CN114959947A - Multifunctional gel probe for sensing and regulating biological information and preparation method thereof - Google Patents
Multifunctional gel probe for sensing and regulating biological information and preparation method thereof Download PDFInfo
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- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L31/145—Hydrogels or hydrocolloids
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- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
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- D01D5/06—Wet spinning methods
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- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
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- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
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- D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
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- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
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- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
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- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/12—Nanosized materials, e.g. nanofibres, nanoparticles, nanowires, nanotubes; Nanostructured surfaces
Abstract
The invention belongs to the technical field of preparation of multifunctional composite probe materials, and discloses a multifunctional gel probe for sensing and adjusting biological information, wherein the cross section of the multifunctional gel probe is of a three-core composite gel structure and consists of a skin layer and a parallel three-component core layer; the skin layer is high molecular polymer hydrogel, and the three components of the core layer are light guide monomer hydrogel, drug-loaded monomer hydrogel and carbon-based hybrid hydrogel respectively; the invention also discloses a preparation method of the multifunctional gel probe for sensing and regulating the biological information. The invention is used for preparing the multifunctional gel probe for sensing and adjusting the biological information, and has the light guide performance, the electric conductivity and the drug slow release function.
Description
Technical Field
The invention belongs to the technical field of preparation of multifunctional composite probe materials, and relates to a preparation method of a multifunctional gel probe for biological information sensing and regulation.
Background
The simultaneous detection and operation of nerve cells in a living body play an important role in understanding the neural circuits of the living body and exploring the pathogenesis of neurological diseases. In recent years, as a variety of neural recording devices have been developed due to advances in material processing technology, analysis of neural circuits requires control of specific nerve cells with stimulation of millisecond accuracy in addition to a neural electric signal recording function. At present, the development of optogenetics greatly improves the accuracy of neuroscience research, and in vivo nerve cells can further realize regulation and treatment through pharmacological compounds. Therefore, the multifunctional probe material with the photoconductive property, the electric conductivity and the drug slow-release function is developed, and the development of the field of neuroscience is greatly promoted.
Disclosure of Invention
The invention aims to provide a preparation method of a multifunctional gel probe for biological information sensing and regulation, which has the light guide performance, the electrical conductivity and the drug slow release function.
The invention also aims to provide a preparation method of the multifunctional gel probe for sensing and adjusting the biological information, which comprises the steps of enabling the skin layer spinning solution and the first to third core layer spinning solutions to pass through a three-core spinning nozzle, then solidifying the three core layer spinning solutions through a coagulating bath, adding an ultraviolet point light source to enable monomers in the first to third core layer spinning solutions to carry out free radical polymerization reaction, and then winding and collecting the three core layer spinning solutions.
In order to achieve the purpose, the invention adopts the following technical scheme:
a multifunctional gel probe for sensing and adjusting biological information is characterized in that the cross section of the multifunctional gel probe for sensing and adjusting the biological information is of a three-core composite gel structure and consists of a skin layer and a parallel three-component core layer; the skin layer is high molecular polymer hydrogel, and the three components of the core layer are light guide monomer hydrogel, drug-carrying monomer hydrogel and carbon-based hybrid hydrogel respectively.
The invention also provides a preparation method of the multifunctional gel probe for sensing and regulating the biological information, which comprises the following steps:
s1, taking a high molecular polymer aqueous solution with the mass fraction of 0.5-20 wt.% as a skin layer spinning solution;
taking a light guide monomer aqueous solution with the mass fraction of 10-90 wt.% as a first core layer spinning solution;
taking a drug-loaded monomer aqueous solution with the mass fraction of 10-90 wt.% as a second core layer spinning solution;
taking a carbon-based hybrid monomer aqueous solution with the mass fraction of 0.5-10 wt.% as a third core layer spinning solution;
s2, extruding the skin layer spinning solution, the first core layer spinning solution, the second core layer spinning solution and the third core layer spinning solution into a water bath of a coagulating bath through a three-core spinning nozzle, setting an ultraviolet point light source at a position 1-100 mm away from a spinning nozzle for solidification to obtain a primary hydrogel fiber, and drying, winding, collecting and reducing by using a reducing agent to obtain the multifunctional gel probe for sensing and adjusting the biological information.
In step S1, the polymer is any one of sodium alginate, chitosan, PVA, and aqueous polyurethane, and the molecular weight of the polymer is M w ＝4000～4000000。
As a second limitation, in step S1, the light-guiding monomer includes a matrix component a, a hydrophilic component, and a photoinitiator B; the mass ratio of the matrix component A to the hydrophilic component to the photoinitiator B is 1: 0-1: 0.001-0.01;
the matrix component A is a bifunctional polyethylene glycol derivative, and the hydrophilic component is an acrylamide derivative.
As a further limitation, the matrix component a is any one of polyethylene glycol bisacrylamide and polyethylene glycol diacrylate;
the hydrophilic component is any one of acrylamide, N-dimethylacrylamide and N-isopropylacrylamide;
the photoinitiator B is 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone.
As a third limitation, in step S1, the drug-loaded monomer includes a matrix component C, drug-loaded nanoparticles, an entrapped drug, and a photoinitiator D;
the mass ratio of the matrix component C, the drug-loaded nanoparticles, the entrapped drug and the photoinitiator D is 1: 0.1-1: 0.05-1: 0.001-0.01;
the matrix component C is a bifunctional polyethylene glycol derivative.
As a further limitation, the matrix component C is any one of polyethylene glycol bisacrylamide and polyethylene glycol diacrylate;
the drug-loaded nano particles are any one of porous silicon dioxide and microgel;
the entrapped medicine is any one of curcumin, adriamycin, catechol, oryzanol and mecobalamin;
the photoinitiator D is 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone.
As a fourth limitation, in step S1, the carbon-based hybrid monomer includes a carbon-based material, a conductive nanofiller;
the mass ratio of the carbon-based material to the conductive nano filler is 1: 0-9.
As a further limitation, the carbon-based material is any one of graphene oxide, graphene and carbon nanotubes;
the conductive nano filler is any one of conductive carbon black, MXene and silver nanowires.
As a fifth limitation, in step S2, the coagulation bath is an aqueous solution of calcium chloride or zinc chloride with a concentration of 0.1 wt.% to 5.0 wt.%;
the extrusion rate of the skin layer spinning solution is 1-100 mL/h; the extrusion rates of the first core layer spinning solution, the second core layer spinning solution and the third core layer spinning solution are 0.1-50 mL/h;
the wavelength of the ultraviolet point light source is 200-400 nm, and the illumination intensity is 0.1-10W/cm 2 (ii) a The winding and collecting linear speed is 0.1-150 m/h.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the technical progress that:
(1) aiming at the difficult points that the mechanical property between the current probe material and organism soft tissue is not suitable to cause tissue damage and the probe function is unstable, a three-core spinning nozzle is used for extruding a skin-core layer spinning solution into a coagulating bath based on a water-phase in-situ polymerization spinning method, then a high-molecular polymer hydrogel coagulated by a skin layer is used for stabilizing a core layer aqueous solution, the solidification of the three core layer spinning solutions is ensured, and a multifunctional gel probe is finally obtained through drafting;
(2) the method comprises the steps of enabling the skin layer spinning solution and the first to third core layer spinning solutions to pass through a three-core spinning nozzle, then solidifying the three core layer spinning solutions through a coagulating bath, adding an ultraviolet point light source to enable monomers in the first to third core layer spinning solutions to carry out free radical polymerization reaction, and then winding and collecting the three core layer spinning solutions, so that the method has a great application prospect in the field of neuroscience;
(3) the diameter of the sheath-core layer of the multifunctional gel probe for sensing and adjusting biological information can be controlled by the extrusion speed ratio, the winding speed, the concentration and the like of the spinning solution, and the preparation method is carried out at room temperature.
The invention belongs to the technical field of preparation of multifunctional composite probe materials, and is used for preparing multifunctional gel probes for biological information sensing and regulation.
Drawings
FIG. 1 is a photo of a photoconductive physical object of the multifunctional gel probe prepared in example 2 of the present invention;
FIG. 2 is a graph showing the conductivity of the multifunctional gel probe prepared in example 2 of the present invention;
FIG. 3 shows the drug release performance of the multifunctional gel probe prepared in example 2 of the present invention;
FIG. 4 is a schematic view of a manufacturing apparatus according to an embodiment of the present invention.
Detailed Description
For the purpose of better explaining the present invention and to facilitate understanding, the present invention will be described in detail by way of specific embodiments with reference to the accompanying drawings.
Example 1A multifunctional gel probe for bioinformation sensing and adjustment
A multifunctional gel probe for sensing and adjusting biological information is characterized in that the cross section of the multifunctional gel probe is of a three-core composite gel structure and consists of a skin layer and a parallel three-component core layer; the skin layer is high molecular polymer hydrogel, and the three components of the core layer are light guide monomer hydrogel, drug-carrying monomer hydrogel and carbon-based hybrid hydrogel respectively.
Example 2 preparation of a multifunctional gel probe for bioinformation sensing and Regulation
The embodiment comprises the following steps:
s1, preparing 2kg of sodium alginate aqueous solution with the mass fraction of 20 wt.% (0.4kg), and uniformly stirring the aqueous solution to obtain the cortex spinning solution, wherein the molecular weight of the sodium alginate is M w ＝4000；
Preparing 2kg of light guide monomer aqueous solution with the mass fraction of 10 wt.% (0.2kg), and uniformly stirring the light guide monomer aqueous solution to be used as a first core layer spinning solution; the light-conducting monomer comprises a matrix component A, a hydrophilic component and a photoinitiator B, wherein the matrix component A adopts polyethylene glycol bisacrylamide, the hydrophilic component adopts acrylamide, and the photoinitiator B adopts 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone; the mass ratio of the polyethylene glycol bisacrylamide to the acrylamide to the 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone is 1:0: 0.005;
preparing 2kg of a drug-loaded monomer aqueous solution with the mass fraction of 20 wt.% (0.4kg), and uniformly stirring the drug-loaded monomer aqueous solution to be used as a second core layer spinning solution; the drug-loaded monomer comprises a matrix component C, drug-loaded nanoparticles, a drug-coated drug and a photoinitiator D; wherein, the matrix component C adopts polyethylene glycol diacrylate, the drug-loaded nano particles adopt porous silicon dioxide, the drug-coated nano particles adopt therapeutic drugs, the step adopts adriamycin, and the photoinitiator D adopts 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone; the mass ratio of the polyethylene glycol diacrylate, the porous silicon dioxide, the adriamycin to the 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone is 1:1:0.5: 0.005;
in the step, the medicine-coated medicine can also adopt other medicines for treatment;
preparing 2kg of carbon-based hybrid monomer aqueous solution with the mass fraction of 10 wt.% (0.2kg), and uniformly stirring the aqueous solution to obtain a third core layer spinning solution; the carbon-based hybrid monomer comprises a carbon-based material and a conductive nano filler; wherein the carbon-based material adopts graphene oxide, and the conductive nano filler adopts silver nanowires; the mass ratio of the graphene oxide to the silver nanowires is 1: 9;
s2, extruding the skin layer spinning solution, the first core layer spinning solution, the second core layer spinning solution and the third core layer spinning solution into a calcium chloride water bath through a three-core spinning nozzle, wherein the three-core spinning nozzle has four spinning solution channels, the skin layer spinning solution is extruded through the skin layer spinning channel, and the extruded skin layer spinning solution can wrap the three core layer spinning solutions. Wherein the extrusion rate of the skin layer spinning solution is 1mL/h, and the extrusion rates of the first core layer spinning solution, the second core layer spinning solution and the third core layer spinning solution are 10 mL/h; setting ultraviolet point light source at a distance of 50mm from the spinneret orifice for curing, wherein the wavelength is 200nm, and the illumination intensity is 5W/cm 2 To obtain the primary hydrogel fiberMaintaining; and drying at 80 ℃ for 0.5h, wherein the linear speed of winding and collecting is 9m/h, and after hydriodic acid is reduced, winding and collecting the primary hydrogel fiber to obtain the multifunctional gel probe for sensing and adjusting the biological information.
In this example, a light guide photograph of the rolled multifunctional gel probe for sensing and adjusting biological information is shown in fig. 1, and it can be seen from fig. 1 that the prepared multifunctional gel probe has excellent light guide characteristics and can transmit laser light into the body. The prepared multifunctional gel probe is subjected to a conductivity characteristic test, a high resistance meter is adopted to measure the resistance of an electrode with the length of 3cm, then the conductivity of the electrode is converted, the test result is shown in fig. 2, it can be known from fig. 2 that the prepared multifunctional gel probe has excellent conductivity characteristics, the conductivity of the multifunctional gel probe is increased along with the increase of the content of the silver nanowires in a conductive path, and when the content of the silver nanowires reaches 50 wt.%, the conductivity of the multifunctional gel probe can reach about 210S/cm. As can be seen from FIG. 3, the multifunctional gel probe can realize sustained release of the drug, release the loaded drug with time, and at 5h, the drug release amount can reach about 25%.
FIG. 4 is a schematic view of an apparatus for preparing a multifunctional gel probe for bioinformation sensing and adjustment according to this example.
Example 3 to 7 preparation method of multifunctional gel probe for bioinformation sensing and adjustment
Examples 3 to 7 are methods for preparing a multifunctional gel probe for sensing and adjusting biological information, and the steps are substantially the same as those in example 2, except for the differences in raw materials and process parameters, as shown in table 1:
TABLE 1 examples 3-7 raw materials, Process parameters
Although the present invention has been described in detail with reference to the above embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described above, or equivalents may be substituted for elements thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The multifunctional gel probe for sensing and adjusting the biological information is characterized in that the cross section of the multifunctional gel probe for sensing and adjusting the biological information is of a three-core composite gel structure and consists of a skin layer and a parallel three-component core layer; the skin layer is high molecular polymer hydrogel, and the three components of the core layer are light guide monomer hydrogel, drug-carrying monomer hydrogel and carbon-based hybrid hydrogel respectively.
2. A preparation method of a multifunctional gel probe for sensing and adjusting biological information is characterized by comprising the following steps:
s1, taking a high molecular polymer aqueous solution with the mass fraction of 0.5-20 wt.% as a skin layer spinning solution;
taking a light guide monomer aqueous solution with the mass fraction of 10-90 wt.% as a first core layer spinning solution;
taking a drug-loaded monomer aqueous solution with the mass fraction of 10-90 wt.% as a second core layer spinning solution;
taking a carbon-based hybrid monomer aqueous solution with the mass fraction of 0.5-10 wt.% as a third core layer spinning solution;
s2, extruding the skin layer spinning solution, the first core layer spinning solution, the second core layer spinning solution and the third core layer spinning solution into a water bath of a coagulating bath through a three-core spinning nozzle, setting an ultraviolet point light source at a position 1-100 mm away from a spinning nozzle for solidification to obtain a primary hydrogel fiber, and drying, winding, collecting and reducing by using a reducing agent to obtain the multifunctional gel probe for sensing and adjusting the biological information.
3. The method for preparing a multifunctional gel probe for bioinformation sensing and adjustment according to claim 2, wherein in step S1, the high molecular polymer is any one of sodium alginate, chitosan, PVA, and aqueous polyurethane, and the molecular weight of the high molecular polymer is M w ＝4000～4000000。
4. The method for preparing a multifunctional gel probe for bioinformation sensing and adjustment according to claim 2, wherein in step S1, the light-guiding monomer comprises a matrix component a, a hydrophilic component and a photoinitiator B; the mass ratio of the matrix component A to the hydrophilic component to the photoinitiator B is 1: 0-1: 0.001-0.01;
the matrix component A is a bifunctional polyethylene glycol derivative, and the hydrophilic component is an acrylamide derivative.
5. The method for preparing a multifunctional gel probe for bioinformation sensing and adjustment according to claim 4, wherein the matrix component A is any one of polyethylene glycol bisacrylamide and polyethylene glycol bisacrylate;
the hydrophilic component is any one of acrylamide, N-dimethylacrylamide and N-isopropylacrylamide;
the photoinitiator B is 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone.
6. The method for preparing the multifunctional gel probe for sensing and adjusting biological information according to claim 2, wherein in step S1, the drug-loaded monomer comprises a matrix component C, drug-loaded nanoparticles, a drug-loaded drug, a photoinitiator D;
the mass ratio of the matrix component C, the drug-loaded nanoparticles, the entrapped drug and the photoinitiator D is 1: 0.1-1: 0.05-1: 0.001-0.01;
the matrix component C is a bifunctional polyethylene glycol derivative.
7. The method for preparing a multifunctional gel probe for bioinformation sensing and adjustment according to claim 6, wherein the matrix component C is any one of polyethylene glycol bisacrylamide and polyethylene glycol bisacrylate;
the drug-loaded nano particles are any one of porous silicon dioxide and microgel;
the entrapped medicine is any one of curcumin, adriamycin, catechol, oryzanol and mecobalamin;
the photoinitiator D is 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone.
8. The method for preparing the multifunctional gel probe for bioinformation sensing and adjustment according to claim 2, wherein in step S1, the carbon-based hybrid monomer comprises a carbon-based material, a conductive nano-filler;
the mass ratio of the carbon-based material to the conductive nano filler is 1: 0-9.
9. The method for preparing the multifunctional gel probe for bioinformation sensing and adjustment according to claim 8, wherein the carbon-based material is any one of graphene oxide, graphene, and carbon nanotubes;
the conductive nano filler is any one of conductive carbon black, MXene and silver nanowires.
10. The method for preparing a multifunctional gel probe for bioinformation sensing and adjustment according to claim 2, wherein the coagulation bath is an aqueous solution of calcium chloride or zinc chloride with a concentration of 0.1 wt.% to 5.0 wt.% in step S2;
the extrusion rate of the skin layer spinning solution is 1-100 mL/h; the extrusion rates of the first core layer spinning solution, the second core layer spinning solution and the third core layer spinning solution are 0.1-50 mL/h;
the wavelength of the ultraviolet point light source is 200-400 nm, and the illumination intensity is 0.1-10W/cm 2 (ii) a The linear speed of the winding and collecting is 0.1 to 150 m-h。
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