技术领域Technical field
本发明属于抗菌涂层技术领域，具体涉及一种用于植入物表面的光动力抗菌涂层及其制备方法。The invention belongs to the technical field of antibacterial coatings, and specifically relates to a photodynamic antibacterial coating used on the surface of implants and a preparation method thereof.
背景技术Background technique
细菌广泛存在于人类生活和工作环境中，细菌感染是全球最严重的健康问题之一，每年导致数百万人患病，并且是20世纪初之前死亡的主要原因。骨修复及替换手术是在大气环境下进行，易将空气中、患者或术者体表的葡萄球菌、绿脓杆菌等病原微生物带入手术部位，从而诱发植入体相关感染。感染一旦发生，将给患者带来极大的痛苦，并将面临翻修手术。为了预防骨植入体相关感染，越来越多的研究关注于植入体的抗菌性能。特别是表面设计策略的出现提供了抗生素的有效替代品，从而阻止了细菌耐药性的可能发展。为了更好地治疗由耐药细菌引起的感染，各种抗菌药物(例如，抗菌肽和两亲物)和抗菌材料(例如，纳米颗粒，水凝胶，工程表面和表面涂层)已经开发出来。由于抗菌材料自身性质以及传统涂覆工艺的限制使得抗菌材料与基底结合力较低，影响抗菌粒子的释放，进而影响抗菌性能。Bacteria are widely present in human living and working environments, and bacterial infections are one of the most serious health problems worldwide, causing millions of people to fall ill every year and being the leading cause of death before the early 20th century. Bone repair and replacement surgeries are performed in an atmospheric environment, and pathogenic microorganisms such as Staphylococcus aeruginosa and Pseudomonas aeruginosa in the air, on the surface of the patient or the surgeon can easily be brought into the surgical site, thereby inducing implant-related infections. Once infection occurs, it will cause great pain to the patient and will require revision surgery. To prevent bone implant-related infections, an increasing number of studies have focused on the antimicrobial properties of implants. In particular, the emergence of surface design strategies offers effective alternatives to antibiotics, thus preventing the possible development of bacterial resistance. To better treat infections caused by drug-resistant bacteria, various antimicrobial drugs (e.g., antimicrobial peptides and amphiphiles) and antimicrobial materials (e.g., nanoparticles, hydrogels, engineered surfaces, and surface coatings) have been developed . Due to the nature of the antibacterial material itself and the limitations of the traditional coating process, the binding force between the antibacterial material and the substrate is low, which affects the release of antibacterial particles and thus the antibacterial performance.
由于抗生素的过度使用，近年来细菌耐药性问题日益严重，致使感染类疾病的死亡率不断增加。因此，迫切需要寻求可有效缓解耐药性问题的新药物和新手段。随着光学技术的进步和新型光敏剂的开发，光动力抗菌治疗(Photodynamic Antibacterial Therapy，PDAT)因其不易产生耐药性的优点而又重新回归人们的视野，且已成为耐药菌感染最具前景的治疗方式之一。PDAT主要采用适当波长的光源激发光敏剂分子以产生活性氧物种(ROS)来氧化破坏磷脂、酶、蛋白质和DNA等生物大分子，从而实现对病原微生物的有效灭活。在实际抗菌应用中，传统小分子光敏剂通常存在有水溶性差、易光漂白、选择性识别弱和治疗效果差等问题。针对上述问题，近年来国内外研究人员设计研发出一些新型抗菌光敏剂，可概括为四类：(1)芳香类有机小分子、(2)非自猝灭有机小分子、(3)共轭聚合物和(4)纳米光敏剂。这些新型抗菌光敏剂可通过优化在体内的输送来改善药物动力学、增加在病灶部位的渗透率和提高靶组织药物浓度等方式来实现高效杀菌，并减轻毒副反应和提高生物利用度，这些进展为PDAT在临床的应用提供了更高的可行性。Due to the overuse of antibiotics, the problem of bacterial resistance has become increasingly serious in recent years, resulting in an increasing mortality rate from infectious diseases. Therefore, there is an urgent need to seek new drugs and new methods that can effectively alleviate the problem of drug resistance. With the advancement of optical technology and the development of new photosensitizers, photodynamic antibacterial therapy (PDAT) has returned to people's vision because of its advantage of not easily developing drug resistance, and has become the most popular method for drug-resistant bacterial infections. One of the promising treatments. PDAT mainly uses light sources of appropriate wavelengths to excite photosensitizer molecules to produce reactive oxygen species (ROS) to oxidize and destroy biological macromolecules such as phospholipids, enzymes, proteins and DNA, thereby achieving effective inactivation of pathogenic microorganisms. In actual antibacterial applications, traditional small molecule photosensitizers usually have problems such as poor water solubility, easy photobleaching, weak selective recognition, and poor therapeutic effect. In response to the above problems, domestic and foreign researchers have designed and developed some new antibacterial photosensitizers in recent years, which can be summarized into four categories: (1) aromatic organic small molecules, (2) non-self-quenching organic small molecules, (3) conjugated polymers and (4) nanophotosensitizers. These new antibacterial photosensitizers can achieve efficient sterilization by optimizing delivery in the body to improve drug kinetics, increase penetration at the lesion site, and increase drug concentration in target tissues, as well as reduce toxic side effects and improve bioavailability. Progress provides higher feasibility for clinical application of PDAT.
因此，如何提供一种具有优异抗菌性能、与基底结合牢固的复合抗菌涂层对抗菌材料的广泛应用具有重要作用。Therefore, how to provide a composite antibacterial coating with excellent antibacterial properties and strong bonding with the substrate plays an important role in the wide application of antibacterial materials.
发明内容Contents of the invention
本发明所要解决的技术问题在于针对上述现有技术的不足，提供一种用于植入物表面的光动力抗菌涂层。该涂层通过控制硼酸，磷酸二乙酯和二乙氧基硅烷的摩尔比使之恰好进行缩聚脱醇反应，生成超支化硼磷硅三元聚合物，利用超支化硼磷硅三元聚合物表面丰富的官能团提高了植入物与涂层的结合强度，此外利用超支化硼磷硅三元聚合物的光催化性延长有效抗菌时间，达到优异的抗菌效果。The technical problem to be solved by the present invention is to provide a photodynamic antibacterial coating for the surface of implants in view of the above-mentioned shortcomings of the prior art. This coating controls the molar ratio of boric acid, diethyl phosphate and diethoxysilane so that they can undergo the condensation polymerization and dealcoholization reaction to generate a hyperbranched boron phosphorus silicon terpolymer. The hyperbranched boron phosphorus silicon terpolymer is utilized. The rich functional groups on the surface improve the bonding strength between the implant and the coating. In addition, the photocatalytic property of the hyperbranched boron phosphorus silicon terpolymer is used to extend the effective antibacterial time and achieve excellent antibacterial effects.
为解决上述技术问题，本发明采用的技术方案是：一种用于植入物表面的光动力抗菌涂层，其特征在于，该抗菌涂层为通过摩尔比为2～4:1～2:1～2的硼酸，磷酸二乙酯类化合物和二乙氧基硅烷类化合物为原料制备的超支化硼磷硅三元聚合物。In order to solve the above technical problems, the technical solution adopted by the present invention is: a photodynamic antibacterial coating for the surface of the implant, which is characterized in that the antibacterial coating is made by passing a molar ratio of 2 to 4:1 to 2: A hyperbranched boron phosphorus silicon terpolymer prepared from 1 to 2 boric acid, diethyl phosphate compounds and diethoxysilane compounds.
本发明通过控制硼酸，磷酸二乙酯类化合物和二乙氧基硅烷类化合物的摩尔比使之恰好进行缩聚脱醇反应，制成超支化硼磷硅三元聚合物，利用超支化硼磷硅三元聚合物表面丰富的官能团提高了植入物与涂层的结合强度，此外可以利用超支化硼磷硅三元聚合物的光催化性延长有效抗菌时间，达到优异的抗菌效果。The present invention controls the molar ratio of boric acid, diethyl phosphate compounds and diethoxysilane compounds so that they can exactly carry out the condensation polymerization and dealcoholization reaction to prepare a hyperbranched boron phosphorus silicon ternary polymer, and utilizes the hyperbranched boron phosphorus silicon The rich functional groups on the surface of the terpolymer improve the bonding strength between the implant and the coating. In addition, the photocatalytic property of the hyperbranched boron phosphorus silicon terpolymer can be used to extend the effective antibacterial time and achieve excellent antibacterial effects.
上述的一种用于植入物表面的光动力抗菌涂层，其特征在于，所述磷酸二乙酯类化合物为磷酸二乙酯、(3-氨丙基)磷酸二乙酯或烯丙基磷酸二乙酯。本发明采用的原料在聚合后具有优异的光物理性能，达到光动力抗菌的特性，磷元素是生物活性元素，有利于生物相相容性和成骨。The above-mentioned photodynamic antibacterial coating for implant surfaces is characterized in that the diethyl phosphate compound is diethyl phosphate, (3-aminopropyl) diethyl phosphate or allyl Diethyl phosphate. The raw materials used in the present invention have excellent photophysical properties after polymerization and achieve photodynamic antibacterial properties. The phosphorus element is a bioactive element and is beneficial to biocompatibility and osteogenesis.
上述的一种用于植入物表面的光动力抗菌涂层，其特征在于，所述二乙氧基硅烷类化合物为二乙氧基硅烷、(3-环氧丙氧基)甲基二乙氧基硅烷或3-氨丙基甲基二乙氧基硅烷。本发明采用的原料在聚合后具有优异的光物理性能，达到光动力抗菌的特性，硅元素是生物活性元素，有利于生物相相容性和成骨。The above-mentioned photodynamic antibacterial coating for implant surfaces is characterized in that the diethoxysilane compound is diethoxysilane, (3-epoxypropoxy)methyldiethyl oxysilane or 3-aminopropylmethyldiethoxysilane. The raw materials used in the present invention have excellent photophysical properties after polymerization and achieve photodynamic antibacterial properties. Silicon element is a bioactive element, which is beneficial to biocompatibility and osteogenesis.
另外，本发明还提供了一种制备用于植入物表面的光动力抗菌涂层的方法，其特征在于，该方法包括以下步骤：In addition, the present invention also provides a method for preparing a photodynamic antibacterial coating for the surface of an implant, which is characterized in that the method includes the following steps:
步骤一、将硼酸、磷酸二乙酯类化合物和二乙氧基硅烷类化合物进行混合，得到原料；Step 1: Mix boric acid, diethyl phosphate compounds and diethoxysilane compounds to obtain raw materials;
步骤二、将步骤一中得到的原料在搅拌条件下进行加热溶解，然后进行蒸馏，得到产物；Step 2: Heat and dissolve the raw materials obtained in Step 1 under stirring conditions, and then distill them to obtain the product;
步骤三、将步骤二中得到的产物进行透析，然后依次进行旋转蒸发和真空干燥，得到超支化硼磷硅三元聚合物；Step 3: dialyze the product obtained in Step 2, then perform rotary evaporation and vacuum drying in sequence to obtain a hyperbranched boron phosphorus silicon terpolymer;
步骤四、将步骤三中得到的超支化硼磷硅三元聚合物加入到高压无气喷涂机中对植入物表面进行喷涂，在植入物表面上得到光动力抗菌涂层。Step 4: Add the hyperbranched boron phosphorus silicon ternary polymer obtained in step 3 to a high-pressure airless spraying machine to spray the surface of the implant to obtain a photodynamic antibacterial coating on the surface of the implant.
本发明通过将硼酸、磷酸二乙酯类化合物和二乙氧基硅烷类化合物进行混合，有利于后续的反应均衡，通过在搅拌条件下进行加热溶解也是为了混合均匀，同时通过加热使粉末原料溶解，使后续的液液反应更充分，通过蒸馏将原料进行液液反应，使原料间发生酯交换缩聚反应，得到初步产物，通过透析除去未反应的小分子物质和分子量不达标的低聚物，通过旋蒸是除去透析时的溶剂，通过真空干燥也有利于充分挥发溶剂，得到纯净的超支化硼磷硅三元聚合物；本发明通过将超支化硼磷硅三元聚合物加入到高压无气喷涂机中对植入物表面进行喷涂，在植入物表面上得到光动力抗菌涂层。In the present invention, boric acid, diethyl phosphate compounds and diethoxysilane compounds are mixed, which is beneficial to the subsequent reaction equilibrium. The heating and dissolving under stirring conditions are also for uniform mixing, and at the same time, the powder raw materials are dissolved by heating. , to make the subsequent liquid-liquid reaction more complete, the raw materials are subjected to a liquid-liquid reaction through distillation, so that a transesterification polycondensation reaction occurs between the raw materials, and a preliminary product is obtained. Unreacted small molecular substances and oligomers with substandard molecular weights are removed through dialysis. Rotary evaporation removes the solvent during dialysis, and vacuum drying is also conducive to fully volatilizing the solvent to obtain a pure hyperbranched boron phosphorus silicon ternary polymer; in the present invention, the hyperbranched boron phosphorus silicon ternary polymer is added to the high-pressure vacuum The surface of the implant is sprayed in an air spraying machine to obtain a photodynamic antibacterial coating on the surface of the implant.
上述的方法，其特征在于，步骤二中所述加热溶解的温度为80℃～100℃，所述蒸馏的温度为140℃～160℃，时间为6h～24h，所述蒸馏在氮气气氛下进行，所述产物进行30min～60min抽真空处理，所述加热溶解和蒸馏在油浴条件下进行。本发明通过控制加热的温度确保原料均能融化为液体，通过控制蒸馏的温度和时间保证了原料充分反应生成超支化硼磷硅三元聚合物，同时防止原料分解和不能充分反应的不足，通过抽真空处理去除产物中的杂质，并且通过控制抽真空的时间保证杂质的充分去除并防止产物变为凝胶，通过采用油浴保证了加热温度均匀。The above method is characterized in that the heating and dissolving temperature in step 2 is 80°C to 100°C, the distillation temperature is 140°C to 160°C, and the time is 6h to 24h, and the distillation is performed under a nitrogen atmosphere. , the product is subjected to vacuum treatment for 30 min to 60 min, and the heating dissolution and distillation are performed under oil bath conditions. The present invention ensures that the raw materials can be melted into liquid by controlling the heating temperature, and ensures that the raw materials are fully reacted to form a hyperbranched boron phosphorus silicon ternary polymer by controlling the temperature and time of distillation, while preventing the decomposition of the raw materials and insufficient reaction. The vacuum treatment removes impurities from the product, and by controlling the vacuuming time, the impurities are fully removed and the product is prevented from turning into a gel. The use of an oil bath ensures uniform heating temperature.
上述的方法，其特征在于，步骤三中所述透析的过程为：向产物中加入无水乙醇并进行搅拌溶解，然后加入到透析袋中进行透析24h～48h，所述透析袋的分子量为3000～5000；所述旋转蒸发的温度为45℃～60℃，所述真空干燥的温度为60℃～100℃，时间为6h～12h。本发明通过采用分子量为3000～5000的透析袋去除小分子量的原料和杂质，保证了超支化硼磷硅三元聚合物的纯度，通过加入无水乙醇使产物溶解便于透析去除原料和杂质，通过控制透析的时间保证了原料和杂质的充分去除，并防止产物水解，通过控制旋转蒸发的温度和真空干燥的温度和时间，充分去除无水乙醇，并且防止超支化硼磷硅三元聚合物凝胶。The above method is characterized in that the dialysis process described in step three is: adding absolute ethanol to the product and stirring to dissolve it, and then adding it to a dialysis bag for dialysis for 24h to 48h. The molecular weight of the dialysis bag is 3000 ~5000; the rotary evaporation temperature is 45°C~60°C, the vacuum drying temperature is 60°C~100°C, and the time is 6h~12h. The present invention ensures the purity of the hyperbranched boron phosphorus silicon ternary polymer by using a dialysis bag with a molecular weight of 3000 to 5000 to remove small molecular weight raw materials and impurities, and dissolves the product by adding absolute ethanol to facilitate dialysis removal of raw materials and impurities. Controlling the dialysis time ensures full removal of raw materials and impurities, and prevents product hydrolysis. By controlling the temperature of rotary evaporation and the temperature and time of vacuum drying, absolute ethanol is fully removed and the hyperbranched boron phosphorus silicon terpolymer is prevented from condensing. glue.
上述的方法，其特征在于，步骤四中所述植入物为钛，所述植入物使用前依次使用丙酮、无水乙醇和去离子水清洗，然后进行真空干燥。本发明通过采用钛作为植入物为广泛使用的植入物，适用范围广，通过对植入物使用前依次使用丙酮、无水乙醇和去离子水清洗，然后进行真空干燥，去除植入物表面的杂质。The above method is characterized in that the implant in step 4 is titanium, and the implant is cleaned with acetone, absolute ethanol and deionized water in sequence before use, and then vacuum dried. The present invention uses titanium as the implant, which is a widely used implant and has a wide range of applications. The implant is cleaned with acetone, absolute ethanol and deionized water in sequence before use, and then vacuum dried to remove the implant. Surface impurities.
上述的方法，其特征在于，步骤四中所述喷涂的过程为：将超支化硼磷硅三元聚合物在低速搅拌条件下加入到高压无气喷涂机的备料罐中，然后进行搅拌分散，之后在中速搅拌下进行加压喷涂；所述低速搅拌的转速为200r/min～400r/min，所述搅拌分散的转速为800r/min～1000r/min，时间为20min～30min，所述中速搅拌的转速为600r/min～800r/min，所述加压的压力为9.8MPa～29.4MPa，所述喷涂采用带有橄榄形孔的喷嘴，所述喷嘴与植入物的距离为10cm～50cm。本发明通过控制喷涂的过程在植入物表面牢固的制备不同厚度的超支化硼磷硅三元聚合物涂层。The above method is characterized in that the spraying process described in step 4 is: adding the hyperbranched boron phosphorus silicon ternary polymer into the preparation tank of the high-pressure airless spray machine under low-speed stirring conditions, and then stirring and dispersing; Then pressurized spraying is carried out under medium-speed stirring; the low-speed stirring speed is 200r/min~400r/min, the stirring and dispersing speed is 800r/min~1000r/min, and the time is 20min~30min. The stirring speed is 600r/min～800r/min, the pressurizing pressure is 9.8MPa～29.4MPa, the spraying uses a nozzle with an olive-shaped hole, and the distance between the nozzle and the implant is 10cm～ 50cm. The present invention firmly prepares hyperbranched boron phosphorus silicon ternary polymer coatings of different thicknesses on the surface of the implant by controlling the spraying process.
上述的方法，其特征在于，步骤四中所述光动力抗菌涂层的厚度为200nm～1400nm。本发明通过控制光动力抗菌涂层的厚度适用于不同的需求，可根据实际需要确定具体的厚度。The above method is characterized in that the thickness of the photodynamic antibacterial coating described in step 4 is 200nm~1400nm. The present invention is suitable for different needs by controlling the thickness of the photodynamic antibacterial coating, and the specific thickness can be determined according to actual needs.
本发明与现有技术相比具有以下优点：Compared with the prior art, the present invention has the following advantages:
1、本发明通过控制硼酸，磷酸二乙酯类化合物和二乙氧基硅烷类化合物的摩尔比使之恰好进行缩聚脱醇反应，制成超支化硼磷硅三元聚合物，利用超支化硼磷硅三元聚合物表面丰富的官能团提高了植入物与涂层的结合强度，此外可以利用超支化硼磷硅三元聚合物的光催化性延长有效抗菌时间，达到优异的抗菌效果。1. The present invention controls the molar ratio of boric acid, diethyl phosphate compounds and diethoxysilane compounds so that the condensation polymerization and dealcoholization reaction can be carried out to produce a hyperbranched boron phosphorus silicon ternary polymer, and utilizes hyperbranched boron The rich functional groups on the surface of the phosphorus silicon terpolymer improve the bonding strength between the implant and the coating. In addition, the photocatalytic property of the hyperbranched boron phosphorus silicon terpolymer can be used to extend the effective antibacterial time and achieve excellent antibacterial effects.
2、本发明采用高压无气喷涂技术，可控性高，沉积温度低，对植入物性能影响较小，且涂层的制备过程绿色环保，不产生废水废气，具有广阔的应用前景。2. The present invention adopts high-pressure airless spraying technology, which has high controllability, low deposition temperature, and little impact on the performance of the implant. The preparation process of the coating is green and environmentally friendly, does not produce waste water and gas, and has broad application prospects.
3、本发明制备的超支化硼磷硅三元聚合物荧光材料的分子量在5000～30000，符合典型的高分子材料的分子量分布，制备的超支化硼磷硅三元聚合物荧光材料量子产率在30％～48％，有效改善了非共轭荧光聚合物发光强度低的问题，为其在生物成像领奠定了基础，制备的荧光材料对于金属离子、pH、极性溶剂、还原剂的变化荧光强度会有所改变，具备多刺激响应特性。3. The molecular weight of the hyperbranched boron phosphorus silicon ternary polymer fluorescent material prepared by the present invention is between 5,000 and 30,000, which is in line with the molecular weight distribution of typical polymer materials. The quantum yield of the prepared hyperbranched boron phosphorus silicon ternary polymer fluorescent material is At 30% to 48%, it effectively improves the problem of low luminescence intensity of non-conjugated fluorescent polymers, laying the foundation for its use in the field of biological imaging. The prepared fluorescent materials are sensitive to changes in metal ions, pH, polar solvents, and reducing agents. The fluorescence intensity will change and it has multi-stimulus response characteristics.
下面通过附图和实施例对本发明的技术方案作进一步的详细描述。The technical solution of the present invention will be described in further detail below through the drawings and examples.
附图说明Description of drawings
图1为本发明的超支化硼磷硅三元聚合物的合成原理图。Figure 1 is a schematic diagram of the synthesis of the hyperbranched boron phosphorus silicon terpolymer of the present invention.
图2为本发明实施例1得到的超支化硼磷硅三元聚合物的GPC曲线。Figure 2 is a GPC curve of the hyperbranched boron phosphorus silicon terpolymer obtained in Example 1 of the present invention.
图3为本发明实施例1得到的超支化硼磷硅三元聚合物的荧光光谱图。Figure 3 is a fluorescence spectrum chart of the hyperbranched boron phosphorus silicon terpolymer obtained in Example 1 of the present invention.
图4为本发明实施例1得到的抗菌涂层与细菌共培养0h下细菌的形貌特征图。Figure 4 is a diagram showing the morphological characteristics of bacteria obtained in Example 1 of the present invention when the antibacterial coating and bacteria were co-cultured for 0 h.
图5为本发明实施例1得到的抗菌涂层与细菌共培养2h下细菌的形貌特征图。Figure 5 is a diagram showing the morphological characteristics of bacteria co-cultured with the antibacterial coating and bacteria obtained in Example 1 of the present invention for 2 hours.
图6为本发明实施例1得到的抗菌涂层与细菌共培养4h下细菌的形貌特征图。Figure 6 is a diagram showing the morphological characteristics of bacteria co-cultured with the antibacterial coating and bacteria obtained in Example 1 of the present invention for 4 hours.
图7为本发明实施例1得到的抗菌涂层与细菌共培养8h下细菌的形貌特征图。Figure 7 is a diagram showing the morphological characteristics of bacteria co-cultured with the antibacterial coating and bacteria obtained in Example 1 of the present invention for 8 hours.
图8为本发明实施例1得到的抗菌涂层与细菌共培养12h下细菌的形貌特征图。Figure 8 is a diagram showing the morphological characteristics of bacteria when the antibacterial coating and bacteria were co-cultured for 12 hours in Example 1 of the present invention.
具体实施方式Detailed ways
图1为本发明的超支化硼磷硅三元聚合物的合成原理图，从图1中可以看出，硼酸，磷酸二乙酯和二乙氧基硅烷发生酯交换缩聚法反应，生成超支化硼磷硅三元聚合物。Figure 1 is a schematic diagram of the synthesis of the hyperbranched boron phosphorus silicon terpolymer of the present invention. It can be seen from Figure 1 that boric acid, diethyl phosphate and diethoxysilane undergo transesterification polycondensation reaction to generate hyperbranched Boron phosphorus silicon terpolymer.
实施例1Example 1
本实施例包括以下步骤：This embodiment includes the following steps:
步骤一、将1mol硼酸、0.5mol烯丙基磷酸二乙酯和0.5mol 3-氨丙基甲基二乙氧基硅烷进行混合，得到原料；Step 1: Mix 1 mol of boric acid, 0.5 mol of allyl diethyl phosphate and 0.5 mol of 3-aminopropylmethyldiethoxysilane to obtain raw materials;
步骤二、将步骤一中得到的原料在搅拌条件下进行加热溶解，然后进行蒸馏，得到产物；所述加热溶解的温度为90℃，所述蒸馏的温度为150℃，时间为12h，所述蒸馏在氮气气氛下进行，所述产物进行30min抽真空处理，所述加热溶解和蒸馏在油浴条件下进行；Step 2: The raw materials obtained in step 1 are heated and dissolved under stirring conditions, and then distilled to obtain the product; the temperature of the heating and dissolving is 90°C, the temperature of the distillation is 150°C, and the time is 12h. Distillation is carried out under a nitrogen atmosphere, the product is subjected to vacuum treatment for 30 minutes, and the heating, dissolution and distillation are carried out under oil bath conditions;
步骤三、将步骤二中得到的产物进行透析，然后依次进行旋转蒸发和真空干燥，得到超支化硼磷硅三元聚合物；所述透析袋的分子量为5000，所述透析的过程为：向产物中加入无水乙醇并进行搅拌溶解，然后加入到透析袋中进行透析48h；所述旋转蒸发的温度为45℃，所述真空干燥的温度为60℃，时间为6h；Step three: dialyze the product obtained in step two, and then perform rotary evaporation and vacuum drying in sequence to obtain a hyperbranched boron phosphorus silicon ternary polymer; the molecular weight of the dialysis bag is 5000, and the dialysis process is: Add absolute ethanol to the product and stir to dissolve, then add it to a dialysis bag for dialysis for 48 hours; the temperature of the rotary evaporation is 45°C, the temperature of the vacuum drying is 60°C, and the time is 6 hours;
步骤四、将步骤三中得到的超支化硼磷硅三元聚合物加入到高压无气喷涂机中对植入物表面进行喷涂，在植入物表面上得到光动力抗菌涂层；所述植入物为钛，所述植入物使用前依次使用丙酮、无水乙醇和去离子水清洗，然后进行真空干燥；所述喷涂的过程为：将超支化硼磷硅三元聚合物在低速搅拌条件下加入到高压无气喷涂机的备料罐中，然后进行搅拌分散，之后在中速搅拌下进行加压喷涂；所述低速搅拌的转速为300r/min，所述搅拌分散的转速为900r/min，时间为25min，所述中速搅拌的转速为700r/min，所述加压的压力为9.8MPa，所述喷涂采用带有橄榄形孔的喷嘴，所述喷嘴与植入物的距离为10cm。Step 4: Add the hyperbranched boron phosphorus silicon ternary polymer obtained in step 3 to a high-pressure airless spraying machine to spray the surface of the implant to obtain a photodynamic antibacterial coating on the surface of the implant; the implant The implant is titanium, and the implant is cleaned with acetone, absolute ethanol and deionized water in sequence before use, and then vacuum dried; the spraying process is: stir the hyperbranched boron phosphorus silicon ternary polymer at a low speed Add to the preparation tank of the high-pressure airless spraying machine under certain conditions, then stir and disperse, and then pressurize and spray under medium-speed stirring; the rotation speed of the low-speed stirring is 300r/min, and the rotation speed of the stirring and dispersion is 900r/min. min, the time is 25min, the medium-speed stirring speed is 700r/min, the pressurizing pressure is 9.8MPa, the spraying uses a nozzle with an olive-shaped hole, and the distance between the nozzle and the implant is 10cm.
经检测，本实施例中在植入物表面上得到光动力抗菌涂的厚度为500nm。After testing, it was found that the thickness of the photodynamic antibacterial coating obtained on the surface of the implant in this example was 500 nm.
图2为本实施例得到的超支化硼磷硅三元聚合物的GPC曲线，从图2中得到的数据中可以计算出，本实施例得到的超支化硼磷硅三元聚合物的数均分子量Mw＝9570，重均分子量Mn＝9740，说明本实施例得到的超支化硼磷硅三元聚合物为高分子材料。Figure 2 is the GPC curve of the hyperbranched boron phosphorus silicon ternary polymer obtained in this example. From the data obtained in Figure 2, it can be calculated that the number average of the hyperbranched boron phosphorus silicon ternary polymer obtained in this example The molecular weight Mw=9570 and the weight average molecular weight Mn=9740 indicate that the hyperbranched boron phosphorus silicon ternary polymer obtained in this example is a polymer material.
图3为本实施例得到的超支化硼磷硅三元聚合物的荧光光谱图，从图3中可以看出，激发波长EX＝430nm，发射波长Em＝498nm，说明本实施例得到的超支化硼磷硅三元聚合物为荧光材料。Figure 3 is the fluorescence spectrum of the hyperbranched boron phosphorus silicon ternary polymer obtained in this example. It can be seen from Figure 3 that the excitation wavelength EX=430nm and the emission wavelength Em=498nm, indicating that the hyperbranched ternary polymer obtained in this example Boron phosphorus silicon terpolymer is a fluorescent material.
图4为本实施例得到的抗菌涂层与细菌共培养0h下细菌的形貌特征图，从图4中可以看出，细菌呈现饱满的球形，结构完整。Figure 4 is a morphological characteristic diagram of the bacteria obtained in this example when the antibacterial coating and bacteria were co-cultured for 0 hours. It can be seen from Figure 4 that the bacteria are full spherical and have a complete structure.
图5为本实施例得到的抗菌涂层与细菌共培养2h下细菌的形貌特征图，从图5中可以看出，细菌细胞膜呈现出皱褶和凹陷形态。Figure 5 is a morphological characteristic diagram of bacteria obtained in this example when the antibacterial coating and bacteria were co-cultured for 2 hours. As can be seen from Figure 5, the bacterial cell membrane exhibits wrinkles and depressions.
图6为本实施例得到的抗菌涂层与细菌共培养4h下细菌的形貌特征图，从图6中可以看出，细菌细胞膜少数膜结构破损和变形。Figure 6 is a morphological characteristic diagram of bacteria obtained in this example when the antibacterial coating and bacteria were co-cultured for 4 hours. It can be seen from Figure 6 that a few membrane structures of the bacterial cell membrane are damaged and deformed.
图7为本实施例得到的抗菌涂层与细菌共培养8h下细菌的形貌特征图，从图7中可以看出，细菌细胞膜大面积膜结构破损和变形。Figure 7 is a morphological characteristic diagram of bacteria obtained in this example when the antibacterial coating and bacteria were co-cultured for 8 hours. It can be seen from Figure 7 that the bacterial cell membrane has a large area of membrane structure damage and deformation.
图8为本实施例得到的抗菌涂层与细菌共培养12h下细菌的形貌特征图，从图8中可以看出，细菌全部被杀死，膜结构破损和变形。Figure 8 is a morphological characteristic diagram of the bacteria obtained in this example when the antibacterial coating and bacteria were co-cultured for 12 hours. It can be seen from Figure 8 that all the bacteria were killed and the membrane structure was damaged and deformed.
从图4～图8中可以看出，本实施例得到的抗菌涂层具有优异的抗菌效果。It can be seen from Figures 4 to 8 that the antibacterial coating obtained in this example has excellent antibacterial effect.
实施例2Example 2
本实施例包括以下步骤：This embodiment includes the following steps:
步骤一、将1.5mol硼酸、0.75mol烯丙基磷酸二乙酯和0.75mol(3-环氧丙氧基)甲基二乙氧基硅烷进行混合，得到原料；Step 1: Mix 1.5 mol of boric acid, 0.75 mol of allyl diethyl phosphate and 0.75 mol of (3-epoxypropoxy)methyldiethoxysilane to obtain raw materials;
步骤二、将步骤一中得到的原料在搅拌条件下进行加热溶解，然后进行蒸馏，得到产物；所述加热溶解的温度为100℃，所述蒸馏的温度为160℃，时间为6h，所述蒸馏在氮气气氛下进行，所述产物进行40min抽真空处理，所述加热溶解和蒸馏在油浴条件下进行；Step 2: The raw materials obtained in step 1 are heated and dissolved under stirring conditions, and then distilled to obtain the product; the temperature of the heating and dissolving is 100°C, the temperature of the distillation is 160°C, and the time is 6 hours. Distillation is carried out under a nitrogen atmosphere, the product is subjected to vacuum treatment for 40 minutes, and the heating, dissolution and distillation are carried out under oil bath conditions;
步骤三、将步骤二中得到的产物进行透析，然后依次进行旋转蒸发和真空干燥，得到超支化硼磷硅三元聚合物；所述透析袋的分子量为3000，所述透析的过程为：向产物中加入无水乙醇并进行搅拌溶解，然后加入到透析袋中进行透析36h；所述旋转蒸发的温度为50℃，所述真空干燥的温度为80℃，时间为12h；Step three: dialyze the product obtained in step two, and then perform rotary evaporation and vacuum drying in sequence to obtain a hyperbranched boron phosphorus silicon ternary polymer; the molecular weight of the dialysis bag is 3000, and the dialysis process is: Add absolute ethanol to the product and stir to dissolve, then add it to a dialysis bag for dialysis for 36 hours; the temperature of the rotary evaporation is 50°C, the temperature of the vacuum drying is 80°C, and the time is 12h;
步骤四、将步骤三中得到的超支化硼磷硅三元聚合物加入到高压无气喷涂机中对植入物表面进行喷涂，在植入物表面上得到光动力抗菌涂层；所述植入物为钛，所述植入物使用前依次使用丙酮、无水乙醇和去离子水清洗，然后进行真空干燥；所述喷涂的过程为：将超支化硼磷硅三元聚合物在低速搅拌条件下加入到高压无气喷涂机的备料罐中，然后进行搅拌分散，之后在中速搅拌下进行加压喷涂；所述低速搅拌的转速为400r/min，所述搅拌分散的转速为800r/min，时间为30min，所述中速搅拌的转速为600r/min，所述加压的压力为15.2MPa，所述喷涂采用带有橄榄形孔的喷嘴，所述喷嘴与植入物的距离为20cm。Step 4: Add the hyperbranched boron phosphorus silicon ternary polymer obtained in step 3 to a high-pressure airless spraying machine to spray the surface of the implant to obtain a photodynamic antibacterial coating on the surface of the implant; the implant The implant is titanium, and the implant is cleaned with acetone, absolute ethanol and deionized water in sequence before use, and then vacuum dried; the spraying process is: stir the hyperbranched boron phosphorus silicon ternary polymer at a low speed Add to the preparation tank of the high-pressure airless spraying machine under certain conditions, then stir and disperse, and then perform pressurized spraying under medium-speed stirring; the low-speed stirring speed is 400r/min, and the stirring and dispersing speed is 800r/min. min, the time is 30min, the medium-speed stirring speed is 600r/min, the pressurizing pressure is 15.2MPa, the spraying uses a nozzle with an olive-shaped hole, and the distance between the nozzle and the implant is 20cm.
经检测，本实施例中在植入物表面上得到光动力抗菌涂的厚度为200nm，本实施例得到的抗菌涂层具有优异的抗菌效果。After testing, the thickness of the photodynamic antibacterial coating obtained on the implant surface in this example is 200 nm, and the antibacterial coating obtained in this example has excellent antibacterial effect.
实施例3Example 3
本实施例包括以下步骤：This embodiment includes the following steps:
步骤一、将2mol硼酸、1mol(3-氨丙基)磷酸二乙酯和1mol(3-环氧丙氧基)甲基二乙氧基硅烷进行混合，得到原料；Step 1: Mix 2 mol of boric acid, 1 mol of (3-aminopropyl) diethyl phosphate and 1 mol of (3-epoxypropoxy) methyldiethoxysilane to obtain raw materials;
步骤二、将步骤一中得到的原料在搅拌条件下进行加热溶解，然后进行蒸馏，得到产物；所述加热溶解的温度为80℃，所述蒸馏的温度为140℃，时间为24h，所述蒸馏在氮气气氛下进行，所述产物进行60min抽真空处理，所述加热溶解和蒸馏在油浴条件下进行；Step 2: The raw materials obtained in step 1 are heated and dissolved under stirring conditions, and then distilled to obtain the product; the temperature of the heating and dissolving is 80°C, the temperature of the distillation is 140°C, and the time is 24h. Distillation is carried out under a nitrogen atmosphere, the product is subjected to vacuum treatment for 60 minutes, and the heating, dissolution and distillation are carried out under oil bath conditions;
步骤三、将步骤二中得到的产物进行透析，然后依次进行旋转蒸发和真空干燥，得到超支化硼磷硅三元聚合物；所述透析袋的分子量为4000，所述透析的过程为：向产物中加入无水乙醇并进行搅拌溶解，然后加入到透析袋中进行透析24h；所述旋转蒸发的温度为60℃，所述真空干燥的温度为100℃，时间为8h；Step three: dialyze the product obtained in step two, and then perform rotary evaporation and vacuum drying in sequence to obtain a hyperbranched boron phosphorus silicon ternary polymer; the molecular weight of the dialysis bag is 4000, and the dialysis process is: Add absolute ethanol to the product and stir to dissolve, then add it to a dialysis bag for dialysis for 24 hours; the temperature of the rotary evaporation is 60°C, the temperature of the vacuum drying is 100°C, and the time is 8 hours;
步骤四、将步骤三中得到的超支化硼磷硅三元聚合物加入到高压无气喷涂机中对植入物表面进行喷涂，在植入物表面上得到光动力抗菌涂层；所述植入物为钛，所述植入物使用前依次使用丙酮、无水乙醇和去离子水清洗，然后进行真空干燥；所述喷涂的过程为：将超支化硼磷硅三元聚合物在低速搅拌条件下加入到高压无气喷涂机的备料罐中，然后进行搅拌分散，之后在中速搅拌下进行加压喷涂；所述低速搅拌的转速为200r/min，所述搅拌分散的转速为1000r/min，时间为20min，所述中速搅拌的转速为800r/min，所述加压的压力为29.4MPa，所述喷涂采用带有橄榄形孔的喷嘴，所述喷嘴与植入物的距离为50cm。Step 4: Add the hyperbranched boron phosphorus silicon ternary polymer obtained in step 3 to a high-pressure airless spraying machine to spray the surface of the implant to obtain a photodynamic antibacterial coating on the surface of the implant; the implant The implant is titanium, and the implant is cleaned with acetone, absolute ethanol and deionized water in sequence before use, and then vacuum dried; the spraying process is: stir the hyperbranched boron phosphorus silicon ternary polymer at a low speed Add to the preparation tank of the high-pressure airless spraying machine under certain conditions, then stir and disperse, and then pressurize and spray under medium-speed stirring; the rotation speed of the low-speed stirring is 200r/min, and the rotation speed of the stirring and dispersion is 1000r/ min, the time is 20min, the medium-speed stirring speed is 800r/min, the pressurizing pressure is 29.4MPa, the spraying uses a nozzle with an olive-shaped hole, and the distance between the nozzle and the implant is 50cm.
经检测，本实施例中在植入物表面上得到光动力抗菌涂的厚度为1400nm，本实施例得到的抗菌涂层具有优异的抗菌效果。After testing, the thickness of the photodynamic antibacterial coating obtained on the implant surface in this example is 1400 nm. The antibacterial coating obtained in this example has excellent antibacterial effect.
实施例4Example 4
本实施例包括以下步骤：This embodiment includes the following steps:
步骤一、将1mol硼酸、1mol磷酸二乙酯和1mol二乙氧基硅烷进行混合，得到原料；Step 1: Mix 1 mol of boric acid, 1 mol of diethyl phosphate and 1 mol of diethoxysilane to obtain raw materials;
步骤二、将步骤一中得到的原料在搅拌条件下进行加热溶解，然后进行蒸馏，得到产物；所述加热溶解的温度为90℃，所述蒸馏的温度为150℃，时间为12h，所述蒸馏在氮气气氛下进行，所述产物进行30min抽真空处理，所述加热溶解和蒸馏在油浴条件下进行；Step 2: The raw materials obtained in step 1 are heated and dissolved under stirring conditions, and then distilled to obtain the product; the temperature of the heating and dissolving is 90°C, the temperature of the distillation is 150°C, and the time is 12h. Distillation is carried out under a nitrogen atmosphere, the product is subjected to vacuum treatment for 30 minutes, and the heating, dissolution and distillation are carried out under oil bath conditions;
步骤三、将步骤二中得到的产物进行透析，然后依次进行旋转蒸发和真空干燥，得到超支化硼磷硅三元聚合物；所述透析袋的分子量为5000，所述透析的过程为：向产物中加入无水乙醇并进行搅拌溶解，然后加入到透析袋中进行透析48h；所述旋转蒸发的温度为45℃，所述真空干燥的温度为60℃，时间为6h；Step three: dialyze the product obtained in step two, and then perform rotary evaporation and vacuum drying in sequence to obtain a hyperbranched boron phosphorus silicon ternary polymer; the molecular weight of the dialysis bag is 5000, and the dialysis process is: Add absolute ethanol to the product and stir to dissolve, then add it to a dialysis bag for dialysis for 48 hours; the temperature of the rotary evaporation is 45°C, the temperature of the vacuum drying is 60°C, and the time is 6 hours;
步骤四、将步骤三中得到的超支化硼磷硅三元聚合物加入到高压无气喷涂机中对植入物表面进行喷涂，在植入物表面上得到光动力抗菌涂层；所述植入物为钛，所述植入物使用前依次使用丙酮、无水乙醇和去离子水清洗，然后进行真空干燥；所述喷涂的过程为：将超支化硼磷硅三元聚合物在低速搅拌条件下加入到高压无气喷涂机的备料罐中，然后进行搅拌分散，之后在中速搅拌下进行加压喷涂；所述低速搅拌的转速为300r/min，所述搅拌分散的转速为900r/min，时间为25min，所述中速搅拌的转速为700r/min，所述加压的压力为13.4MPa，所述喷涂采用带有橄榄形孔的喷嘴，所述喷嘴与植入物的距离为30cm。Step 4: Add the hyperbranched boron phosphorus silicon ternary polymer obtained in step 3 to a high-pressure airless spraying machine to spray the surface of the implant to obtain a photodynamic antibacterial coating on the surface of the implant; the implant The implant is titanium, and the implant is cleaned with acetone, absolute ethanol and deionized water in sequence before use, and then vacuum dried; the spraying process is: stir the hyperbranched boron phosphorus silicon ternary polymer at a low speed Add to the preparation tank of the high-pressure airless spraying machine under certain conditions, then stir and disperse, and then pressurize and spray under medium-speed stirring; the rotation speed of the low-speed stirring is 300r/min, and the rotation speed of the stirring and dispersion is 900r/min. min, the time is 25min, the medium-speed stirring speed is 700r/min, the pressurizing pressure is 13.4MPa, the spraying uses a nozzle with an olive-shaped hole, and the distance between the nozzle and the implant is 30cm.
经检测，本实施例中在植入物表面上得到光动力抗菌涂的厚度为600nm。After testing, it was found that the thickness of the photodynamic antibacterial coating obtained on the surface of the implant in this example was 600 nm.
以上所述，仅是本发明的较佳实施例，并非对本发明作任何限制。凡是根据发明技术实质对以上实施例所作的任何简单修改、变更以及等效变化，均仍属于本发明技术方案的保护范围内。The above descriptions are only preferred embodiments of the present invention and do not limit the present invention in any way. Any simple modifications, changes and equivalent changes made to the above embodiments based on the technical essence of the invention still fall within the protection scope of the technical solution of the invention.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211521840.3ACN115737923B (en) | 2022-11-30 | 2022-11-30 | Photodynamic antibacterial coating for implant surface and preparation method thereof |
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| CN202211521840.3ACN115737923B (en) | 2022-11-30 | 2022-11-30 | Photodynamic antibacterial coating for implant surface and preparation method thereof |
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| CN115737923A CN115737923A (en) | 2023-03-07 |
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| CN202211521840.3AActiveCN115737923B (en) | 2022-11-30 | 2022-11-30 | Photodynamic antibacterial coating for implant surface and preparation method thereof |
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| CN116712606B (en)* | 2023-06-13 | 2025-07-22 | 西北有色金属研究院 | Preparation method of graphene-based composite antibacterial coating for titanium-tantalum alloy surface |
| Publication number | Priority date | Publication date | Assignee | Title |
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