CN115304793B - Bionic hydrogel constructed by nano photoelectric composite semiconductor based on red light response and preparation method thereof - Google Patents
Bionic hydrogel constructed by nano photoelectric composite semiconductor based on red light response and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of bionic hydrogel constructed by a nanometer photoelectric composite semiconductor based on red light response, which comprises the steps of firstly preparing photoelectric composite semiconductor nano particles by taking dispersion liquid in which a water-soluble anionic surfactant and a conductor material are dispersed, an n-type semiconductor solution and a p-type semiconductor solution as raw materials through hydrothermal reaction; then taking acetic acid solution of collagen and photoinitiator buffer solution of modified oxidized hyaluronic acid as raw materials to prepare hydrogel precursor mixed solution; and adding the photoelectric composite semiconductor nano particles into the hydrogel precursor mixed solution, and standing and illuminating to obtain the bionic hydrogel. The bionic hydrogel prepared by the invention has good red light response, and can be used as a photoinduction electric stimulation treatment platform to regulate electrophysiology and regeneration microenvironment.
Description
Technical Field
The invention belongs to the technical fields of biomedical materials and biomedical engineering, relates to photoelectric composite semiconductors and hydrogels, and in particular relates to a far-end electro-stimulation bionic hydrogel constructed by a red light response type photoelectric composite semiconductor and a collagen-based hydrogel and a preparation method thereof.
Background
Electrical signals are associated with various biological processes such as nerve impulses, cell migration, and wound healing. The inherent chemotaxis of cells makes electrical stimulation an effective method for non-drug treatment and regeneration. However, direct electrical stimulation typically requires complex circuitry and external power supply equipment. Thus, in biological applications, it is often desirable to achieve controlled distal stimulation by means of biocompatible carriers or signal transduction to achieve an effect on the target location. And the remote photoelectric stimulation is used as an exogenous photosensitive method, and has the advantages of being passive, noninvasive, accurate, controllable and the like.
Photovoltaic semiconductors can be photonically activated to produce electrical signals to achieve controllable distal stimulation, and have been widely used in the energy field. However, the current state of the art photovoltaic semiconductors are generally excited by means of high energy rays (e.g. ultraviolet radiation), which bring about low tissue penetration and biological hazards that greatly limit their application in the field of biomedical engineering. To date, the construction of heterostructures has been one of the most effective methods to expand the light absorption range and prevent electron-hole pair recombination. In general, an ideal compound semiconductor should have a heterostructure with a 'p-n' junction to allow efficient separation of electron-hole pairs. The n-type semiconductor takes free electrons as a dominant electron, and as an electron donor, the photo-generated electrons can migrate to a conduction band of the p-type semiconductor taking holes as a dominant electron when being excited by photons, so that the rapid recombination of electron-hole pairs is avoided, and the enhanced photovoltaic conversion is realized. Further, when such a photovoltaic heterostructure is conjugated with a conductor (e.g., carbon-based material, conductive polymer, metal oxide, etc.), it acts as a carrier and an electron conductor to transfer photo-generated electrons, which will further increase the light conversion efficiency.
Although photovoltaic semiconductors have been well applied in energy and environment, the research and development of a passive, non-pharmaceutical and non-invasive electrical stimulation treatment platform is urgently needed in cooperation with biocompatible scaffolds and replacing traditional wired electrical stimulation in the biomedical engineering field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the bionic hydrogel constructed by the nanometer photoelectric composite semiconductor with red light response and the preparation method thereof, and the prepared photoelectric conductive collagen-based hydrogel has good biocompatibility, electrical responsiveness excited by red light, stable physicochemical property and good conductivity, so that the tissue repair material with far-end electrical stimulation can be realized, and a biological treatment platform is hopeful to be provided for nerve regeneration, skin repair and the like.
The invention is characterized in that photoelectric composite semiconductor nano particles are firstly prepared, then the prepared photoelectric composite semiconductor nano particles are mixed with hydrogel precursors, and then the photoelectric conductive bionic hydrogel is obtained through collagen self-assembly and photo-crosslinking.
Based on the inventive thought, the preparation method of the bionic hydrogel constructed by the nano photoelectric composite semiconductor based on red light response provided by the invention comprises the following steps:
(1) The preparation method of the photoelectric composite semiconductor nano-particles comprises the following substeps:
(11) Mixing a dispersion liquid in which a water-soluble anionic surfactant and a conductor material are dispersed, an n-type semiconductor solution and a p-type semiconductor solution under stirring, and adding a hydrolysis-promoting agent;
(12) Adding a reducing agent into the suspension obtained in the step (11) under the stirring condition, and uniformly mixing; then carrying out hydrothermal reaction at 180-200 ℃, and filtering, washing and drying the obtained reaction liquid to obtain photoelectric composite semiconductor nano particles;
the n-type semiconductor and the p-type semiconductor are respectively titanium salt and bismuth salt, and the molar ratio of titanium ions in the titanium salt to bismuth ions in the bismuth salt is 2:1 to 1:2; the mass ratio of the conductor material to the n-type semiconductor and the p-type semiconductor is 1: (70-120);
(2) Preparation of hydrogel precursor Mixed solution
The method comprises the steps of mixing an acetic acid solution of collagen and a photoinitiator buffer solution of modified oxidized hyaluronic acid according to a volume ratio of 1:1, uniformly mixing to obtain a hydrogel precursor mixed solution;
the concentration of collagen in the acetic acid solution of the collagen is 8-12 mg/mL;
the concentration of the modified oxidized hyaluronic acid is 15-20 mg/mL;
the concentration of the photoinitiator is 2.5-5 mg/mL;
(3) Preparation of bionic hydrogel
And (3) adding the photoelectric composite semiconductor nano particles prepared in the step (1) into the hydrogel precursor mixed solution prepared in the step (2) at a final concentration of 0.1-1 mg/mL, fully and uniformly mixing, and standing and illuminating the obtained mixed solution to obtain the bionic hydrogel.
According to the preparation method of the bionic hydrogel, the step (1) needs to prepare the high-conductivity composite photoelectric composite semiconductor nano particles. Firstly, uniformly dispersing the water-soluble anionic surfactant and the conductive material in deionized water to form a dispersion liquid in which the water-soluble anionic surfactant and the conductive material are dispersed; the water-soluble anionic surfactant is poly (sodium 4-styrene sulfonate) (PSS) or Sodium Dodecyl Sulfonate (SDS); the mass ratio of the water-soluble anionic surfactant to the conductor material is 10-15:1; the conductive material is Graphene Oxide (GO) or carbon oxide nanotubes (o-CNTs), and is purchased from the middle-family time nanometer. Simultaneously, respectively dissolving n-type semiconductor and p-type semiconductor raw materials in deionized water to form an n-type semiconductor solution and a p-type semiconductor solution; the titanium salt is titanium sulfate (Ti (SO) 4 ) 2 ) The method comprises the steps of carrying out a first treatment on the surface of the The bismuth salt is bismuth nitrate pentahydrate (Bi (NO 3 ) 3 ·5H 2 O). Dropwise adding the n-type semiconductor solution and the p-type semiconductor solution to a mixture containing a water-soluble anionic surfactant and a conductive agent dispersed therein while stirring at room temperatureAnd (3) uniformly mixing the materials in the dispersion liquid of the bulk materials, and adding a hydrolysis promoting agent into the mixed liquid for continuous stirring for 10-30 min so as to promote the formation of hydrolysis precursors. The hydrolysis promoter is sodium carbonate or sodium phosphate; the ratio of the amount of the hydrolysis-promoting agent substance to the sum of the amounts of the n-type semiconductor and the p-type semiconductor substance is 5 (2-3). Thereafter, the resulting suspension is transferred to a closed vessel (e.g., autoclave) and a reducing agent is added thereto to prepare Bi by a hydrothermal method 2 S 3 /TiO 2 rGO photoelectric composite semiconductor nano-particles, bi 2 S 3 And TiO 2 Evenly distributed on the surface of rGO. The reducing agent is an excessive L-cysteine or thiourea and other sulfur-containing reducing agent, and the molar ratio of the reducing agent to bismuth salt is 1-1.2: 1 to 2. The hydrothermal reaction time is 2-8 h. And after the hydrothermal reaction, the solid precipitate obtained by filtering the reaction liquid is alternately washed for more than 3 times by deionized water and absolute ethyl alcohol, and is dried to obtain the photoelectric composite semiconductor nano particles for later use. The photoelectric effect of the prepared photoelectric composite semiconductor particles is obviously enhanced in the visible light range of 400-760 nm, so that the photoelectric effect under red light response can be realized.
According to the preparation method of the bionic hydrogel, the step (2) is to prepare the hydrogel precursor mixed solution. Firstly preparing an acetic acid solution of collagen and a photoinitiator buffer solution of modified oxidized hyaluronic acid, and then uniformly mixing the acetic acid solution and the photoinitiator buffer solution with equal volumes to obtain a hydrogel precursor mixed solution. The acetic acid solution of the Collagen is prepared by dissolving Collagen (Collagen) in the acetic acid solution under the ice bath condition of 0-4 ℃, and regulating the pH value of the system to 7-8 by using an alkaline solution; the concentration of acetic acid in the acetic acid solution is 0.4-1M. The modified oxidized hyaluronic acid is methacrylic anhydride modified oxidized hyaluronic acid. The photoinitiator buffer solution is obtained by dissolving a photoinitiator in PBS buffer solution; the photoinitiator was I2959. The photoinitiator buffer solution of the modified oxidized hyaluronic acid is obtained by dissolving the modified oxidized hyaluronic acid in the photoinitiator buffer solution, and the concentration of the modified oxidized hyaluronic acid is 15-20 mg/mL.
The preparation method of the bionic hydrogel comprises the following steps of (3) uniformly dispersing photoelectric composite semiconductor nano particles in a hydrogel precursor mixed solutionAfter standing, the collagen completes self-assembly, and aldehyde groups in the oxidized hyaluronic acid and amine groups on the collagen form imine dynamic covalent bonds; then ultraviolet irradiation is used for initiating methacrylic anhydride photopolymerization to obtain the required photoelectric conductive bionic hydrogel; meanwhile, hydrogen bonds are formed between residual oxygen-containing groups on rGO and a hydrogel network, and the photoelectric composite semiconductor nano particles and collagen/modified oxidized hyaluronic acid are combined to form the bionic hydrogel with red light response. In a preferred implementation, the rest conditions are: placing for 10-30 min at 30-40 ℃; the illumination conditions are as follows: ultraviolet light (365 nm, 1-3W/cm) 2 ) Irradiating for 15-30 s.
The invention further provides bionic hydrogel constructed based on the nanometer photoelectric composite semiconductor with red light response, which is prepared by the method.
The bionic hydrogel constructed by the nano photoelectric composite semiconductor based on red light response has the following beneficial effects:
(1) According to the invention, under a hydrothermal condition, the high-conductivity carbon material composite red light response semiconductor heterostructure is prepared by using a chemical reduction one-pot method.
(2) The modified natural high molecular hyaluronic acid and collagen are used as the matrix material of the hydrogel, and the collagen autodress, the imine dynamic covalent bond and the photopolymerization crosslinking network are utilized to improve the stability and mechanical properties of the hydrogel and provide good biocompatibility and bioadhesion sites.
(3) The invention combines photoelectric composite semiconductor nano particles and collagen/modified hyaluronic acid to form red light response conductive hydrogel by utilizing hydrogen bond action, and the red light response conductive hydrogel is used as a photoinduction electric stimulation treatment platform.
Drawings
FIG. 1 is an SEM photograph of an electro-optical nano-semiconductor prepared in example 6 of the present invention;
FIG. 2 is a TEM photograph of the electro-optical nano-semiconductor prepared in example 6 of the present invention;
FIG. 3 is a surface photovoltage spectrum of the optoelectronic nano-semiconductor prepared in example 6 of the present invention;
FIG. 4 is a photocurrent characterization of the photoelectric conductive water biomimetic hydrogels prepared in examples 5, 6, and 7 and comparative example 1 according to the present invention;
FIG. 5 shows the biological activity of the photoelectric conductive water biomimetic hydrogel prepared in example 6 of the present invention, and the promotion effect of the photoelectric stimulation on cell proliferation, spreading and migration.
Detailed Description
The present invention is described in detail below by way of examples, which are necessary to be noted here for further illustration of the invention and are not to be construed as limiting the scope of the invention, since a person skilled in the art can make some insubstantial modifications and adaptations in light of the above description of the invention.
0.5M Na used in the following examples 2 CO 3 The solution is according to Na 2 CO 3 Final concentration, it was dissolved in deionized water.
The 0.5M acetic acid solution used in the examples below was prepared by mixing it with deionized water uniformly according to the final concentration of acetic acid.
The 5M NaOH solution used in the examples below was prepared by dissolving it in deionized water according to the final concentration of NaOH.
The PBS buffer used in the following examples was obtained by dissolving I2959 in PBS buffer at a final concentration of I2959, and the PBS buffer was obtained by outsourcing.
The modified oxidized hyaluronic acid used in the following examples was methacrylic anhydride modified oxidized hyaluronic acid. The preparation method comprises the following steps: first, sodium hyaluronate (60 to 80kDa, hua Xi Biotechnology Co., ltd.) was dissolved in 200mL of ultrapure water at a concentration of 10mg/mL, and 1.5mL of a sodium periodate aqueous solution at a concentration of 0.5M was added dropwise to the HA solution. After stirring the mixture at 25 ℃ for 4 hours, 1mL of ethylene glycol is added dropwise to the solution to terminate the reaction, and the reaction solution is dialyzed by water and freeze-dried and stored in a refrigerator at-20 ℃ to obtain oxidized hyaluronic acid (AHA). Next, AHA was dissolved in ultrapure water at a concentration of 10mg/mL, and then an excess amount of methacrylic anhydride (16 mL, a company of koku-long chemicals, inc.) was added dropwise to the aqueous solution while maintaining the reaction solution at ph=8 and stirring at 4 ℃ for 24 hours. The white flocculated material was then precipitated with copious amounts of ethanol and washed by centrifugation to give methacrylic anhydride modified oxidized hyaluronic acid (AHAMA). After dialysis and lyophilization, they were stored at-20℃and protected from light.
Example 1
The steps for preparing the bionic hydrogel constructed by the nano photoelectric composite semiconductor in the embodiment are as follows:
(1) The preparation method of the photoelectric composite semiconductor nano-particles comprises the following substeps:
(11) Dissolving 150mg of PSS in 20mL of deionized water, adding 10mg of GO into the solution, performing ultrasonic dispersion for 5min to uniformly disperse GO in the PSS solution, and marking the solution as solution A; subsequently, 480mg of Ti (SO 4 ) 2 And 485mg Bi (NO) 3 ) 3 ·5H 2 O was dissolved in 20ml deionized water, recorded as solutions B and C, respectively; after the two solutions B, C are completely dissolved, clarified and transparent, dropwise adding the solutions B and C into the solution A under the stirring condition to obtain a mixed solution; then 10mL of 0.5M Na 2 CO 3 The solution is added to the mixed liquor to promote the formation of the hydrolytic precursor.
(12) Adding 115 mgL-cysteine into the suspension obtained in the step (11) under stirring, and continuously stirring for 15min to uniformly mix the reducing agent and the suspension; then transferring the mixture into a 100mL PTFE autoclave, and heating the mixture to 180 ℃ in a temperature-controlled muffle furnace for reaction for 8 hours; after the hydrothermal reaction, filtering the obtained solid precipitate, and alternately washing the solid precipitate with deionized water and absolute ethyl alcohol for 3 times to obtain Bi 2 S 3 /TiO 2 And (3) drying the rGO photoelectric composite semiconductor nano particles for later use.
(2) Preparation of hydrogel precursor Mixed solution
Pre-dissolving collagen in 0.5M acetic acid according to the final concentration of 10mg/mL under the ice bath condition of 4 ℃, and then neutralizing with NaOH aqueous solution to pH=7 to obtain an acetic acid solution of collagen; according to the final concentration of AHAMA of 20mg/mL, dissolving AHAMA in buffer solution with the concentration of 2.5mg/mLI2959 to obtain photoinitiator buffer solution of AHAMA; subsequently, the photoinitiator buffer of AHAMA and the acetic acid solution of collagen were thoroughly mixed in a volume ratio of 1:1.
(3) Preparation of bionic hydrogel
Immediately adding the photoelectric composite semiconductor nano particles prepared in the step (1) into the hydrogel precursor mixed solution prepared in the step (2) at the final concentration of 0.1mg/mL, and fully and uniformly mixing; the mixture was then poured into a mold, followed by placing in a 37℃incubator for 30 minutes, followed by UV light (365 nm, 1W/cm) 2 ) Irradiating for 30 seconds; and demolding to obtain the bionic hydrogel constructed by the photoelectric composite semiconductor.
Example 2
The steps for preparing the bionic hydrogel constructed by the nano photoelectric composite semiconductor in the embodiment are as follows:
(1) The preparation method of the photoelectric composite semiconductor nano-particles comprises the following substeps:
(11) Dissolving 150mg of SDS in 20mL of deionized water, adding 10mg of GO into the solution, performing ultrasonic dispersion for 5min to uniformly disperse GO in the PSS solution, and marking the solution as solution A; subsequently, 480mg of Ti (SO 4 ) 2 And 485mg Bi (NO) 3 ) 3 ·5H 2 O was dissolved in 20ml deionized water, recorded as solutions B and C, respectively; after the two solutions B, C are completely dissolved, clarified and transparent, dropwise adding the solutions B and C into the solution A under the stirring condition to obtain a mixed solution; then 10mL of 0.5M Na 2 CO 3 The solution is slowly added to the mixed liquor to promote the formation of hydrolytic precursors.
(12) Adding 115 mgL-cysteine into the suspension obtained in the step (11) under stirring, and continuously stirring for 15min to uniformly mix the reducing agent and the suspension; then transferring the mixture into a 100mL PTFE autoclave, and heating the mixture to 180 ℃ in a temperature-controlled muffle furnace for reaction for 8 hours; after the hydrothermal reaction, filtering the obtained solid precipitate, and alternately washing the solid precipitate with deionized water and absolute ethyl alcohol for 3 times to obtain Bi 2 S 3 /TiO 2 And (3) drying the rGO photoelectric composite semiconductor nano particles for later use.
(2) Preparation of hydrogel precursor Mixed solution
Pre-dissolving collagen in 0.5M acetic acid according to the final concentration of 10mg/mL under the ice bath condition of 4 ℃, and then neutralizing with NaOH aqueous solution to pH=7 to obtain an acetic acid solution of collagen; according to the final concentration of AHAMA of 20mg/mL, dissolving AHAMA in buffer solution with the concentration of 2.5mg/mL I2959 to obtain photoinitiator buffer solution of AHAMA; subsequently, the photoinitiator buffer of AHAMA and the acetic acid solution of collagen were thoroughly mixed in a volume ratio of 1:1.
(3) Preparation of bionic hydrogel
Immediately adding the photoelectric composite semiconductor nano particles prepared in the step (1) into the hydrogel precursor mixed solution prepared in the step (2) at the final concentration of 0.1mg/mL, and fully and uniformly mixing; the mixture was then poured into a mold, followed by placing in a 37℃incubator for 30 minutes, followed by UV light (365 nm, 3W/cm) 2 ) Irradiating for 15 seconds; and demolding to obtain the bionic hydrogel constructed by the photoelectric composite semiconductor.
Example 3
The steps for preparing the bionic hydrogel constructed by the nano photoelectric composite semiconductor in the embodiment are as follows:
(1) The preparation method of the photoelectric composite semiconductor nano-particles comprises the following substeps:
(11) Dissolving 150mgPSS in 20mL deionized water, adding 10mg o-CNTs into the solution, performing ultrasonic dispersion for 5min to uniformly disperse the o-CNTs in the PSS solution, and marking the solution as solution A; subsequently, 480mg of Ti (SO 4 ) 2 And 485mg Bi (NO) 3 ) 3 ·5H 2 O was dissolved in 20ml deionized water, recorded as solutions B and C, respectively; after the two solutions B, C are completely dissolved, clarified and transparent, dropwise adding the solutions B and C into the solution A under the stirring condition to obtain a mixed solution; then 10mL of 0.5M Na 2 CO 3 The solution is slowly added to the mixed liquor to promote the formation of hydrolytic precursors.
(12) Adding 115 mgL-cysteine into the suspension obtained in the step (11) under stirring, and continuously stirring for 15min to uniformly mix the reducing agent and the suspension; then transferring the mixture into a 100mL PTFE autoclave, and heating the mixture to 180 ℃ in a temperature-controlled muffle furnace for reaction for 8 hours; after the hydrothermal reaction, filtering the obtained solid precipitate, and alternately washing the solid precipitate with deionized water and absolute ethyl alcohol for 3 times to obtain Bi 2 S 3 /TiO 2 And (3) drying the rGO photoelectric composite semiconductor nano particles for later use.
(2) Preparation of hydrogel precursor Mixed solution
Pre-dissolving collagen in 0.5M acetic acid according to the final concentration of 10mg/mL under the ice bath condition of 4 ℃, and then neutralizing with NaOH aqueous solution to pH=7 to obtain an acetic acid solution of collagen; according to the final concentration of AHAMA of 20mg/mL, dissolving AHAMA in buffer solution with the concentration of 2.5mg/mL I2959 to obtain photoinitiator buffer solution of AHAMA; subsequently, the photoinitiator buffer of AHAMA and the acetic acid solution of collagen were thoroughly mixed in a volume ratio of 1:1.
(3) Preparation of bionic hydrogel
Immediately adding the photoelectric composite semiconductor nano particles prepared in the step (1) into the hydrogel precursor mixed solution prepared in the step (2) at the final concentration of 0.1mg/mL, and fully and uniformly mixing; the mixture was then poured into a mold, followed by placing in a 37℃incubator for 30 minutes, followed by UV light (365 nm, 3W/cm) 2 ) Irradiating for 15 seconds; and demolding to obtain the bionic hydrogel constructed by the photoelectric composite semiconductor.
Example 4
The steps for preparing the bionic hydrogel constructed by the nano photoelectric composite semiconductor in the embodiment are as follows:
(1) The preparation method of the photoelectric composite semiconductor nano-particles comprises the following substeps:
(11) Dissolving 150mg of PSS in 20mL of deionized water, adding 10mg of GO into the solution, performing ultrasonic dispersion for 5min to uniformly disperse GO in the PSS solution, and marking the solution as solution A; subsequently, 240mg of Ti (SO 4 ) 2 And 485mg Bi (NO) 3 ) 3 ·5H 2 O was dissolved in 20ml deionized water, recorded as solutions B and C, respectively; after the two solutions B, C are completely dissolved, clarified and transparent, dropwise adding the solutions B and C into the solution A under the stirring condition to obtain a mixed solution; then 10mL of 0.5M Na 2 CO 3 The solution is slowly added to the mixed liquor to promote the formation of hydrolytic precursors.
(12) Adding 115 mgL-cysteine into the suspension obtained in the step (11) under stirring, and continuously stirring for 15min to uniformly mix the reducing agent and the suspension; then transferred to a 100mL PTFE autoclave at control Wen MaHeating to 180 ℃ in a furfurer for reaction for 8 hours; after the hydrothermal reaction, filtering the obtained solid precipitate, and alternately washing the solid precipitate with deionized water and absolute ethyl alcohol for 3 times to obtain Bi 2 S 3 /TiO 2 And (3) drying the rGO photoelectric composite semiconductor nano particles for later use.
(2) Preparation of hydrogel precursor Mixed solution
Pre-dissolving collagen in 0.5M acetic acid according to the final concentration of 10mg/mL under the ice bath condition of 4 ℃, and then neutralizing with NaOH aqueous solution to pH=7 to obtain an acetic acid solution of collagen; according to the final concentration of AHAMA of 20mg/mL, dissolving AHAMA in buffer solution with the concentration of 2.5mg/mL I2959 to obtain photoinitiator buffer solution of AHAMA; subsequently, the photoinitiator buffer of AHAMA and the acetic acid solution of collagen were thoroughly mixed in a volume ratio of 1:1.
(3) Preparation of bionic hydrogel
Immediately adding the photoelectric composite semiconductor nano particles prepared in the step (1) into the hydrogel precursor mixed solution prepared in the step (2) at the final concentration of 0.1mg/mL, and fully and uniformly mixing; the mixture was then poured into a mold, followed by placing in a 37℃incubator for 30 minutes, followed by UV light (365 nm, 3W/cm) 2 ) Irradiating for 15 seconds; and demolding to obtain the bionic hydrogel constructed by the photoelectric composite semiconductor.
Example 5
The steps for preparing the bionic hydrogel constructed by the nano photoelectric composite semiconductor in the embodiment are as follows:
(1) The preparation method of the photoelectric composite semiconductor nano-particles comprises the following substeps:
(11) Dissolving 150mg of PSS in 20mL of deionized water, adding 10mg of GO into the solution, performing ultrasonic dispersion for 5min to uniformly disperse GO in the PSS solution, and marking the solution as solution A; subsequently, 480mg of Ti (SO 4 ) 2 And 485mg Bi (NO) 3 ) 3 ·5H 2 O was dissolved in 20ml deionized water, recorded as solutions B and C, respectively; after the two solutions B, C are completely dissolved, clarified and transparent, dropwise adding the solutions B and C into the solution A under the stirring condition to obtain a mixed solution; then 10mL of 0.5M Na 2 CO 3 Slowly adding the solution to the mixed solution to promote hydrolysis of the precursorIs formed by the steps of (a).
(12) Adding 115 mgL-cysteine into the suspension obtained in the step (11) under stirring, and continuously stirring for 15min to uniformly mix the reducing agent and the suspension; then transferring the mixture into a 100mL PTFE autoclave, and heating the mixture to 180 ℃ in a temperature-controlled muffle furnace for reaction for 8 hours; after the hydrothermal reaction, filtering the obtained solid precipitate, and alternately washing the solid precipitate with deionized water and absolute ethyl alcohol for 3 times to obtain Bi 2 S 3 /TiO 2 And (3) drying the rGO photoelectric composite semiconductor nano particles for later use.
(2) Preparation of hydrogel precursor Mixed solution
Pre-dissolving collagen in 0.5M acetic acid according to the final concentration of 10mg/mL under the ice bath condition of 4 ℃, and then neutralizing with NaOH aqueous solution to pH=7 to obtain an acetic acid solution of collagen; according to the final concentration of AHAMA of 20mg/mL, dissolving AHAMA in buffer solution with the concentration of 2.5mg/mL I2959 to obtain photoinitiator buffer solution of AHAMA; subsequently, the photoinitiator buffer of AHAMA and the acetic acid solution of collagen were thoroughly mixed in a volume ratio of 1:1.
(3) Preparation of bionic hydrogel
Immediately adding the photoelectric composite semiconductor nano particles prepared in the step (1) into the hydrogel precursor mixed solution prepared in the step (2) at the final concentration of 0.1mg/mL, and fully and uniformly mixing; the mixture was then poured into a mold, followed by placing in a 37℃incubator for 30 minutes, followed by UV light (365 nm, 3W/cm) 2 ) Irradiating for 15 seconds; and demolding to obtain the bionic hydrogel constructed by the photoelectric composite semiconductor.
Example 6
The steps for preparing the bionic hydrogel constructed by the nano photoelectric composite semiconductor in the embodiment are as follows:
(1) The preparation method of the photoelectric composite semiconductor nano-particles comprises the following substeps:
(11) Dissolving 150mg of PSS in 20mL of deionized water, adding 10mg of GO into the solution, performing ultrasonic dispersion for 5min to uniformly disperse GO in the PSS solution, and marking the solution as solution A; subsequently, 480mg of Ti (SO 4 ) 2 And 485mg Bi (NO) 3 ) 3 ·5H 2 O was dissolved in 20mL deionized water, respectively, and recorded asSolutions B and C; after the two solutions B, C are completely dissolved, clarified and transparent, dropwise adding the solutions B and C into the solution A under the stirring condition to obtain a mixed solution; then 10mL of 0.5M Na 2 CO 3 The solution is slowly added to the mixed liquor to promote the formation of hydrolytic precursors.
(12) Adding 115 mgL-cysteine into the suspension obtained in the step (11) under stirring, and continuously stirring for 15min to uniformly mix the reducing agent and the suspension; then transferring the mixture into a 100mL PTFE autoclave, and heating the mixture to 180 ℃ in a temperature-controlled muffle furnace for reaction for 8 hours; after the hydrothermal reaction, filtering the obtained solid precipitate, and alternately washing the solid precipitate with deionized water and absolute ethyl alcohol for 3 times to obtain Bi 2 S 3 /TiO 2 And (3) drying the rGO photoelectric composite semiconductor nano particles for later use.
(2) Preparation of hydrogel precursor Mixed solution
Pre-dissolving collagen in 0.5M acetic acid according to the final concentration of 10mg/mL under the ice bath condition of 4 ℃, and then neutralizing with NaOH aqueous solution to pH=7 to obtain an acetic acid solution of collagen; according to the final concentration of AHAMA of 20mg/mL, dissolving AHAMA in buffer solution with the concentration of 2.5mg/mL I2959 to obtain photoinitiator buffer solution of AHAMA; subsequently, the photoinitiator buffer of AHAMA and the acetic acid solution of collagen were thoroughly mixed in a volume ratio of 1:1.
(3) Preparation of bionic hydrogel
Immediately adding the photoelectric composite semiconductor nano particles prepared in the step (1) into the hydrogel precursor mixed solution prepared in the step (2) at the final concentration of 0.5mg/mL, and fully and uniformly mixing; the mixture was then poured into a mold, followed by placing in a 37℃incubator for 30 minutes, followed by UV light (365 nm, 3W/cm) 2 ) Irradiating for 15 seconds; and demolding to obtain the bionic hydrogel constructed by the photoelectric composite semiconductor.
Example 7
The steps for preparing the bionic hydrogel constructed by the nano photoelectric composite semiconductor in the embodiment are as follows:
(1) The preparation method of the photoelectric composite semiconductor nano-particles comprises the following substeps:
(11) 150mg PSS was dissolved in 20mL deionized water, as described aboveAdding 10mg of GO into the solution, and performing ultrasonic dispersion for 5min to uniformly disperse GO in the PSS solution, wherein the solution is marked as solution A; subsequently, 480mg of Ti (SO 4 ) 2 And 485mg Bi (NO) 3 ) 3 ·5H 2 O was dissolved in 20ml deionized water, recorded as solutions B and C, respectively; after the two solutions B, C are completely dissolved, clarified and transparent, dropwise adding the solutions B and C into the solution A under the stirring condition to obtain a mixed solution; then 10mL of 0.5M Na 2 CO 3 The solution is slowly added to the mixed liquor to promote the formation of hydrolytic precursors.
(12) Adding 115 mgL-cysteine into the suspension obtained in the step (11) under stirring, and continuously stirring for 15min to uniformly mix the reducing agent and the suspension; then transferring the mixture into a 100mL PTFE autoclave, and heating the mixture to 180 ℃ in a temperature-controlled muffle furnace for reaction for 8 hours; after the hydrothermal reaction, filtering the obtained solid precipitate, and alternately washing the solid precipitate with deionized water and absolute ethyl alcohol for 3 times to obtain Bi 2 S 3 /TiO 2 And (3) drying the rGO photoelectric composite semiconductor nano particles for later use.
(2) Preparation of hydrogel precursor Mixed solution
Pre-dissolving collagen in 0.5M acetic acid according to the final concentration of 10mg/mL under the ice bath condition of 4 ℃, and then neutralizing with NaOH aqueous solution to pH=7 to obtain an acetic acid solution of collagen; according to the final concentration of AHAMA of 20mg/mL, dissolving AHAMA in buffer solution with the concentration of 2.5mg/mL I2959 to obtain photoinitiator buffer solution of AHAMA; subsequently, the photoinitiator buffer of AHAMA and the acetic acid solution of collagen were thoroughly mixed in a volume ratio of 1:1.
(3) Preparation of bionic hydrogel
Immediately adding the photoelectric composite semiconductor nano particles prepared in the step (1) into the hydrogel precursor mixed solution prepared in the step (2) at the final concentration of 1mg/mL, and fully and uniformly mixing; the mixture was then poured into a mold, followed by placing in a 37℃incubator for 30 minutes, followed by UV light (365 nm, 3W/cm) 2 ) Irradiating for 15 seconds; and demolding to obtain the bionic hydrogel constructed by the photoelectric composite semiconductor.
Example 8
The steps for preparing the bionic hydrogel constructed by the nano photoelectric composite semiconductor in the embodiment are as follows:
(1) The preparation method of the photoelectric composite semiconductor nano-particles comprises the following substeps:
(11) Dissolving 100mg of PSS in 20mL of deionized water, adding 10mg of GO into the solution, performing ultrasonic dispersion for 5min to uniformly disperse GO in the PSS solution, and marking the solution as solution A; subsequently, 240mg of Ti (SO 4 ) 2 And 970mg Bi (NO) 3 ) 3 ·5H 2 O was dissolved in 20ml deionized water, recorded as solutions B and C, respectively; after the two solutions B, C are completely dissolved, clarified and transparent, dropwise adding the solutions B and C into the solution A under the stirring condition to obtain a mixed solution; then 10mL of 0.5M Na 2 CO 3 The solution is slowly added to the mixed liquor to promote the formation of hydrolytic precursors.
(12) Under the stirring condition, 150 mgL-cysteine is added into the suspension obtained in the step (11), and stirring is continued for 15min, so that the reducing agent and the suspension are uniformly mixed; then transferring the mixture into a 100mL PTFE autoclave, and heating the mixture to 200 ℃ in a temperature-controlled muffle furnace for reaction for 2h; after the hydrothermal reaction, filtering the obtained solid precipitate, and alternately washing the solid precipitate with deionized water and absolute ethyl alcohol for 3 times to obtain Bi 2 S 3 /TiO 2 And (3) drying the rGO photoelectric composite semiconductor nano particles for later use.
(2) Preparation of hydrogel precursor Mixed solution
Pre-dissolving collagen in 0.5M acetic acid according to the final concentration of the collagen of 8mg/mL under the ice bath condition of 0 ℃, and then neutralizing with NaOH aqueous solution until the pH value is=7 to obtain an acetic acid solution of the collagen; according to the final concentration of AHAMA of 15mg/mL, dissolving AHAMA in buffer solution with the concentration of 5mg/mL I2959 to obtain photoinitiator buffer solution of AHAMA; subsequently, the photoinitiator buffer of AHAMA and the acetic acid solution of collagen were thoroughly mixed in a volume ratio of 1:1.
(3) Preparation of bionic hydrogel
Immediately adding the photoelectric composite semiconductor nano particles prepared in the step (1) into the hydrogel precursor mixed solution prepared in the step (2) at the final concentration of 0.5mg/mL, and fully and uniformly mixing; then the mixed solution is injected into a mould, then placed in a constant temperature box at 37 ℃ for 10 minutes, and then placed in the ultravioletExternal light (365 nm, 1W/cm) 2 ) Irradiating for 30 seconds; and demolding to obtain the bionic hydrogel constructed by the photoelectric composite semiconductor.
Example 9
The steps for preparing the bionic hydrogel constructed by the nano photoelectric composite semiconductor in the embodiment are as follows:
(1) The preparation method of the photoelectric composite semiconductor nano-particles comprises the following substeps:
(11) Dissolving 150mg of PSS in 20mL of deionized water, adding 10mg of GO into the solution, performing ultrasonic dispersion for 5min to uniformly disperse GO in the PSS solution, and marking the solution as solution A; subsequently, 240mg of Ti (SO 4 ) 2 And 970mg Bi (NO) 3 ) 3 ·5H 2 O was dissolved in 20ml deionized water, recorded as solutions B and C, respectively; after the two solutions B, C are completely dissolved, clarified and transparent, dropwise adding the solutions B and C into the solution A under the stirring condition to obtain a mixed solution; then 10mL of 0.5M Na 2 CO 3 The solution is slowly added to the mixed liquor to promote the formation of hydrolytic precursors.
(12) Under the stirring condition, 150 mgL-cysteine is added into the suspension obtained in the step (11), and stirring is continued for 15min, so that the reducing agent and the suspension are uniformly mixed; then transferring the mixture into a 100mL PTFE autoclave, and heating the mixture to 200 ℃ in a temperature-controlled muffle furnace for reaction for 4 hours; after the hydrothermal reaction, filtering the obtained solid precipitate, and alternately washing the solid precipitate with deionized water and absolute ethyl alcohol for 3 times to obtain Bi 2 S 3 /TiO 2 And (3) drying the rGO photoelectric composite semiconductor nano particles for later use.
(2) Preparation of hydrogel precursor Mixed solution
Pre-dissolving collagen in 0.5M acetic acid according to the final concentration of the collagen of 12mg/mL under the ice bath condition of 4 ℃, and then neutralizing with NaOH aqueous solution until the pH value is=7 to obtain an acetic acid solution of the collagen; according to the final concentration of AHAMA of 18mg/mL, dissolving AHAMA in buffer solution with the concentration of 2.5mg/mL I2959 to obtain photoinitiator buffer solution of AHAMA; subsequently, the photoinitiator buffer of AHAMA and the acetic acid solution of collagen were thoroughly mixed in a volume ratio of 1:1.
(3) Preparation of bionic hydrogel
Immediately step (c)(1) The prepared photoelectric composite semiconductor nano particles are added into the hydrogel precursor mixed solution prepared in the step (2) at the final concentration of 0.1mg/mL and are fully and uniformly mixed; the mixture was then poured into a mold, followed by placing in a 37℃incubator for 20 minutes, followed by UV light (365 nm, 2W/cm) 2 ) Irradiating for 15 seconds; and demolding to obtain the bionic hydrogel constructed by the photoelectric composite semiconductor.
Comparative example 1
(1) Preparation of hydrogel precursor Mixed solution
Pre-dissolving collagen in 0.5M acetic acid according to the final concentration of 10mg/mL under the ice bath condition of 4 ℃, and then neutralizing with NaOH aqueous solution to pH=7 to obtain an acetic acid solution of collagen; according to the final concentration of AHAMA of 20mg/mL, dissolving AHAMA in buffer solution with the concentration of 0.25% (w/v) I2959 to obtain photoinitiator buffer solution of AHAMA; subsequently, the photoinitiator buffer of AHAMA and the acetic acid solution of collagen were thoroughly mixed in a volume ratio of 1:1.
(3) Preparation of bionic hydrogel
The hydrogel precursor mixture was poured into a mold, then placed in a 37℃incubator for 30 minutes, and then subjected to ultraviolet light (365 nm, 3W/cm) 2 ) Irradiating for 15 seconds; and demolding to obtain the bionic hydrogel constructed by the photoelectric composite semiconductor. The optoelectronic semiconductor nano-particles and hydrogel samples prepared in the above part of examples are subjected to structural and performance characterization as follows:
typical ultrathin flexible sheets of reduced graphene oxide (rGO) are shown in fig. 1a and 2 a. Bi prepared synthetically in example 6 2 S 3 /TiO 2 The surface topography of/rGO is shown in FIGS. 1b and 2 b. Wherein Bi is 2 S 3 Edge [001 ]]The crystal planes grow directionally, resulting in a rod-like morphology. Bi (Bi) 2 S 3 And TiO 2 Evenly distributed on the surface of rGO. In high resolution transmission electron microscopy, tiO 2 (101) And Bi (Bi) 2 S 3 (130) Is marked with thin lines. The thickness of the synthesized rGO is about 5-10nm, and Bi 2 S 3 Is about 150nm in diameter and 300-500nm in length. In addition, tiO 2 The particle size of (2) is much smaller, about 20nm, and Bi 2 S 3 A heterostructure is formed.
To prove Bi 2 S 3 、TiO 2 Conjugation with rGO can realize photoelectric response of red light excitation, and Surface Photovoltage Spectrum (SPS) reveals rGO and TiO 2 ，Bi 2 S 3 /TiO 2 Separation and transport of charge carriers in/rGO and medium. As shown in fig. 3, pure rGO shows little surface photovoltage signal. For TiO 2 Nanoparticles, recording weak photovoltage signals of ultraviolet excitation light of 300nm to 400 nm. More importantly, bi 2 S 3 /TiO 2 The surface photovoltage response of/rGO is obviously enhanced in the visible light range of 400-760 nm. Therefore, bi 2 S 3 /TiO 2 The response of the photoelectric effect is successfully extended to the red region by/rGO.
The magnitude of the photoresponse currents of the biomimetic hydrogels in examples 5, 6 and 7 and comparative example 1 was further examined by means of patch clamp technology. As shown in FIG. 4, the hydrogel without the photoelectric semiconductor was not generated by irradiation of 625nm laser, and the photocurrent response amplitude was increased with the increase of the concentration of the photoelectric semiconductor, and a current amplitude of about 200pA was obtained at a concentration of 1 mg/mL.
Based on the physicochemical properties, the biological effect of the photoelectric composite semiconductor bionic hydrogel on cells is evaluated. Cell experiment NIH-3T3 cells (mouse embryo fibroblasts) were co-cultured with the biomimetic hydrogel prepared in example 6 in a 48-well plate, and the cultured cells were divided into a no-light group cell and an illumination group cell, the no-light group cell was co-cultured with the biomimetic hydrogel without any light stimulation, and the illumination group was irradiated with 625nm pulsed laser twice daily for 20 minutes; the control group was without any material or stimulus. By performing FDA/PI live-dead cell staining experiments on NIH-3T3 cells, the experimental results are shown in FIG. 5a, the comparison of the non-illumination group and the control group shows that the cell compatibility determination has no obvious toxicity, and the cell proliferation is effectively promoted under the action of illumination, especially on the 3 rd day of the logarithmic growth phase. In addition, by conducting a phalloidin/DAPI staining experiment on NIH-3T3 cells, the experimental results are shown in FIG. 5b, where NIH-3T3 cells have a larger diffusion area and a higher actin filament density, which provides a driving force for cell migration. Further evaluation of the cell migration ability was performed by a scratch test, when NIH-3T3 cell fusion rate reached 80% or more, scratches of about 500 μm in width were made on the bottom of the dish, the hydrogel was covered and irradiated with light, and the migration of the scratched edge cells was observed, as shown in fig. 5c, and the scratch test demonstrated that the irradiated group showed faster migration rate within 24 hours.
In summary, the invention provides a novel bionic hydrogel for passive photoelectric stimulation treatment for tissue engineering repair. Compared with traditional wired electrical stimulation, the light-activated strategy has the advantages of non-invasive, non-complex circuit and accurate and controllable performance. Moreover, common photovoltaic materials require short wavelength photon excitation, with poor tissue penetration and strong biohazard. The invention realizes wider light absorption and higher light conversion efficiency than the conventional ultraviolet excitation by constructing the p-n heterostructure nano particles to be loaded on the carbon-based conductive material. In addition, a rationally designed biomimetic hydrogel matrix composed of collagen and hyaluronic acid provides suitable bioactivity, interfacial adhesion, mechanical matching and electron transfer properties. Therefore, the photoelectric conductive bionic hydrogel provides an optical driving electric stimulation platform so as to adjust electrophysiology and regenerate microenvironment. The implementation of electro-optic stimulation has broad prospects for non-drug therapy and modulation of electrically-related biological processes, including osseointegration, nerve regeneration, electronic skin and wound healing.
The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments, and any other changes, modifications, substitutions, simplifications, and combinations thereof, which do not depart from the spirit and principle of the present invention, should be made in the equivalent manner, and are included in the protection scope of the present invention.
Claims (9)
1. The preparation method of the bionic hydrogel constructed by the nano photoelectric composite semiconductor based on red light response is characterized by comprising the following steps of:
(1) The preparation method of the photoelectric composite semiconductor nano-particles comprises the following substeps:
(11) Mixing a dispersion liquid in which a water-soluble anionic surfactant and a conductive material are dispersed, an n-type semiconductor solution and a p-type semiconductor solution under stirring, and adding a hydrolysis-promoting agent;
(12) Adding a reducing agent into the suspension obtained in the step (11) under the stirring condition, and uniformly mixing; then carrying out hydrothermal reaction at 180-200 ℃, and filtering, washing and drying the obtained reaction liquid to obtain photoelectric composite semiconductor nano particles;
the n-type semiconductor and the p-type semiconductor are respectively titanium salt and bismuth salt, and the molar ratio of titanium ions in the titanium salt to bismuth ions in the bismuth salt is 2: 1-1: 2; the conductive material is graphene oxide or carbon oxide nanotubes; the mass ratio of the conductive material to the n-type semiconductor and the p-type semiconductor is 1: (70-120);
(2) Preparation of hydrogel precursor Mixed solution
The method comprises the steps of mixing an acetic acid solution of collagen and a photoinitiator buffer solution of modified oxidized hyaluronic acid according to a volume ratio of 1:1, uniformly mixing to obtain a hydrogel precursor mixed solution; the photoinitiator buffer solution of the modified oxidized hyaluronic acid is obtained by dissolving the modified oxidized hyaluronic acid in the photoinitiator buffer solution; the modified oxidized hyaluronic acid is methacrylic anhydride modified oxidized hyaluronic acid;
the concentration of collagen in the acetic acid solution of the collagen is 8-12 mg/mL;
the concentration of the modified oxidized hyaluronic acid is 15-20 mg/mL;
the concentration of the photoinitiator is 2.5-5 mg/mL;
(3) Preparation of bionic hydrogel
And (3) adding the photoelectric composite semiconductor nano particles prepared in the step (1) into the hydrogel precursor mixed solution prepared in the step (2) at a final concentration of 0.1-1 mg/mL, fully and uniformly mixing, and standing and illuminating the obtained mixed solution to obtain the bionic hydrogel.
2. The method for preparing the bionic hydrogel constructed by the nano photoelectric composite semiconductor based on red light response according to claim 1, wherein in the step (11), the water-soluble anionic surfactant and the conductive material are uniformly dispersed in deionized water to form a dispersion liquid in which the water-soluble anionic surfactant and the conductive material are dispersed; the water-soluble anionic surfactant is poly (sodium 4-styrene sulfonate) or sodium dodecyl sulfonate.
3. The method for preparing the bionic hydrogel constructed by the nano photoelectric composite semiconductor based on the red light response according to claim 1, wherein in the step (11), n-type semiconductor and p-type semiconductor raw materials are respectively dissolved in deionized water to form an n-type semiconductor solution and a p-type semiconductor solution; the titanium salt is titanium sulfate; the bismuth salt is bismuth nitrate pentahydrate.
4. The method for preparing the bionic hydrogel constructed by the nano photoelectric composite semiconductor based on the red light response according to claim 1, wherein in the step (11), the hydrolysis-promoting agent is sodium carbonate or sodium phosphate; the ratio of the amount of the hydrolysis-promoting agent substance to the sum of the amounts of the n-type semiconductor and the p-type semiconductor substance is 5 (2-3).
5. The method for preparing the bionic hydrogel constructed by the nano photoelectric composite semiconductor based on the red light response according to claim 1, wherein in the step (12), the reducing agent is L-cysteine or thiourea, and the molar ratio of the reducing agent to bismuth salt is 1-1.2: 1-2.
6. The method for preparing the bionic hydrogel constructed by the nano photoelectric composite semiconductor based on the red light response, which is disclosed in claim 1, is characterized in that in the step (12), the hydrothermal reaction temperature is 180-200 ℃, and the reaction time is 2-8 hours.
7. The method for preparing the bionic hydrogel constructed based on the red light response nano photoelectric composite semiconductor according to any one of claims 1 to 6, wherein in the step (2), the acetic acid solution of the collagen is prepared by dissolving the collagen in the acetic acid solution under the ice bath condition, and adjusting the pH value of the system to 7-8 by using an alkaline solution; the concentration of acetic acid in the acetic acid solution is 0.4-1M.
8. The method for preparing the bionic hydrogel constructed based on the red light response nano photoelectric composite semiconductor according to any one of claims 1 to 6, wherein the photoinitiator is I2959, and the photoinitiator buffer is obtained by dissolving the photoinitiator in PBS buffer.
9. The biomimetic hydrogel constructed based on the red light response nano photoelectric composite semiconductor prepared by the method of any one of claims 1 to 8.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1961043A (en) * | 2004-05-31 | 2007-05-09 | 财团法人川村理化学研究所 | Composite nanofiber, composite nanofiber mass, composite structure, and processes for producing these |
| EP2607404A1 (en) * | 2011-12-21 | 2013-06-26 | Université de Liège | Composition and preparation of hydrogel nanocomposites with improved mechanical properties and use thereof. |
| CN113564630A (en) * | 2021-07-05 | 2021-10-29 | 江苏大学 | Application of metallic aerogel catalytic material in preparation of anion membrane electrolytic cell for electrocatalytic reduction of CO2 reaction |
| CN113842497A (en) * | 2021-09-28 | 2021-12-28 | 太原理工大学 | Preparation method of CuS @ Cur hybrid hydrogel dressing with light-operated antibacterial and self-healing functions |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170232157A1 (en) * | 2016-02-11 | 2017-08-17 | Arizona Board Of Regents On Behalf Of Arizona State University | Tissue integrating materials for wound repair |
| US10493432B2 (en) * | 2017-02-16 | 2019-12-03 | Carnegie Mellon University | Photocatalyst / carbon nanotube aerogel composites |
-
2022
- 2022-09-02 CN CN202211068883.0A patent/CN115304793B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1961043A (en) * | 2004-05-31 | 2007-05-09 | 财团法人川村理化学研究所 | Composite nanofiber, composite nanofiber mass, composite structure, and processes for producing these |
| EP2607404A1 (en) * | 2011-12-21 | 2013-06-26 | Université de Liège | Composition and preparation of hydrogel nanocomposites with improved mechanical properties and use thereof. |
| CN113564630A (en) * | 2021-07-05 | 2021-10-29 | 江苏大学 | Application of metallic aerogel catalytic material in preparation of anion membrane electrolytic cell for electrocatalytic reduction of CO2 reaction |
| CN113842497A (en) * | 2021-09-28 | 2021-12-28 | 太原理工大学 | Preparation method of CuS @ Cur hybrid hydrogel dressing with light-operated antibacterial and self-healing functions |
Non-Patent Citations (3)
| Title |
|---|
| Bi2S3-TiO2-RGO 复合材料的制备及可见光 下光催化降解罗丹明B 的研究;李亚楠;《中国优秀硕士学位论文全文数据库（电子期刊）》;20191231(第07期);B014-605 * |
| Enhanced Adsorption and Removal of Ciprofloxacin on Regenerable Long TiO2 Nanotube/Graphene Oxide Hydrogel Adsorbents;Zhuang, Yuan等;《JOURNAL OF NANOMATERIALS》;20151231;第2015卷;678 * |
| One-Pot Synthesis of Bi2S3/TiO2/rGO Heterostructure with Red Light-Driven Photovoltaic Effect for Remote Electrotherapy-Assisted Wound Repair;《SMALL》;20230228;第19卷(第7期);1-13 * |
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