CN103611189A - Bacteriostatic composition, implant material and preparation method thereof - Google Patents
Bacteriostatic composition, implant material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a bacteriostatic composition, an implant material coated with the bacteriostatic composition and a preparation method thereof. The bacteriostatic composition comprises expanded polytetrafluoroethylene and a bacteriostatic agent. The implant material is coated with the bacteriostatic composition by a high-voltage electrospinning technology, and the implant material with a bacteriostatic function can be obtained. The expanded polytetrafluoroethylene in the bacteriostatic composition can be used for effectively immobilizing the bacteriostatic agent. Swelling leakage cannot happen even in a complicated environment in a body by utilizing the 'hard shell' structure formed by high-voltage electrospinning, the bacteriostatic agent can be immobilized more effectively, is firmly combined with the material, cannot be easily released, is low in bio-toxicity and excellent in biocompatibility. The preparation method is simple in process, easy to operate and low in cost, and is convenient to realize large-scale production.
Description
Technical field
The present invention relates to embedded material technical field, relate in particular to a kind of bacteria inhibiting composition, embedded material and preparation method thereof.
Background technology
Biomaterial and artificial organ are applied to clinical medicine more and more widely.In the continuous progressive society of science and technology, almost everyone is at likely forever or temporarily implantable bioartificial material or artificial organ in vivo in life.As surgery sewing material, various invasive conduits, various tissues and organ for articles for use: artificial joint, Cardiac valve prosthesis, artificial intraocular lenses and even artificial heart-lung kidney etc.And the most important reason of restriction these biomaterials of broader applications and artificial organ is the infection (Biomaterial-centered infection, BCI) centered by biomaterial.Therefore, the research about pathogenesis, Clinical symptoms, pathophysiological change and the prevention of BCI, has seemed more and more important.
A key factor that causes BCI is exactly bacteria planting.Various microorganisms (antibacterial etc.) are often fallen human body from varying environment, and can settle down and constantly grow, raise up seed at certain position, and this phenomenon is commonly referred to " bacteria planting ".In general, be to form biomembrane as microorganisms such as antibacterial or yeast---be the infectiousness cellular layer of stick-slip, glue sample.The microorganism of field planting must rely on human body constantly to supply with nutrient substance ability Growth and reproduction, and then human body is exerted an influence (as causing infection).In order to prevent post-operative infection, usually first to patient, use in the preoperative the broad ectrum antibiotic of various brute forces, attempt to perform the operation under " absolutesterility " condition, to guarantee successful surgery.Also can adopt narrow-spectrum antibiotic, remove targetedly a certain bacterioid.Embedded material, as a kind of foreign body, once infect, in most cases needs to be taken out, and particularly for the long period after implanting, the infected occurs, and generally all bacteria planting causes slowly, and established fibrous capsule can hinder the performance of antibiotic effect.
By implantation material surface or structure is anticipated and microorganism cannot be adhered at implantation material surface, as a kind of means more widely, enjoy people to pay close attention to.For example, the embedded material of script fine pore is made to macrovoid size, as the PP hernia paster of macropore, macrophage can be entered effectively between hole, engulf to cause the microorganism of infecting, yet this kind of method is for baroque orthopaedics implant or to need the embedded material of high support strength be inapplicable.And for example, on implantation material surface, apply some antibacterial material, as degradable chitosan, thereby prevent that antibacterial and yeast are parasitic on this surface, hinder its field planting on this surface, but owing to belonging to bio-extract because of chitosan, be easy to exist foreign protein, therefore anaphylactic patient's number increases, in addition, chitosan degradation speed is in vivo very fast, for what prevent for a long time bacteria planting, is disadvantageous; Or, thereby directly apply some antibacterial at implantation material surface, stop bacteria planting, yet these antibacterial also have cytotoxicity or bio-toxicity to a certain degree, in antibacterial, can have release in various degree, may cause antibacterial poisoning.Therefore, select rational fungistatic coating, stoping long-term effectively Microorganism colonization is to have very much actual clinical meaning.
Summary of the invention
The object of the present invention is to provide a kind of bacteria inhibiting composition, be coated with embedded material of described bacteria inhibiting composition and preparation method thereof, this bacteria inhibiting composition is coated in implantation material surface and forms fungistatic coating, and antibacterial is wherein combined firmly with material, can be released, bio-toxicity is low and have good biocompatibility; This preparation method can be in the even film forming of implantation material surface, and it is combined with embedded material firmly, difficult drop-off, therefore good to the fixed effect of antibacterial.
For reaching this object, the present invention by the following technical solutions:
In first aspect, the invention provides a kind of bacteria inhibiting composition, comprise expanded PTFE and antibacterial.
Expanded PTFE (the expended polytetrafluoroethylene that the present invention adopts, ePTFE) there is complete biologically inert, can stand to be exposed to the test of the biochemistry corrosion of aqueous environment, body temperature, blood and body fluid, and some complication that can effectively stop embedded material to cause, as the leaching of blood coagulation, rejection, infection and cytotoxic chemical thing, therefore Yi Bei food and drug administration (Food andDrug Administration, FDA) approval is for the manufacture of long-term embedded material.Described expanded PTFE is medical grade material, and the residual quantities such as heavy metal all should meet embedded material standard; Wherein, heavy metal total content (in lead) is answered≤300 μ g/g, and monomer residue is answered <2%, and catalyst residue is answered <200 μ g/g.
Preferably, the weight average molecular weight of described expanded PTFE is 50,000～500,000, for example 50,000,60,000,80,000,100,000,120,000,150,000,180,000,200,000,240,000,250,000,270,000,300,000,320,000,350,000,380,000,400,000,420,000,450,000,480,000,490,000 or 500,000.
Preferably, described antibacterial is selected from solution-type antibacterial, parabens, cationic surfactant, alcohols antibacterial and metal species antibacterial.
More preferably, described solution-type antibacterial is selected from chlorhexidine acetate, A.SAP; Described parabens is selected from methyl hydroxybenzoate and ethyl hydroxybenzoate; Described cationic surfactant is selected from benzalkonium chloride and benzalkonium bromide; Described alcohols antibacterial is selected from chlorobutanol; Described metal species antibacterial is selected from nanometer silver and Nano-Zinc.
Above-mentioned antibacterial can be used separately a kind of, also can be used in combination two or more, typical case but the example combinations of indefiniteness comprise: chlorhexidine acetate and A.SAP, methyl hydroxybenzoate and ethyl hydroxybenzoate, benzalkonium chloride and benzalkonium bromide, benzalkonium chloride, benzalkonium bromide and chlorobutanol, nanometer silver and Nano-Zinc, chlorhexidine acetate and methyl hydroxybenzoate, ethyl hydroxybenzoate and benzalkonium chloride, benzalkonium bromide and chlorobutanol, etc.
Preferably, in described bacteria inhibiting composition, the weight of antibacterial is with expanded PTFE weighing scale 0.1%-1%, for example 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9% or 1.0%.
Preferably, described bacteria inhibiting composition also comprises dicyandiamide solution, and described dicyandiamide solution comprises chlorine trifluoride and/or chlorine pentafluoride.In the present invention, solvent can vapor away in final electrostatic spinning process, so bacteria inhibiting composition of the present invention can be the compositions that comprises or do not comprise dicyandiamide solution.
In second aspect, the invention provides the preparation method of the bacteria inhibiting composition as described in first aspect, described method comprises: described expanded PTFE is dissolved in dicyandiamide solution, is mixed with solution, add described antibacterial, ultrasonic dispersion stirring obtain described bacteria inhibiting composition.
Preferably, described dicyandiamide solution comprises DMF, and described dicyandiamide solution also optionally comprises one or more in oxolane (Tetrahydrofuran, THF), butanone and NaCl aqueous solution.
Preferably, the concentration of expanded PTFE described in described solution is 5-20%(w/v), 6%(w/v for example), 8%(w/v), 10%(w/v), 12%(w/v), 14%(w/v), 16%(w/v), 18%(w/v) or 19%(w/v), wherein wt (w) is in unit gram (g), volume (v)Yi unit milliliter (mL) meter, weight/volume (w/v) is in unit grams per milliliter (g/mL).
Preferably, the time of described ultrasonic dispersion is 10-20min, for example 12min, 14min, 16min, 18min or 19min.
Preferably, the time of described stirring is 2-5h, for example 2h, 2.5h, 3h, 3.5h, 4h, 4.5h or 5h.
The bacteria inhibiting composition of preparing by said method, described expanded PTFE mixes with antibacterial is full and uniform, even film forming while being beneficial to high-voltage electrostatic spinning.
In the third aspect, the invention provides a kind of surface-coated just like the embedded material of the bacteria inhibiting composition described in first aspect.
Preferably, described embedded material is coated in its surface by high-voltage electrostatic spinning by described bacteria inhibiting composition and obtains.
Expanded PTFE is due to its good biological and chemical stability, and optional dissolution solvent is less, and traditional solution plated film can cause applying inhomogeneous.The adhesion of this material and antibacterial also a little less than, utilize high-voltage electrostatic spinning, its special film-forming process is that first solidify fiber outside, and " duricrust " of formation be even if structure swelling can not occur yet under complex environment in vivo to be revealed, can be effectively fixing antibacterial; By regulate electric field, injection stream can be at the material surface of arbitrary shape even film forming, due to its nonwoven in form continuous film forming, thereby can well be combined with embedded material, difficult drop-off.
Preferably, described embedded material is artificial joint, Cardiac valve prosthesis, artificial intraocular lenses, the artificial heart, artificial lung or artificial kidney.
In fourth aspect, the invention provides the preparation method of the embedded material as described in the third aspect, described method comprises:
Described bacteria inhibiting composition is injected to syringe, add rustless steel syringe needle, adopting voltage is 10～30KV positive electric field high voltage power supply, maintenance solution flow rate is 1～5mL/h, receiving range is 5～25cm, the embedded material that needs are applied connects the negative electric field high voltage power supply that voltage is 100-800V, applies, and finally will apply complete embedded material room temperature vacuum drying 24-48h.
In the preparation method of above-mentioned embedded material, the voltage of positive electric field high voltage power supply can be 12KV, 15KV, 18KV, 22KV, 25KV, 27KV or 29KV; Solution flow rate can be 1.5mL/h, 2mL/h, 2.5mL/h, 3mL/h, 3.5mL/h, 4mL/h or 4.5mL/h; Receiving range can be 6cm, 7cm, 9cm, 11cm, 13cm, 15cm, 17cm, 19cm, 21cm, 23cm or 24cm; Negative electric field high voltage power supply can be 100V, 200V, 300V, 400V, 500V, 600V, 700V or 800V; The vacuum drying time can be 25h, 27h, 29h, 31h, 35h, 38h, 40h, 42h, 44h or 46h.
As an optimal technical scheme of the present invention, described method comprises:
(1) described expanded PTFE is dissolved in described dicyandiamide solution, being mixed with concentration is 5-20%(w/v) solution, adding weight content is the antibacterial of the 0.1%-1% of described expanded PTFE weight content, ultrasonic dispersion 10-20min, and in 80-100 ℃ of stirring 2-5h, obtain described bacteria inhibiting composition;
(2) solution of described bacteria inhibiting composition is injected to syringe, add rustless steel syringe needle, adopting voltage is 10～30KV positive electric field high voltage power supply, maintenance solution flow rate is 1～5mL/h, receiving range is 5～25cm, the embedded material that needs are applied connects the negative electric field high voltage power supply that voltage is 100-800V, applies, and finally will apply complete embedded material room temperature vacuum drying 24-48h.
Aspect the 5th, the invention provides the embedded material that the preparation method as described in fourth aspect makes.
Beneficial effect of the present invention is: bacteria inhibiting composition of the present invention adopts expanded PTFE and antibacterial to combine, wherein the effectively fixing antibacterial of expanded PTFE.In addition, utilize high-voltage electrostatic spinning, its special film-forming process is that first solidify fiber outside, " duricrust " forming is even if can there is not swelling leakage under complex environment in vivo in structure yet, can be more fixing antibacterial, in antibacterial insert material wherein, be not released completely, bio-toxicity is low and have good biocompatibility; Utilize high-voltage electrostatic spinning can be at the implantation material surface of arbitrary shape even film forming, it is combined with embedded material firmly, difficult drop-off, therefore fabulous to the fixed effect of antibacterial; Preparation method of the present invention, technique is simple, easy operating, with low cost, be convenient to realize large-scale production.
The specific embodiment
Below in conjunction with embodiment, embodiment of the present invention are described in detail.It will be understood to those of skill in the art that following examples are only the preferred embodiments of the present invention, so that understand better the present invention, thereby should not be considered as limiting scope of the present invention.For a person skilled in the art, the present invention can have various modifications and variations, within the spirit and principles in the present invention all, any modification of doing, is equal to and replaces or improvement etc., within all should being included in protection scope of the present invention.Experimental technique in following embodiment, if no special instructions, is conventional method; Experiment material used, if no special instructions, is and is purchased available from routine biochemistry chemical reagent work.
Embodiment 1
Be prepared as follows the embedded material coating with bacteria resistance function:
(1) mixed solution of preparation expanded PTFE and antibacterial: the expanded PTFE of 200,000 molecular weight (ePTFE) is dissolved in to chlorine trifluoride, being mixed with concentration is 15%(W/V) mixed solution 20ml, adding therein concentration is 10% chlorhexidine acetate solution 0.06ml, according to effective bacteriostatic ingredients, calculate, antibacterial weight content is in polymer weight 0.2%; After ultrasonic 20 minutes, make it dispersed, 80 ℃ are stirred 4 hours.
(2) prepare compound fungistatic coating: by above-mentioned mixed solution, inject 5ml glass mould syringe, add rustless steel syringe needle No. 5, adopt the positive electric field high voltage power supply that voltage is 25KV, solution flow rate is 2mL/h, and receiving range is 18cm; In the rotatable metal conductor rod that the negative electric field high voltage power supply that it is 100V that the hernia paster that needs are applied is placed in voltage is connected, rotary speed is 100r/min, after 10 meters of spinning, will apply complete material room temperature vacuum drying 24 hours, remove residual solvent, and preserve in 4 ℃ of drying baker.
According to ISO11737(2009) carry out bacteriostatic experiment, the fungistatic coating of above-mentioned preparation carried out antibacterial culturing after 3 days, and viable count can not be detected in surface, and surperficial bacteriostasis rate reaches more than 99.99%.In addition, be placed on the middle half a year of phosphate buffer (PBS solution) of 37 ℃, the release of chlorhexidine acetate do not detected.According to GBT16886.5(2003) in BiologicalEvaluationofMedicalDevice the 5th part carry out vitro cytotoxicity test, in 3T6 cell culture experiments, 3T6 cell can be in coating material surface adhesion, well-grown in containing the cell culture fluid of coating, adherent good with culture dish, the fungistatic coating that proof obtains, can effectively stop biomembrane to form at implantation material surface, and have good biocompatibility.
Embodiment 2
Be prepared as follows the embedded material coating with bacteria resistance function:
(1) mixed solution of preparation expanded PTFE and antibacterial: the expanded PTFE of 50,000 molecular weight (ePTFE) is dissolved in to chlorine pentafluoride, being mixed with concentration is 20%(W/V) mixed solution 20ml, adding therein concentration is 10% chlorhexidine acetate solution 0.04ml, according to effective bacteriostatic ingredients, calculate, antibacterial weight content is in polymer weight 0.1%; After ultrasonic 10 minutes, make it dispersed, 80 ℃ are stirred 3 hours.
(2) prepare compound fungistatic coating: by above-mentioned mixed solution, inject 5ml glass mould syringe, add rustless steel syringe needle No. 5, adopt the positive electric field high voltage power supply that voltage is 10KV, solution flow rate is 5mL/h, and receiving range is 5cm; In the rotatable metal conductor rod that the negative electric field high voltage power supply that it is 100V that the hernia paster that needs are applied is placed in voltage is connected, rotary speed is 100r/min, after 10 meters of spinning, will apply complete material room temperature vacuum drying 36 hours, remove residual solvent, and preserve in 4 ℃ of drying baker.
According to ISO11737(2009) carry out bacteriostatic experiment, the fungistatic coating of above-mentioned preparation carried out antibacterial culturing after 3 days, and viable count can not be detected in surface, and surperficial bacteriostasis rate reaches more than 99.99%.In addition, be placed on the middle half a year of phosphate buffer (PBS solution) of 37 ℃, the release of chlorhexidine acetate do not detected.According to GBT16886.5(2003) in BiologicalEvaluationofMedicalDevice the 5th part carry out vitro cytotoxicity test, in 3T6 cell culture experiments, 3T6 cell can be in coating material surface adhesion, well-grown in containing the cell culture fluid of coating, adherent good with culture dish, the fungistatic coating that proof obtains, can effectively stop biomembrane to form at implantation material surface, and have good biocompatibility.
Embodiment 3
Be prepared as follows the embedded material coating with bacteria resistance function:
(1) mixed solution of preparation expanded PTFE and antibacterial: the mixed solvent (wherein the volume ratio of chlorine trifluoride and chlorine pentafluoride is 2:1) that the expanded PTFE of 500,000 molecular weight (ePTFE) is dissolved in to chlorine trifluoride and chlorine pentafluoride, being mixed with concentration is 5%(W/V) mixed solution 20ml, adding therein concentration is 10% Benza 0.1ml, according to effective bacteriostatic ingredients, calculate, antibacterial weight content is 1% of polymer weight content; After ultrasonic 20 minutes, make it dispersed, 100 ℃ are stirred 5 hours.
(2) prepare compound fungistatic coating: by above-mentioned mixed solution, inject 5ml glass mould syringe, add rustless steel syringe needle No. 5, adopt the positive electric field high voltage power supply that voltage is 30KV, solution flow rate is 1mL/h, and receiving range is 25cm; In the rotatable metal conductor rod that the negative electric field high voltage power supply that it is 800V that the hernia paster that needs are applied is placed in voltage is connected, rotary speed is 100r/min, after 10 meters of spinning, will apply complete material room temperature vacuum drying 48 hours, remove residual solvent, and preserve in 4 ℃ of drying baker.
According to ISO11737(2009) carry out bacteriostatic experiment, the fungistatic coating of above-mentioned preparation carried out antibacterial culturing after 3 days, and viable count can not be detected in surface, and surperficial bacteriostasis rate reaches more than 99.99%.In addition, be placed on the middle half a year of phosphate buffer (PBS solution) of 37 ℃, the release of benzalkonium chloride do not detected.According to GBT16886.5(2003) in BiologicalEvaluationofMedicalDevice the 5th part carry out vitro cytotoxicity test, in 3T6 cell culture experiments, 3T6 cell can be in coating material surface adhesion, well-grown in containing the cell culture fluid of coating, adherent good with culture dish, the fungistatic coating that proof obtains, can effectively stop biomembrane to form at implantation material surface, and have good biocompatibility.
Embodiment 4
Be prepared as follows the embedded material coating with bacteria resistance function:
(1) mixed solution of preparation expanded PTFE and antibacterial: the expanded PTFE of 350,000 molecular weight (ePTFE) is dissolved in to chlorine trifluoride, being mixed with concentration is 10%(W/V) mixed solution 20ml, adding therein concentration is 1% A.SAP solution 0.5ml, according to effective bacteriostatic ingredients, calculate, antibacterial weight content is in polymer weight 0.25%; After ultrasonic 20 minutes, make it dispersed, 90 ℃ are stirred 5 hours.
(2) prepare compound fungistatic coating: by above-mentioned mixed solution, inject 5ml glass mould syringe, add rustless steel syringe needle No. 5, adopt the positive electric field high voltage power supply that voltage is 20KV, solution flow rate is 2mL/h, and receiving range is 18cm; In the rotatable metal conductor rod that the negative electric field high voltage power supply that it is 100V that the hernia paster that needs are applied is placed in voltage is connected, rotary speed is 100r/min, after 10 meters of spinning, will apply complete material room temperature vacuum drying 24 hours, remove residual solvent, and preserve in 4 ℃ of drying baker.
According to ISO11737(2009) carry out bacteriostatic experiment, the fungistatic coating of above-mentioned preparation carried out antibacterial culturing after 3 days, and viable count can not be detected in surface, and surperficial bacteriostasis rate reaches more than 99.99%.In addition, be placed on the middle half a year of phosphate buffer (PBS solution) of 37 ℃, the release of A.SAP do not detected.According to GBT16886.5(2003) in BiologicalEvaluationofMedicalDevice the 5th part carry out vitro cytotoxicity test, in 3T6 cell culture experiments, 3T6 cell can be in coating material surface adhesion, well-grown in containing the cell culture fluid of coating, adherent good with culture dish, the fungistatic coating that proof obtains, can effectively stop biomembrane to form at implantation material surface, and have good biocompatibility.
Applicant's statement, the present invention illustrates detailed features of the present invention and method detailed by above-described embodiment, but the present invention is not limited to above-mentioned detailed features and method detailed, do not mean that the present invention must rely on above-mentioned detailed features and method detailed could be implemented.Person of ordinary skill in the field should understand, any improvement in the present invention is selected the selection of the equivalence replacement of component and the interpolation of auxiliary element, concrete mode etc., within all dropping on protection scope of the present invention and open scope to the present invention.
Claims (10)
1. a bacteria inhibiting composition, is characterized in that, described bacteria inhibiting composition comprises expanded PTFE and antibacterial.
2. bacteria inhibiting composition according to claim 1, is characterized in that, the weight average molecular weight of described expanded PTFE is 50,000～500,000;
Preferably, described antibacterial is selected from solution-type antibacterial, parabens, cationic surfactant, alcohols antibacterial and metal species antibacterial;
More preferably, described solution-type antibacterial is selected from chlorhexidine acetate, A.SAP; Described parabens is selected from methyl hydroxybenzoate and ethyl hydroxybenzoate; Described cationic surfactant is selected from benzalkonium chloride and benzalkonium bromide; Described alcohols antibacterial is selected from chlorobutanol; Described metal species antibacterial is selected from nanometer silver and Nano-Zinc.
3. bacteria inhibiting composition according to claim 1 and 2, is characterized in that, in described bacteria inhibiting composition, the weight content of antibacterial is with expanded PTFE weighing scale 0.1%-1%.
4. according to the bacteria inhibiting composition described in claim 1-3 any one, it is characterized in that, described bacteria inhibiting composition also comprises dicyandiamide solution, and described dicyandiamide solution comprises chlorine trifluoride and/or chlorine pentafluoride.
5. the preparation method of the bacteria inhibiting composition as described in claim 1-4 any one, it is characterized in that, described method comprises: described expanded PTFE is dissolved in dicyandiamide solution, is mixed with solution, add described antibacterial, ultrasonic dispersion stirring obtain described bacteria inhibiting composition;
Preferably, described dicyandiamide solution comprises chlorine trifluoride and/or chlorine pentafluoride;
Preferably, the concentration of expanded PTFE described in described solution is 5-20%(w/v);
Preferably, the time of described ultrasonic dispersion is 10-20min;
Preferably, the time of described stirring is 2-5h.
6. a surface-coated is just like the embedded material of the bacteria inhibiting composition described in claim 1-4 any one.
7. embedded material according to claim 6, is characterized in that, described embedded material is coated in its surface by high-voltage electrostatic spinning by described bacteria inhibiting composition and obtains;
Preferably, described embedded material is artificial joint, Cardiac valve prosthesis, artificial intraocular lenses, the artificial heart, artificial lung or artificial kidney.
8. the preparation method of the embedded material as described in claim 6 or 7, is characterized in that, described method comprises:
Described bacteria inhibiting composition is injected to syringe, add rustless steel syringe needle, adopting voltage is 10～30KV positive electric field high voltage power supply, maintenance solution flow rate is 1～5mL/h, receiving range is 5～25cm, the negative electric field high voltage power supply that the embedded material that needs are applied is 100-800V with voltage is connected, and applies, and finally will apply complete embedded material room temperature vacuum drying 24-48h.
9. preparation method according to claim 8, is characterized in that, described bacteria inhibiting composition obtains as follows:
Described expanded PTFE is dissolved in described dicyandiamide solution, being mixed with concentration is 5-20%(w/v) solution, adding weight content is the antibacterial with expanded PTFE weighing scale 0.1%-1%, ultrasonic dispersion 10-20min, and in 80-100 ℃ of stirring 2-5h, obtain described bacteria inhibiting composition.
10. the embedded material making by the preparation method described in claim 8 or 9.
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| CN104389106A (en) * | 2014-11-12 | 2015-03-04 | 无锡中科光远生物材料有限公司 | Polytetrafluoroethylene superfine fiber film and preparation method thereof |
| CN104645943A (en) * | 2014-12-26 | 2015-05-27 | 张红梅 | Method for preparing renewable anti-bacteria fiber for adsorbing heavy metal motes |
| CN107158483A (en) * | 2017-07-12 | 2017-09-15 | 上海微特生物技术有限公司 | A kind of sterile working method for improving biodegradable stent systematic function |
| CN108641506A (en) * | 2018-04-19 | 2018-10-12 | 苏州诺升功能高分子材料股份有限公司 | A kind of preparation method of the composite nano anti-biotic dispersant based on polytetrafluoroethylene (PTFE) |
| CN108641506B (en) * | 2018-04-19 | 2021-02-26 | 苏州诺升功能高分子材料股份有限公司 | Preparation method of polytetrafluoroethylene-based composite nano antibacterial dispersant |
| RU2825387C1 (en) * | 2023-11-24 | 2024-08-26 | Венера Рустамовна Лучшева | Bioactive coating with antibacterial effect |
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