CN100455276C - Preparation method of intraocular lens coated with titanium dioxide-based nano film layer on surface - Google Patents
Preparation method of intraocular lens coated with titanium dioxide-based nano film layer on surface Download PDFInfo
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- CN100455276C CN100455276C CNB2006100188020A CN200610018802A CN100455276C CN 100455276 C CN100455276 C CN 100455276C CN B2006100188020 A CNB2006100188020 A CN B2006100188020A CN 200610018802 A CN200610018802 A CN 200610018802A CN 100455276 C CN100455276 C CN 100455276C
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Abstract
本发明涉及一种表面涂覆二氧化钛基纳米薄膜层的人工晶状体的制备方法，它包括以下制备步骤：先在二氧化钛溶胶中加入贵金属组分中的一种获得二氧化钛光催化剂溶胶；接着采用提拉或浸渍或喷涂技术将二氧化钛光催化剂溶胶在人工晶状体表面制备出二氧化钛光催化剂纳米薄膜；最后通过等离子体射频工艺使涂覆在人工晶状体表面的二氧化钛光催化剂纳米薄膜成为透明的二氧化钛基纳米薄膜，获得表面涂覆二氧化钛基纳米薄膜层的人工晶状体。本发明可制备出表面涂覆二氧化钛基纳米薄膜的人工晶状体，该人工晶状体在植入摘除白内障后的晶状体囊袋内后，可利用二氧化钛光催化剂对细胞增殖的抑制和氧化作用来抑制晶状体上皮细胞增殖。The invention relates to a preparation method of an intraocular lens coated with a titanium dioxide-based nano film layer on the surface, which comprises the following preparation steps: first adding one of the noble metal components to the titanium dioxide sol to obtain the titanium dioxide photocatalyst sol; then using pulling or The titanium dioxide photocatalyst sol is prepared on the surface of the intraocular lens by dipping or spraying technology to prepare a titanium dioxide photocatalyst nano-film; finally, the titanium dioxide photocatalyst nano-film coated on the surface of the intraocular lens is turned into a transparent titanium dioxide-based nano-film by plasma radio frequency technology, and the surface Intraocular lenses coated with titania-based nanofilm layers. The invention can prepare an intraocular lens coated with a titanium dioxide-based nano-film on the surface. After the intraocular lens is implanted into the lens capsular bag after cataract removal, the inhibition and oxidation of the cell proliferation by the titanium dioxide photocatalyst can be used to inhibit the lens epithelial cells. proliferation.
Description
Technical field
The present invention relates to a kind of process for manufacturing intraocular lenses of surface-coated titanium dioxide base nano thin layer, a kind of specifically extract cataract by modus operandi after, be implanted into surface-coated one deck in lens capsule bag simultaneously and have the intraocular lens of titanium deoxid film of photocatalysis to reduce the method that after cataract takes place.
Background technology
Cataract is that crystalline lens takes place muddyly to become opaquely by transparent in the eyes, hinders light and enters ophthalmic, thereby affect one's power of vision even cause losing one's sight, and be the main disease of blinding.At present the effective method of treatment cataract is the crystalline lens by the surgical removal muddiness, and the implantable artificial crystalline lens, to obtain the rehabilitation of vision.But 20～50% adult patient is arranged approximately, 100% teenager, child patient postcataract three months to four in the period of, because of epithelial cell proliferation residual or newborn in the lens capsule bag, and migrate on the cyst membrane of back, form opaque coating, be posterior capsule opacification (PCO), also be referred to as after cataract.It is the long term complication that postcataract affects one's power of vision and recover most, also is the cataract blind person postoperative main cause of blinding again.
At present, the control after cataract, reduce again the method that the blinding factor adopted and have (1) to improve surgical condition, improve the operation quality; (2) use the medicine that various block cells are bred; (3) gene therapy, gene antisense technology, suicide gene, gene transfection etc.; (4) improve artificial crystalline lens material and shape and the intraocular lens surface modified.These methods are mainly based on reduce residual lens epithelial cells (LEC) and cortex by operation as far as possible, prevent hypertrophy, migration and extracellular matrix synthetic of residual LEC by medicine.But because the ophthalmic toxicity is obvious, poor specificity, or curative effect not high still can not safe and effectively be applied to so far clinical.Thereby how thoroughly to remove LEC, and remove the material base of hyperplasia, be the approaches and methods that fundamentally prevents PCO.
Photodynamic therapy (PDT) is to play the method for therapeutical effect by the optical excitation chemistry photosensitizer (medicine) of a certain wavelength.It mainly is to excite by the molecular energy transfer process to produce high activity singlet oxygen system, finally produces enough oxygen species with cytotoxicity, and causes tissue necrosis.This method has been applied to tumor treatment such as skin, esophagus, bladder, bronchus, lungs.Also have the scholar to be applied to the research of PCO treatment, Yasmine etc. study the removal of LEC in the capsule bag with Bacteriochlorin A (BCA) light dynamic method, and confirm that by experiment in vitro the propagation of LEC can be suppressed fully under certain condition.And Hyoung etc. treat PCO with rose-bengal (Rose Bengal) as photosensitizer, and zoopery proves that this photosensitizer can effectively kill and wound the LEC of rabbit, can reduce the incidence rate of lagophthalmos PCO.But conjunctival congestion, edema all take place in these methods, incision corneal edema and slight iritis, even there is genotoxic potential in the corneal inner cortex.Therefore, can the feasibility of this technology find a kind of safer and more effective material to substitute photosensitizer with regard to being to a great extent, to reduce or eliminate the toxicity to eye.
Photocatalysis is one of the most active chemical research of recent two decades field, in numerous photocatalysts, and quasiconductor titanium dioxide (TiO
2) to have chemical property stable, acidproof, alkaline-resisting because of it, excellent biological compatibility, characteristics such as harmless and become optimal photocatalyst.Recent study also shows, TiO
2Can effectively kill tumor cell, thereby photocatalyst TiO
2Might be used to prevent and treat PCO as the substitute of photosensitizer.
Summary of the invention
In order to solve the existing problem of present photodynamic therapy after cataract, the invention provides a kind of process for manufacturing intraocular lenses of surface-coated titanium dioxide base nano thin layer, its objective is in conjunction with the characteristics of titanium dioxide optical catalyst and under illumination, make the action principle of biomolecule inactivation even oxidation Decomposition, by the inventive method at the transparent titanium dioxide base nano thin film of intraocular lens's surface-coated last layer, after in the lens capsule bag of this intraocular lens being implanted after extracing cataract, can utilize the inhibitory action of titanium dioxide optical catalyst thin film on cell proliferation and Oxidation to reach the effect that suppresses proliferation of lens epithelial cells.
Technical scheme of the present invention is as follows:
A kind of process for manufacturing intraocular lenses of surface-coated titanium dioxide base nano thin layer is characterized in that, comprises following preparation process:
(1) elder generation with the hydrolysis of alkoxide of titanium, obtains the colloidal sol of homogeneous transparent under the condition of acid pH＜5, regulates pH value to 2～5 of this colloidal sol afterwards by dialysis, obtains the TiO 2 sol that needs; Then add a kind of to prepare the titanium dioxide optical catalyst colloidal sol that natural light is had certain Absorption in the noble metal component with the form of chlorate or metal-sol in the TiO 2 sol that makes, the control addition is to guarantee not gel of TiO 2 sol during adding;
(2) utilize the titanium dioxide optical catalyst colloidal sol of step (1) preparation, adopt to lift or flood or spray or other technology goes out the titanium dioxide optical catalyst nano thin-film in intraocular lens's surface preparation;
(3) surface-coated being had the intraocular lens of titanium dioxide optical catalyst nano thin-film put into radio-frequency (RF) plasma generator, is 99.999% O with purity
2Radio frequency plasma, radio-frequency power is 20～80W, vacuum is 20～60Pa, processing time is 5～120min, then soak 24h～72h with deionized water, at last at 80 ℃ or be lower than under 80 ℃ the temperature and dried 2～48 hours, drying time and bake out temperature are inversely proportional to, make the titanium dioxide optical catalyst nano thin-film that is coated in the intraocular lens surface become transparent titanium dioxide base nano thin film, finally obtain the intraocular lens of surface-coated titanium dioxide base nano thin layer.
The further improvement of such scheme is: step (2) is before intraocular lens's surface preparation goes out transparent titanium dioxide optical catalyst nano thin-film, adopt sulfonation method or plasma technique that pretreatment is carried out on intraocular lens's surface earlier, to improve surface hydrophilicity.
The intraocular lens's of above-mentioned surface-coated titanium dioxide base nano thin layer purposes is: the intraocular lens of described surface-coated titanium dioxide base nano thin layer, can be used for implanting and extractd in the lens capsule bag after the cataract, when the light of suitable wavelength by transparent cornea when pupil directly focuses on intraocular lens surface and the posterior lens capsule face, can excite the catalysis of titanium dioxide optical catalyst nano thin-film, oxidation, decomposition to remain in the epithelial cell on lens capsule bag surface, thereby reach the purpose that prevents that after cataract from taking place.
Effect of the present invention is with superiority: (1) compares TiO with other photosensitizer
2Can not cause leukopenia, the toxicity test also shows TiO
2To the eye nonirritant; (2) TiO
2Thin film has good hydrophilic durability and easy and biocompatible; (3) since crystalline lens at eyeball anatomy and biological particularity, behind diffusing big pupil, crystalline lens can be exposed in the scope of radiation of visible light fully, thereby easily receives the natural light of required wavelength.
The specific embodiment
Concrete technical scheme of the present invention is as follows:
One. the process for manufacturing intraocular lenses of surface-coated titanium dioxide base nano thin layer is characterized in that: comprise intraocular lens and the titanium dioxide base nano thin layer that is coated on the intraocular lens surface.
Two. the process for manufacturing intraocular lenses of surface-coated titanium dioxide base nano thin layer:
(1) preparation of TiO 2 sol and modification thereof
(1) preparation of TiO 2 sol: under the condition of acid pH＜5,, obtain the colloidal sol of homogeneous transparent, regulate pH value to 2～5 of colloidal sol afterwards by dialysis with alkoxide (for example tetraisopropyl titanate, the butyl titanate) hydrolysis of titanium.
(2) modification of TiO 2 sol: add a kind of to prepare the titanium dioxide optical catalyst colloidal sol that natural light is had certain Absorption in a certain amount of Pt or Au or other noble metal component with the form of chlorate or metal-sol in above-mentioned colloidal sol, the control addition is to guarantee not gel of colloidal sol during adding.The solids content of the titanium dioxide in the colloidal sol is 0.1～5.0wt%, and the weight content ratio of Pt or Au and solid titanium dioxide is 10
-4～10
-1
(2) pretreatment of PMMA material surface has two kinds of methods:
(1) sulfonation method: concentrated sulphuric acid and distilled water were closed postcooling in 5: 1 by volume～1: 1, the intraocular lens is immersed in 1s～10s in this solution, take out rapidly then, clean surperficial debris with distilled water, dry back is standby;
(2) Cement Composite Treated by Plasma: the intraocular lens is put into radio-frequency (RF) plasma generator, is 99.999% O with purity
2Radio frequency plasma, radio-frequency power are 20～80W, and vacuum is 20～60Pa, and be standby behind processing 0.5～3min.
(3) preparation method of intraocular lens's surface titanium dioxide based nano film has two kinds
Method one: intraocular lens clean after the surface preparation is immersed through in the TiO 2 sol after the chemical modification, then lift the intraocular lens with certain speed, form a sol pellicle on its surface, be placed in the radio-frequency (RF) plasma generator after thin film dries, use O
2(O
2Purity be 99.999%) radio frequency plasma carries out surface treatment, radio-frequency power is 20～80W, vacuum is 20～60Pa, processing time is that 5～120min is (in this process, by the plasma oxidation effect, and utilize the energy of its generation or localized hyperthermia can obtain suitable titanium dioxide crystal phase structure).After Cement Composite Treated by Plasma finishes, sample is soaked 24～72h with deionized water, then at 80 ℃ or be lower than 80 ℃ of oven dry 2～48 hours down, drying time and bake out temperature are inversely proportional to.Also can adopt dipping or spraying or other technology at intraocular lens's plated film, the intraocular lens behind the plated film carries out post processing by above-mentioned same plasma technique.The intraocular lens who is coated with the titanium dioxide base nano thin film can implant in the usual way and extract in the lens capsule bag after the cataract.
Method two: adopt bionical film technique directly the titanium dioxide precursor solution to be deposited on intraocular lens's surface, be deposit fluid promptly with titanium isopropoxide solution or other organic titanium alkoxide solutions, with polyvinyl alcohol, or Polyethylene Glycol, or other water-soluble, film-forming thing conduct and the interactional bionical organic interface of inorganic ions, be lower than under 90 ℃ the temperature, with pH value is 1～5, and the titanium isopropoxide solution or other organic titanium alkoxide that contain 2～8wt%, and the polyvinyl alcohol of 0.5～5w%, or Polyethylene Glycol, or the alcoholic solution of other water-soluble, film-forming thing, directly by lifting, or dipping, the spraying or other method go out the titanium dioxide active membrane in intraocular lens's surface preparation.
Three, the intraocular lens's of described surface-coated titanium dioxide base nano thin layer purposes is: the intraocular lens of this surface-coated titanium dioxide base nano thin layer, can be used for implanting and extractd in the lens capsule bag after the cataract, when the light of suitable wavelength by transparent cornea when pupil directly focuses on intraocular lens surface and the posterior lens capsule face, can excite the catalysis of titanium dioxide optical catalyst nano thin-film, oxidation, decomposition to remain in the epithelial cell on lens capsule bag surface, thereby reach the purpose that prevents that after cataract from taking place.
The invention will be further described below in conjunction with embodiment.
Embodiment 1: the preparation of TiO 2 sol and chemical modification
Be made into homogeneous solution in the deionized water with 150 milliliters of 1.1 milliliters of concentrated nitric acids (68%) addings, under strong agitation 12.5 milliliters of tetraisopropyl titanates are slowly splashed in the acidic aqueous solution, the suspension that contains white precipitate that hydrolysis obtains continues to stir the colloidal sol that forms homogeneous transparent until the white precipitate dissolving down at 40 ℃.Colloidal sol packed into carry out dialysis with 2 liters of deionized waters in the dialyser bag and handle, changing water to the final pH value of dialysis water every 12 hours is 3.0.Colloidal sol is taken out from dialysis bag, make concentration and be about 2.5% TiO 2 sol.The Au colloidal sol of then getting 100 milliliters of this colloidal sols and 1 milliliter of 1 grams per liter for preparing mixes, and makes Au/TiO
2Colloidal sol.
Embodiment 2: intraocular lens's surface TiO
2The preparation of base nanometer photocatalyst film
Earlier pretreatment is carried out by sulfonation method in the intraocular lens surface, promptly earlier concentrated sulphuric acid and distilled water were mixed postcooling in 2: 1 by volume, then the intraocular lens is immersed in 1s in this solution, take out then, with the debris on the clean surface of distilled water, drying.
Above-mentioned pretreated intraocular lens is put into a silk screen, silk screen is put into the Au/TiO that embodiment 1 makes
2In the colloidal sol, lift out, after drying it is seated in the radio-frequency (RF) plasma generator, use O with the speed of 1cm/min
2(O
2Purity be 99.999%) radio frequency plasma carries out surface treatment, radio-frequency power is 20W, vacuum is 25Pa, the processing time is 20min.After Cement Composite Treated by Plasma finishes, sample is soaked 36h with deionized water,, make and be coated with TiO then at 80 ℃ or be lower than 80 ℃ of down oven dry 4h
2The intraocular lens of photocatalyst film.
According to the preparation process of embodiment 1 and embodiment 2, the change preparation condition can obtain other several groups and be coated with TiO
2Intraocular lens's sample of thin film is shown in Table 1.
Table 1: the modifying artificial crystalline lens sample (adopting sulfonation method that pretreatment is carried out on the intraocular lens surface) that adopts the different condition preparation
Changing preprocess method, be about to the intraocular lens and put into radio-frequency (RF) plasma generator, is 99.999% O with purity
2Radio frequency plasma, radio-frequency power are 20～80W, and vacuum is 20～60Pa, and be standby behind processing 0.5～3min, adopts different condition can obtain other several groups and be coated with TiO
2Intraocular lens's sample of thin film is shown in Table 2.
Table 2: the modifying artificial crystalline lens sample (the using plasma technology is carried out pretreatment to the intraocular lens surface) that adopts the different condition preparation
Embodiment 3: the cell killing experiment that is coated with the intraocular lens of thin film
Under the aseptic condition, reject buphthalmos muscular tissue, expose clean sclera, be immersed in the normal saline that contains 3.2 ten thousand U/mL gentamycins 1 hour, then with 75% alcohol-pickled 10mins, the aseptic PBS liquid of reuse washes 3 times.Gong Yuan cuts off cornea along the angle, tears iris off, exposes and the intercepting anterior lens capsule, and it is cut into some fragments, places to be added with six orifice plates that 3mL contains the DMEM culture fluid of 20% calf serum, and a glance crystalline peplos is placed a hole.In 37 ℃, contain 5%CO
2Cell culture incubator in leave standstill cultivation, change liquid once after 7-10 days, changed liquid once in later about 3 days.After cultured cells grew up to the Asia and converged in six orifice plates former generation, become single cell suspension with 0.25% trypsinization, went down to posterity, divide with the DMEM culture fluid that contains 20% calf serum and kind go down to posterity in the 75mL culture bottle, changed liquid once in 2-3 days by 1: 2 with 0.02%EDTA.Experiment is chosen 2-5 for lens epithelial cells.Digestion cattle lens epithelial cells is coated with TiO what embodiment 2 made
2The 1st group of intraocular lens's print of thin film and be not coated with TiO
2On intraocular lens's print (autoclaving) of thin film, every adds cattle lens epithelial cells suspension 180 μ L, makes it evenly be covered with slide and don't long outside slide as far as possible, and reduces the error of respectively organizing the creep plate cell concentration as far as possible.After 4-8 hour, add culture fluid 820 μ L, making the culture fluid final volume is 1mL, treats to carry out following three kinds of experiments respectively after cell grows to monolayer.
1.MTT method detects the postradiation cell survival rate of UVA
After cattle lens epithelial cells creep plate (cell grows to monolayer) is carried out on two groups of print surfaces,, as seen be not coated with TiO under the light microscopic through UVA irradiation different time
2Intraocular lens's superficial cell metamorphosis of thin film not clearly is not coated with TiO
2The intraocular lens of thin film, irradiation became circle with regard to most of contraction of visible cell more than 30 minutes, and cell surface has a large amount of blister projections, shows cell death.Two groups of prints are after the identical time of irradiation, and the cell survival rate of two groups of sample surfaces is variant, is coated with TiO
2The cell survival rate of thin film group is lower than and is not coated with TiO
2The cell survival rate of thin film group; Behind illumination 40min, be coated with TiO
2The cell survival rate of thin film group obviously is not coated with TiO
2The blank print of thin film group significantly reduces (seeing table 3 for details).
Table 3MTT method test result
Table 3 result shows, under identical irradiation time, is coated with TiO
2The cell survival rate of thin film group print is not coated with TiO
2Thin film group print low, particularly in light application time during greater than 30min, difference is more unobvious.
2.HE observation of cell form under the staining light microscopic
After cattle lens epithelial cells creep plate (cell grows to monolayer) is carried out on two groups of print surfaces, shine through UVA, illuminating method is all consistent with the MMT method with the time.Be not coated with TiO
2Intraocular lens's superficial cell of thin film is adherent good, is evenly distributed, and cellular morphology is normal, and cell connects closely, and chromatin is evenly distributed, and kernel is obvious, does not all have significant change until 30 minutes cells of irradiation.But shine more than 40 minutes, the visible part cellular morphology change as: cellular contraction, gap increase, and kytoplasm concentrates etc.And be coated with TiO
2In intraocular lens's group of thin film, after not shining, shine 10 minutes, 20 minutes, the cellular morphology on intraocular lens surface is normal substantially, but it is obvious to shine more than 30 minutes cell change: cellular contraction becomes circle, and intercellular substance increases, and karyopyknosis is obvious, do not see kernel, the part after birth breaks, and cell disruption is a fragment, shows to be coated with TiO
2The lip-deep cell death of the intraocular lens of thin film.
3.AO-EB the test of observation of cell form and cell mortality under the staining fluorescence microscope.
After cattle lens epithelial cells creep plate (cell grows to monolayer) is carried out on two groups of print surfaces, shine through UVA, illuminating method is all consistent with the MMT method with the time.Each is organized cell and only shone respectively 20 minutes and 30 minutes.Be not coated with TiO
2Intraocular lens's superficial cell nuclear chromatin of thin film green and is normal configuration.Be coated with TiO
2The most of nuclear chromatins of intraocular lens's superficial cell of thin film salmon pink, the part nuclear structure is normal, part is the pyknosis shape, show the apoptosis and the phenomena of mortality, shine that cell mainly shows as the apoptotic cells form after 20 minutes, shine that the cell overwhelming majority shows as dead cellular morphology after 30 minutes.
The concrete result of variations of its two groups of print superficial cells sees Table 4.
Table 4AO-EB method test result
Table 4 result shows, behind the illumination 20min, is not coated with TiO
2Intraocular lens's superficial cell apoptosis rate 4.3% of thin film; Be coated with TiO
2Intraocular lens's superficial cell apoptosis rate 19.1% of thin film.And behind the illumination 30min, be not coated with TiO
2Intraocular lens's superficial cell mortality rate 56.9% of thin film; Be coated with TiO
2The cell mortality 92.1% of intraocular lens's superficial cell of thin film.
Above-mentioned experimental result shows, under the UVA irradiation, and nano-TiO
2The base optic catalytic agent film has the cell on intraocular lens surface and significantly kills and wounds and inhibitory action.
Embodiment 4: the cell migration experiment
Scribble the TiO that is coated with of cell tissue on the surface that will make by embodiment 2
2The 7th group of intraocular lens's print of thin film and be not coated with TiO
2The blank print of the intraocular lens of thin film carries out cell migration experiment contrast.The cell climbing sheet growth is merged to monolayer, wash twice with PBS, hungry serum (containing 10g/LBSA and volume fraction is the DMEM culture fluid of 1% hyclone) is cultivated about 24h, in the middle of slide, scratch cell with aseptic dropper, the back is washed (removal cell debris) twice with PBS, adds the fresh hungry serum about 3ml, cultivates 24h and 48h, take a picture respectively and compare, with the record of the scale on the eyepiece distance of dividing a word with a hyphen at the end of a line.It the results are shown in Table shown in 5.
Table 5: the experimental result of dividing a word with a hyphen at the end of a line after cell scratches
Table 4 result shows that cell scratched after 48 hours, did not plate TiO
2Thin film group (dividing a word with a hyphen at the end of a line) apart from mean 0.951 be coated with TiO
2The cell migration distance of thin film group (dividing a word with a hyphen at the end of a line apart from mean 0.640) has the significance difference.This illustrates nano-TiO
2Dividing a word with a hyphen at the end of a line of base optic catalytic agent film pair cell can produce certain inhibitory action
Embodiment 5: the hydrophilic test
The compatibility of intraocular lens and organism can be represented that hydrophilic can draw by the height of more static hydrolysis contact angle by its surface hydrophilicity.For this reason, the 4th group of print and the uncoated TiO that embodiment 2 are made
2Blank intraocular lens's print of thin film is through UVA (dominant wavelength 365nm, intensity of illumination 0.5mW/cm
2) activation is after 5 minutes, goes up at OCA20 type contact angle instrument (German Dataphysics Instruments Gmbh-data physical apparatus company) and adopts sessile drop method to measure the contact angle of film surface to water, the volume of water droplet is 5 μ L.The several contact angles of METHOD FOR CONTINUOUS DETERMINATION are averaged then during experiment, and measurement error is ± 2 °.The result is:
Be not coated with TiO
2Intraocular lens's group of thin film: 15.8 ± 2 °;
Be coated with TiO
2The intraocular lens of thin film group: contact angle is little can't be measured to instrument.
The result shows that the intraocular lens's print surface hydrophilicity that is coated with the TiO2 thin film is fine, illustrates that itself and life body have the good compatibility.
Embodiment 6: intraocular lens's surface TiO
2Bionical one-tenth film preparation and performance test thereof
Earlier the intraocular lens is cleaned 2 times～3 times through ultrasonic cleaner in NaOH and acetone soln successively, remove the oils and fats and the dirt on surface, use the vacuum drying oven dry for standby.Add the 3g isopropyl titanate in the 100ml alcoholic solution, 10mL 3～7%PVA aqueous solution adds the dense HNO of dropping 0.1mL
3, in water-bath, be heated to 80 ℃ in the stirring, keep 4h.Then above-mentioned clean intraocular lens speed with 1cm/min in this solution is lifted, make TiO after drying
2Active membrane.
Change isopropyl titanate concentration, pH value, or replace polyvinyl alcohol, make other film forming precursor aqueous solutions, thereby make other TiO on the intraocular lens surface with Macrogol 2000
2Anti-produced film.Totally 4 groups in sample is numbered 13～16.
Above-mentioned sample is carried out cell killing, cell migration and hydrophilic (water droplet contact angle) by the method for embodiment 3, embodiment 4 and embodiment 5 respectively, and contrast with blank sample.Above-mentioned preparation condition and the performance of respectively organizing sample relatively is shown in Table 6.
Table 6 utilizes anti-intraocular lens and the performance thereof that embrane method prepares that generate under different condition
| Test group | The solution pH value | Isopropyl titanate content (wt%) | Film forming matter and content thereof (wt%) | Treatment temperature (℃) | AO-EB method 30min cell mortality (%) | 48h cell migration distance (mm) | The water droplet contact angle (°) |
| 13 | 1 | 2.0 | Polyvinyl alcohol 5.0 | 60 | 95.3±1.70％ | 0.8193±0.1305 | 1.0 |
| 14 | 3 | 8.0 | Polyvinyl alcohol 2.0 | 20 | 93.6±1.80％ | 0.8324±0.1290 | 2.0 |
| 15 | 3 | 4.5 | Polyethylene Glycol 0.5 | 80 | 92.8±1.30％ | 0.8211±0.1305 | 1.0 |
| 16 | 5 | 3.0 | Polyethylene Glycol 2.0 | 60 | 95.1±1.90％ | 0.8308±0.1280 | 0.8 |
Claims (6)
1. the process for manufacturing intraocular lenses of a surface-coated titanium dioxide base nano thin layer is characterized in that, comprises following preparation process:
(1) elder generation with the hydrolysis of alkoxide of titanium, obtains the colloidal sol of homogeneous transparent under the condition of acid pH＜5, regulates pH value to 2～5 of this colloidal sol afterwards by dialysis, obtains the TiO 2 sol that needs; Then add a kind of to prepare the titanium dioxide optical catalyst colloidal sol that natural light is had certain Absorption in the noble metal component with the form of chlorate or metal-sol in the TiO 2 sol that makes, the control addition is to guarantee not gel of TiO 2 sol during adding;
(2) utilize the titanium dioxide optical catalyst colloidal sol of step (1) preparation, adopt to lift or flood or spray or other technology goes out the titanium dioxide optical catalyst nano thin-film in intraocular lens's surface preparation;
(3) surface-coated being had the intraocular lens of titanium dioxide optical catalyst nano thin-film put into radio-frequency (RF) plasma generator, is 99.999% O with purity
2Radio frequency plasma, radio-frequency power is 20～80W, vacuum is 20～60Pa, processing time is 5～120min, then soak 24h～72h with deionized water, at last at 80 ℃ or be lower than under 80 ℃ the temperature and dried 2～48 hours, drying time and bake out temperature are inversely proportional to, make the titanium dioxide optical catalyst nano thin-film that is coated in the intraocular lens surface become transparent titanium dioxide base nano thin film, finally obtain the intraocular lens of surface-coated titanium dioxide base nano thin layer.
2. preparation method according to claim 1, it is characterized in that: step (2) is before intraocular lens's surface preparation goes out transparent titanium dioxide optical catalyst nano thin-film, adopt sulfonation method or plasma technique that pretreatment is carried out on intraocular lens's surface earlier, to improve surface hydrophilicity.
3. preparation method according to claim 1 is characterized in that: the alkoxide of described titanium is tetraisopropyl titanate or butyl titanate.
4. preparation method according to claim 1 is characterized in that: described noble metal component is Pt or Au.
5. preparation method according to claim 4 is characterized in that: in the titanium dioxide optical catalyst colloidal sol that step (1) obtains, the solids content of titanium dioxide is 0.1～5.0wt%, and the weight content ratio of Pt or Au and solid titanium dioxide is 10
-4～10
-1
6. preparation method according to claim 2, it is characterized in that: described sulfonation method preprocessing process is: concentrated sulphuric acid and distilled water were mixed postcooling in 5: 1 by volume～1: 1, the intraocular lens is immersed in 1s～10s in this solution, take out rapidly then, clean surperficial debris with distilled water, dry back is standby;
Described plasma technique preprocessing process is: the intraocular lens is put into radio-frequency (RF) plasma generator, is 99.999% O with purity
2Radio frequency plasma, radio-frequency power are 20～80W, and vacuum is 20～60Pa, and be standby behind processing 0.5～3min.
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| CN102614031B (en) | 2011-01-28 | 2015-06-03 | 清华大学 | Neural implant |
| TWI477599B (en) | 2011-01-28 | 2015-03-21 | 鴻海精密工業股份有限公司 | Cultivating substrate |
| CN103099706B (en) * | 2013-02-08 | 2016-01-27 | 首都医科大学附属北京同仁医院 | A kind of for intraocular lens preventing and treating after cataract and preparation method thereof |
| CN106492287B (en) * | 2016-10-27 | 2019-06-14 | 国家纳米科学中心 | A kind of iron-based magnetic nanoparticle area modified intraocular lens and its preparation method and use |
| CN114712026B (en) * | 2022-05-12 | 2024-11-12 | 温州医科大学附属眼视光医院 | A method for constructing an animal model of total opacity cataract |
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| US20040082996A1 (en) * | 2002-10-25 | 2004-04-29 | Ming-Ling Tsai | Intraocular lens with photocatalytic coating |
| CN1493395A (en) * | 2002-10-28 | 2004-05-05 | ���Ĵ���ѧ | Nano titanium dioxide photocatalytic film, preparation and application thereof |
| CN1608601A (en) * | 2003-05-07 | 2005-04-27 | 蔡明霖 | Artificial crystals with photocatalytic coating |
| CN1668375A (en) * | 2002-07-12 | 2005-09-14 | 清华大学 | Method of making photocatalyst by loading titanium dioxide film on surface of flexible substrate |
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| CN1668375A (en) * | 2002-07-12 | 2005-09-14 | 清华大学 | Method of making photocatalyst by loading titanium dioxide film on surface of flexible substrate |
| US20040082996A1 (en) * | 2002-10-25 | 2004-04-29 | Ming-Ling Tsai | Intraocular lens with photocatalytic coating |
| CN1493395A (en) * | 2002-10-28 | 2004-05-05 | ���Ĵ���ѧ | Nano titanium dioxide photocatalytic film, preparation and application thereof |
| CN1608601A (en) * | 2003-05-07 | 2005-04-27 | 蔡明霖 | Artificial crystals with photocatalytic coating |
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| CN1833618A (en) | 2006-09-20 |
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