CN110101902A - Purposes of the semiconductor nano photosensitive material in preparation vision repair materials - Google Patents

Purposes of the semiconductor nano photosensitive material in preparation vision repair materials Download PDF

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CN110101902A
CN110101902A CN201810108874.7A CN201810108874A CN110101902A CN 110101902 A CN110101902 A CN 110101902A CN 201810108874 A CN201810108874 A CN 201810108874A CN 110101902 A CN110101902 A CN 110101902A
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vision
repair materials
nano
retina
semiconductor nano
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CN110101902B (en
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张嘉漪
唐静
秦楠
种颜
郑耿锋
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Fudan University
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/025—Other specific inorganic materials not covered by A61L27/04 - A61L27/12
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/04—Metals or alloys
    • A61L27/047—Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/10—Ceramics or glasses
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2400/00—Materials characterised by their function or physical properties
    • A61L2400/12—Nanosized materials, e.g. nanofibres, nanoparticles, nanowires, nanotubes; Nanostructured surfaces
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/16—Materials or treatment for tissue regeneration for reconstruction of eye parts, e.g. intraocular lens, cornea

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Transplantation (AREA)
  • Epidemiology (AREA)
  • Veterinary Medicine (AREA)
  • Dermatology (AREA)
  • Medicinal Chemistry (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Public Health (AREA)
  • General Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Materials For Medical Uses (AREA)

Abstract

The invention belongs to semiconductor nano photosensitive material technical fields, it is related to a kind of purposes that the semiconductor nano material with photosensitization is new, more particularly to purposes of the semiconductor nano photosensitive material in preparation vision repair materials, semiconductor nano photosensitive material material of the invention is similar to retinal light injury photoreceptor, for orderly, one-dimensional gold modification TiOx nano linear array；Has specific surface area height, material view membrane interaction area is big, and charge mobility is big, the good feature of biocompatibility, stability, and photoreceptor can be replaced by being applied to isolated retina and intravital mouse, and retina is made to generate light reaction；It can be used for preparing vision repair materials and repair the defects of vision.Be verified by experiments, the vision repair materials can repairing retina gangliocyte make generate light reaction, repair visual cortex nerve cell make generate light reaction.

Description

Purposes of the semiconductor nano photosensitive material in preparation vision repair materials
Technical field
The invention belongs to semiconductor nano photosensitive material technical fields, are related to a kind of semiconductor nano material with photosensitization Expect new purposes, and in particular to purposes of the semiconductor nano photosensitive material in preparation vision repair materials, which can Vision reparation for the defects of vision.
Background technique
Prior art discloses retinas to be important organum photoreceptori, and optical signal can be converted into electricity by its photoreceptor cell Signal, and retinal ganglial cells are transferred to by inner retina cell, higher visual center is transferred to by optic nerve.View Film degenerative disease such as retinal pigment degeneration and macular degeneration etc. will lead to photoreceptor cell damage and even disappear completely, And then it is even as blind as a bat to cause vision to be degenerated.
The solution of the clinical retina degenerative disease used has at present: using retina prosthetic appliance, that is, in head External near infrared signal detector is placed in portion, and places photodiode array under retina, is visited with receiving external signal The collected signal of device is surveyed, the symptom of retina degeneration illness is alleviated, however, clinical practice is shown, the letter that detector is collected Number often due to head movement and cannot keep stabilization, always affect therapeutic effect.Therefore, it can be used as the sense of artificial photoreceptor Luminescent material is just becoming the research hotspot of this field, and still, there are following defects by existing photosensitive material people, e.g., needs to signal Generation, conduction and treatment process carry out additional microelectronics processing etc., directly limit the application in body.
Studies have reported that the preparation in relation to optical electro-chemistry sensing material and nano-wire array composite material etc., so far even The report that vision repair materials are used to prepare in relation to the semiconductor nano material with photosensitization is had no, based on the prior art Status, present inventor is quasi- to provide the purposes for having the semiconductor nano material of photosensitization new, and in particular to semiconductor Purposes of the nanometer photosensitive material in preparation vision repair materials, the repair materials can be used for the vision reparation of the defects of vision.
Summary of the invention
It is new object of the present invention is to overcome the shortcomings of existing technologies, provide the semiconductor nano material with photosensitization Purposes, and in particular to purposes of the semiconductor nano photosensitive material in preparation vision repair materials, the repair materials can be used for regarding Feel the vision reparation of defect.Semiconductor nano photosensitive material of the invention helps to make up nethike embrane degenerative disease intervention stratege It is insufficient.
The present invention is based on the form of photoreceptor cell and structures, are used to prepare vision using semiconductor nano photosensitive material Repair materials can largely avoid of the existing technology above-mentioned ask on the basis of guaranteeing same photosensitive property Topic, and shown through experiment, good result is achieved using upper in body in vitro.
Semiconductor nano material of the present invention with photosensitization, for the titanium oxide (Au-TiO of gold modification2) receive Nanowire arrays, by the stannic oxide (FTO) and Au-TiO of substrate of glass, fluorine doped2Nano-wire array composition；TiO2Nano-wire array Surface covers reproducibility gold salt, is grown on FTO, has the specific direction perpendicular to substrate；Nano wire average diameter is about 100nm, average length are about 2pm.
The semiconductor nano material with photosensitization is prepared by following methods,
1.TiO2The preparation of nano wire:
Glass or poly- first of the titanium dioxide nano thread by hydro-thermal method vertical-growth in tin oxide (FTO) coating of Fluorin doped On radical siloxane (PDMS), in the embodiment of the present invention, typical synthesis has been carried out, in the process, 0.1 gram of titanium foil and 18 milliliters 0.1M HCl solution is put into polytetrafluoroethyllining lining stainless steel cauldron, later, the PDMS leaching after ultrasonic cleaning in 30 minutes Enter acetone, ethyl alcohol and deionized water (DI) to carry out 150 DEG C of 12 hours water in electric oven in 1: 1: 1 (v/v) mixed solution Thermal synthesis；
2.Au-TiO2The synthesis of nano wire: in TiO2After the completion of nano wire preparation, by liquid phase reduction in TiO2Nanometer Au nanoparticle is deposited on line, in short, the FTO substrate with titanium dioxide nano thread is dipped into 0.01M HAuCl4Solution 2h in (0.2M NaOH, which is added, adjusts pH value to 4.5), later, sample carries out deionized water and thoroughly cleans, and is air-dried, 300 DEG C annealing 2 hours, be made gold modification titanium oxide (Au-TiO2) nano-wire array material.
Further, the titanium oxide (Au- of the semiconductor nano material gold modification produced by the present invention with photosensitization TiO2) nano-wire array material can be used for preparing vision repair materials.
Vision repair materials of the present invention are tested, in the embodiment of the present invention, for the material being implanted into body, nanometer Line synthesize after, FTO substrate grown have TiO2 nano wire side cover a strata methyl methacrylate (PMMA), 85 DEG C It is incubated for 5min, other side etching 9 hours in hydrogen fluoride solution (20%) are reduced to be 100 μm or less in the thickness of FTO substrate Afterwards, PMMA is removed with acetone；It is tested applied to isolated retina, the retinal ganglial cells of blind mouse are to black light (375nm), blue light (470nm) and green light (546nm) are reactionless, after its retina is bonded with this material, in 1 second nearly purple Strong action potential, and the retina neural of its reaction and wild-type mice are generated under the irradiation of outer light, blue light and green light Ganglion cell is similar.
In another embodiment of the present invention, test mice experiment is carried out, blind mouse eye receives the irradiation of black light, Visual cortex neuron not apparent increase of discharge frequency between to the photophase, after being implanted into material of the present invention in blind mouse eye 2 days, 2 months and after 5 months, in 1 second black light illumination period, visual cortex neuron had apparent discharge frequency to increase Phenomenon；Applied to experiment mice, the eyes after blind mouse implantation material are being significantly stronger than it separately to pupil contraction degree between the photophase One eye without being implanted into material, and it is similar with wild-type mice, the experimental results showed that pupil of this material to experiment mice Effect is obviously improved to light reflex.
The experimental results showed that repair materials of the invention are similar to retinal photoreceptor, it is orderly, one-dimensional nanometer linear array Column；Has specific surface area height, material view membrane interaction area is big, and charge mobility is big, and biocompatibility, stability are good Feature.
Detailed description of the invention
Fig. 1: retina and material application schematic diagram,
Wherein: left: wild-type mice retina；It is right: blind Mouse Retina；1 photoreceptor cell, 2 nano-wire arrays, 3 Gangliocyte.
Fig. 2: mouse isolated retina gangliocyte to ultraviolet (left side), blue light (in), the signal of the reaction of green light (right side) Figure, wherein
A. under at 1 second to light stimulus, the nervous activity of wild-type mice isolated retina gangliocyte；B. it was given at 1 second Under light stimulus, the nervous activity of blind mouse isolated retina gangliocyte respectively；C. under at 1 second to light stimulus, blind mouse from After stereoscopic nethike embrane is bonded with nano-wire array, the nervous activity of gangliocyte；Between when horizontal line is represented to light.
Fig. 3: after intravital mouse receives ultraviolet light stimulus in 1 second, the scatterplot of visual cortex neuron action potential and time are straight Fang Tu,
Wherein, reaction of the blind mouse visual cortex of a. to ultraviolet light；B. 2 days after blind mouse implantation material, visual cortex is to ultraviolet The reaction of light；C. 2 months after blind mouse implantation material, reaction of the visual cortex to ultraviolet light；D. 5 after blind mouse implantation material Month, reaction of the visual cortex to ultraviolet light；E. reaction of the wild-type mice visual cortex to ultraviolet light；Between when dotted line frame is represented to light.
Fig. 4: pupillary light reflex that intravital mouse stimulates black light and green light as a result,
Wherein, a. mouse pupillary light reflex logging mode figure；B. in the case where 20 seconds black lights stimulate, to before light and to light When mouse pupil picture；C. in the case where 20 seconds black lights stimulate, mouse pupil contraction ration statistics figure；D. it is stimulated in 20 seconds green lights Under, mouse pupil picture when to before light and to light；E. in the case where 20 seconds green lights stimulate, mouse pupil contraction ration statistics figure.
Specific embodiment
Embodiment 1
Material preparation:
TiO2The preparation of nano wire: titanium dioxide nano thread passes through hydro-thermal method vertical-growth in the tin oxide of Fluorin doped (FTO) on the glass or polymethyl siloxane (PDMS) coated.In primary typical synthesis process, 0.1 gram of titanium foil and 18 Milliliter 0.1M HCl solution is put into polytetrafluoroethyllining lining stainless steel cauldron.Later, after ultrasonic cleaning in 30 minutes PDMS immerses acetone, ethyl alcohol and deionized water (DI) to carry out in electric oven 150 DEG C 12 small in 1: 1: 1 (v/v) mixed solution When hydrothermal synthesis；
Au-TiO2The synthesis of nano wire: in TiO2After the completion of nano wire preparation, by liquid phase reduction in TiO2Nano wire Upper deposition Au nanoparticle.In brief, the FTO substrate with titanium dioxide nano thread is dipped into 0.01M HAuCl4Solution 2h in (0.2M NaOH, which is added, adjusts pH value to 4.5).Later, sample progress deionized water is thoroughly cleaned, and is air-dried, 300 DEG C annealing 2 hours；
For the material being implanted into body, after nano wire synthesizes, FTO substrate grown has the side of TiO2 nano wire to cover One strata methyl methacrylate (PMMA), 85 DEG C of incubation 5min, other side etching 9 hours in hydrogen fluoride solution (20%), After the thickness of FTO substrate is reduced to as 100 0 or less μ, PMMA is removed with acetone.
2 isolated test of embodiment
Repair materials obtained are in the application of isolated retina and the record of light reaction: mouse used in the present embodiment is, blind Mouse is the rd1-cDTA transgenic mice of 8-12 week old, and wild-type mice is the C57B1/6 mouse of 8-12 week old；When test material When expecting the vision repair to isolated retina, the outer layer and area of active blind Mouse Retina will be quickly removed and kept About 1cm2Material tight fitting, and be put in ganglionic layer of retina in incubation slot upward, using patch clamp technique with this Examination on experimental operation well known to field carries out whole-cell recording technique to gangliocyte, and blind mouse and wild-type mice are then by taking-up Retina, which is placed directly in incubation slot, carries out whole-cell recording technique；Polished bard energizing mode is often near ultraviolet, blue light or green light, when giving light between It is often 1s, as the result is shown: being applied to isolated retina, the retinal ganglial cells of blind mouse are blue to black light (375nm) Light (470nm) and green light (546nm) are reactionless, after its retina is bonded with material, 1 second black light, blue light and Strong action potential is generated under the irradiation of green light, and its reaction is similar to the retinal ganglial cells of wild-type mice.
Embodiment 3
Repair materials obtained carry out the record of the application and light reaction of test mice: being about 0.5-1.5mm by area2's Material is implanted between blind eyeball of mouse retina and pigment epithelial layer, after at least 2 days surgery recovery phases, is applied raw in body electricity Reason technology carries out light reaction record with opposite side visual cortex of the Examination on experimental operation well known in the art to implantation eye；It, will when record Mouse head is fixed, and is put in a skylight in skull appropriate area, is inserted electrodes into visual cortex, and source alignment is implanted into eye, records opposite side The light reaction of visual cortex neuron.Blind mouse and wild-type mice are then directly carried out in body electrophysiological recording；Polished bard energizing mode is normal It is often 1s between giving when light for black light；As the result is shown: testing the irradiation that blind mouse eye receives black light, visual cortex Neuron not apparent increase of discharge frequency between to the photophase；2 days in blind mouse eye after implantation material of the present invention, 2 A month and after 5 months, in 1 second black light illumination period, visual cortex neuron had apparent discharge frequency to increase phenomenon.
Embodiment 4
Promotion of the repair materials obtained to the pupillary light reflex phenomenon of experiment mice: with described in embodiment 3, by area About 0.5-1.5mm2The blind eyeball of mouse retina of material implantation experiment and pigment epithelial layer between, postoperative recovery 2 days；? After material implant surgery restores 2 days, mouse scalp is cut off, skull is exposed, 2 cranium holes is bored in skull appropriate location, by cranium Nail insertion cranium hole, and fixed with dental cement, pupillary reflex record is carried out after restoring 2 days；When record, fixed mouse is followed closely by cranium LED is placed in immediately ahead of eyeball by head, and is recorded it to the shooting of this eyeball camera and changed to the pupil before and after light, blind small The wherein one eye eyeball implantation material of mouse is simultaneously recorded as implantation material group, and another eyes are not processed and as blank control Group record records while calculating pupil area size, and it is 20 seconds between giving when light that stimulation used, which is black light and green light,；As a result Display: eyes after testing blind mouse implantation material are not implanted into material being significantly stronger than its another to pupil contraction degree between the photophase The eyes of material, and it is similar with wild-type mice, the experimental results showed that, pupil of the repair materials produced by the present invention to experiment mice Effect is obviously improved to light reflex.

Claims (6)

1. purposes of the semiconductor nano photosensitive material in preparation vision repair materials, the material are the titanium oxide of gold modification Au-TiO2Nanowire arrays, by the stannic oxide FTO and Au-TiO of substrate, fluorine doped2Nano-wire array is made.
2. purposes according to claim 1, which is characterized in that the TiO2Nano-wire array surface covers reproducibility gold salt, It is grown on FTO, there is the specific direction perpendicular to substrate.
3. purposes according to claim 1, which is characterized in that the nano wire average diameter is 100nm, and average length is 2μm。
4. purposes according to claim 1, which is characterized in that the vision repair materials are the vision for repairing the defects of vision Repair materials.
5. purposes according to claim 1, which is characterized in that the vision repair materials repairing retina gangliocyte Make to generate light reaction.
6. purposes according to claim 1, which is characterized in that the vision repair materials, which repair visual cortex nerve cell, to be made Generate light reaction.
CN201810108874.7A 2018-02-01 2018-02-01 Application of semiconductor nano photosensitive material in preparation of visual repair material Active CN110101902B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113633820A (en) * 2021-08-09 2021-11-12 复旦大学 Nanowire array and preparation method and application thereof
CN115444970A (en) * 2022-09-13 2022-12-09 复旦大学附属中山医院 Nanowire array of ocular fundus implant material and edge covering method thereof

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WO2014022828A1 (en) * 2012-08-02 2014-02-06 The Regents Of The University Of California Integrated nanowire array devices for detecting and/or applying electrical signals to tissue
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Publication number Priority date Publication date Assignee Title
CN113633820A (en) * 2021-08-09 2021-11-12 复旦大学 Nanowire array and preparation method and application thereof
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CN115444970A (en) * 2022-09-13 2022-12-09 复旦大学附属中山医院 Nanowire array of ocular fundus implant material and edge covering method thereof

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