A method for preparing an accommodative intraocular lens driven by visible light / sunlight
The visible light/sunlight-driven accommodative intraocular lens prepared by light-driven method solves the problem of accommodative intraocular lens relying on the capsular bag and ciliary muscle, realizes a larger focal length adjustment range and minimally invasive surgery, and meets the needs of vision at all distances.
Patent Information
- Application Number
- CN202210299736.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2022-03-21
- Publication Date
- 2025-10-03
- Estimated Expiration
- 2042-03-21
AI Technical Summary
The accommodative function of existing accommodative intraocular lenses depends on the lens capsule. Affected by aging or secondary cataracts, the capsule hardens, affecting the accommodative function and failing to provide sufficient postoperative refractive adjustment range.
Visible light/sunlight-driven accommodative intraocular lenses are prepared using a light-driven method. By combining photothermal conversion materials with temperature-responsive liquid crystal polymers, changes in shape and focal length are achieved, avoiding reliance on the mechanical action of the intraocular capsule and ciliary muscle.
It provides a wider focal length adjustment range, avoids the effects of age-related changes in the ciliary muscle and capsular bag hardening, is driven by clean energy light, uses materials that cause little damage to the human body, enables minimally invasive surgery, and meets all-distance vision needs.
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Figure CN114587709B_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of medical artificial lenses, and in particular to a method for preparing an accommodative artificial lens driven by visible light / sunlight. Background Art
[0002] With the emergence of phacoemulsification technology and foldable intraocular lenses, cataract surgery has made great progress, but it has also brought higher expectations to patients. The requirements for postoperative effects of cataract surgery are getting higher and higher, and the requirements for the functions of intraocular lenses are also increasing, especially for patients with cataracts and presbyopia.
[0003] Accommodating intraocular lenses achieve dynamic changes in refractive power through the use of different strategies, either alone or in combination. These include single-optic or dual-optic intraocular lenses based on positional changes, accommodative intraocular lenses based on shape and refractive index changes, and injectable intraocular lens technology. These not only provide patients with a full range of vision that gradually transitions from near to far, but also avoid the adverse visual symptoms associated with multifocal intraocular lenses, effectively improving patients' postoperative visual function and quality of life. However, the biggest problem with this type of intraocular lens is that its accommodative function relies primarily on the function of the lens capsular bag. However, in most patients, aging or secondary cataracts can cause capsule contraction and hardening, thereby affecting the function of the capsular bag, which in turn seriously affects the accommodative function of this type of intraocular lens. As a result, the actual refractive power adjustment range after surgery is far lower than that of normal people, and it is unable to provide sufficient accommodative power after surgery.
[0004] Cross-linked liquid crystal polymers possess both the anisotropy of liquid crystals and the elasticity of polymer networks, exhibiting excellent stimulus-responsiveness, molecular synergy, and elasticity. They can undergo phase changes in response to a variety of external stimuli, influencing the structure or ordering of the liquid crystal molecules and, consequently, altering the overall macroscopic shape of the material. Through the rational design of their molecular structure and orientation, these materials can be manipulated in response to various stimuli, including light, heat, voltage, magnetic fields, and humidity. This manifests in repeatable, reversible, and wide-ranging strain-driven behaviors, including expansion, contraction, bending, twisting, and vibration. While limited research has been conducted on these materials for the fabrication of adjustable lenses, relevant studies have demonstrated their potential as adaptive optical elements, primarily leveraging their temperature response to adjust lens focal length. However, the temperature response threshold of 100°C for currently studied liquid crystal polymers presents challenges for in vivo applications. Compared to temperature response, light response is more readily implemented and more precisely controlled.
[0005] Therefore, it is particularly necessary and urgent to simulate the structural characteristics and regulatory mechanism of the human eye lens and develop a light-responsive accommodative artificial lens. Summary of the Invention
[0006] In order to solve the above-mentioned technical problems existing in the prior art, the present invention provides a method for preparing an accommodative intraocular lens driven by visible light / sunlight. The accommodative intraocular lens prepared by this method adopts a light-driven driving mode, which does not rely on the mechanical action of the intraocular capsular bag and ciliary muscle, and can avoid age-related changes in the ciliary muscle and postoperative capsular bag sclerosis and fibrosis that affect the lens's accommodation function.
[0007] To achieve the above objectives, the present invention provides a method for preparing an accommodative intraocular lens driven by visible light / sunlight, which comprises the following steps:
[0008] 1) mixing a polymerizable bifunctional liquid crystal monomer and a polymerizable bifunctional non-liquid crystal monomer in a molar ratio of 80:20 to 70:30 to obtain a mixture;
[0009] 2) injecting the mixture obtained in step 1) into a mold, thermally curing the mixture under heating conditions, and demolding the mixture after curing to obtain a temperature-responsive liquid crystal polymer, wherein the mold cavity is in the shape of an intraocular lens that conforms to ergonomics;
[0010] 3) Laminating two sheets of the temperature-responsive liquid crystal polymer prepared in step 2), uniformly coating the space between the two laminated layers with a photothermal conversion material, and photocuring the layers under light to obtain a visible light / sunlight-driven accommodative intraocular lens.
[0011] As a further preferred technical solution of the present invention, the polymerizable bifunctional liquid crystal monomer in step 1) is one or more of the compounds represented by the following molecular structural formulas 1-4:
[0012]
[0013] Where R is n is a positive integer from 1 to 12;
[0014] The polymerizable bifunctional non-liquid crystal monomer in step 1) is a compound represented by the following molecular structural formula 5:
[0015]
[0016] Wherein, n is a positive integer from 4 to 23.
[0017] As a further preferred technical solution of the present invention, a thiol monomer, a free radical photoinitiator, a catalyst and a cross-linking agent are further added to the mixture in step 1), wherein the added mass fraction of the thiol monomer is 12%-20%, the added amounts of the photoinitiator and the catalyst are 0.2%-2% of the total mass of the mixture, respectively, and the added amount of the cross-linking agent accounts for 10%-20% of the total molecular weight of the mixture.
[0018] As a further preferred technical solution of the present invention, the thiol monomer is a compound represented by the following molecular structural formula 6:
[0019]
[0020] Wherein, n is a positive integer from 1 to 12.
[0021] As a further preferred technical solution of the present invention, the free radical photoinitiator is benzil dimethyl ether, and the catalyst is triethylamine.
[0022] As a further preferred technical solution of the present invention, the cross-linking agent is pentaerythritol tetrakis-3-mercaptopropionate.
[0023] As a further preferred technical solution of the present invention, the thermal curing in step 2) is carried out in an oven at a temperature of 70-100° C. and a curing time of 8-24 hours.
[0024] As a further preferred technical solution of the present invention, the photothermal conversion material is one or a mixture of several of azobenzene derivatives, carbon-based photothermal conversion agents, metal nanomaterials, and organic dyes.
[0025] As a further preferred technical solution of the present invention, the photothermal conversion material is CuS nanoparticles, and the concentration of the CuS nanoparticle solution is 0.005-0.5 mg / ml.
[0026] As a further preferred technical solution of the present invention, the specific operations in step 3) include:
[0027] 3.1) Coating one side of each of the two temperature-responsive liquid crystal polymers prepared in step 2) with a photothermal conversion material. After the photothermal conversion material is dried, the two temperature-responsive liquid crystal polymers are laminated together, with the side coated with the photothermal conversion material serving as the laminating surface, so that the coated photothermal conversion material is sandwiched between the two layers.
[0028] 3.2) mechanically stretching the two sheets of temperature-responsive liquid crystal polymer bonded together to 120-150% of their original length;
[0029] 3.3) When the wavelength is 350-365nm and the intensity is 10-30mW / cm 2 The photocuring is carried out under light with a polymerization time of 0.2-3 hours to obtain an accommodative intraocular lens driven by visible light / sunlight.
[0030] The method for preparing the visible light / sunlight driven accommodative intraocular lens of the present invention can achieve the following beneficial effects by adopting the above technical solution:
[0031] 1) The accommodating intraocular lens prepared by the present invention is driven by light, which does not rely on the mechanical action of the intraocular capsular bag or ciliary muscle. This can avoid the effects of age-related changes in the ciliary muscle and postoperative capsular bag sclerosis and fibrosis that affect the lens's accommodation function. Compared with electric drive, sunlight is a directly accessible clean energy source that is less harmful to materials and the human body and avoids risks such as leakage, making it an ideal drive method.
[0032] 2) The liquid crystal polymer material used in the present invention possesses the anisotropy of liquid crystals. Under external field stimulation, the orientation of the liquid crystal molecules changes, which manifests as a change in refractive index. The coordinated movement of the liquid crystal molecules also manifests as a macroscopic change in shape. This dual effect allows the accommodative intraocular lens to provide a wider focal length adjustment range, meeting the patient's vision needs at all distances.
[0033] 3) The accommodative intraocular lens prepared by the present invention is a photodeformable intraocular lens material, which is completely controlled by light and does not require the intervention of any batteries, motors, or gears. Products made of this material can be easily miniaturized and can be implanted into the eye through a smaller incision, causing little trauma to the eye, meeting the requirements of minimally invasive surgery, and facilitating the patient's postoperative recovery. It is a safe and effective intraocular lens material for the human body. BRIEF DESCRIPTION OF THE DRAWINGS
[0034] The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
[0035] Figure 1 This is a comparison chart of the imaging performance of the samples prepared in Example 5 under light driving;
[0036] Figure 2 The stress-strain curves of the samples prepared in Examples 1-5 are shown;
[0037] Figure 3 Spectral transmittance curves of the samples prepared in Examples 5-8;
[0038] Figure 4 The photothermal effect curves of the samples prepared in Examples 5-8 are shown;
[0039] Figure 5 The photoinduced deformation curves of the samples prepared in Examples 5-8;
[0040] The purpose, features and advantages of the present invention will be further described with reference to the accompanying drawings and in conjunction with the embodiments. DETAILED DESCRIPTION
[0041] The present invention will be further described below with reference to the accompanying drawings and specific embodiments. Terms such as "upper," "lower," "left," "right," "center," and "one" used in the preferred embodiments are for ease of description and are not intended to limit the scope of the present invention. Changes or adjustments to these relative terms, without substantially altering the technical content, are also considered within the scope of the present invention.
[0042] By combining a photothermal conversion material with a temperature-responsive liquid crystal polymer, this invention achieves visible light / sunlight-driven changes in the shape and focal length of an intraocular lens, thereby meeting patients' vision needs at all distances. The degree of deformation of the intraocular lens can be adjusted by controlling the intensity of the visible light / sunlight and the concentration of the nanoparticles, enabling personalized customization of the intraocular lens. The present method for preparing an accommodative intraocular lens driven by visible light / sunlight is expected to play an important role in the treatment of cataracts and presbyopia.
[0043] In order to enable those skilled in the art to further understand the technical solution of the present invention, the technical solution of the present invention is further described in detail below by way of examples.
[0044] The following embodiments all take CuS nanoparticles as the photothermal conversion material.
[0045] Example 1
[0046] This embodiment prepares an accommodative intraocular lens driven by visible light / sunlight, and the preparation method thereof includes the following steps:
[0047] (1) preparing a liquid crystal mixture: taking 1,4-bis-[4-(6-acryloyloxyhexyloxy)benzoyloxy]-2-methylbenzene (C6M) and polyethylene glycol diacrylate (PEGDA) in a molar ratio of 80:20, and then taking 19% of 6-dioxa-1,8-octanedithiol, 9% of pentaerythritol tetrakis-3-mercaptopropionate, 0.5% of benzil dimethyl ether, and 0.5% of triethylamine by mass, and mixing and stirring to obtain a mixture;
[0048] (2) After the mixture is thoroughly stirred, it is injected into a mold with an intraocular lens structure as the mold cavity, and then the mold is transferred to a 100°C oven to thermally cure the mixture for 12 hours.
[0049] (3) The temperature-responsive liquid crystal polymer formed in the mold was taken out, and a CuS nanoparticle solution with a concentration of 0.05 mg / ml was coated on one surface of the polymer, and the polymer was placed in an environment of 70° C. for drying.
[0050] (4) Two layers of temperature-responsive liquid crystal polymer coated with CuS nanoparticle solution that have been dried are bonded together and then mechanically stretched with the aid of a clamp to 150% of the original length in the horizontal direction. The film is then stretched at 365 nm and 13 mW / cm 2 The film was photocured under ultraviolet light for 1 hour to obtain an accommodative intraocular lens (also known as a liquid crystal lens) driven by visible light / sunlight.
[0051] Example 2
[0052] This embodiment prepares an accommodative intraocular lens driven by visible light / sunlight, and the preparation method thereof includes the following steps:
[0053] (1) Prepare a liquid crystal mixture: 1,4-bis-[4-(6-acryloyloxyhexyloxy)benzoyloxy]-2-methylbenzene (C6M) and polyethylene glycol diacrylate (PEGDA) in a molar ratio of 77:23, and 19% of 6-dioxa-1,8-octanedithiol, 9% of pentaerythritol tetrakis-3-mercaptopropionate, 0.5% of benzil dimethyl ether, and 0.5% of triethylamine, by mass percentage, are mixed and stirred to obtain a mixture.
[0054] (2) After the mixture is thoroughly stirred, it is injected into a mold with an intraocular lens structure as the mold cavity, and then the mold is transferred to a 100°C oven for thermal curing for 12 hours.
[0055] (3) The temperature-responsive liquid crystal polymer formed in the mold was taken out, and a CuS nanoparticle solution with a concentration of 0.05 mg / ml was coated on one surface of the polymer, and the polymer was placed in an environment of 70° C. for drying.
[0056] (4) Two layers of temperature-responsive liquid crystal polymer coated with CuS nanoparticle solution that have been dried are attached to each other and then mechanically stretched with the aid of a clamp to 150% of the original length in the horizontal direction. The film is then stretched at 365 nm and 13 mW / cm 2 Light cure under UV light for 1 hour.
[0057] Example 3
[0058] This embodiment prepares an accommodative intraocular lens driven by visible light / sunlight, and the preparation method thereof includes the following steps:
[0059] (1) preparing a liquid crystal mixture: mixing 1,4-bis-[4-(6-acryloyloxyhexyloxy)benzoyloxy]-2-methylbenzene (C6M) and polyethylene glycol diacrylate (PEGDA) in a molar ratio of 72:28, and, by mass percentage, 19% of 6-dioxa-1,8-octanedithiol, 9% of pentaerythritol tetrakis-3-mercaptopropionate, 0.5% of benzil dimethyl ether, and 0.5% of triethylamine, and stirring to obtain a mixture;
[0060] (2) The mixture was thoroughly stirred and injected into a mold with an intraocular lens structure as the mold cavity, and then the mold was transferred to a 100°C oven for thermal curing for 12 hours.
[0061] (3) The temperature-responsive liquid crystal polymer formed in the mold was taken out, and a CuS nanoparticle solution with a concentration of 0.05 mg / ml was coated on its surface, and the polymer was placed in an environment of 70° C. for drying.
[0062] (4) Two layers of temperature-responsive liquid crystal polymer coated with CuS nanoparticle solution that have been dried are attached to each other and then mechanically stretched with the aid of a clamp to 150% of the original length in the horizontal direction. The film is then stretched at 365 nm and 13 mW / cm 2 Light cure under UV light for 1 hour.
[0063] Example 4
[0064] This embodiment prepares an accommodative intraocular lens driven by visible light / sunlight, and the preparation method thereof includes the following steps:
[0065] (1) preparing a liquid crystal mixture: 1,4-bis-[4-(6-acryloyloxyhexyloxy)benzoyloxy]-2-methylbenzene (C6M) and polyethylene glycol diacrylate (PEGDA) were mixed in a molar ratio of 70:30, and 19% of 6-dioxa-1,8-octanedithiol, 9% of pentaerythritol tetrakis-3-mercaptopropionate, 0.5% of benzil dimethyl ether, and 0.5% of triethylamine were mixed by mass percentage, and stirred to obtain a mixture;
[0066] (2) The mixture was thoroughly stirred and injected into a mold with an intraocular lens structure as the mold cavity, and then the mold was transferred to a 100°C oven for thermal curing for 12 hours.
[0067] (3) The temperature-responsive liquid crystal polymer formed in the mold was taken out, and a CuS nanoparticle solution with a concentration of 0.05 mg / ml was coated on one surface of the polymer, and the polymer was placed in an environment of 70° C. for drying.
[0068] (4) Two layers of dried temperature-responsive liquid crystal polymer coated with CuS nanoparticle solution were attached to each other, and the coated photothermal conversion material was sandwiched between the two layers. The two layers were then mechanically stretched with the aid of a clamp, stretched horizontally to 150% of the original length, and the wavelength was 13 mW / cm at 365 nm. 2 The film is cured under ultraviolet light for 1 hour to obtain an accommodative intraocular lens driven by visible light / sunlight, also known as a liquid crystal lens.
[0069] Example 5
[0070] This embodiment prepares an accommodative intraocular lens driven by visible light / sunlight, and the preparation method thereof includes the following steps:
[0071] (1) preparing a liquid crystal mixture: mixing 1,4-bis-[4-(6-acryloyloxyhexyloxy)benzoyloxy]-2-methylbenzene (C6M) and polyethylene glycol diacrylate (PEGDA) in a molar ratio of 75:25, and, by mass percentage, 19% of 6-dioxa-1,8-octanedithiol, 9% of pentaerythritol tetrakis-3-mercaptopropionate, 0.5% of benzil dimethyl ether, and 0.5% of triethylamine, and stirring to obtain a mixture;
[0072] (2) The mixture was thoroughly stirred and injected into a mold with an intraocular lens structure as the cavity, and then the mold was transferred to a 100°C oven for thermal curing for 12 hours.
[0073] (3) The temperature-responsive liquid crystal polymer formed in the mold was taken out, and a CuS nanoparticle solution with a concentration of 0.05 mg / ml was coated on its surface, and the polymer was placed in an environment of 70° C. for drying.
[0074] (4) Two layers of temperature-responsive liquid crystal polymer coated with CuS nanoparticle solution that have been dried are attached to each other and then mechanically stretched with the aid of a clamp to 150% of the original length in the horizontal direction. The film is then stretched at 365 nm and 13 mW / cm 2 Light cure under UV light for 1 hour.
[0075] The samples prepared in Examples 1-5 were tested as follows:
[0076] Figure 1 This is a macroscopic display of the imaging performance of the sample prepared in Example 5 under light drive, and the grid size is observed through the product of Example 5 under the conditions of visible light illumination and the conditions of removing visible light illumination.
[0077] The sample of Example 5 was placed in front of a standard-sized grid paper, and the convex surface of the sample was irradiated with sunlight of different intensities to observe its deformation process and the change in the size of the grid paper below. The results are as follows: Figure 1As shown, under illumination conditions, the sample can shrink along the long axis direction, and the degree of convexity of the front surface also increases accordingly. The grid size visible through the optical center area increases and the grid clarity decreases. After the illumination is stopped, the sample can return to its original shape. The grid size and clarity visible through the optical center area also return to their initial size, and its degree of deformation can increase with increasing illumination intensity. Because the photothermal conversion material coated on the surface of the liquid crystal polymer can absorb visible light / sunlight to generate heat, and conduct the heat to the entire liquid crystal polymer, the liquid crystal polymer in the shape of a convex lens undergoes a phase transition behavior, changes in shape, increases in surface curvature, increases in refractive power, and magnifies the real image. Due to the change in focal length, the real image becomes blurred. After the illumination is removed, the liquid crystal polymer gradually cools and returns to its initial shape. The same tests were performed on the samples of Examples 1-4, respectively, and the same effects were obtained, which shows that the accommodative intraocular lens of the present invention achieves focal length adjustment under visible light or sunlight.
[0078] According to relevant national standards, the samples prepared in Examples 1-5 were cut into long strips using a cutter of standard size. The samples were clamped on a special fixture of a tensile machine at a stretching speed of 5.00 mm / min. The data was transmitted to a computer via a pressure sensor. The tensile stress-strain curve of each sample during the tensile deformation process was recorded, and the characteristic points on the curve were calculated to obtain the elongation at break. The results are shown in FIG. Figure 2 As shown in the figure, the ratio of C6M:PEGDA corresponding to each curve is the molar ratio of 1,4-bis-[4-(6-acryloyloxyhexyloxy)benzoyloxy]-2-methylbenzene (C6M) and polyethylene glycol diacrylate (PEGDA) in each example of Examples 1-5. Figure 2 Comparative analysis of the various curves reveals that varying the molar ratio of the bifunctional liquid crystal monomer to the non-liquid crystal monomer within the temperature-responsive liquid crystal polymer increases the proportion of non-liquid crystal monomer, leading to improved mechanical properties and a corresponding increase in elongation at break. Compared to currently commercially available intraocular lens materials, this material exhibits improved mechanical properties. Its higher elongation at break reflects its greater flexibility, toughness, and elasticity. This allows it to be folded and implanted into the eye through a smaller incision during implantation, allowing it to unfold quickly and freely within the eye, facilitating minimally invasive surgery.
[0079] Example 6
[0080] This embodiment prepares an accommodative intraocular lens driven by visible light / sunlight, and the preparation method thereof includes the following steps:
[0081] (1) C6M and polyethylene glycol diacrylate were mixed in a molar ratio of 75:25, and 19% of 6-dioxa-1,8-octanedithiol, 9% of pentaerythritol tetrakis-3-mercaptopropionate, 0.5% of benzil dimethyl ether, and 0.5% of triethylamine were mixed by mass to obtain a mixture;
[0082] (2) The mixture was thoroughly stirred and injected into a mold with an intraocular lens structure as the cavity, and then the mold was transferred to a 100°C oven for thermal curing for 12 hours.
[0083] (3) The temperature-responsive liquid crystal polymer formed in the mold was taken out, and a CuS nanoparticle solution with a concentration of 0.005 mg / ml was coated on its surface, and the polymer was placed in an environment of 70° C. for drying.
[0084] (4) Two layers of temperature-responsive liquid crystal polymer coated with CuS nanoparticle solution that have been dried are attached to each other and then mechanically stretched with the aid of a clamp to 150% of the original length in the horizontal direction. The film is then stretched to 13 mW / cm at 365 nm. 2 Light cure under UV light for 1 hour.
[0085] Example 7
[0086] This embodiment prepares an accommodative intraocular lens driven by visible light / sunlight, and the preparation method thereof includes the following steps:
[0087] (1) C6M: polyethylene glycol diacrylate in a molar ratio of 75:25, and 19% of 6-dioxa-1,8-octanedithiol, 9% of pentaerythritol tetrakis-3-mercaptopropionate, 0.5% of benzil dimethyl ether, and 0.5% of triethylamine, by mass percentage, were mixed and stirred to obtain a mixture;
[0088] (2) The mixture was thoroughly stirred and injected into a mold with an intraocular lens structure as the cavity, and then the mold was transferred to a 100°C oven for thermal curing for 12 hours.
[0089] (3) The temperature-responsive liquid crystal polymer formed in the mold was taken out, and a CuS nanoparticle solution with a concentration of 0.1 mg / ml was coated on its surface, and the mixture was placed in an environment of 70° C. for drying.
[0090] (4) Two layers of temperature-responsive liquid crystal polymer coated with CuS nanoparticle solution that have been dried are attached to each other and then mechanically stretched with the aid of a clamp to 150% of the original length in the horizontal direction. The film is then stretched to 13 mW / cm at 365 nm. 2 Light cure under UV light for 1 hour.
[0091] Example 8
[0092] This embodiment prepares an accommodative intraocular lens driven by visible light / sunlight, and the preparation method thereof includes the following steps:
[0093] (1) C6M: polyethylene glycol diacrylate in a molar ratio of 75:25, and 20% of 6-dioxa-1,8-octanedithiol, 8% of pentaerythritol tetrakis-3-mercaptopropionate, 0.5% of benzil dimethyl ether, and 0.5% of triethylamine, calculated by mass percentage, were mixed to obtain a mixture;
[0094] (2) The mixture was thoroughly stirred and injected into a mold with an intraocular lens structure as the cavity, and then the mold was transferred to a 100°C oven for thermal curing for 12 hours.
[0095] (3) The temperature-responsive liquid crystal polymer formed in the mold was taken out, and a CuS nanoparticle solution with a concentration of 0.2 mg / ml was coated on its surface, and the mixture was placed in an environment of 70° C. for drying.
[0096] (4) Two layers of temperature-responsive liquid crystal polymer coated with CuS nanoparticle solution that have been dried are attached to each other and then mechanically stretched with the aid of a clamp to 150% of the original length in the horizontal direction. The film is then stretched to 13 mW / cm at 365 nm. 2 Light cure under UV light for 1 hour.
[0097] For an efficient light-driven system, photothermal effect and light-driven behavior are the most important features. Unlike traditional photothermal drive systems, the samples prepared by the present invention have the following advantages. First, this material exhibits a more significant photothermal effect. As the light intensity or nanoparticle concentration increases, the surface temperature rises sharply, and a large deformation can be produced within the temperature and light intensity range that the human body can tolerate. Second, this material can work under visible light and sunlight, rather than ultraviolet or near-infrared light used by most light drivers, which is more friendly to biological use. Based on the above characteristics, the samples prepared in Examples 5-8 were tested as follows:
[0098] The spectral transmittance of the samples prepared in Examples 5-8 at 37°C was measured using an ultraviolet-visible-near infrared spectrophotometer. The results are as follows: Figure 3 As shown, the curves in the figure are differentiated based on the different concentrations of the CuS nanoparticle solutions in Examples 5-8. Comparative analysis shows that when the molar ratio of the bifunctional liquid crystal monomer to the non-liquid crystal monomer in the temperature-responsive liquid crystal polymer is fixed at 75:25, the spectral transmittance of the prepared samples gradually decreases with increasing concentrations of the applied CuS nanoparticles. Good optical transparency is a fundamental requirement for implantable intraocular lens materials. When coated with a relatively low concentration of the photothermal conversion material, the samples prepared by the present invention achieve a spectral transmittance of 80% in the visible light band, meeting the requirements for lens materials.
[0099] The samples prepared in Examples 5-8 were irradiated with light sources of different intensities emitted by a solar simulator for 60 seconds. The temperature on the accommodative intraocular lens was measured by an infrared thermal imager. The surface temperature change was recorded as shown in the figure. Figure 4 As shown in the figure, the curves are differentiated according to the different concentrations of the CuS nanoparticle solutions in Examples 5-8. A comparative analysis shows that when the molar ratio of the bifunctional liquid crystal monomer to the non-liquid crystal monomer in the temperature-responsive liquid crystal polymer is fixed at 75:25, the sample temperature increases with increasing light intensity at the same CuS nanoparticle concentration. At the same light intensity, the temperature of the prepared samples gradually increases with increasing concentration of the coated CuS nanoparticles.
[0100] The samples prepared in Examples 5-8 were irradiated with light sources of different intensities emitted by a solar simulator for 60 seconds, and the deformation before and after irradiation was measured using a vernier caliper. The results are shown in the figure. Figure 5 As shown, the curves in the figure are differentiated according to the different concentrations of the CuS nanoparticle solutions in Examples 5-8. A comparative analysis shows that when the molar ratio of the bifunctional liquid crystal monomer to the non-liquid crystal monomer in the temperature-responsive liquid crystal polymer is fixed at 75:25, the deformation increases with increasing light intensity at the same CuS nanoparticle concentration. At the same light intensity, the deformation of the prepared sample increases with increasing the concentration of the coated CuS nanoparticles.
[0101] CuS nanoparticles are black and water-soluble, while liquid crystal polymer materials are oil-soluble. If they are directly incorporated into the system of the present invention or high concentrations of nanoparticles are used, phase separation is difficult to avoid, resulting in light scattering that affects the overall optical properties of the material. On the one hand, the product prepared by the present invention has a high photothermal effect, such as Figure 4-5 As shown in the figure, a significant temperature change can be generated under low light intensity, thereby driving the material to undergo considerable deformation. On the other hand, the present invention adopts a method of coating a CuS nanoparticle solution to combine it with a liquid crystal matrix, which ensures the photothermal effect while also avoiding the occurrence of phase separation in the system, thereby reducing the influence of photothermal molecules on the overall optical performance of the lens to a certain extent. Figure 3 As shown, the product prepared by the present invention still achieves a spectral transmittance of 70%-80% in the visible light band, demonstrating high optical transparency. Therefore, comprehensive consideration and analysis indicate that a lower concentration of CuS nanoparticles can achieve the objectives of the present invention, with a solution concentration of 0.005-0.5 mg / ml being the preferred concentration.
[0102] Although specific embodiments of the present invention are described above, those skilled in the art should understand that these are merely examples and that various changes or modifications may be made to the embodiments without departing from the principles and essence of the present invention. The scope of protection of the present invention is limited only by the appended claims.
Claims
1. A method for preparing an accommodative intraocular lens driven by visible light / sunlight, characterized in that: The following steps are involved: 1) mixing a polymerizable bifunctional liquid crystal monomer and a polymerizable bifunctional non-liquid crystal monomer in a molar ratio of 80:20 to 70:30 to obtain a mixture; The polymerizable bifunctional liquid crystal monomer in step 1) is one or more of the compounds represented by the following molecular structural formulas 1-4: ; Where R is , n is a positive integer from 1 to 12; The polymerizable bifunctional non-liquid crystal monomer in step 1) is a compound represented by the following molecular structural formula 5: ; Wherein, n is a positive integer from 4 to 23; The mixture of step 1) is further added with a thiol monomer, a free radical photoinitiator, a catalyst, and a crosslinking agent, wherein the added mass fraction of the thiol monomer is 12%-20%, the added amounts of the photoinitiator and the catalyst are 0.2%-2% of the total mass of the mixture, respectively, and the added amount of the crosslinking agent accounts for 10%-20% of the total molecular weight of the mixture; The thiol monomer is a compound represented by the following molecular structural formula 6: Wherein, n is a positive integer from 1 to 12; The free radical photoinitiator is benzil dimethyl ether, and the catalyst is triethylamine; The cross-linking agent is pentaerythritol tetrakis-3-mercaptopropionate; 2) injecting the mixture obtained in step 1) into a mold, thermally curing the mixture under heating conditions, and demolding the mixture after curing to obtain a temperature-responsive liquid crystal polymer, wherein the mold cavity is in the shape of an intraocular lens that conforms to ergonomics; 3) Laminating two sheets of the temperature-responsive liquid crystal polymer prepared in step 2), uniformly coating the space between the two laminated layers with a photothermal conversion material, and photocuring the layers under light to obtain a visible light / sunlight-driven accommodative intraocular lens; The photothermal conversion material is CuS nanoparticles, and the concentration of the CuS nanoparticle solution is 0.005-0.5 mg / ml; The specific operations in step 3) include: 3.1) Take two sheets of temperature-responsive liquid crystal polymer prepared in step 2) and coat one side of each sheet with a photothermal conversion material. After the photothermal conversion material has dried, laminate the two sheets of temperature-responsive liquid crystal polymer using the side coated with the photothermal conversion material as the laminating surface, so that the coated photothermal conversion material is sandwiched between the two layers. 3.2) Mechanically stretching the two bonded sheets of temperature-responsive liquid crystal polymer to 120-150% of their original length; 3.3) When the wavelength is 350-365nm and the intensity is 10-30 mW / cm 2 The photocuring is carried out under light with a polymerization time of 0.2-3 hours to obtain an accommodative intraocular lens driven by visible light / sunlight.
2. The method for preparing the visible light / sunlight driven accommodative intraocular lens according to claim 1, characterized in that: The thermal curing in step 2) is carried out in an oven at a temperature of 70-100°C and a curing time of 8-24 hours.
Citation Information
Patent Citations
Acrylic acid ester shape-memory intraocular lens material and preparation method thereof
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Method for realizing rapid curing of powder coating by using photothermal effect
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