CN113047045B - Flexible optical fiber and preparation method and application thereof - Google Patents

Flexible optical fiber and preparation method and application thereof Download PDF

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CN113047045B
CN113047045B CN202110334848.8A CN202110334848A CN113047045B CN 113047045 B CN113047045 B CN 113047045B CN 202110334848 A CN202110334848 A CN 202110334848A CN 113047045 B CN113047045 B CN 113047045B
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optical fiber
flexible optical
inner core
polyvinyl alcohol
solution
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CN113047045A (en
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曹燚
王璐璐
钟成
孙重阳
阎梦萦
叶丰明
鲁艺
王立平
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Shenzhen Institute of Advanced Technology of CAS
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
    • D06M15/333—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61N—ELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
    • A61N5/00—Radiation therapy
    • A61N5/06—Radiation therapy using light
    • A61N5/0613—Apparatus adapted for a specific treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0209—Multistage baking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61N—ELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
    • A61N5/00—Radiation therapy
    • A61N5/06—Radiation therapy using light
    • A61N2005/063—Radiation therapy using light comprising light transmitting means, e.g. optical fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2256/00—Wires or fibres
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds

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Abstract

The invention provides a flexible optical fiber and a preparation method and application thereof, wherein the flexible optical fiber comprises an inner core and a coating layer coated on the outer side of the inner core; the inner core is made of silicon rubber, and the coating layer is made of gel polymer. The elasticity, toughness and flexibility of the flexible optical fiber are obviously improved through the design of a double-layer structure and the synergistic compounding of materials; meanwhile, the double-layer structure formed by the specific materials can improve the light transmission performance of the flexible optical fiber, so that the light transmittance is improved; the flexible optical fiber has excellent mechanical property, light transmission property and biocompatibility, can be safely and stably implanted into a body for a long time, and fully meets the application requirements in the optogenetic technology.

Description

Flexible optical fiber and preparation method and application thereof
Technical Field
The invention belongs to the technical field of biomedical materials, and particularly relates to a flexible optical fiber and a preparation method and application thereof.
Background
The optogenetic technique is a neural regulation technique which has been developed in the last decade, and has been widely used in the field of neurobiology due to its very high temporal specificity. The main principle of the photo genetic technology is that a gene technology is adopted to express a photosensitive gene in a specific type of nerve cell, so that a photosensitive ion channel is formed on a cell membrane; the ion channels can respectively generate selectivity to the passing of cations or anions under the illumination stimulation of specific wavelength, thereby causing the membrane potential on two sides of the cell membrane to change and achieving the aim of selectively exciting or inhibiting the cell. In order to achieve optogenetic modulation at the living body level, one typically directs laser light of a specific wavelength to a target location through an optical waveguide embedded in the body. Therefore, two major bases of optogenetic technology are light sensing gene technology and laser transduction technology.
Silica fibers or glass fibers have very high permeability and are often used for laser light transmission. For example, CN110559499A discloses a microdialysis probe capable of performing optogenetic stimulation, which includes an optical fiber module and a dialysis module, wherein the optical fiber module includes an optical fiber connector and a quartz optical fiber, the dialysis module includes a probe housing, and the head of the probe housing is connected to the optical fiber connector through a limiting block, so that the optical fiber module and the dialysis module are combined together, thereby realizing the synchronous operation of optogenetic stimulation and microdialysis, and being capable of detecting the molecular level change brought by the activation of a specific neuron by light waves in real time and synchronously. However, the silica fiber or glass fiber has a high modulus, and in the central part, since the skull supports the fiber, the positions in the brain are substantially fixed, and thus the silica fiber or glass fiber is widely used. However, in the peripheral nerve part, because the peripheral nerve is thin and deep, the running is complex, and the Endoconcha nerve does not adhere to the skeleton to run, the quartz fiber or the glass fiber is difficult to be fixedly irradiated to a certain specific point, and particularly, the application of the quartz fiber or the glass fiber is greatly limited in the free-moving animal body.
CN111939472A discloses an intracranial stimulation recording system, which comprises a flexible optical fiber, a laser and a flexible deep brain electrode, wherein the flexible optical fiber is connected with the laser, and the flexible deep brain electrode is fixed on the flexible optical fiber through a clamp. According to the system, the flexible deep brain electrode is attached to the surface of the flexible optical fiber, the laser is used as a light source, the functions of optical pulse nerve stimulation and nerve electrophysiological signal acquisition can be integrated, meanwhile, optogenetic excitation and inhibition are realized, and the damage to brain tissues caused by heating of an LED chip is avoided; the fibroin is adopted as the main materials of the substrate layer, the insulating layer and the packaging layer of the flexible deep brain electrode, and the flexible optical fiber material is combined, so that the mechanical compliance of the implanted device to brain tissues can be improved, and the neuroinflammation caused by the long-term in vivo implantation of the device is reduced. However, the existing flexible optical fiber can only overcome the problems of flexibility and deformation, has poor performance in the aspects of elasticity and light transmittance, and is not beneficial to laser conduction implanted into a body; moreover, the flexible optical fiber is easily stretched by the movement of the animal after being implanted in the animal body, resulting in the change of the stimulation site.
Therefore, it is an urgent problem in the art to develop a flexible optical fiber having excellent elasticity, flexibility and optical transparency to meet the application requirements in optogenetic technology.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a flexible optical fiber and a preparation method and application thereof, wherein the flexible optical fiber has a double-layer structure, has excellent elasticity and flexibility by the structural design and material compounding of an inner core and a coating layer, can improve the light transmission efficiency, has high light transmission and good biocompatibility, and can fully meet the application requirements in the optogenetic technology.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a flexible optical fiber, which includes an inner core and a cladding layer coated outside the inner core; the inner core is made of silicon rubber, and the coating layer is made of gel polymer.
The flexible optical fiber provided by the invention has a double-layer sheath-core structure consisting of an inner core and a coating layer, wherein the inner core is made of silicon rubber, the coating layer is made of gel polymer, and the coating layer can form a hydrogel layer in a water environment after being implanted into a body. The invention obviously improves the elasticity, toughness and flexibility of the flexible optical fiber through the structural design and the synergistic compounding of materials; meanwhile, the double-layer structure made of the specific material can improve the light transmission performance of the flexible optical fiber, particularly improve the light transmission performance of the flexible optical fiber in a liquid environment (such as an implant), improve the total reflection of light, reduce light loss and improve light transmittance; the flexible optical fiber has excellent mechanical property, light transmission property and biocompatibility, and can be safely and stably implanted into a body for a long time.
Preferably, the diameter of the inner core is 50-1000 μm, such as 60 μm, 80 μm, 100 μm, 120 μm, 150 μm, 180 μm, 200 μm, 220 μm, 250 μm, 280 μm, 300 μm, 320 μm, 350 μm, 380 μm, 400 μm, 450 μm, 500 μm, 550 μm, 600 μm, 650 μm, 700 μm, 750 μm, 800 μm, 850 μm, 900 μm or 950 μm, and the specific values therebetween are limited to space and for simplicity, and the invention does not exhaust the specific values included in the range, and more preferably 100-400 μm.
Preferably, the coating layer has a thickness of 30 to 100 μm, such as 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm or 95 μm, and specific values therebetween, which are not intended to be exhaustive for the invention and for the sake of brevity.
Preferably, the silicone rubber is polydimethylsiloxane.
Preferably, the refractive index of the silicone rubber is 1.41-1.45, and may be, for example, 1.415, 1.42, 1.425, 1.43, 1.435, 1.44 or 1.445, and specific values therebetween, which are limited by space and for the sake of brevity, the present invention is not exhaustive of the specific values included in the range.
Preferably, the light transmittance of the silicone rubber is equal to or more than 98%, and can be 98.2%, 98.5%, 98.8%, 99%, 99.2%, 99.5%, 99.8% or the like, for example.
As a preferred technical scheme of the invention, the refractive index of the silicone rubber is 1.41-1.45, the light transmittance is not less than 98%, and the silicone rubber has high clarity and high transparency and is beneficial to improving the light transmission performance of the flexible optical fiber. The silicone rubber is commercially available, and may be, for example, Dow Corning DC184 silicone rubber.
Preferably, the inner core is prepared by a method comprising: and pouring the precursor solution of the silicon rubber in a heating device, so that the precursor solution falls under the action of gravity and forms filaments to obtain the inner core.
As a preferred technical scheme of the invention, the inner core is obtained by a specific method, the precursor solution of the silicon rubber has proper viscosity, can be automatically stretched into a filament shape under the action of gravity when poured in a heating device, can be quickly solidified to form the inner core in the falling process, has high preparation efficiency, and can be controlled within 1s in total time. Compared with the traditional injection molding, the inner core provided by the invention has the advantages that the preparation time is short, the efficiency is high, a mold is not needed, the smoothness of the surface of the inner core is higher, and the comprehensive performance of the flexible optical fiber can be further improved.
Preferably, the precursor solution comprises a combination of a silicone rubber prepolymer and a curing agent.
The mass ratio of the silicone rubber prepolymer to the curing agent is preferably (8-15: 1), and may be, for example, 8.5:1, 9:1, 9.5:1, 10:1, 10.5:1, 11:1, 11.5:1, 12:1, 12.5:1, 13:1, 13.5:1, 14:1, or 14.5: 1.
Preferably, the precursor solution is prepared by the following method: and mixing the silicon rubber prepolymer with a curing agent, fully stirring, vacuumizing and removing bubbles to obtain the precursor solution.
Preferably, the internal temperature of the heating device is 250-350 ℃, for example, 255 ℃, 260 ℃, 265 ℃, 270 ℃, 275 ℃, 280 ℃, 285 ℃, 290 ℃, 295 ℃, 300 ℃, 305 ℃, 310 ℃, 315 ℃, 320 ℃, 325 ℃, 330 ℃, 335 ℃, 340 ℃ or 345 ℃, and the specific values therebetween are limited to the space and the specific values included in the range are not exhaustive for the sake of brevity.
Preferably, the heating device is a heating furnace.
Preferably, the heating furnace has a cylindrical inner cavity.
Preferably, a force opposite to the direction of gravity is also applied during the pouring; by applying a force opposite to the direction of gravity, the drop of the precursor solution and the diameter of the filaments are controlled, resulting in cores of different diameters.
Preferably, the refractive index of the gel polymer is 1.32-1.38, for example, 1.325, 1.33, 1.335, 1.34, 1.345, 1.35, 1.355, 1.36, 1.365, 1.37 or 1.375, and specific values therebetween, which are not exhaustive and included in the range for brevity.
Preferably, the gel polymer comprises any one or a combination of at least two of polyacrylic acid, polymethacrylic acid, polyacrylamide, polymethacrylamide, polyvinyl alcohol-polyacrylic acid cross-linked polymer, vinyl alcohol-acrylic acid copolymer, alginate-acrylamide copolymer, polyethylene glycol, polysaccharide or polypeptide, and further preferably polyvinyl alcohol-polyacrylic acid cross-linked polymer.
Preferably, the molar ratio of polyvinyl alcohol to polyacrylic acid in the polyvinyl alcohol-polyacrylic acid crosslinked polymer is 1 (0.2 to 0.8), and may be, for example, 1:0.25, 1:0.3, 1:0.35, 1:0.4, 1:0.45, 1:0.5, 1:0.55, 1:0.6, 1:0.65, 1:0.7, 1:0.75, or 1: 0.78.
Preferably, the weight average molecular weight of the polyvinyl alcohol is 85000-100000, such as 86000, 87000, 88000, 89000, 90000, 91000, 92000, 93000, 94000, 95000, 96000, 97000, 98000 or 99000, and the specific values therebetween are not exhaustive, but for the sake of brevity and brevity.
In a second aspect, the present invention provides a method of manufacturing a flexible optical fiber according to the first aspect, the method comprising: and coating the solution of the gel polymer on the surface of the inner core, and drying to obtain the flexible optical fiber.
Preferably, the gel polymer is a polyvinyl alcohol-polyacrylic acid cross-linked polymer, and the preparation method of the solution of the gel polymer comprises the following steps: mixing polyvinyl alcohol, acrylic acid, an initiator and water to obtain a prepolymerization solution; and reacting the pre-polymerization solution to obtain the solution of the gel polymer.
Preferably, the weight average molecular weight of the polyvinyl alcohol is 85000-100000, such as 86000, 87000, 88000, 89000, 90000, 91000, 92000, 93000, 94000, 95000, 96000, 97000, 98000 or 99000, and the specific values therebetween are not exhaustive, but for the sake of brevity and brevity.
Preferably, the molar ratio of the acrylic acid to the vinyl alcohol repeat units in the polyvinyl alcohol is (0.2-0.8): 1, and may be, for example, 0.25:1, 0.3:1, 0.35:1, 0.4:1, 0.45:1, 0.5:1, 0.55:1, 0.6:1, 0.65:1, 0.7:1, 0.75:1, or 0.78: 1.
Preferably, the initiator is a persulfate, more preferably ammonium persulfate.
Preferably, the mass of the initiator is 0.2-1% based on 100% of the mass of the acrylic acid, and may be, for example, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.55%, 0.6%, 0.65%, 0.7%, 0.75%, 0.8%, 0.85%, 0.9%, 0.95%, or 0.98%, and specific points therebetween are not intended to be limiting to space and for brevity, and the invention is not intended to be exhaustive of the specific points included in the range.
Preferably, the mass percentage of the polyvinyl alcohol in the prepolymerization solution is 1-10%, for example, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, or 9.5%, and specific values therebetween, including space and brevity, are not exhaustive.
Preferably, the reaction temperature is 70-90 ℃, for example, 71 ℃, 73 ℃, 75 ℃, 77 ℃, 79 ℃, 80 ℃, 81 ℃, 83 ℃, 85 ℃, 87 ℃ or 89 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the range.
Preferably, the reaction time is 12-72 h, for example, 14h, 16h, 18h, 20h, 22h, 24h, 26h, 28h, 30h, 32h, 40h, 48h, 56h, 64h or 70h, and the specific values therebetween are not exhaustive, and for brevity and clarity, the invention is not limited to the specific values included in the range.
Preferably, the reaction is carried out under oxygen-scavenging conditions.
Preferably, the inner core is subjected to plasma sputtering treatment.
Preferably, the method of coating is dip coating.
Preferably, the drying comprises a first stage drying and a second stage drying.
Preferably, the temperature of the first stage drying is 15 to 40 ℃, for example, 16 ℃, 18 ℃, 20 ℃, 21 ℃, 23 ℃, 25 ℃, 27 ℃, 29 ℃, 30 ℃, 31 ℃, 33 ℃, 35 ℃, 37 ℃ or 39 ℃, and the specific values therebetween are limited by space and simplicity, and the invention is not exhaustive list of the specific values included in the range, and further preferably room temperature.
Preferably, the temperature of the second stage drying is 70-85 ℃, such as 71 ℃, 73 ℃, 75 ℃, 77 ℃, 79 ℃, 80 ℃, 81 ℃, 82 ℃, 83 ℃ or 84 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the range.
Preferably, the second stage drying time is 4-24 h, for example, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h or 22h, and the specific values therebetween are limited by space and for brevity, the invention is not exhaustive.
Preferably, the preparation method specifically comprises the following steps:
(1) pouring a precursor solution of the silicon rubber in a heating device, so that the precursor solution falls under the action of gravity and forms a filament to obtain an inner core; the internal temperature of the heating device is 250-350 ℃;
(2) mixing polyvinyl alcohol, acrylic acid, an initiator and water to obtain a prepolymerization solution; after the prepolymerization solution is deoxidized, reacting for 12-72 h at 70-90 ℃ to obtain a solution of a gel polymer; coating the solution of the gel polymer on the surface of the inner core obtained in the step (1), drying at 15-40 ℃ until no liquid flows, heating to 70-85 ℃ and drying for 4-24 hours to obtain the flexible optical fiber;
the mass percentage of polyvinyl alcohol in the prepolymerization solution is 1-10%, and the molar ratio of the acrylic acid to the vinyl alcohol repeating units in the polyvinyl alcohol is (0.2-0.8): 1; the mass of the persulfate is 0.2-1% based on 100% of the mass of the acrylic acid.
In a third aspect, the present invention provides a use of a flexible optical fibre according to the first aspect in a fibre optic implant or a nerve electrode.
Compared with the prior art, the invention has the following beneficial effects:
the flexible optical fiber provided by the invention has a double-layer structure consisting of an inner core and a coating layer, wherein the inner core is made of silicon rubber, the coating layer is made of gel polymer, and the coating layer forms a hydrogel layer in a water environment after being implanted into a body. According to the invention, through the design of the structure and the synergistic compounding of materials, the elasticity, toughness and flexibility of the flexible optical fiber are obviously improved, the flexible optical fiber can be bent at any angle (up to 360 ℃) according to application requirements, and can be stretched by more than 3 times without influencing the physical performance of the flexible optical fiber; meanwhile, the double-layer structure made of the specific material can improve the light transmission performance of the flexible optical fiber, particularly improve the light conduction performance of the flexible optical fiber in a liquid environment implanted in a body, improve the total reflection of light, reduce light loss and improve light transmittance. The flexible optical fiber has excellent mechanical property, light transmission property and biocompatibility, can be safely and stably implanted into a body for a long time, and fully meets the application requirements in the optogenetic technology.
Drawings
FIG. 1 is a schematic view of a process for preparing an inner core of example 1;
FIG. 2 is an optical test chart of the core of examples 1 to 6;
FIG. 3 is a graph showing the results of the elasticity test of the flexible optical fiber provided in example 1;
FIG. 4 is a graph showing the results of flexibility tests on the flexible optical fiber provided in example 1;
fig. 5 is a graph showing the results of the biocompatibility test of the flexible optical fiber provided in example 1.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
A flexible optical fiber comprises an inner core and a cladding layer coated outside the inner core; the diameter of the inner core is 200 mu m, the material is polydimethylsiloxane (PDMS, Dow Corning DC184), the thickness of the coating layer is 50 mu m, and the material is polyvinyl alcohol-polyacrylic acid cross-linked polymer (PVA-PAA cross-linked polymer); the preparation method comprises the following steps:
(1) mixing the prepolymer of PDMS and a curing agent in a mass ratio of 10:1, fully and uniformly stirring, and vacuumizing to remove bubbles to obtain a precursor solution of silicon rubber;
(2) placing the precursor solution obtained in the step (1) in a heating furnace at 300 ℃, pouring the precursor solution from the upper part of the heating furnace, and allowing the precursor solution to fall under the action of gravity to form filaments; applying an upward force during pouring to obtain an inner core with a diameter of 200 μm; the preparation process schematic diagram of the inner core is shown in figure 1;
(3) mixing polyvinyl alcohol (PVA, purchased from Sigma 341584-500G) with pure water, and stirring at 80 ℃ until the PVA is completely dissolved to obtain a PVA solution with the PVA mass percentage content of 5%; uniformly mixing 55g of the PVA solution, 2.3g of acrylic acid (AA, purity 98%) and 10mg of Ammonium Persulfate (APS), and adding water to 100mL to obtain a prepolymerization solution; the prepolymerization solution was sufficiently deoxygenated, sealed, and reacted at 80 ℃ for 3 days to obtain a solution of a gel polymer (PVA-PAA solution).
And (3) soaking the inner core obtained in the step (2) in a PVA-PAA solution to coat the PVA-PAA solution on the surface of the inner core, airing the inner core at room temperature, and fully drying the inner core in an oven at 80 ℃ overnight to obtain the flexible optical fiber.
Examples 2 to 6
A flexible optical fiber comprises an inner core and a cladding layer coated outside the inner core; it is different from example 1 only in that the inner cores have diameters of 50 μm, 100 μm, 300 μm, 500 μm, 1000 μm, respectively, and are prepared by controlling the magnitude of the upward force applied when pouring in step (2); the other raw materials and the process were the same as in example 1. The optical patterns of the cores of different diameters in examples 1-6 are shown in FIG. 2.
Example 7
A flexible optical fiber, which is different from example 1 only in that the preparation method of the inner core in the step (2) is a molding method, specifically: placing the precursor solution in a cavity of a tubular mold for molding to obtain an inner core with the diameter of 200 mu m; the other raw materials and the process were the same as in example 1.
Comparative example 1
A flexible optical fiber, which is different from example 1 only in that it does not contain a coating layer, i.e., a PDMS flexible optical fiber having a diameter of 200 μm.
Comparative example 2
A flexible optical fiber is made of PVA-PAA cross-linked polymer and is prepared by the following steps:
mixing PVA with pure water, stirring at 80 ℃ until the PVA is completely dissolved to obtain a PVA solution with the PVA mass percentage of 5%; uniformly mixing 55g of the PVA solution, 2.3g of acrylic acid (AA, purity 98%) and 10mg of Ammonium Persulfate (APS), and adding water to 100mL to obtain a prepolymerization solution; and (3) placing the prepolymerization solution in a cavity of a tubular mold, reacting for 72h at 80 ℃ in a fully deoxygenated environment, and dehydrating and drying to obtain the flexible optical fiber.
And (3) performance testing:
(1) elasticity test
The flexible optical fibers provided in examples 1 to 7 are subjected to tensile tests, and exemplarily, a graph of the elasticity test result of the flexible optical fiber in example 1 is shown in fig. 3, and as can be seen from fig. 3, the unstretched length of the flexible optical fiber is about 1cm, the length after one-time stretching can reach 2cm, the length after two-time stretching is about 3cm, and the flexible optical fiber is stretched by more than 3 times (or 4 times) without affecting the physical properties of the flexible optical fiber and has excellent elasticity; the flexible optical fibers with inner cores of different diameters in the embodiments 2 to 6 also have high elasticity which is stretched by 3 to 4 times without affecting other performances.
In the flexible optical fiber provided in embodiment 7, the PDMS inner core is prepared by a mold molding method, which results in a decrease in the overall elasticity of the flexible optical fiber, and the elasticity performance is significantly inferior to that of the flexible optical fibers in embodiments 1 to 6.
(2) Flexibility test
The flexible optical fibers provided in examples 1 to 7 are subjected to a simulated bending test in vivo, for example, a flexibility test result of the flexible optical fiber in example 1 is shown in fig. 4, and the flexible optical fiber can be easily bent by more than 180 ° and shows excellent flexibility. The flexible optical fibers with different diameters in the embodiments 1-6 can be bent at will according to actual application requirements (bending angle is 360 degrees), and the flexibility is good.
(3) Optical transmission performance
Assembling a flexible optical fiber to be tested into a ceramic head, and reserving a length of 3cm outside the ceramic head; adjusting the output power of the laser to a fixed value of 30mW, and measuring the output light intensity P of the flexible optical fiber at the moment1(ii) a Then cutting the flexible optical fiber to 1cm, and measuring the output light intensity P of the flexible optical fiber again0。
Using the calculation formula for light loss: optical fiber loss P0(dB/cm)＝(10/Ln)log(Pin/Pout) Ln; wherein, PinLight intensity value at 2cm, PoutIs the light intensity value at 3cm, Ln is P0、P1A length of 1 cm; the light loss value is obtained by the above formula.
Light transmittance of Pin/Pout。
The flexible optical fiber was tested for light transmittance and light loss according to the above-described methods, and the data are shown in table 1.
TABLE 1
Figure BDA0002997025570000111
Figure BDA0002997025570000121
The flexible optical fiber provided by the invention has high light transmittance and low optical loss value, and the double-layer structure consisting of the inner core and the cladding layer can enable the flexible optical fiber to show excellent optical transmission performance in a liquid environment implanted in a body. The flexible optical fibers in comparative examples 1 and 2 have a single-layer structure, and after being implanted into a body, the light transmission performance of the flexible optical fibers is reduced due to the fact that the body is in a liquid environment and the refractive index of liquid is different from that of air; also, the flexible optical fiber of comparative example 2 is made of gel polymer, has high water absorption rate, rapidly swells in vivo to increase volume, and is also disadvantageous to light transmission.
(4) Biocompatibility testing
The flexible optical fiber provided in example 1 was implanted into animals and the number of cells at the implantation site (ipsilateral) and at the symmetrical implantation site (contralateral) was measured after 1 month of culture by the following specific method:
c57 mice were selected and implanted in the right neck. The fiber was in full contact with the submandibular gland of the right neck. After one month of implantation, the left and right submaxillary glands were removed, respectively. Paraffin sectioning experiments were performed. After staining and photographing, counting is carried out. The graph of the result of the biocompatibility test of the flexible optical fiber is shown in fig. 5, and the number of cells at the implantation position (ipsilateral) and the implantation symmetrical position (contralateral) of the flexible optical fiber has no significant difference, which indicates that the flexible optical fiber provided by the invention has excellent biocompatibility.
The applicant states that the present invention is illustrated by the above examples of a flexible optical fiber and a method for making and using the same, but the present invention is not limited to the above process steps, i.e. it does not mean that the present invention must rely on the above process steps to be implemented. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.

Claims (36)

1. The flexible optical fiber is characterized by comprising an inner core and a coating layer coated outside the inner core; the inner core is made of silicon rubber, and the coating layer is made of gel polymer;
the inner core is prepared by the following method, and the method comprises the following steps: and pouring the precursor solution of the silicon rubber in a heating device, so that the precursor solution falls under the action of gravity and forms filaments to obtain the inner core.
2. The flexible optical fiber of claim 1, wherein the inner core has a diameter of 50-1000 μm.
3. The flexible optical fiber of claim 1, wherein the inner core has a diameter of 100 to 400 μm.
4. The flexible optical fiber according to claim 1, wherein the thickness of the cladding layer is 30 to 100 μm.
5. The flexible optical fiber of claim 1, wherein the silicone rubber is polydimethylsiloxane.
6. The flexible optical fiber according to claim 1, wherein the refractive index of the silicone rubber is 1.41 to 1.45.
7. The flexible optical fiber of claim 1, wherein the light transmittance of the silicone rubber is greater than or equal to 98%.
8. The flexible optical fiber of claim 1, wherein the precursor solution comprises a combination of a silicone rubber prepolymer and a curing agent.
9. The flexible optical fiber according to claim 8, wherein the mass ratio of the silicone rubber prepolymer to the curing agent is (8-15): 1.
10. The flexible optical fiber according to claim 1, wherein the internal temperature of the heating device is 250 to 350 ℃.
11. The flexible optical fiber of claim 1, wherein the heating device is a furnace.
12. The flexible optical fiber of claim 1, wherein a force opposite to the direction of gravity is also applied during the pouring.
13. The flexible optical fiber according to claim 1, wherein the gel polymer has a refractive index of 1.32 to 1.38.
14. The flexible optical fiber of claim 1, wherein the gel polymer comprises any one or a combination of at least two of polyacrylic acid, polymethacrylic acid, polyacrylamide, polymethacrylamide, polyvinyl alcohol-polyacrylic acid cross-linked polymer, vinyl alcohol-acrylic acid copolymer, alginate-acrylamide copolymer, polyethylene glycol, polysaccharide, or polypeptide.
15. The flexible optical fiber of claim 14, wherein the gel polymer is a polyvinyl alcohol-polyacrylic acid cross-linked polymer.
16. The flexible optical fiber according to claim 14, wherein the gel polymer and the polyvinyl alcohol-polyacrylic acid crosslinked polymer have a molar ratio of polyvinyl alcohol to polyacrylic acid of 1 (0.2-0.8).
17. The flexible optical fiber according to claim 16, wherein the polyvinyl alcohol has a weight average molecular weight of 85000 to 100000.
18. A method of making a flexible optical fiber according to any one of claims 1 to 17, comprising: and coating the solution of the gel polymer on the surface of the inner core, and drying to obtain the flexible optical fiber.
19. The method of claim 18, wherein the gel polymer is a polyvinyl alcohol-polyacrylic acid crosslinked polymer, and the method of preparing the solution of the gel polymer comprises: mixing polyvinyl alcohol, acrylic acid, an initiator and water to obtain a prepolymerization solution; and reacting the pre-polymerization solution to obtain the solution of the gel polymer.
20. The method according to claim 19, wherein the polyvinyl alcohol has a weight average molecular weight of 85000 to 100000.
21. The method according to claim 19, wherein the molar ratio of the repeating units of vinyl alcohol in the acrylic acid to the polyvinyl alcohol is (0.2-0.8): 1.
22. The method according to claim 19, wherein the initiator is a persulfate.
23. The method of claim 19, wherein the initiator is ammonium persulfate.
24. The method according to claim 19, wherein the mass of the initiator is 0.2 to 1% based on 100% by mass of the acrylic acid.
25. The method according to claim 19, wherein the mass percentage of the polyvinyl alcohol in the pre-polymerization solution is 1 to 10%.
26. The method according to claim 19, wherein the reaction temperature is 70 to 90 ℃.
27. The preparation method of claim 19, wherein the reaction time is 12-72 hours.
28. The method of claim 19, wherein the reaction is carried out under oxygen-scavenging conditions.
29. The method of claim 18, wherein the core is a plasma sputter treated core.
30. The method of claim 18, wherein the coating is by dip coating.
31. The method of claim 18, wherein the drying includes a first stage drying and a second stage drying.
32. The method of claim 31, wherein the first stage drying temperature is 15-40 ℃.
33. The method of claim 31, wherein the second stage drying temperature is 70-85 ℃.
34. The method of claim 31, wherein the second stage drying time is 4-24 hours.
35. The method of claim 22, comprising the steps of:
(1) pouring a precursor solution of the silicon rubber in a heating device, so that the precursor solution falls under the action of gravity and forms a filament to obtain an inner core; the internal temperature of the heating device is 250-350 ℃;
(2) mixing polyvinyl alcohol, acrylic acid, an initiator and water to obtain a prepolymerization solution; after the prepolymerization solution is deoxidized, reacting for 12-72 h at 70-90 ℃ to obtain a solution of a gel polymer; dip-coating the solution of the gel polymer on the surface of the inner core obtained in the step (1), drying at 15-40 ℃ until no liquid flows, heating to 70-85 ℃ and drying for 4-24 hours to obtain the flexible optical fiber;
the mass percentage of polyvinyl alcohol in the prepolymerization solution is 1-10%, and the molar ratio of the acrylic acid to the vinyl alcohol repeating units in the polyvinyl alcohol is (0.2-0.8): 1; the mass of the persulfate is 0.2-1% based on 100% of the mass of the acrylic acid.
36. Use of a flexible optical fibre according to any one of claims 1 to 17 in a fibre optic implant or a nerve electrode.
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