Anti-swelling hydrogel optical fiber constructed based on interfacial free radical polymerization and preparation method of anti-swelling hydrogel optical fiber
The anti-swelling hydrogel optical fiber is prepared by the interfacial free radical polymerization method, which solves the flexibility and preparation problems of traditional optical fiber materials, realizes continuous production and excellent anti-swelling performance, and is suitable for the biomedical field.
Patent Information
- Application Number
- CN202510753078.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-06
- Publication Date
- 2025-10-10
AI Technical Summary
Existing glass optical fiber materials cannot meet the requirements of applications such as optogenetics, implantable optoelectronic medicine, and biosensors in terms of flexibility and mechanical properties, and traditional hydrogel optical fiber preparation methods make it difficult to achieve continuity and anti-swelling properties.
The anti-swelling hydrogel optical fiber was prepared by in-situ growing the sheath layer on the core layer using the interfacial free radical polymerization method, using acryloyl poloxamer, hydroxyethyl acrylate and sodium alginate as the core layer materials, and N-isopropylacrylamide and polyethylene glycol diacrylate as the sheath layer materials, combined with wet spinning and interfacial free radical polymerization.
The continuous preparation of hydrogel optical fibers has been achieved, which have good anti-swelling properties and light-conducting characteristics, making them suitable for biomedical applications. Conductive or anti-inflammatory substances can be added to the sheath to expand their functions.
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Figure CN120759004A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the technical field of hydrogel optical fibers, and particularly relates to an anti-swelling hydrogel optical fiber based on interfacial radical polymerization and a preparation method thereof. BACKGROUND
[0002] Traditional optical fiber material SiO2 has excellent light transmission efficiency and has been widely used in information communication, optical engineering, biomedical endoscopy and other fields. However, in emerging applications such as optogenetics, implantable optoelectronic medicine and biosensors, it is necessary to implant optical fibers along complex paths into deep tissues, which requires the optical fibers to have the characteristics of softness, smoothness and flexibility to adapt to the mechanical properties of tissues. Rigid glass optical fibers cannot meet these requirements, because their mechanical properties do not match those of soft tissues, which can lead to adverse consequences such as tissue damage, inflammation and rejection. Therefore, there is an urgent need to develop a new generation of flexible optical fibers to adapt to a wider range of application scenarios. As a typical soft material, hydrogels have similar modulus to human tissues, high biocompatibility, excellent lubricity and high tensile properties, and have shown great potential in biomedical applications. In addition, hydrogel optical fibers with a special core-sheath structure can effectively reduce light scattering loss when light is reflected on the interface between different media, thereby significantly improving energy utilization and selective exposure in practical applications.
[0003] Chen et al. (Natl Sci Rev., 2020, 8, 9, nwaa209) proposed a concept of integrating light-triggered dynamic wet spinning, which can continuously produce core-sheath hydrogel optical fibers with adjustable fiber diameter, and the preparation of the core-sheath structure is performed using a coaxial needle. This method has certain difficulty in operation. Liu et al. (Nat. Methods., 2023, 20, 11, 1802-1809) used a template method to prepare an anti-fatigue hydrogel optical fiber with good optical transmission performance, but this method cannot realize the continuous production of hydrogel optical fibers. In addition, implantable optical fibers should have good anti-swelling properties. Therefore, it is necessary to develop a hydrogel optical fiber with good anti-swelling properties. SUMMARY
[0004] The technical problem to be solved by the present application is to provide an anti-swelling hydrogel optical fiber based on interfacial radical polymerization and a preparation method thereof, which has good anti-swelling properties and light guiding properties.
[0005] The application provides an anti-swelling hydrogel optical fiber based on interfacial radical polymerization construction, which is obtained based on the principle of interfacial radical polymerization by in-situ growth of a sheath layer on a core layer; the material of the core layer comprises acryloyl poloxamer, hydroxyethyl acrylate and sodium alginate; and the material of the sheath layer comprises N-isopropyl acrylamide and polyethylene glycol diacrylate.
[0006] The application further provides a preparation method of the anti-swelling hydrogel optical fiber based on interfacial radical polymerization construction, comprising the following steps:
[0007] (1) injecting a core layer precursor spinning solution into a coagulation bath through a polytetrafluoroethylene tube connected with a syringe to form a hydrogel optical fiber core layer, and collecting and curing and cross-linking under a UV lamp; wherein the core layer precursor spinning solution is prepared by uniformly mixing acryloyl poloxamer, hydroxyethyl acrylate, sodium alginate and a photoinitiator;
[0008] (2) soaking the hydrogel optical fiber core layer in an ammonium persulfate solution to load persulfate ions;
[0009] (3) soaking the hydrogel optical fiber core layer loaded with persulfate ions in a sheath layer precursor solution to grow a sheath layer, and then curing and cross-linking under a UV lamp to obtain the anti-swelling hydrogel optical fiber; wherein the sheath layer precursor solution is prepared by uniformly mixing N-isopropyl acrylamide, polyethylene glycol diacrylate, tetramethyl ethylenediamine and a photoinitiator.
[0010] Preferably, the amount of acryloyl poloxamer in step (1) is 5-15 wt% of the mass of the core layer precursor spinning solution; the amount of hydroxyethyl acrylate is 10-15 wt% of the mass of the core layer precursor spinning solution; and the amount of sodium alginate is 1-2 wt% of the mass of the core layer precursor spinning solution.
[0011] Preferably, the inner diameter of the polytetrafluoroethylene tube in step (1) is 0.3-2 mm, the spinning solution extrusion speed is 1-2 mL / min, and the winding speed of the collecting device is 50-100 r / min.
[0012] Preferably, the curing and cross-linking time in steps (1) and (3) is 1-5 min.
[0013] Preferably, the coagulation bath in step (1) is a calcium chloride solution with a concentration of 0.1-0.5 mol / L.
[0014] Preferably, the concentration of the ammonium persulfate solution in step (2) is 1-5 wt%, and the soaking time is 30-60 s.
[0015] Preferably, the N-isopropyl acrylamide in step (3) is used in an amount of 10-30wt% of the mass of the sheath precursor solution; the polyethylene glycol diacrylate is used in an amount of 5-10wt% of the mass of the sheath precursor solution; and the tetramethyl ethylene diamine is used in an amount of 1-5wt% of the mass of the sheath precursor solution.
[0016] Preferably, the photoinitiator in steps (1) and (3) is lithium phenyl-2,4,6-trimethylbenzoylphosphinate, and is used in an amount of 0.1-0.5wt% of the mass of the solution including the core precursor spinning solution or the sheath precursor solution.
[0017] Preferably, the soaking time in step (3) is 30-60s.
[0018] The application also provides a use of the anti-swelling hydrogel optical fiber based on interfacial radical polymerization in biomedicine.
[0019] Advantages
[0020] (1) The application effectively realizes good anti-swelling performance of the hydrogel optical fiber by taking acrylpoloxamer as the main component of the core layer of the hydrogel optical fiber. The acrylpoloxamer is a temperature-sensitive nanomicelle, which forms a hydrophobic collapse to form a thermal response fragment to offset the swelling trend of the hydrogel, and has excellent anti-swelling performance at a normal human body temperature of 37℃, thereby laying a good foundation for the application of the hydrogel optical fiber provided by the application in the field of biomedicine.
[0021] (2) The preparation method of the hydrogel optical fiber provided by the application combines wet spinning and interfacial radical polymerization, and simply and efficiently realizes continuous production of the hydrogel optical fiber with adjustable diameter and adjustable length.
[0022] (3) The sheath layer of the hydrogel optical fiber provided by the application can add conductive substances, anti-inflammatory substances and the like to realize different technical requirements, has functional expansion, and has great application potential in the field of implantable optical medical instruments. BRIEF DESCRIPTION OF DRAWINGS
[0023] Figure 1 FIG. 1 is a schematic diagram of the anti-swelling hydrogel optical fiber and a preparation device schematic diagram of the application.
[0024] Figure 2 FIG. 5 is a swelling curve diagram of the core layer of the hydrogel optical fiber at different temperatures in the PBS buffer within 60h in Example 1.
[0025] Figure 3 FIG. 7 is a mechanical property diagram of the core layer of the hydrogel optical fiber with different acrylpoloxamer contents in Example 2.
[0026] Figure 4 a is the optical transparency of the hydrogel optical fiber core layer with different acryloylpoloxamer contents in Example 3.
[0027] Figure 4 b is the optical transparency of the hydrogel optical fiber sheath with different N-isopropylacrylamide contents in Example 3.
[0028] Figure 5 This is a diagram showing the light-guiding performance of the hydrogel optical fiber in Example 4.
[0029] Figure 6 a is the light-guiding properties of hydrogel optical fibers with different acryloylpoloxamer contents and different diameters in Example 4.
[0030] Figure 6 b is the light-guiding performance of the hydrogel optical fiber core layer and the core-sheath structure hydrogel optical fiber in Example 4. DETAILED DESCRIPTION
[0031] 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.
[0032] Example 1
[0033] Swelling behavior of the hydrogel optical fiber core layer:
[0034] (1) Dissolve 1.5 g of acryloyl poloxamer, 0.1 g of sodium alginate, and 0.05 g of lithium phenyl-2,4,6-trimethylbenzoylphosphinate in 8 mL of deionized water, add 1 mL (1.1 g) of hydroxyethyl acrylate, and stir well.
[0035] (2) The core layer precursor spinning solution obtained above was injected into a circular polytetrafluoroethylene mold with a diameter of 2 mm and UV cross-linked for 10 minutes.
[0036] (3) Weigh the weight of the core hydrogel sample and record it as W0. Then, place the sample in a centrifuge tube filled with 10 mL of PBS buffer and soak it. The ambient temperature is controlled at 4°C or 37°C. Set up three parallel tubes for each group. Take out the sample at regular intervals and record the weight as W. t The swelling rate curve was drawn by the weight change at different time points, and the swelling rate (SR) at time t was calculated according to the following formula: SR (%) = (W t -W0) / W0×100%.
[0037] like Figure 2As shown, the hydrogel optical fiber core layer provided by the present invention has excellent anti-swelling performance. Different from 4°C, the swelling rate of the core layer hydrogel at the human body temperature of 37°C is extremely low, which is conducive to the implantation of hydrogel optical fiber into deep tissues of the human body.
[0038] Example 2
[0039] Mechanical properties of hydrogel optical fiber core layer:
[0040] (1) The steps for preparing the hydrogel optical fiber core layer precursor spinning solution are basically the same as step (1) in Example 1, except that the precursor spinning solutions with different contents of acryloyl poloxamer are prepared.
[0041] (2) The core layer precursor spinning solution was injected into a national standard type 3 dumbbell-shaped polytetrafluoroethylene mold and UV cross-linked for 10 minutes.
[0042] (3) The core layer hydrogel sample after UV cross-linking was immersed in a 0.1 mol / L calcium chloride solution for 30 min and then taken out and dried.
[0043] (4) The breaking strength and breaking elongation of the hydrogel optical fiber core layer were measured using a universal material testing machine, with 5 parallels set up in each group.
[0044] like Figure 3 As shown, the breaking stress of the hydrogel optical fiber core layer provided by the present invention when the acryloyl poloxamer content is 15 wt % is 111 kPa, and the corresponding elongation at break is 288%.
[0045] Example 3
[0046] Optical transparency of hydrogel optical fiber core and sheath:
[0047] (1) The steps for preparing the hydrogel optical fiber core layer precursor spinning solution are basically the same as step (1) in Example 1, except that the precursor spinning solutions with different contents of acryloyl poloxamer are prepared.
[0048] (2) The core layer precursor spinning solution obtained above was injected into a circular polytetrafluoroethylene mold with a diameter of 3 mm and UV cross-linked for 10 minutes.
[0049] (3) 1 g / 2 g / 3 g of N-isopropylacrylamide and 0.03 g of lithium phenyl-2,4,6-trimethylbenzoylphosphinate were dissolved in 7.5 mL of deionized water, and 0.5 mL (0.56 g) of polyethylene glycol diacrylate and 0.25 mL (0.19 g) of tetramethylethylenediamine were added and stirred evenly to obtain sheath precursor solutions with different contents of N-isopropylacrylamide.
[0050] (4) Dissolve 1.5 g of ammonium persulfate in 48.5 mL of deionized water and mix well to obtain an ammonium persulfate solution.
[0051] (5) The sheath precursor solution was injected into a circular polytetrafluoroethylene mold with a diameter of 3 mm, dropped into the above ammonium persulfate solution, uniformly mixed, taken out after the polymerization reaction was completed, and ultraviolet cross-linked for 5 min.
[0052] The optical transparency of the hydrogel optical fiber core layer and the sheath layer was measured by a UV-visible spectrometer.
[0053] As shown in Figure 4 a, the optical transparency of the hydrogel optical fiber core layer provided by the application reaches 90% in most visible regions when the acryloylpoloxamer mass concentration is 15wt%. High transparency means less absorption and scattering of light, which greatly reduces the loss of light in the core layer during the propagation of light in the optical fiber, and effectively ensures the transmission of light.
[0054] As shown in Figure 4 b, the optical transparency of the hydrogel optical fiber sheath layer provided by the application is low when the N-isopropyl acrylamide mass concentration is 20wt%. In contrast to the core layer, the low optical transparency of the sheath layer can limit light, reducing the leakage of light to the surrounding environment, so that the core layer can more effectively transmit light.
[0055] Example 4
[0056] Light guiding performance of the hydrogel optical fiber:
[0057] (1) The steps for preparing the hydrogel optical fiber core layer precursor spinning solution are basically the same as those in step (1) of Example 1, except that precursor spinning solutions with different contents of acryloylpoloxamer are prepared.
[0058] (2) The steps for preparing the hydrogel optical fiber sheath layer precursor solution are basically the same as those in step (3) of Example 3, except that the content of N-isopropyl acrylamide is 2g.
[0059] (3) The core layer precursor spinning solution with different contents of acryloylpoloxamer was injected into a 0.1 mol / L calcium chloride solution coagulation bath through a polytetrafluoroethylene tube connected to a syringe, the inner diameter of the polytetrafluoroethylene tube was 1 mm, the spinning solution extrusion speed was 1.6 mL / min, and the winding speed of the collection device was 80 r / min. The collected and cross-linked under the ultraviolet lamp for 3 min.
[0060] (4) The obtained hydrogel optical fiber core layer was soaked in a 3wt% ammonium persulfate solution to load persulfate ions, and the soaking time was 30s.
[0061] (5) The core layer hydrogel optical fiber loaded with persulfate ions is immersed in the sheath precursor solution to grow the sheath and is cured and crosslinked under a UV lamp, the immersion time is 30s, and the curing and crosslinking time is 3min, to obtain a core-sheath structure hydrogel optical fiber, and the light guiding performance is as shown in Figure 5
[0062] An 808nm near-infrared light source is used, the laser is focused on the tip of the optical fiber, the propagation path of the near-infrared light emitted perpendicularly to the optical fiber axis in the hydrogel optical fiber is analyzed under a fixed device, three parallels are set in each group, the data is obtained by using imageJ software, and the light attenuation value of the hydrogel optical fiber (about 5cm) in air is calculated and analyzed.
[0063] As shown in Figure 6 a, with the increase of the diameter, the light attenuation value decreases, because the light needs to cover a longer distance to be reflected on the core-sheath interface when propagating on the optical fiber, thereby causing attenuation. When the acryloyl poloxamer concentration in the core layer increases from 5wt% to 15wt%, the corresponding light attenuation value decreases from 0.41dB / cm to 0.1dB / cm. This is because the higher the acryloyl poloxamer concentration, the higher the transmittance of the core layer optical fiber, and the smaller the attenuation value. When the acryloyl poloxamer mass concentration in the core layer increases to 15wt%, the light attenuation value of the hydrogel optical fiber with a diameter of 1mm is 0.1dB / cm.
[0064] As shown in Figure 6 b, the light attenuation value of the hydrogel optical fiber core layer is much larger than that of the core-sheath structure hydrogel optical fiber, because the hydrogel optical fiber with a special core-sheath structure can effectively reduce the light scattering loss when the light is reflected on the interface of different media, and the single-layer hydrogel optical fiber does not have such boundary conditions to guide the light to be totally reflected. The light is more likely to be lost from the side of the optical fiber during propagation, resulting in a larger light attenuation value.
[0065] The present application prepares a core-sheath structure hydrogel optical fiber based on the wet spinning and interfacial radical polymerization method, which simply and efficiently realizes the continuous preparation of the hydrogel optical fiber, and the hydrogel optical fiber has excellent anti-swelling performance and good optical transmission performance, and is expected to be applied in the biomedical field.
[0066] The preferred embodiments of the present application are described above, but the protection scope of the present application is not limited thereto. Various modifications and substitutions of the present application within the technical scope disclosed by the present application should be covered within the protection scope of the present application by those skilled in the art. Therefore, the protection scope of the present application should be defined by the appended claims.
Claims
1. An anti-swelling hydrogel optical fiber constructed based on interfacial free radical polymerization, characterized by: The hydrogel optical fiber is obtained by in-situ growing a sheath layer on a core layer based on the principle of interfacial free radical polymerization; the material of the core layer includes acryloyl poloxamer, hydroxyethyl acrylate and sodium alginate; the material of the sheath layer includes N-isopropyl acrylamide and polyethylene glycol diacrylate.
2. A method for preparing an anti-swelling hydrogel optical fiber based on interfacial free radical polymerization, comprising the following steps: (1) injecting the core layer precursor spinning solution into a coagulation bath through a syringe connected to a polytetrafluoroethylene tube to form a hydrogel optical fiber core layer, collecting it and curing and cross-linking it under an ultraviolet lamp; wherein, The core layer precursor spinning solution is prepared by uniformly mixing acryloyl poloxamer, hydroxyethyl acrylate, sodium alginate and a photoinitiator; (2) immersing the hydrogel optical fiber core layer in an ammonium persulfate solution to load persulfate ions; (3) Immersing the core layer of the hydrogel optical fiber loaded with persulfate ions in a sheath precursor solution to grow a sheath, and then curing and cross-linking the solution under ultraviolet light to obtain the anti-swelling hydrogel optical fiber; wherein the sheath precursor solution is prepared by uniformly mixing N-isopropylacrylamide, polyethylene glycol diacrylate, tetramethylethylenediamine, and a photoinitiator.
3. The preparation method according to claim 2, wherein: The amount of acryloyl poloxamer in step (1) is 5-15wt% of the mass of the core layer precursor spinning solution; the amount of hydroxyethyl acrylate is 10-15wt% of the mass of the core layer precursor spinning solution; and the amount of sodium alginate is 1-2wt% of the mass of the core layer precursor spinning solution.
4. The preparation method according to claim 2, wherein: The inner diameter of the polytetrafluoroethylene tube in step (1) is 0.3-2 mm, the spinning solution extrusion speed is 1-2 mL / min, and the winding speed of the collecting device is 50-100 r / min.
5. The preparation method according to claim 2, wherein: The curing and cross-linking time in steps (1) and (3) is 1-5 minutes.
6. The preparation method according to claim 2, wherein: The coagulation bath in step (1) is a calcium chloride solution with a concentration of 0.1-0.5 mol / L.
7. The preparation method according to claim 2, characterized in that: The concentration of the ammonium persulfate solution in step (2) is 1-5 wt %; the soaking time is 30-60 s.
8. The preparation method according to claim 2, wherein: The amount of N-isopropylacrylamide used in step (3) is 10-30 wt% of the mass of the sheath precursor solution; the amount of polyethylene glycol diacrylate used is 5-10 wt% of the mass of the sheath precursor solution; and the amount of tetramethylethylenediamine used is 1-5 wt% of the mass of the sheath precursor solution.
9. The preparation method according to claim 2, wherein: The photoinitiator in steps (1) and (3) is lithium phenyl-2,4,6-trimethylbenzoylphosphinate; the amount used is 0.1-0.5 wt% of the solution mass.
10. Application of the anti-swelling hydrogel optical fiber constructed based on interfacial free radical polymerization as claimed in claim 1 in biomedicine.