrogen peroxide sensor of this embodiment is as follows:
[0052] (1) The degummed silk fiber bundles were immersed in 250 mL of 40°C acetic acid aqueous solution (pH = 3) and treated at room temperature for 15 min. The degummed silk fiber bundles were then repeatedly rinsed with deionized water to obtain surface-activated silk fiber bundles.
[0053] (2) Soak the activated silk fiber bundle in potassium ferricyanide solution (bath ratio: 1:100, 600 mg / L, 40°C) for 15 min, then rinse with deionized water 2 to 3 times and set aside.
[0054] (3) Under the premise of protecting from light, the silk fiber bundles adsorbed with ferricyanide ions were placed in ammonium ferric citrate solution (bath ratio: 1:100, 850 mg / L, 40°C) and irradiated with an 80W ultraviolet lamp for 30 min. After being taken out, they were rinsed with deionized water three times to obtain the silk fiber bundles with in situ deposition of Prussian blue PB@ASF for later use.
[0055] (4) Repeat steps S2 and S3 for 7 times to obtain the PB@ASF fiber bundles deposited 7 times. Finally, the prepared PB@ASF fiber bundles were dried at room temperature and stored in a vacuum dryer for later use.
[0056] (5) The PB@ASF fibers were fixed on the working electrode in a transverse arrangement to obtain a PB@ASF fiber sensor with a transverse structure.
[0057] The sensitivity, stability, cyclicity, repeatability and anti-interference performance of the PB@ASF fiber sensor for detecting hydrogen peroxide were tested, and the results are shown in Table 1.
[0058] Example 4
[0059] The construction method of the silk fiber-based flexible wearable hydrogen peroxide sensor of this embodiment is as follows:
[0060] (1) The degummed silk fiber bundles were immersed in 250 mL of acetic acid aqueous solution (pH = 3) at 45 °C and treated at room temperature for 20 min. The degummed silk fiber bundles were then repeatedly rinsed with deionized water to obtain surface-activated silk fiber bundles.
[0061] (2) Soak the activated silk fiber bundles in potassium ferricyanide solution (bath ratio: 1:200, 800 mg / L, 45°C) for 20 min, then rinse with deionized water 2 to 3 times and set aside.
[0062] (3) Under the premise of protecting from light, the silk fiber bundle adsorbed with ferricyanide ions was placed in ammonium ferric citrate solution (bath ratio: 1:200, 900 mg / L, 45°C) and irradiated with an 85W ultraviolet lamp for 35 min. After being taken out, it was rinsed with deionized water three times to obtain the silk fiber bundle PB@ASF with in situ deposition of Prussian blue for later use.
[0063] (4) Repeat steps S2 and S3 for 9 times to obtain the PB@ASF fiber bundles deposited 9 times. Finally, the prepared PB@ASF fiber bundles were dried at room temperature and stored in a vacuum desiccator for later use.
[0064] (5) The PB@ASF fibers were fixed on the working electrode in a spiral arrangement to obtain a PB@ASF fiber sensor with a spiral structure.
[0065] (6) The mechanical properties and conductivity of the PB@ASF fiber deposited 9 times were tested, and the washability of the PB@ASF fiber sensor was tested. Figure 5-7 .
[0066] Comparative Example 1
[0067] The construction method of the silk fiber-based flexible wearable hydrogen peroxide sensor of this embodiment is as follows:
[0068] (1) The degummed silk fiber bundles were immersed in 250 mL of acetic acid aqueous solution (pH = 3) at 45 °C and treated at room temperature for 20 min. The degummed silk fiber bundles were then repeatedly rinsed with deionized water to obtain surface-activated silk fiber bundles.
[0069] (2) Soak the activated silk fiber bundles in potassium ferricyanide solution (bath ratio: 1:200, 800 mg / L, 45°C) for 20 min, then rinse with deionized water 2 to 3 times and set aside.
[0070] (3) Under the premise of protecting from light, the silk fiber bundle adsorbed with ferricyanide ions was placed in ammonium ferric citrate solution (bath ratio: 1:200, 900 mg / L, 45°C) and irradiated with an 85W ultraviolet lamp for 35 min. After being taken out, it was rinsed with deionized water three times to obtain the silk fiber bundle PB@ASF with in situ deposition of Prussian blue for later use.
[0071] (4) Repeat steps S2 and S3 10 times with the obtained PB@ASF fiber bundle to obtain a PB@ASF fiber bundle deposited 10 times. Finally, the prepared PB@ASF fiber bundle is dried at room temperature and stored in a vacuum desiccator for later use.
[0072] (5) The PB@ASF fibers were fixed on the working electrode in a spiral arrangement to obtain a PB@ASF fiber sensor with a spiral structure.
[0073] The sensitivity, stability, cyclicity, repeatability and anti-interference performance of the PB@ASF fiber sensor for detecting hydrogen peroxide were tested, and the results are shown in Table 1.
[0074] Table 1 Performance test results of hydrogen peroxide sensors constructed in Examples 1-4 and Comparative Example 1
[0075]
[0076] In summary, the stability, cyclicity and repeatability of the fiber sensor of the present invention for hydrogen peroxide are all above 95%, and the deposition is the largest at the 9th time. The sensitivity at this time is the highest, which is 21.82 μA·mM -1 cm -2 The stability, cyclicity, and repeatability of hydrogen peroxide detection reached as high as 96.12%, 98.60%, and 96.50%, respectively, with the highest anti-interference performance reaching 27.41%. Comparative Example 1 underwent 10 in-situ depositions. Compared to the morphology of Example 4, the surface of the comparative example showed a large amount of particle aggregation, a rough fiber morphology, and cracks, which hindered the sufficient contact between Prussian blue and hydrogen peroxide, resulting in a slight decrease in sensitivity, stability, cyclicity, repeatability, and anti-interference performance.
[0077] Considering that the in-situ deposition process only modifies the silk surface and does not change its internal structure, the flexibility and biocompatibility of the fiber sensor are greatly guaranteed. Therefore, this fiber sensor can be applied to the textile and clothing fields.
[0078] Matters not covered by the present invention are known technologies.
[0079] The above embodiments are intended only to illustrate the technical concepts and features of the present invention. Their purpose is to enable those skilled in the art to understand the contents of the present invention and implement them accordingly. They are not intended to limit the scope of protection of the present invention. Any equivalent changes or modifications made in accordance with the spirit of the present invention are intended to be covered by the scope of protection of the present invention.
Claims
1. A method for constructing a silk fiber-based flexible wearable hydrogen peroxide sensor, characterized in that The following steps are involved: S1: soaking the degummed silk fiber bundle in a weak acid aqueous solution at a certain temperature for a period of time, and then repeatedly rinsing with deionized water to remove excess electrolytes to obtain a surface-activated silk fiber bundle; S2: soaking the surface-activated silk fiber bundle obtained in S1 in a potassium ferricyanide solution of a certain concentration for a period of time at a certain temperature, and then rinsing with deionized water to obtain a silk fiber bundle adsorbing ferrocyanide ions for later use; S3: Protect from light, soak the silk fiber bundle adsorbing ferrocyanide ions obtained in S2 in a certain concentration of ammonium ferric citrate solution at a certain temperature, irradiate with a UV lamp of a certain power for a period of time, take out and rinse with deionized water to obtain the silk fiber bundle PB@ASF with in situ deposition of Prussian blue; S4: Repeat steps S2 and S3 with the silk fiber bundle PB@ASF obtained in S3 to obtain PB@ASF fiber bundles with different deposition times; S5: The PB@ASF fiber bundle obtained in S4 was fixed on the working electrode to obtain silk fiber-based flexible wearable hydrogen peroxide sensors of different morphologies that responded well to hydrogen peroxide.
2. The method for constructing a silk fiber-based flexible wearable hydrogen peroxide sensor according to claim 1, characterized in that: In S1, the degummed silk fiber bundle is immersed in a weak acid aqueous solution at 30-45° C. for 5-20 minutes.
3. The method for constructing a silk fiber-based flexible wearable hydrogen peroxide sensor according to claim 1, characterized in that: The pH of the weak acid aqueous solution in S1 is 3, and the weak acid is carbonic acid, acetic acid or phosphoric acid.
4. The method for constructing a silk fiber-based flexible wearable hydrogen peroxide sensor according to claim 1, characterized in that: In S2, the activated silk fiber bundle is immersed in a potassium ferricyanide solution with a concentration of 50~1000 mg / L, a bath ratio of 1:(10-200), a soaking temperature of 30~45℃, and a soaking time of 5~20 min. After soaking, the silk fiber bundle is rinsed with deionized water for 2~3 times and set aside.
5. The method for constructing a silk fiber-based flexible wearable hydrogen peroxide sensor according to claim 1, characterized in that: In S3, protected from light, the silk fiber bundles adsorbing ferrocyanide ions were immersed in an ammonium ferric citrate solution with a concentration of 50~1000 mg / L, a bath ratio of 1:(10-200), an immersion temperature of 30~45℃, an immersion time of 5~35 min, an ultraviolet lamp with a power of 30~85W, and an irradiation time of 5~35 min. After taking out, they were rinsed with deionized water three times to obtain the silk fiber bundles with in situ Prussian blue deposition PB@ASF.
6. The method for constructing a silk fiber-based flexible wearable hydrogen peroxide sensor according to claim 1, characterized in that: In S4, the obtained PB@ASF fiber bundle is repeated in steps S2 and S3 1 to 9 times to obtain PB@ASF fiber bundles with different deposition times. Finally, the prepared PB@ASF fiber bundle is dried at room temperature and stored in a vacuum desiccator for future use.
7. The method for constructing a silk fiber-based flexible wearable hydrogen peroxide sensor according to claim 1, characterized in that: In S5, the PB@ASF fibers were fixed on the working electrode in a horizontal, spiral, or vertical arrangement to obtain PB@ASF fiber sensors with different structures.
8. A silk fiber-based flexible wearable hydrogen peroxide sensor obtained by the construction method according to any one of claims 1 to 7.