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WO2014059738A1 - 抗菌导尿管及其制备方法 - Google Patents

抗菌导尿管及其制备方法 Download PDF

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Publication number
WO2014059738A1
WO2014059738A1 PCT/CN2012/087954 CN2012087954W WO2014059738A1 WO 2014059738 A1 WO2014059738 A1 WO 2014059738A1 CN 2012087954 W CN2012087954 W CN 2012087954W WO 2014059738 A1 WO2014059738 A1 WO 2014059738A1
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WIPO (PCT)
Prior art keywords
catheter
solution
polymer
antibacterial
nano
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Application number
PCT/CN2012/087954
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English (en)
French (fr)
Inventor
蔡文胜
吴晓迪
Original Assignee
Cai Wensheng
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Publication of WO2014059738A1 publication Critical patent/WO2014059738A1/zh

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/08—Materials for coatings
    • A61L29/085—Macromolecular materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/14—Materials characterised by their function or physical properties, e.g. lubricating compositions
    • A61L29/16—Biologically active materials, e.g. therapeutic substances
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/102—Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2400/00—Materials characterised by their function or physical properties
    • A61L2400/12—Nanosized materials, e.g. nanofibres, nanoparticles, nanowires, nanotubes; Nanostructured surfaces

Definitions

  • the invention belongs to the field of medical instruments and preparation methods thereof.
  • the catheter is mainly used for clinical stroke, fracture and severe patient retention. It is one of the most commonly used medical devices in hospitals. About 25% of inpatients use catheters during their stay. During use, urinary tract infections are often associated with catheters due to various factors. It has been reported that CAUTI accounts for 30% of all clinical bacterial infections. As the retention time increases, the catheter infection rate increases. During the use of the catheter, usually the bacterial infection rate after a simple catheterization is about 1 to 5 %, 25% of the catheter with a retention period of more than 7 days can cause bacterial infection, catheterization time is more than 14 days, urinary tract infection The incidence is between 90 and 100%, and CAUTI is the most common type of clinical bacterial infection.
  • anti-bacterial catheters are a more effective means than clinical use of antibiotics.
  • clinical data (Franken et al., 2007)
  • antibacterial catheters can reduce the incidence of blood infections by 15 times in central venous catheter use and reduce the incidence of bacterial infections in the urinary catheter by 3 times. Therefore, the development of a medical catheter with antibacterial function is of great significance in reducing the occurrence of CAUTI and reducing the cost of clinical treatment.
  • Chinese Patent Publication No. CN2529660 describes the preparation of a dosing zone below the catheter balloon, which is used to add various antibiotics depending on the situation.
  • Chinese invention patent application 200810200169. 6 Silver-based inorganic antibacterial agent using zirconium phosphate as a carrier is incorporated into a catheter material to prepare a sustained-release antibacterial medical catheter.
  • Chinese invention patent application 200810203587. 0 discloses a preparation method of an organic/inorganic composite antibacterial catheter, which is mixed with a high-speed stirring of an inorganic antibacterial agent and a silicone emulsion, mixed into a raw material of a catheter, and coated on the surface after molding.
  • Chinese invention patent application 200810200169. 6 discloses a silver-based inorganic antibacterial agent which is doped with zirconium phosphate as a carrier in a medical catheter material, which is characterized in that an antibacterial masterbatch is prepared by using a silver-based inorganic antibacterial agent and a small amount of medical catheter material, and then The antibacterial masterbatch and the remainder of the catheter material are extruded to prepare an antibacterial catheter.
  • antibacterial medical catheters that have been introduced at home and abroad mainly have the following categories:
  • surface coating antibacterial reagent the surface of the catheter is coated with various antibiotics, the antibiotics coated on the surface of the catheter are generally used Compound antibiotics or broad-spectrum antibiotics, such as minocycline/rifampicin.
  • Nano-metals use nanotechnology to nano-metalize them to produce antibacterial effects.
  • nano-silver makes a qualitative leap in the bactericidal ability of silver, and only a very small amount of nano-silver can produce a strong bactericidal effect.
  • the antibacterial effect of nano-silver, its bactericidal mechanism and catalyst reaction are similar, that is, when the nano-silver is close to viruses, fungi, bacteria or phage, it produces active silver cation (Ag+) substances and oxygen metabolism on the surface of bacteria.
  • the enzyme (a SH) binds, destroys the activity of the bacterial cell synthetase, blocks the metabolism of the bacteria and causes it to suffocate and die.
  • nano-metal particles are unstable, easy to aggregate, and more difficult to apply directly on the surface of various urinary catheters. Therefore, they are generally mixed in the urinary catheter material, as described in Chinese Patent No. 200510041228. This technique is costly, and a large amount of silver ions that are directly mixed may also affect other properties of the catheter material, while the antibacterial effect of the catheter is determined only by a small amount of nano-silver coating on the surface.
  • Another nano-silver coating method is to electroplate metal silver or vacuum silver plating on the metal or plastic surface through the surface of the catheter.
  • the secondary coating method requires high equipment and increases the cost of the process.
  • the object of the present invention is to provide an antibacterial catheter which is simple, low in cost, durable in antibacterial, effective in effect, and controllable in effect.
  • Another object of the present invention is to provide a method for preparing the above urinary catheter.
  • the method is simple and easy, and the cost is low, and the antibacterial property of the final product is stable and effective, and the effect can be controlled.
  • An antibacterial catheter comprising a catheter, further comprising an antibacterial layer disposed on a surface of the catheter, the antibacterial layer being composed of polymer-coated nano metal particles aggregated, the nano metal being an antibacterial nanometer metal.
  • the polymer-coated nano metal particles can form a chemical bond or an ionic bond with the surface of the catheter through the surface active group of the polymer, so that the polymer-coated nano metal particles directly adhere to the surface of the medical catheter, and firmly adhere. , so that the nano metal particles are not easy to elute, achieving long-lasting, effective, and stable antibacterial effects.
  • the antibacterial layer can control the amount, speed and duration of the slow release of metal cations by the nano metal particles through different polymers and coating thicknesses to achieve a sustained, stable and long-lasting antibacterial effect on the surface.
  • the nano metal having antibacterial property refers to metal particles having a particle diameter generally less than 100 nm, and has a killing effect on bacteria, viruses, yeasts, fungi, etc., and inhibits growth functions such as silver, copper, zinc or titanium, and most preferably silver. .
  • the polymer is a functional group of fluorenyl silicon germanium (preferably one or more of an amine group, a carboxyl group, a hydroxyl group, a thiol group, a cyclopropenyl group or an aldehyde group functional group),
  • ion-charged polymer electrolytes preferably polyacrylic acid, polyallylamine salt
  • polyvinylpyrrolidone polyethylene oxide or polyethylene glycol.
  • the polymer-coated nano-metal particles have a particle diameter of 2 to 150 nm, preferably 5 to 100 nm, more preferably 30 to 100 nm, and most preferably 30 to 50 nm.
  • a method for preparing the aforementioned antibacterial catheter comprises the following steps in sequence:
  • the polymer encapsulates the nano metal
  • the particle diameter of the fine particles is 2 to 150 nm, preferably 5 to 100 nm, more preferably 30 to 100 nm, and most preferably 30 to 50 nm.
  • the polymer-coated nano metal particle solution is attached to the surface of the catheter, and the antibacterial catheter is obtained by washing and drying.
  • the method of encapsulating the nano metal by the polymer increases the solution stability of the nano metal particles without aggregation.
  • the polymer encapsulates the nano-metal, so that the nano-metal is firmly bonded to the surface of the catheter through chemical bonds, so that the anti-bacterial catheter is resistant to rinsing and immersion, and the polymer coating also increases the time for the slow release of the nano-metal to maintain the long-term antibacterial effect of the surface.
  • the nano-metal particles are slowly controlled to release the amount, speed and duration of the metal cations by different polymers and adjusting the polymer-coated nano-metal concentration or coating thickness to achieve a sustained, stable and long-lasting antibacterial effect on the surface.
  • the nano metal is silver
  • the step of adding a polymer solution to the nano silver solution to modify the nano silver polymer package comprises:
  • the weight of the solution is 100 parts by weight of 100-300 PPM of the nano-silver solution, 100 parts by weight of 100-1000 parts of ethanol (preferably 300 parts), stirred for 15 minutes, the pH of the solution is adjusted to alkaline, adding parts by weight 0. 1-1 Parts (preferably 1 part) tetraethylsilane and 3-aminopropyltriethoxysilane mixed in a weight ratio of 1:1, stirring is continued at room temperature, and the product is purified by centrifugation to obtain a silicone-coated surface aminated. Nano silver particles.
  • the step of preparing the nano metal-polymer composite by adding the polymer solution to the nano silver solution is as follows:
  • aqueous solution of PVP is added to the nanosilver solution to form a complex.
  • the PVP aqueous solution has a mass concentration of 1 to 10%
  • the nano silver solution concentration is 100-300 PPM
  • the PVP aqueous solution and the nano silver solution are mixed at a weight ratio of 1:1 -1 :10.
  • the polymer-coated nano-metal particle solution is attached to the surface of the catheter by dipping or coating.
  • the soaking is a soaking in heat.
  • the pretreatment is to soak the catheter with a surface void enlargement agent, or the surface of the catheter is modified by a silicon germanium coupling reagent.
  • the urinary catheter is immersed by heating, the surface void enlargement agent is used, or the surface of the urinary catheter is modified by the silicon germanium coupling reagent, thereby further enhancing the bonding force between the antibacterial layer and the surface of the catheter, so that The combination is stronger.
  • Advantageous Effects of Invention The antibacterial catheter provided by the present invention and the preparation method thereof are simple and easy to operate, and the cost is low.
  • Adopt The method for preparing polymer-coated nano-silver overcomes the instability of ordinary nano-silver colloidal particles, is easy to aggregate, and is more difficult to be directly applied uniformly on the surface of various urinary catheters. After application, the antibacterial layer is easy to elute and is not resistant to soaking.
  • the polymer-coated nano-silver prepared by the invention can be directly and uniformly coated on the surface of the catheter (see FIG. 5), and the polymer coating layer delays the release rate of silver ions from the nano silver particles, and increases the surface antibacterial time.
  • the polymer-coated nano-silver antibacterial catheter remained immersed in physiological saline for 15 days and remained antibacterial. It overcomes the common antibacterial agent directly doped in the catheter and has a large antibacterial dose and high cost, and the antibacterial agent incorporated only has an antibacterial effect on the surface penetrated into the surface, and the antibacterial material is incorporated at the same time. Defects that may affect other properties of the catheter. DRAWINGS
  • FIG. 1 is a TEM image of a nano silver solution according to an embodiment of the present invention.
  • FIG. 2 is a UV/VIS spectrum diagram of a nano silver solution according to an embodiment of the present invention.
  • Figure 3 is a TEM image of a nano silver solution of Example 2 of the present invention.
  • Example 4 is a UV/VIS spectrum diagram of a nano silver solution of Example 2 of the present invention.
  • Figure 5 is a TEM image of a silicone-coated nanosilver solution of Example 3 of the present invention.
  • Figure 6 is an SEM image of an antibacterial catheter of Example 6 of the present invention.
  • Fig. 7 is a view showing the antibacterial effect of the antibacterial catheter of the tenth embodiment of the present invention. detailed description
  • Antibacterial catheter One: Antibacterial catheter:
  • An antibacterial catheter comprising a catheter, further comprising an antibacterial layer disposed on a surface of the catheter; the antibacterial layer is composed of polymer-coated nano metal particles, and the particle size of the polymer-coated nano metal particles is 2 to 150 nm. It is preferably 5 to 100 nm, more preferably 30 to 100 calendars, and most preferably 30 to 50 nm.
  • the nanometal is a nanometal having antibacterial properties such as silver, copper, zinc or titanium, and most preferably silver.
  • the polymer is a functional group of fluorenyl silicon germanium (preferably one or more of an amine group, a carboxyl group, a hydroxyl group, a thiol group, a cyclopropenyl group or an aldehyde group), and an ion-charged polymer electrolyte (preferably polyacrylic acid, polyallylamine salt), polyvinylpyrrolidone, polyethylene oxide or polyethylene glycol.
  • fluorenyl silicon germanium preferably one or more of an amine group, a carboxyl group, a hydroxyl group, a thiol group, a cyclopropenyl group or an aldehyde group
  • an ion-charged polymer electrolyte preferably polyacrylic acid, polyallylamine salt
  • polyvinylpyrrolidone polyethylene oxide or polyethylene glycol.
  • a method for preparing the aforementioned antibacterial catheter comprises the following steps in sequence:
  • A preparing a nano metal solution (the present invention does not limit how to prepare a nano metal solution, various preparation methods are available, and the following examples are merely examples);
  • Example 1 B. adding a polymer solution in the nano metal solution, modifying the nano metal polymer or preparing the nano metal-polymer composite to obtain a polymer-coated nano metal particle solution; c. Attaching the polymer-coated nano metal particle solution to the surface of the catheter, and drying and drying to obtain an antibacterial catheter ⁇ Example 1:
  • the benzoyl sulfonimide solution is prepared by using o-benzoyl sulfonimide as a stabilizer and tetramethylethylenediamine as a reducing agent. Add 10ml 0. 1 ⁇ 0. 5 mol/L AgN0 3 solution to mix well, add 2ml mass concentration of 1 ⁇ 10% TMEDA (tetramethylethylenediamine), and react for 1h with stirring. Thus, a nanosilver solution having a turbid yellow color was prepared. The supernatant was centrifuged to obtain a yellow-brown transparent nanosilver solution.
  • the particle diameter distribution and particle shape of the nanosilver solution were synthesized by TEM observation, and as a result, the nanosilver solution having an average particle diameter of less than 10 nm as shown in Fig. 1 was spherical in shape.
  • the nanosilver solution was determined by UV/VIS spectroscopy. As a result, as shown in Fig. 2, the absorption peak of the nanosilver solution was 418 nm.
  • Example 2
  • the particle diameter distribution and particle shape of the nanosilver solution were synthesized by TEM observation. As a result, a nanosilver solution having a uniform particle size of 12 to 15 nm was obtained as shown in Fig. 3, and the shape was spherical particles.
  • the nanosilver solution was determined by UV/VIS spectroscopy. As a result, as shown in Fig. 4, the absorption peak of the nanosilver particles was 390 nm.
  • Example 3
  • nano silver prepared in the above Examples 1 and 2 can be modified by polymer encapsulation.
  • nano silver solution having a concentration of 100-300 ppm obtained by weight, 300 parts of ethanol was added, and stirred at 100 to 400 rpm for 15 minutes, and the pH of the solution was adjusted to be alkaline with ammonia water, and 1 part by weight was added: 1 mixed tetraethylsilane and 3-aminopropyltriethoxysilane, stirring at room temperature for 18 to 24 hours, and the product is purified by centrifugation at 2000 ⁇ 10000 rpm to obtain a silicone-coated surface aminated.
  • the new nano-silver particles as shown in Figure 5, have a UV absorption peak of 399 nm with a particle size of 100 nm.
  • Example 4 Example 4:
  • Preparation of nanosilver-polymer composites Adding a polymer PVP (polyvinylpyrrolidone), PEG (polyethylene glycol) or PVA (polyvinyl alcohol) aqueous solution to a concentration of 100-300 PPM nano silver solution prepared in Example 1-2 to form a nanometer Silver-polymer composite.
  • PVP polyvinylpyrrolidone
  • PEG polyethylene glycol
  • PVA polyvinyl alcohol
  • Nanosilver-polymer composite coated catheter
  • Example 4 40 ml of the Example 4 nanosilver-polymer composite solution was added to a 35 cm long test tube, and the catheter was immersed therein for several hours, and the catheter was taken out and rinsed with water to dry. A catheter with a yellow-green coating is obtained.
  • Example 6 40 ml of the Example 4 nanosilver-polymer composite solution was added to a 35 cm long test tube, and the catheter was immersed therein for several hours, and the catheter was taken out and rinsed with water to dry. A catheter with a yellow-green coating is obtained.
  • Example 6 40 ml of the Example 4 nanosilver-polymer composite solution was added to a 35 cm long test tube, and the catheter was immersed therein for several hours, and the catheter was taken out and rinsed with water to dry. A catheter with a yellow-green coating is obtained.
  • the polymer-coated nanosilver microparticle solutions prepared in the above Examples 3 and 4 can be subjected to dip coating.
  • Example 3 40 ml of the polymer-coated nanosilver microparticle solution prepared in Example 3 was placed in a test tube having a length of 35 cm, and the catheter was immersed therein for several hours, and the catheter was taken out and rinsed with water to dry. A catheter with a brown-yellow coating is obtained.
  • Example 8 40 ml of the polymer-coated nanosilver particle solution of Example 3 was placed in a test tube of 35 cm in length, and the catheter was immersed therein for several hours under heating, and the catheter was taken out and rinsed with water to dry. A catheter with a dark brown coating is obtained.
  • Example 8 40 ml of the polymer-coated nanosilver particle solution of Example 3 was placed in a test tube of 35 cm in length, and the catheter was immersed therein for several hours under heating, and the catheter was taken out and rinsed with water to dry. A catheter with a dark brown coating is obtained.
  • Example 8 40 ml of the polymer-coated nanosilver particle solution of Example 3 was placed in a test tube of 35 cm in length, and the catheter was immersed therein for several hours under heating, and the catheter was taken out and rinsed with water to dry. A catheter with a dark brown coating is obtained.
  • Example 8 40 ml of the polymer-coated nanosilver particle solution of Example 3 was placed in
  • the polymer-coated nanosilver microparticle solutions prepared in Examples 3 and 4 can be subjected to dip coating.
  • Example 3 40 ml of the polymer-coated nano-silver particle solution of Example 3 was added to a test tube of 35 cm in length, and the catheter was soaked with a surface void enlargement agent (such as methanol), and then immersed in a nanosilver solution for several hours to take out the guide. Rinse the tube with water and dry it. A catheter with a dark brown coating is obtained.
  • a surface void enlargement agent such as methanol
  • Example 9 Adding appropriate functional groups to the surface of the catheter through a silicon germanium coupling reagent increases the affinity of the catheter for nanosilver: with a certain concentration of r-aminopropyltrimethoxysilane (or maleic acid propyl triethoxylate) Silicon germanium, 3-thiopropyltriethoxysilane, 3-glycidoxypropyl-dimethylethoxysilane, etc.), soak the catheter under heating for several hours, take out the lead The urinary tube was rinsed and air-dried. 40 ml of the polymer-coated nano-silver particle solution prepared in Example 3, 4 was added to a test tube of 35 cm in length, and the catheter was immersed therein for several hours. The catheter was taken out and rinsed with water. . A catheter with a bright yellow coating is obtained. Experimental Example 10:
  • the catheter was coated with the catheter of Example 6 and cut into 2 cm long sections. Escherichia col i ATCC 25922 strain was used for the antibacterial experiment. The size of the antibacterial ring region is measured (the shortest distance between the outermost edge of the material and the innermost edge of the bacterial growth).
  • the antibacterial area of E. coli is l ⁇ 0. 2cm. As shown in Fig. 7, a large number of bacteria grow around the uncoated catheter on the right side, whereas the left side uses a nanosilver-coated catheter to form a distinct antibacterial area. It can be seen that the nano silver coated catheter has good antibacterial properties.
  • the 5 bis bacteriostatic zone is formed by the in vitro antibacterial property of the urinary tube. There are differences in the methods of different sizes of bacteriostatic areas.
  • Example 12 A 5 cm X 5 Cm silica gel sheet conforming to the material of the catheter was coated with the nano silver of Example 2 in the same manner as in Example 6. Escherichia col i ATCC 25922 strain was used for the antibacterial experiment. According to the filming method in GB/T 21510-2008, the antibacterial rate is 100%.
  • Experimental Example 12

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Abstract

一种抗菌导尿管及其制备方法。所述抗菌导尿管包括导尿管和设于所述导尿管表面的抗菌层。所述抗菌层由聚合物和包裹在聚合物中的具有抗菌性能的纳米金属微粒构成。所述制备方法包括：制备纳米金属溶液；在纳米金属溶液中加入聚合物溶液，进行纳米金属聚合物包裹改性或制备纳米金属-聚合物复合物，从而得到聚合物包裹纳米金属微粒溶液；将聚合物包裹纳米金属微粒溶液附着至导尿管表面；清洗干燥得到抗菌导尿管。所述产品和方法的优点包括操作简单，成本低，抗菌持久稳定，效果可控。

Description

抗菌导尿管及其制备方法
技术领域
本发明属于医疗器械及其制备方法领域。
背景技术
导尿管主要用于临床中风， 骨折和重症病人滞留导尿， 是医院里最常使用的医疗器械 之一， 大约 25%的住院病人在滞留期间使用导尿管。 在使用过程中， 由于各种因素， 经常伴 随着导管引起的尿道感染。 有报道， 在所有的临床细菌感染中， CAUTI占 30%。 随滞留时间 增加，导尿管感染率增加。在导尿管的使用过程中，通常一次简单导尿后细菌感染率约为 1〜 5 % , 25%的滞留期超过 7天的导管会引发细菌感染， 导尿时间超过 14天， 尿路感染发生率 在 90〜100 %， CAUTI是最常见的一种临床细菌感染。
为了减少和控制 CAUTI 的发生率， 在临床中采用了各种管理和技术策略， 包括严格的 无菌操作规程， 减少不必要的导尿管使用， 以及使用具有抗菌性能的导尿管等。 其中， 抗 菌导管是比临床使用抗生素更为有效的一种手段。根据临床数据显示（Franken 等， 2007)， 抗菌导管可以减少中心静脉导管使用中血液感染发生率 15倍， 减少导尿管细菌感染发生率 3倍。所以开发具有抗菌功能的医用导尿管对减少 CAUTI发生和降低临床治疗费用具有重大 意义。
各式各样的抗菌技术被应用到医用导管中去开发抗菌医疗导管。 中国专利公开号 CN2529660 描述了在导尿管球囊下方制作一段加药区， 使用时根据不同情况加入各种抗生 素。中国发明专利申请 200810200169. 6用磷酸锆为载体的银系无机抗菌剂掺入导管材料中， 制成缓释性抗菌医用导管。 中国发明专利申请 200810203587. 0公开一种有机 /无机复合抗 菌导尿管的制备方法， 将无机抗菌剂和有机硅乳化液混合高速搅拌， 混合到导尿管原材料 中， 成型后在表面涂敷有季胺盐的抗菌涂层。 中国发明专利申请 200810200169. 6公开了一 种在医用导管材料中搀杂磷酸锆为载体的银系无机抗菌剂， 其特征在于将银系无机抗菌剂 和少量医用导管材料制备抗菌色母料， 再将抗菌母料和其余部分导管材料挤出成型制备抗 菌导管。
总体上， 国内外已经问世的抗菌医用导尿管主要有以下几类：
1 ; 直接掺入抗菌试剂： 如以上几个方面数个专利申请所示， 在导管材料中掺入银系抗 菌剂或其它广谱抗生素。 这种方法掺入抗菌剂量大、 成本高， 且掺入的抗菌试剂只有渗透 到表面的部分才能起到抗菌作用， 同时掺入的抗菌材料有可能影响导尿管的其他性能。
2； 表面涂敷抗菌试剂： 在导管表面涂有各类抗生素， 导管表面涂敷的抗生素一般采用 复合抗生素或广谱抗生素， 例如米诺环素 /利福平类。
纳米金属是利用纳米技术将金属纳米化， 使其产生抗菌作用。 如纳米银使银的杀菌能 力产生了质的飞跃， 只用极少量的纳米银即可产生强力的杀菌作用。 纳米银发挥出的抗菌 效果， 其杀菌机制和触媒反应类似， 就在于当纳米银靠近病毒、 真菌类、 细菌或者嗜菌体 时， 其产生的活性银阳离子 （Ag+) 物质与细菌表面的氧代谢酶 （一 SH) 结合， 破坏细菌细 胞合成酶的活性， 阻断菌体代谢使其窒息而死。
所以纳米金属颗粒中金属阳离子的持续和缓慢释放是其保证杀菌和抗菌效果持久行的 根本原因。 普通的纳米金属颗粒不稳定， 易聚集， 更难以直接均匀涂在各种导尿管的表面， 所以一般都是采用混杂在导尿管材料中， 如中国发明专利 200510041228. 6所描述的， 但这 种技术成本高， 直接混杂的大量银离子也可能影响导尿管材料的其他性能， 同时而导尿管 的抗菌效果只是由表面的少量纳米银涂层决定。
另一种纳米银的涂层方法是通过导管表面电镀金属银或真空镀银在金属或塑料表面， 次种涂层方法对设备要求高， 增加了工艺的成本。
发明内容
本发明的目的在于： 提供一种简单， 成本低， 抗菌持久稳定有效、 效果可控制的抗菌导 尿管。
本发明的另一目的在于提供上述导尿管的制备方法， 其方法简便易行， 成本低， 最终成 品的抗菌持久稳定有效、 效果可控制。
本发明目的通过下述技术方案来实现：
一种抗菌导尿管， 包括导尿管， 还包括设于所述导尿管表面的抗菌层， 所述抗菌层由聚 合物包裹纳米金属微粒聚集构成， 所述纳米金属为具有抗菌性能的纳米金属。
上述方案中，聚合物包裹纳米金属微粒可以通过聚合物表面活性基团与导尿管表面形成 化学键或离子键结合， 使聚合物包裹纳米金属微粒直接粘附在医用导尿管表面， 牢固粘接， 使纳米金属颗粒不易洗脱， 实现长久、 有效、 稳定的抗菌效果。 抗菌层可以通过不同的聚 合物及涂层厚度控制纳米金属颗粒缓慢释放金属阳离子的量、 速度及持续时间， 在表面达 到持续、 稳定、 长久的抗菌效果。
所述具有抗菌性能的纳米金属是指颗粒直径一般小于 100纳米的金属颗粒， 对细菌，病 毒， 酵母， 真菌等具有杀死， 抑制生长功能， 如银、 铜、 锌或钛等， 最优选银。
作为优选方式， 所述聚合物为带功能团的垸基硅垸 （优选胺基、 羧基、 羟基、 氢硫基、 环丙垸基或醛基功能基团中的一种或多种）、 带有离子电荷聚合物电解质 （优选聚丙烯酸， 聚烯丙基胺盐 ）、 聚乙烯吡咯垸酮、 聚环氧乙垸或聚乙二醇。 作为优选方式， 所述聚合物包裹纳米金属微粒的粒径为 2〜150nm， 优选 5〜100nm， 更 优选 30〜100nm， 最优选 30〜50nm。
一种前述的抗菌导尿管的制备方法， 依次包括以下步骤：
A、 制备纳米金属溶液；
B、在纳米金属溶液中加入聚合物溶液， 进行纳米金属聚合物包裹改性或制备纳米金属- 聚合物复合物， 得到聚合物包裹纳米金属微粒溶液； 作为优选方式， 所述聚合物包裹纳米 金属微粒的粒径为 2〜150nm， 优选 5〜100nm， 更优选 30〜100nm， 最优选 30〜50nm。
C、 将聚合物包裹纳米金属微粒溶液附至导尿管表面， 清洗干燥即得到抗菌导尿管。 上述方案中， 通过聚合物包裹纳米金属的方法增加了纳米金属颗粒的溶液稳定性， 不聚 集。 同时， 聚合物包裹纳米金属， 使纳米金属通过化学键与导尿管表面牢固结合， 使抗菌 导管耐冲洗， 耐浸泡， 聚合物包裹还增加纳米金属缓慢释放的时间， 保持表面长期抗菌效 果。 通过不同的聚合物及调节聚合物包裹的纳米金属浓度或涂层厚度控制纳米金属颗粒缓 慢释放金属阳离子的量、 速度及持续时间， 在表面达到持续、 稳定、 长久的抗菌效果。
作为优选方式， 所述纳米金属为银， 在纳米银溶液中加入聚合物溶液， 进行纳米银聚合 物包裹改性的步骤具体包括：
取得到的浓度为 100-300PPM的纳米银溶液重量份 100份，加入重量份 100-1000份乙醇 (优选 300份）， 搅拌 15分钟， 调节溶液 pH至碱性， 加入重量份 0. 1-1份 （优选 1份） 重 量比 1 : 1混合的四乙基硅垸和 3-氨基丙基三乙氧基硅垸， 在室温下继续搅拌， 产物离心纯 化， 获得有机硅包裹表面胺基化的纳米银微粒。
作为优选方式， 所述纳米金属为银， 在纳米银溶液中加入聚合物溶液， 制备纳米金属- 聚合物复合物的步骤具体包括：
将 PVP的水溶液， 加入纳米银溶液中， 形成复合物。 作为优选方式， 所述 PVP水溶液的 质量百分浓度为 1〜10%， 纳米银溶液浓度为 100-300PPM, 按重量比 1 : 1 -1 : 10的比例混合 PVP 水溶液与纳米银溶液。
作为优选方式， 所述 C步中， 通过浸泡或涂敷的方式将聚合物包裹纳米金属微粒溶液附 至导尿管表面。 作为优选方式， 所述浸泡为加热浸泡。
作为优选方式， 所述 C步之前， 导尿管经过了预处理， 所述预处理为用表面空隙增大剂 浸泡导尿管， 或通过硅垸偶联试剂改性导尿管表面。
上述方案中， 通过加热浸泡、 用表面空隙增大剂浸泡导尿管， 或通过硅垸偶联试剂改性 导尿管表面， 进一步增强了抗菌层和导尿管表面间的结合力， 使两者结合更牢固。 本发明的有益效果： 本发明提供的抗菌导尿管及其制备方法， 简便易行， 成本低。采用 本发明方法制备聚合物包裹纳米银克服了普通的纳米银胶体颗粒不稳定， 易聚集， 更难以 直接均匀涂在各种导尿管的表面， 涂敷后抗菌层易洗脱、 不耐浸泡的缺点； 本发明制备的 聚合物包裹的纳米银能直接均匀涂敷在导管表面（见图 5 )， 同时聚合物包裹层延缓了银离 子从纳米银颗粒中释放的速度， 增加了表面抗菌时间， 聚合物包裹纳米银抗菌导尿管在生 理盐水中浸泡 15天依然保持抗菌性能。 克服了普通的直接在导尿管中掺杂抗菌剂存在的掺 入抗菌剂量大、 成本高， 且掺入的抗菌试剂只有渗透到表面的部分才能起到抗菌作用， 同 时掺入的抗菌材料有可能影响导尿管的其他性能的缺陷。 附图说明
图 1是本发明实施例 1纳米银溶液的 TEM图；
图 2是本发明实施例 1纳米银溶液的 UV/VIS光谱图；
图 3是本发明实施例 2纳米银溶液的 TEM图；
图 4是本发明实施例 2纳米银溶液的 UV/VIS光谱图；
图 5是本发明实施例 3有机硅包裹纳米银溶液的 TEM图；
图 6是本发明实施例 6抗菌导尿管的 SEM图；
图 7是本发明实施例 10抗菌导尿管的抗菌效果图。 具体实施方式
下列非限制性实施例用于说明本发明。
一： 抗菌导尿管：
一种抗菌导尿管， 包括导尿管， 还包括设于导尿管表面的抗菌层， 抗菌层由聚合物包裹 纳米金属微粒聚集构成， 聚合物包裹纳米金属微粒的粒径为 2〜150nm， 优选 5〜100nm， 更 优选 30〜100歷， 最优选 30〜50nm。 纳米金属为具有抗菌性能的纳米金属， 如银、 铜、 锌 或钛等， 最优选银。 聚合物为带功能团的垸基硅垸 （优选胺基、 羧基、 羟基、 氢硫基、 环 丙垸基或醛基功能基团中的一种或多种）、 带有离子电荷聚合物电解质 （优选聚丙烯酸， 聚 烯丙基胺盐 ）、 聚乙烯吡咯垸酮、 聚环氧乙垸或聚乙二醇。
二： 抗菌导尿管的制备：
一种前述的抗菌导尿管的制备方法， 依次包括以下步骤：
A、 制备纳米金属溶液 （本发明并不限制如何制备纳米金属溶液， 现有各种制备方法均 可， 以下实施例中仅为举例）；
B、在纳米金属溶液中加入聚合物溶液， 进行纳米金属聚合物包裹改性或制备纳米金属- 聚合物复合物， 得到聚合物包裹纳米金属微粒溶液； c、 将聚合物包裹纳米金属微粒溶液附至导尿管表面， 清洗干燥即得到抗菌导尿管 < 实施例 1 :
纳米银颗粒的制备：
通过使用邻苯甲酰磺酰亚胺为稳定剂， 四甲基乙二胺做还原剂制备纳米银溶液： 向 10ml浓度为 0. 1〜1 mol/L邻苯甲酰磺酰亚胺溶液中，加入 10ml 0. 1〜0. 5 mol/L AgN03 溶液混合均匀， 加入 2ml 质量体积浓度为 1〜10% 的 TMEDA (四甲基乙二胺）， 搅拌下反应 lh。 由此制备出颜色为浑浊黄色的纳米银溶液。 离心取上清液为黄褐色透明纳米银溶液。
通过 TEM观察合成出纳米银溶液的颗粒直径分布和颗粒形状，结果如附图 1所示平均粒 径为小于 10nm的纳米银溶液， 形状为球形颗粒。
通过 UV/VIS光谱法测定纳米银溶液。 结果如图 2所示， 纳米银溶液吸收峰为 418nm。 实施例 2 :
通过使用 NaBH4做还原剂和稳定剂合成纳米银：
在烧瓶中加入 10ml 0. l〜2 m mol/L NaBH4溶液， 搅拌下向其中加入 10ml 0. l〜2 m mol/L AgN03, 继续搅拌反应 20min。 由此制备出颜色为黄色的纳米银溶液。
通过 TEM观察合成出纳米银溶液的颗粒直径分布和颗粒形状，结果如图 3所示平均粒径 为 12〜15nm大小均匀的纳米银溶液， 形状为球形颗粒。
通过 UV/VIS光谱法测定纳米银溶液。 结果如图 4， 纳米银颗粒吸收峰为 390nm。 实施例 3 :
聚合物改性纳米银制备：
以上实施例 1、 2所制备的纳米银都可以进行聚合物包裹改性。
按重量份计， 取得到的浓度为 100-300ppm的纳米银溶液 100份， 加入 300份乙醇， 在 100〜400 rpm搅拌 15分钟， 用氨水调节溶液 pH至碱性， 加入 1份重量比 1： 1混合的四乙 基硅垸和 3-氨基丙基三乙氧基硅垸，在室温下继续搅拌 18〜24 小时，产物在 2000〜10000 rpm高速离心纯化， 获得有机硅包裹表面胺基化的新型纳米银微粒， 如图 5所示， 粒径为 lOOnmo 纳米银溶液紫外吸收峰为 399nm。 实施例 4:
纳米银-聚合物复合物制备： 将聚合物 PVP (聚乙烯吡咯垸酮）、 PEG (聚乙二醇） 或 PVA (聚乙烯醇） 水溶液按一定 比例加入实施例 1-2制备的 浓度为 100-300PPM纳米银溶液中，形成纳米银-聚合物复合物。 如制备质量百分比 1〜10%PVP 水溶液， 按重量比 1 : 1 -1 : 10的比例混合 PVP 水溶液与实施 例 2中制备的浓度为 100-300PPM的纳米银， 得到聚合物包裹纳米银微粒溶液， 其中聚合物 包裹纳米银微粒的粒径为 30nm。 实施例 5:
纳米银-聚合物复合物涂层导尿管：
取 40ml实施例 4纳米银-聚合物复合溶液加入长度为 35cm试管中， 把导尿管浸泡于其 中数小时， 取出导尿管用水冲洗干净晾干。 得到颜色为黄绿色涂层的导尿管。 实施例 6:
通过浸泡的方法涂覆纳米银：
以上实施例 3， 4中制备的聚合物包裹纳米银微粒溶液都可以进行浸泡涂覆。
取 40ml实施例 3中制备的聚合物包裹纳米银微粒溶液加入长度为 35cm试管中，把导管 浸泡于其中数小时， 取出导尿管用水冲洗干净晾干。 得到颜色为棕黄色涂层的导尿管。
SEM 扫描如图 6所示， 图中白色即为纳米银大小约为 12〜20nm。 实施例 7:
通过加热浸泡的方法涂覆纳米银：
取 40ml实施例 3中聚合物包裹纳米银微粒溶液加入长度为 35cm试管中，加热情况下把 导管浸泡于其中数小时， 取出导尿管用水冲洗干净晾干。 得到颜色为深褐色涂层的导尿管。 实施例 8:
通过暂时增大导尿管表面空隙， 增大纳米银吸附量：
实施例 3和 4中制备的聚合物包裹纳米银微粒溶液都可以进行浸泡涂覆。
取 40ml实施例 3中聚合物包裹纳米银微粒溶液加入长度为 35cm试管中，取用表面空隙 增大剂 （如甲醇，） 浸泡导尿管， 再放入纳米银溶液中浸泡数小时， 取出导尿管用水冲洗干 净晾干。 得到颜色为深褐色涂层的导尿管。 实施例 9: 通过硅垸偶联试剂改性导尿管表面引入适当官能团增加导尿管对纳米银亲和性： 用一定浓度 r-氨丙基三甲氧基硅垸 （或马来酰胺酸丙基三乙氧基硅垸， 3-硫基丙基三乙 氧基硅垸， 3-环氧丙氧基丙基 -二甲基乙氧基硅垸 等）， 在加热条件浸泡导尿管数小时， 取出 导尿管并冲洗晾干， 取 40ml实施例 3， 4 中制备的聚合物包裹纳米银微粒溶液加入长度为 35cm试管中， 把导尿管浸泡于其中数小时， 取出导尿管用水冲洗干净晾干。 得到颜色为亮 黄色涂层的导尿管。 实验实施例 10:
聚合物包裹纳米银涂覆导尿管体外抗菌性能实验：
将导尿管用实施例 6涂敷的导管， 切成大小为 2cm长小节。 将大肠杆菌 （Escherichia col i ) ATCC 25922菌株用于抗菌实验。 测量其抗菌环区域大小 (是指材料的最外缘至细菌生 长的最内缘之间的最短距离）。
对大肠杆菌抗菌区域大小为 l ± 0. 2cm。 如图 7所示， 右侧未涂覆导尿管周围有大量细 菌生长， 相反左侧使用纳米银涂覆导尿管周围形成明显抗菌区域。 可见纳米银涂覆导尿管 有良好抗菌性能。
对前述各实施例中不同聚合物包裹纳米银微粒溶液和不同涂覆方法涂覆的导尿管进行 体外抗菌性能实验测定， 能形成 0. 5〜2. 5cm抑菌区域。 抑菌区域大小不同方法有所差异。 实验实施例 11 :
纳米银涂覆硅胶片表面抗菌实验：
将与导尿管材质一致的 5cmX 5Cm硅胶片用实施例 2中纳米银，按实施例 6的方法涂覆。 将大肠杆菌 ( Escherichia col i ) ATCC 25922菌株用于抗菌实验。 按照 GB/T 21510— 2008 中贴膜法进行测定， 抗菌率为 100%。 实验实施例 12:
根据实验实施例 10的描述测试大肠杆菌抗菌导管的抗菌环的方法， 将得到的抗菌导管 在生理盐水中浸泡 15天后分别测试大肠杆菌和金黄色葡萄球菌的抗菌性能， 分别得到大小 为 0. 5cm抗菌环， 显示导管对这两种细菌有强力抗菌效果。 以上所述仅为本发明的较佳实施例而已， 并不用以限制本发明， 凡在本发明的精神和原 则之内所作的任何修改、 等同替换和改进等， 均应包含在本发明的保护范围之内。

Claims

WO 2014/059738 权 利 要 求 书 PCT/CN2012/087954
1. 一种抗菌导尿管， 包括导尿管， 其特征在于： 还包括设于所述导尿管表面的抗菌层， 所述 抗菌层由聚合物包裹纳米金属微粒聚集构成， 所述纳米金属为具有抗菌性能的纳米金属。
2. 如权利要求 1所述的抗菌导尿管， 其特征在于： 所述聚合物为带功能团的垸基硅垸、 带有 离子电荷聚合物电解质、 聚乙烯吡咯垸酮、 聚环氧乙垸或聚乙二醇。
3. 如权利要求 1所述的抗菌导尿管，其特征在于:所述聚合物包裹纳米金属微粒的粒径为 2〜 150nm。
4. 一种权利要求 1至 3中任一权利要求所述的抗菌导尿管的制备方法，其特征在于依次包括 以下步骤：
A、 制备纳米金属溶液；
B、 在纳米金属溶液中加入聚合物溶液， 进行纳米金属聚合物包裹改性或制备纳米金属 -聚合 物复合物， 得到聚合物包裹纳米金属微粒溶液；
C, 将聚合物包裹纳米金属微粒溶液附至导尿管表面， 清洗干燥即得到抗菌导尿管。
5. 如权利要求 4所述的抗菌导尿管的制备方法， 其特征在于： 所述纳米金属为银， 在纳米银 溶液中加入聚合物溶液， 进行纳米银聚合物包裹改性的步骤具体包括：
取得到的浓度为 100-300PPM的纳米银溶液重量份 100份， 加入重量份 100-1000份乙醇， 搅 拌 15分钟， 调节溶液 pH至碱性， 加入重量份 0. 1-1份重量比 1 : 1混合的四乙基硅垸和 3-氨 基丙基三乙氧基硅垸， 在室温下继续搅拌， 产物离心纯化， 获得有机硅包裹表面胺基化的纳 米银微粒。
6. 如权利要求 4所述的抗菌导尿管的制备方法， 其特征在于： 所述纳米金属为银， 在纳米银 溶液中加入聚合物溶液， 制备纳米金属 -聚合物复合物的步骤具体包括：
将 PVP的水溶液， 加入纳米银溶液中， 形成复合物。
7. 如权利要求 6所述的抗菌导尿管的制备方法， 其特征在于： 所述 PVP水溶液的质量百分浓 度为 1〜10%， 纳米银溶液浓度为 100-300PPM, 按重量比 1 : 1 _1： 10的比例混合 PVP 水溶液 与纳米银溶液。
8. 如权利要求 4所述的抗菌导尿管的制备方法， 其特征在于： 所述 C步中， 通过浸泡或涂敷 的方式将聚合物包裹纳米金属微粒溶液附至导尿管表面。
9. 如权利要求 8所述的抗菌导尿管的制备方法， 其特征在于： 所述浸泡为加热浸泡。
10. 如权利要求 4所述的抗菌导尿管的制备方法， 其特征在于： 所述 C步之前， 导尿管经过 了预处理， 所述预处理为用表面空隙增大剂浸泡导尿管， 或通过硅垸偶联试剂改性导尿管表 面。
PCT/CN2012/087954 2012-10-19 2012-12-30 抗菌导尿管及其制备方法 WO2014059738A1 (zh)

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