CN115920110A - Preparation method of nano metal boride composite material - Google Patents
Preparation method of nano metal boride composite material Download PDFInfo
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Abstract
Description
技术领域technical field
本发明属于新材料领域,涉及到一种纳米金属硼化物复合材料的制备方法。The invention belongs to the field of new materials, and relates to a preparation method of a nanometer metal boride composite material.
背景技术Background technique
细菌感染威胁着人类健康,不但会引起皮肤和软组织感染,诱发炎症性疾病,而且伤口长时间得不到愈合常会引起其他病变,出现败血症等并发症。随着抗生素的广泛使用,细菌耐药性已成为威胁全球人类及动物安全的重大问题,特别是“超级耐药菌”的出现极大地削弱了抗生素的治疗效果,开发新型广谱抗菌材料势在必行。相比较抗生素抗菌,无机纳米材料凭借着独特的结构、较大的比表面积、稳定的物化性质和优异的光热转换效率等可用于抗菌载药材料,可以通过释放抗菌组分、生成ROS、中断物质或能量传递、抑制酶活性等多种方式发挥其抗菌作用,使细菌不易产生耐药性,为治疗细菌引起的伤口愈合和感染性疾病提供了全新的策略。Bacterial infection is a threat to human health. It not only causes skin and soft tissue infection, induces inflammatory diseases, but also causes other lesions and complications such as sepsis if the wound is not healed for a long time. With the widespread use of antibiotics, bacterial resistance has become a major problem threatening the safety of humans and animals around the world. In particular, the emergence of "super-resistant bacteria" has greatly weakened the therapeutic effect of antibiotics. It is imperative to develop new broad-spectrum antibacterial materials. must do. Compared with antibiotics, inorganic nanomaterials can be used as antibacterial drug-loaded materials due to their unique structure, large specific surface area, stable physical and chemical properties, and excellent photothermal conversion efficiency. They can release antibacterial components, generate ROS, interrupt Material or energy transfer, inhibition of enzyme activity and other ways to exert its antibacterial effect make bacteria less resistant to drug resistance, providing a new strategy for the treatment of wound healing and infectious diseases caused by bacteria.
金属硼化物是过渡金属与硼生成的硬质化合物,在阻燃、耐热、高硬、高强、催化、超导等领域展现了广阔的应用。金属硼化物具有类似于石墨的硼原子层状结构、以及硼原子和金属原子间M~B键,这使得该类化合物具有一定的导电性和光热转换能力;同时由于有硼元素的存在,可能赋予其更大的生物活性和相容性,还可以参与人体代谢、调节人体激素以及具有一定的抗炎作用。但是目前还缺少简便的制备纳米金属硼化物的方法,传统高温合成、硼热化学法、熔融电解法和碳热法制备的硼化物粉体尺寸大、分散性差、易发生聚集沉降,且单一金属硼化物抗菌活性不高,很难满足实际抗菌领域的要求。Metal borides are hard compounds formed by transition metals and boron, and have been widely used in the fields of flame retardancy, heat resistance, high hardness, high strength, catalysis, and superconductivity. Metal borides have a layered structure of boron atoms similar to graphite, and the M-B bond between boron atoms and metal atoms, which makes this type of compound have certain electrical conductivity and light-to-heat conversion ability; at the same time, due to the presence of boron element, It may endow it with greater biological activity and compatibility, and it can also participate in human metabolism, regulate human hormones and have certain anti-inflammatory effects. However, there is still a lack of convenient methods for preparing nano-metal borides. The boride powders prepared by traditional high-temperature synthesis, boron thermochemistry, molten electrolysis, and carbothermal methods have large sizes, poor dispersion, and are prone to aggregation and sedimentation. The antibacterial activity of borides is not high, and it is difficult to meet the requirements of the actual antibacterial field.
发明内容Contents of the invention
针对纳米金属硼化物制备困难、易团聚、单一抗菌性能不高以及粉体应用局限性等问题,本发明的目的是提供一种纳米金属硼化物复合材料的制备方法,通过表面活性剂辅助超声剥离块体金属硼化物,获得纳米片并对其表面改性,将具有光动力抗菌功能的吲哚菁绿装载到材料表面而获得具有优异多效协同抗菌功能的金属硼化物纳米复合材料,并利用静电纺丝技术与高聚物共纺制备成伤口敷料。Aiming at the problems of difficult preparation of nano-metal borides, easy agglomeration, low single antibacterial performance, and powder application limitations, the purpose of the present invention is to provide a preparation method of nano-metal boride composite materials, which can be stripped by surfactant-assisted ultrasonic stripping Bulk metal borides, obtaining nanosheets and modifying their surface, loading indocyanine green with photodynamic antibacterial function on the surface of the material to obtain metal boride nanocomposites with excellent multi-effect synergistic antibacterial function, and using Electrospinning technology and co-spinning of polymers are used to prepare wound dressings.
本发明的技术方案为:Technical scheme of the present invention is:
一种纳米金属硼化物复合材料的制备方法,步骤如下:A preparation method of nanometer metal boride composite material, the steps are as follows:
步骤1,将金属硼化物用液氮冷冻后分散在有机溶剂中,加入表面活性剂,通过超声辅助在0~20℃温度条件下剥离、离心分离、无水乙醇和去离子水洗涤、干燥得到金属硼化物纳米片;其中,表面活性剂与金属硼化物的质量比为1:20~1:1,超声功率为200~800w,时间为1~5h;Step 1, freeze the metal boride with liquid nitrogen and disperse it in an organic solvent, add a surfactant, peel off at a temperature of 0-20°C with the assistance of ultrasound, centrifuge, wash with absolute ethanol and deionized water, and dry to obtain Metal boride nanosheets; wherein, the mass ratio of surfactant to metal boride is 1:20-1:1, the ultrasonic power is 200-800w, and the time is 1-5h;
步骤2,将步骤1得到的金属硼化物纳米片加入含有改性剂的水溶液中,在恒温水浴条件下混合搅拌,洗涤、干燥后制得改性修饰的金属硼化物纳米片;其中,改性剂的浓度为5~20mg/mL,改性剂与金属硼化物的质量比为2:1~25:1,搅拌时间6~24h,反应温度为20~50℃;Step 2, adding the metal boride nanosheets obtained in step 1 into an aqueous solution containing a modifier, mixing and stirring in a constant temperature water bath, washing and drying to prepare modified metal boride nanosheets; wherein, the modified The concentration of the agent is 5-20mg/mL, the mass ratio of the modifier to the metal boride is 2:1-25:1, the stirring time is 6-24h, and the reaction temperature is 20-50°C;
步骤3,将步骤2得到的改性修饰的金属硼化物纳米片与吲哚菁绿溶液混合,高速搅拌0.5~2h,然后在0~35℃下水浴中避光低速搅拌自组装反应,待反应完全后离心、洗涤、干燥,得到纳米金属硼化物复合粉体材料;其中,高速为600~1000rpm,低速为100~300rpm;Step 3, mixing the modified metal boride nanosheets obtained in step 2 with the indocyanine green solution, stirring at high speed for 0.5-2 hours, and then stirring the self-assembly reaction at a low speed in a water bath at 0-35° C. After completion, centrifuge, wash, and dry to obtain nano-metal boride composite powder materials; among them, the high speed is 600-1000rpm, and the low speed is 100-300rpm;
步骤4,将步骤3中得到的纳米金属硼化物复合粉体材料分散在含有纺丝助剂的溶液中,加入有机高聚物溶液,共混搅拌均匀制备静电纺丝液;采用静电纺丝技术进行纺丝,用接收器收集获得纳米金属硼化物复合材料;其中,搅拌时间为3~24h;静电纺丝温度为10~30℃;电压为13~22kV;进样速度为0.5~3.5mL/h;接收器距离为5~25cm,转速为50~150rpm。Step 4, dispersing the nano-metal boride composite powder material obtained in step 3 in a solution containing a spinning aid, adding an organic polymer solution, blending and stirring evenly to prepare an electrospinning liquid; using electrospinning technology Carry out spinning, and collect nano-metal boride composite materials with a receiver; wherein, the stirring time is 3-24 hours; the electrospinning temperature is 10-30°C; the voltage is 13-22kV; the injection speed is 0.5-3.5mL/ h; The receiver distance is 5-25cm, and the rotation speed is 50-150rpm.
步骤1中液氮冷冻时间为0.5~12h。In step 1, the liquid nitrogen freezing time is 0.5-12 hours.
步骤1中金属硼化物为二硼化锆、二硼化铌、二硼化钛、二硼化铪、二硼化铬和二硼化镁中的一种。The metal boride in step 1 is one of zirconium diboride, niobium diboride, titanium diboride, hafnium diboride, chromium diboride and magnesium diboride.
步骤1中金属硼化物在有机溶剂中的浓度为0.5~2.0mg/mL。The concentration of the metal boride in the organic solvent in step 1 is 0.5-2.0 mg/mL.
步骤1中有机溶剂为乙二醇、DMF、N~甲基吡咯烷酮、异丙醇、N,N~二甲基甲酰胺、乙醇、乙腈中的一种或其和水的混合溶剂。The organic solvent in step 1 is one of ethylene glycol, DMF, N-methylpyrrolidone, isopropanol, N,N-dimethylformamide, ethanol, acetonitrile or a mixed solvent with water.
步骤1中表面活性剂为聚醚P123、十二烷基苯磺酸钠、聚醚F68、十六烷基三甲基溴化铵、聚乙烯吡咯烷酮、十二烷基硫酸中的一种。In step 1, the surfactant is one of polyether P123, sodium dodecylbenzenesulfonate, polyether F68, cetyltrimethylammonium bromide, polyvinylpyrrolidone, and dodecylsulfuric acid.
步骤1中表面活性剂在剥离体系中的浓度为100~1000μg/mL。The concentration of the surfactant in the stripping system in step 1 is 100-1000 μg/mL.
步骤2中的改性剂为壳聚糖、季铵化壳聚糖、双胍盐壳聚糖、氨基聚乙二醇、巯基聚乙二醇、透明质酸中的一种。The modifying agent in step 2 is one of chitosan, quaternized chitosan, biguanide chitosan, amino polyethylene glycol, mercapto polyethylene glycol, and hyaluronic acid.
步骤3中,吲哚菁绿溶液的溶剂为水、乙醇和PBS中的一种。In step 3, the solvent of the indocyanine green solution is one of water, ethanol and PBS.
步骤3中,吲哚菁绿在反应体系中的浓度为0.05~1mg/mL;吲哚菁绿与改性修饰的金属硼化物纳米片的质量比为1:2~50;干燥条件为冷冻干燥、真空干燥或鼓风干燥。In step 3, the concentration of indocyanine green in the reaction system is 0.05-1 mg/mL; the mass ratio of indocyanine green to the modified metal boride nanosheets is 1:2-50; the drying condition is freeze-drying , Vacuum drying or blast drying.
步骤4中,有机高聚物为聚乙烯醇(PVA)、聚乳酸(PLA)、聚丙烯腈(PAN)和聚已内酯(PCL)中的一种。In step 4, the organic polymer is one of polyvinyl alcohol (PVA), polylactic acid (PLA), polyacrylonitrile (PAN) and polycaprolactone (PCL).
步骤4中,有机高聚物溶液的溶剂为水、二甲基甲酰胺、乙醇、二氯甲烷和三氯甲烷中的一种。In step 4, the solvent of the organic polymer solution is one of water, dimethylformamide, ethanol, dichloromethane and chloroform.
步骤4中,含有纺丝助剂为乙醇、聚乙烯吡咯烷酮(PVP)、聚乙二醇中的一种或两种以上的混合液。In step 4, the spinning aid is one or a mixture of two or more of ethanol, polyvinylpyrrolidone (PVP), and polyethylene glycol.
步骤4中,纳米金属硼化物复合粉体材料和有机高聚物的质量比为1:10~100。In step 4, the mass ratio of the nano metal boride composite powder material to the organic high polymer is 1:10-100.
与现有技术相比,本发明的效果和益处为,通过助剂辅助超声溶液剥离、表面改性方法提升金属硼化物纳米片分散性,还可以增强材料对于细菌的黏附作用;通过装载吲哚菁绿构建近红外响应型的光热与光动力联合抗菌材料,可实现对大肠杆菌、金黄色葡萄球菌、耐甲氧西林金黄色葡萄球菌的高效抗菌;通过静电纺丝技术可以制备功能性伤口抗菌敷料,生物相容性好。材料制备过程绿色环保,操作简单易行。制备的复合抗菌材料具有广谱抗菌、持久性、不产生耐药性等特点,可用于抗菌喷剂、防护涂层、医用敷料等领域,在诊疗一体化领域也具有广阔应用前景。Compared with the prior art, the effect and benefit of the present invention are that the dispersibility of the metal boride nanosheets can be improved through auxiliary agent-assisted ultrasonic solution stripping and surface modification methods, and the adhesion of the material to bacteria can also be enhanced; by loading indole Cyan Green constructs a near-infrared responsive photothermal and photodynamic antibacterial material, which can achieve high-efficiency antibacterial effects against Escherichia coli, Staphylococcus aureus, and methicillin-resistant Staphylococcus aureus; functional wounds can be prepared by electrospinning technology Antibacterial dressing with good biocompatibility. The material preparation process is green and environmentally friendly, and the operation is simple and easy. The prepared composite antibacterial material has the characteristics of broad-spectrum antibacterial, persistence, and no drug resistance. It can be used in antibacterial sprays, protective coatings, medical dressings, etc., and has broad application prospects in the field of integrated diagnosis and treatment.
附图说明Description of drawings
图1为制备的二硼化锆纳米片的AFM图。Figure 1 is the AFM image of the prepared zirconium diboride nanosheets.
图2为制备的二硼化钛/壳聚糖/吲哚菁绿/聚乳酸基复合纳米纤维膜的SEM图。Fig. 2 is the SEM image of the prepared titanium diboride/chitosan/indocyanine green/polylactic acid-based composite nanofiber membrane.
具体实施方式Detailed ways
为了使得本领域技术人员能够更加清楚地了解本发明的技术方案,以下将结合具体的实施例说明本发明的技术方案。In order to enable those skilled in the art to understand the technical solution of the present invention more clearly, the technical solution of the present invention will be described below in conjunction with specific embodiments.
同样应理解,以下实施例只用于对本发明进行进一步说明,不能理解为对本发明保护范围的限制,本领域的技术人员根据本发明的上述内容作出的一些非本质的改进和调整均属于本发明的保护范围。It should also be understood that the following examples are only used to further illustrate the present invention, and should not be construed as limiting the protection scope of the present invention. Some non-essential improvements and adjustments made by those skilled in the art according to the above contents of the present invention all belong to the present invention scope of protection.
下述示例具体的工艺参数等也仅是合适范围中的一个示例,即本领域技术人员可以通过本文的说明做合适的范围内选择,而并非要限定于下文示例的具体数值。The specific process parameters and the like in the following examples are only examples of suitable ranges, that is, those skilled in the art can make a selection within a suitable range through the description herein, and are not limited to the specific values exemplified below.
实施例1Example 1
1.将60mg二硼化锆粉体在液氮中冷冻1h后分散在90mL乙二醇中,之后加入60mg表面活性剂聚醚F68,在5℃水浴中以400w功率进行超声剥离2h,以2500r/min的转速离心5min,去掉块状未剥离的二硼化锆粉,保留上清液,二次离心,转速为12000r/min的转速,离心20min,收集沉淀,用无水乙醇和去离子水分别交替洗涤三次,冷冻干燥24小时制得二硼化锆纳米片。1. Freeze 60mg of zirconium diboride powder in liquid nitrogen for 1 hour and disperse it in 90mL of ethylene glycol, then add 60mg of surfactant polyether F68, perform ultrasonic peeling at 400w power for 2 hours in a water bath at 5°C, and disperse at 2500r Centrifuge at a speed of 12000r/min for 5min, remove the blocky unstripped zirconium diboride powder, retain the supernatant, and centrifuge for a second time at a speed of 12000r/min, centrifuge for 20min, collect the precipitate, and wash with absolute ethanol and deionized water Alternately washed three times respectively, freeze-dried for 24 hours to prepare zirconium diboride nanosheets.
2.将5mg制备的二硼化锆纳米片分散在5mL水溶液中,将季铵盐壳聚糖80mg溶于5mL去离子水中制备季铵盐壳聚糖水溶液,在超声作用下将二者混匀,室温搅拌6h。悬浮液用去离子水洗涤三次,冷冻干燥24小时制得季铵化壳聚糖修饰的二硼化锆纳米片。2. Disperse 5 mg of zirconium diboride nanosheets prepared in 5 mL of aqueous solution, dissolve 80 mg of quaternary ammonium chitosan in 5 mL of deionized water to prepare an aqueous solution of quaternary ammonium chitosan, and mix the two evenly under the action of ultrasound , Stir at room temperature for 6h. The suspension was washed three times with deionized water and freeze-dried for 24 hours to prepare quaternized chitosan-modified zirconium diboride nanosheets.
3.将5mg改性后二硼化锆纳米片与5mL300μg·mL-1的吲哚菁绿PBS溶液混合,高速搅拌0.5h,后在15℃下避光低速搅拌组装12h;之后离心,PBS洗涤3次,真空干燥后获得二硼化锆纳米片复合材料。3. Mix 5 mg of modified zirconium diboride nanosheets with 5 mL of 300 μg·mL -1 indocyanine green PBS solution, stir at high speed for 0.5 h, and then assemble at 15°C with low speed stirring in the dark for 12 h; after that, centrifuge and wash with PBS 3 times, the zirconium diboride nanosheet composite material was obtained after vacuum drying.
4.将1g聚乳酸溶于10.5mL二氯甲烷,将50mg二硼化锆纳米片复合材料和60mgPVP分散于10.5mL二氯甲烷中。将两种溶液混合避光搅拌10h。在电压为19kV,进样速度为1mL/h,接收器距离为12cm,转速为75rpm,温度为20℃下进行纺丝制备成复合纤维膜材料。4. 1 g of polylactic acid was dissolved in 10.5 mL of dichloromethane, and 50 mg of zirconium diboride nanosheet composite material and 60 mg of PVP were dispersed in 10.5 mL of dichloromethane. The two solutions were mixed and stirred for 10 h in the dark. The composite fiber membrane material was prepared by spinning at a voltage of 19kV, an injection speed of 1mL/h, a receiver distance of 12cm, a rotation speed of 75rpm, and a temperature of 20°C.
测试结果表明,制备的二硼化锆纳米片复合材料在浓度为250μg·mL-1时,在功率为1.5W/cm~2的808nm近红外光照射10min下,温度可以升高到45℃。对耐甲氧西林金黄色葡萄球菌和大肠杆菌的抑菌率分别为95.52%和96.96%。制备的静电纺丝膜在功率为1.5W/cm~2的808nm近红外光照射5min下,温度可以升高到55℃。对耐甲氧西林金黄色葡萄球菌和大肠杆菌的抑菌率分别为99.68%和99.91%。伤口感染愈合实验表明,经过14天,空白组愈合率为80.56%,使用复合纤维膜的伤口愈合率为99.25%。The test results show that the temperature of the prepared zirconium diboride nanosheet composite can rise to 45℃ under the irradiation of 808nm near-infrared light with a power of 1.5W/cm ~2 for 10min at a concentration of 250μg·mL -1 . The antibacterial rates against methicillin-resistant Staphylococcus aureus and Escherichia coli were 95.52% and 96.96%, respectively. The temperature of the prepared electrospun membrane can rise to 55° C. under the irradiation of 808 nm near-infrared light with a power of 1.5 W/cm 2 for 5 minutes. The antibacterial rates against methicillin-resistant Staphylococcus aureus and Escherichia coli were 99.68% and 99.91%, respectively. The wound infection healing experiment showed that after 14 days, the healing rate of the blank group was 80.56%, and the healing rate of the wound using the composite fiber membrane was 99.25%.
实施例2Example 2
1.将80mg液氮中冷冻1.5h的二硼化铌粉体分散在和80mL DMF中,加入40mg表面活性剂PVP,在5℃水浴中以300w功率进行探针超声剥离3.5h,以2500r/min的转速离心8min,去掉块状未剥离的二硼化铌粉,保留上清液,二次离心,转速为12000r/min的转速,离心20min,收集沉淀,用无水乙醇和去离子水分别交替洗涤三次,冷冻干燥24小时制得干燥的二硼化铌纳米片。1. Disperse 80mg of niobium diboride powder frozen in liquid nitrogen for 1.5h in 80mL of DMF, add 40mg of surfactant PVP, perform ultrasonic peeling of the probe at 300w power in a 5°C water bath for 3.5h, and use 2500r/ Centrifuge at a speed of 12000r/min for 8min to remove the lumpy unstripped niobium diboride powder, retain the supernatant, and centrifuge for a second time at a speed of 12000r/min for 20min, collect the precipitate, and separate it with absolute ethanol and deionized water. Alternately washed three times, freeze-dried for 24 hours to prepare dry niobium diboride nanosheets.
2.将10mg二硼化铌纳米片分散在10mL去离子水中,将100mg壳聚糖溶于10mL去离子水,在浴超声作用下将二者混匀,室温搅拌18h。悬浮液用去离子水洗涤三次,冷冻干燥24h制得壳聚糖修饰的二硼化铌纳米片。2. Disperse 10 mg of niobium diboride nanosheets in 10 mL of deionized water, dissolve 100 mg of chitosan in 10 mL of deionized water, mix the two evenly under the action of ultrasonic bath, and stir at room temperature for 18 hours. The suspension was washed three times with deionized water and freeze-dried for 24 hours to prepare chitosan-modified niobium diboride nanosheets.
3.将10mg改性后纳米片与10mL500μg·mL-1浓度的吲哚菁绿乙醇溶液混合,高速搅拌1h,后在20℃下避光低速搅拌组装6h。离心,无水乙醇洗涤3次,冷冻干燥后制得二硼化铌纳米片复合材料。3. Mix 10 mg of modified nanosheets with 10 mL of ethanol solution of indocyanine green at a concentration of 500 μg·mL -1 , stir at high speed for 1 h, and then assemble at 20° C. under low-speed stirring in the dark for 6 h. Centrifuge, wash with absolute ethanol for 3 times, and freeze-dry to prepare the niobium diboride nanosheet composite material.
4.将0.5g聚乙烯醇于10mL去离子水,将10mg二硼化铌纳米片复合材料和25mg PVP分散于8mL去离子水中。将两种溶液混合避光搅拌16h。在电压为16kV,进样速度为2mL/h,接收器距离为10cm,转速为120rpm。温度为20℃下进行纺丝制备成复合纤维膜。4. Disperse 0.5g of polyvinyl alcohol in 10mL of deionized water, 10mg of niobium diboride nanosheet composite and 25mg of PVP in 8mL of deionized water. The two solutions were mixed and stirred in the dark for 16h. The voltage is 16kV, the injection speed is 2mL/h, the receiver distance is 10cm, and the rotation speed is 120rpm. Spinning is performed at a temperature of 20° C. to prepare a composite fiber membrane.
测试结果表明,制备的二硼化铌纳米片复合材料在浓度为250μg·mL-1时,在功率为1.5W/cm~2的808nm近红外光照射10min下,温度可以升高到45℃。对耐甲氧西林金黄色葡萄球菌和大肠杆菌的抑菌率分别为90.24%和92.78%。制备的静电纺丝膜在功率为1.5W/cm~2的808nm近红外光照射5min下,温度可以升高到45℃。对耐甲氧西林金黄色葡萄球菌和大肠杆菌的抑菌率分别为93.87%和95.02%。伤口感染愈合实验表明,经过14天,使用复合纤维膜的伤口愈合率为95.25%,空白组愈合率为80.56%。The test results show that when the concentration of the prepared niobium diboride nanosheet composite is 250μg·mL -1 , the temperature can rise to 45℃ under the irradiation of 808nm near-infrared light with a power of 1.5W/cm ~2 for 10min. The antibacterial rates against methicillin-resistant Staphylococcus aureus and Escherichia coli were 90.24% and 92.78%, respectively. The temperature of the prepared electrospun membrane can rise to 45° C. under the irradiation of 808 nm near-infrared light with a power of 1.5 W/cm 2 for 5 minutes. The antibacterial rates against methicillin-resistant Staphylococcus aureus and Escherichia coli were 93.87% and 95.02%, respectively. The wound infection healing experiment showed that after 14 days, the wound healing rate of the composite fiber membrane was 95.25%, and the healing rate of the blank group was 80.56%.
实施例3Example 3
1.将120mg液氮中冷冻4h的二硼化铪粉体分散在100mL N~甲基吡咯烷酮中,加入80mg表面活性剂聚醚P123,在10℃水浴中以550w功率进行探针超声剥离4.5h,以2500r/min的转速离心10min,去掉块状未剥离的二硼化铪粉,保留上清液,二次离心,转速为12000r/min的转速,离心20min,收集沉淀,用无水乙醇和去离子水分别交替洗涤三次,干燥24h制得干燥的二硼化铪纳米片。1. Disperse 120 mg of hafnium diboride powder frozen in liquid nitrogen for 4 hours in 100 mL of N-methylpyrrolidone, add 80 mg of surfactant polyether P123, and perform ultrasonic peeling of the probe for 4.5 hours in a 10°C water bath with a power of 550w , centrifuge at a speed of 2500r/min for 10min, remove the blocky unstripped hafnium diboride powder, retain the supernatant, and centrifuge for a second time at a speed of 12000r/min, centrifuge for 20min, collect the precipitate, and wash with absolute ethanol and The deionized water was alternately washed three times, and dried for 24 hours to obtain dry hafnium diboride nanosheets.
2.将二硼化铪纳米片分散在3ml去离子水中,将90mg壳聚糖双胍盐溶于3mL去离子水,在浴超声作用下将二者混匀,室温搅拌12h。悬浮液用去离子水洗涤三次去除未装载的壳聚糖双胍盐,干燥24小时制得壳聚糖双胍盐修饰的二硼化铪。2. Disperse hafnium diboride nanosheets in 3ml of deionized water, dissolve 90mg of chitosan biguanide salt in 3mL of deionized water, mix the two evenly under the action of ultrasonic bath, and stir at room temperature for 12h. The suspension was washed three times with deionized water to remove unloaded chitosan biguanide salt, and dried for 24 hours to prepare chitosan biguanide salt-modified hafnium diboride.
3.将6mg改性后纳米片与6mL300μg·mL-1浓度的吲哚菁绿水溶液混合,高速搅拌0.5h,后在25℃下避光低速搅拌组装10h。离心,去离子水洗涤3次,冷冻干燥后获得二硼化铪纳米片复合材料。3.
4.将0.8g聚乳酸溶于9.5mL三氯甲烷,将25mg二硼化铪纳米片复合材料分散于9.5mL三氯甲烷和10.5mL乙醇的混合溶液中。将两种溶液混合避光搅拌12h。在电压为20.5kV,进样速度为1.5mL/h,接收器距离为15cm,转速为55rpm。温度为25℃下进行纺丝制备成复合纤维膜材料。4. Dissolve 0.8g of polylactic acid in 9.5mL of chloroform, and disperse 25mg of hafnium diboride nanosheet composite in a mixed solution of 9.5mL of chloroform and 10.5mL of ethanol. The two solutions were mixed and stirred in the dark for 12h. The voltage is 20.5kV, the injection speed is 1.5mL/h, the receiver distance is 15cm, and the rotation speed is 55rpm. Spinning is carried out at a temperature of 25° C. to prepare a composite fiber membrane material.
测试结果表明,制备的二硼化铪纳米片复合材料在浓度为200μg·mL-1时,在功率为1.5W/cm~2的808nm近红外光照射10min下,温度可以升高到53℃;对耐甲氧西林金黄色葡萄球菌和大肠杆菌的抑菌率分别为99.44%和99.21%。制备的静电纺丝膜在功率为1.5W/cm~2的808nm近红外光照射5min下,温度可以升高到50℃;对耐甲氧西林金黄色葡萄球菌和大肠杆菌的抑菌率分别为98.79%和99.13%。伤口感染愈合实验表明,经过14天,空白组愈合率为80.56%,使用复合纤维膜的伤口愈合率为98.64%。The test results show that when the prepared hafnium diboride nanosheet composite material has a concentration of 200 μg·mL -1 and is irradiated with 808nm near-infrared light with a power of 1.5W/cm ~2 for 10min, the temperature can rise to 53℃; The antibacterial rates against methicillin-resistant Staphylococcus aureus and Escherichia coli were 99.44% and 99.21%, respectively. The prepared electrospun membrane was irradiated with 808nm near-infrared light with a power of 1.5W/cm ~2 for 5min, and the temperature could rise to 50°C; 98.79% and 99.13%. The wound infection healing experiment showed that after 14 days, the healing rate of the blank group was 80.56%, and the healing rate of the wound using the composite fiber membrane was 98.64%.
实施例4Example 4
1.将100mg液氮冷冻1h的二硼化钛粉体分散在150m异丙醇中,加入100mg十六烷基三甲基溴化铵,在10℃水浴中以300w功率进行探针超声剥离5h,以2500r/min的转速离心5min,去掉块状未剥离的二硼化钛粉,保留上清液,二次离心,转速为12000r/min的转速,离心20min,收集沉淀,用无水乙醇和去离子水分别交替洗涤三次,干燥24h制得干燥的二硼化钛纳米片。1. Disperse 100 mg of titanium diboride powder frozen in liquid nitrogen for 1 h in 150 m of isopropanol, add 100 mg of cetyltrimethylammonium bromide, and perform ultrasonic stripping of the probe at 300 w in a water bath at 10 ° C for 5 h , centrifuged at a speed of 2500r/min for 5min, removed the massive unstripped titanium diboride powder, retained the supernatant, and centrifuged for a second time at a speed of 12000r/min, centrifuged for 20min, collected the precipitate, and washed with absolute ethanol and The deionized water was alternately washed three times, and dried for 24 hours to obtain dry titanium diboride nanosheets.
2.将10mg二硼化钛纳米片分散在10mL去离子水中,取120mg巯基聚乙二醇溶于10mL去离子水,在浴超声作用下将二者混匀,室温搅拌24h。悬浮液用去离子水洗涤三次,冷冻干燥24h制得巯基聚乙二醇修饰的二硼化钛纳米片。2. Disperse 10 mg of titanium diboride nanosheets in 10 mL of deionized water, dissolve 120 mg of mercaptopolyethylene glycol in 10 mL of deionized water, mix the two evenly under the action of ultrasonic bath, and stir at room temperature for 24 hours. The suspension was washed three times with deionized water, and freeze-dried for 24 hours to prepare titanium diboride nanosheets modified with mercaptopolyethylene glycol.
3.将6mg改性后纳米片与6mL600μg·mL-1浓度的吲哚菁绿PBS溶液混合,高速搅拌2h,后在30℃下避光低速搅拌组装6h。离心,PBS洗涤3次,冷冻干燥后获得二硼化钛纳米片复合材料。3.
4.将1g聚已内酯溶于10mL二甲基甲酰胺,将45mg二硼化钛纳米片复合材料和100mg PVP分散于5mL二甲基甲酰胺溶液中。将两种溶液混合避光搅拌10h。在电压为20kV,进样速度为0.5mL/h,接收器距离为20cm,转速为125rpm。温度为20℃下进行纺丝制备成复合纤维膜材料。4. Dissolve 1g of polycaprolactone in 10mL of dimethylformamide, and disperse 45mg of titanium diboride nanosheet composites and 100mg of PVP in 5mL of dimethylformamide solution. The two solutions were mixed and stirred for 10 h in the dark. The voltage is 20kV, the injection speed is 0.5mL/h, the receiver distance is 20cm, and the rotation speed is 125rpm. Spinning is carried out at a temperature of 20° C. to prepare a composite fiber membrane material.
测试结果表明,制备的二硼化钛纳米片复合材料在浓度为200μg·mL-1时,在功率为1.5W/cm~2的808nm近红外光照射10min下,温度可以升高到48℃。对耐甲氧西林金黄色葡萄球菌和大肠杆菌的抑菌率分别为96.32%和97.89%。测试结果表明,制备的静电纺丝膜在功率为1.5W/cm~2的808nm近红外光照射5min下,温度可以升高到55℃。对耐甲氧西林金黄色葡萄球菌和大肠杆菌的抑菌率分别为99.05%和99.84%。伤口感染愈合实验表明,经过14天,使用复合纤维膜的伤口愈合率为93.19%,空白组愈合率为80.56%。The test results show that when the concentration of the prepared titanium diboride nanosheet composite is 200μg·mL -1 , the temperature can rise to 48℃ under the irradiation of 808nm near-infrared light with a power of 1.5W/cm ~2 for 10min. The antibacterial rates against methicillin-resistant Staphylococcus aureus and Escherichia coli were 96.32% and 97.89%, respectively. The test results show that the temperature of the prepared electrospun membrane can rise to 55°C under the irradiation of 808nm near-infrared light with a power of 1.5W/cm ~2 for 5min. The antibacterial rates against methicillin-resistant Staphylococcus aureus and Escherichia coli were 99.05% and 99.84%, respectively. The wound infection healing experiment showed that after 14 days, the wound healing rate of the composite fiber membrane was 93.19%, and the healing rate of the blank group was 80.56%.
实施例5Example 5
1.将75mg液氮冷冻10h的二硼化铬粉体分散在75mL乙二醇中,加入25mg表面活性剂P123,在5℃水浴中以250w功率进行探针超声剥离5h,以2500r/min的转速离心5min,去掉块状未剥离的二硼化铬粉,保留上清液,二次离心,转速为12000r/min的转速,离心20min,收集沉淀,用无水乙醇和去离子水分别交替洗涤三次,干燥24h制得干燥的二硼化铬纳米片。1. Disperse 75mg of chromium diboride powder frozen in liquid nitrogen for 10h in 75mL of ethylene glycol, add 25mg of surfactant P123, perform ultrasonic stripping of the probe at 250w power in a 5°C water bath for 5h, and use 2500r/min Centrifuge at a speed of 5 minutes, remove the massive unstripped chromium diboride powder, retain the supernatant, and centrifuge for a second time at a speed of 12000r/min, centrifuge for 20 minutes, collect the precipitate, and wash alternately with absolute ethanol and deionized water Three times, drying for 24 hours to obtain dry chromium diboride nanosheets.
2.将12mg二硼化铬纳米片分散在10mL去离子水中,将120mg透明质酸溶于10mL去离子水,在浴超声作用下将二者混匀,室温搅拌24h。悬浮液用去离子水洗涤三次去除未装载的透明质酸,冷冻干燥24h制得透明质酸修饰的二硼化铬纳米片。2. Disperse 12 mg of chromium diboride nanosheets in 10 mL of deionized water, dissolve 120 mg of hyaluronic acid in 10 mL of deionized water, mix the two evenly under the action of ultrasonic bath, and stir at room temperature for 24 hours. The suspension was washed three times with deionized water to remove unloaded hyaluronic acid, and freeze-dried for 24 hours to prepare hyaluronic acid-modified chromium diboride nanosheets.
3.将10mg改性后纳米片与10mL450μg·mL-1浓度的吲哚菁绿乙醇溶液混合,高速搅拌2h,后在20℃下避光低速搅拌组装12h。离心,乙醇洗涤3次,冷冻干燥后获得二硼化铬纳米片复合材料。3. Mix 10 mg of the modified nanosheets with 10 mL of ethanol solution of indocyanine green at a concentration of 450 μg·mL -1 , stir at high speed for 2 h, and then assemble at 20 ° C for 12 h in the dark under low speed stirring. Centrifuge, wash with ethanol three times, and freeze-dry to obtain the chromium diboride nanosheet composite material.
4.将1.5g聚丙烯腈溶于13.5mL二甲基甲酰胺,将100mg二硼化铬纳米片复合材料分散于9mL二甲基甲酰胺和1.5mL乙醇的混合溶液中。将两种溶液混合避光搅拌24h。在电压为13.8kV,进样速度为0.5mL/h,接收器距离为10cm,转速为100rpm。温度为25℃下进行纺丝制备成复合纤维膜材料。4. Dissolve 1.5g of polyacrylonitrile in 13.5mL of dimethylformamide, and disperse 100mg of chromium diboride nanosheet composite in a mixed solution of 9mL of dimethylformamide and 1.5mL of ethanol. The two solutions were mixed and stirred in the dark for 24h. The voltage is 13.8kV, the injection speed is 0.5mL/h, the receiver distance is 10cm, and the rotation speed is 100rpm. Spinning is carried out at a temperature of 25° C. to prepare a composite fiber membrane material.
测试结果表明,制备的二硼化铬纳米片复合材料在浓度为400μg·mL-1时,在功率为1.5W/cm~2的808nm近红外光照射10min下,温度可以升高到49℃。对耐甲氧西林金黄色葡萄球菌和大肠杆菌的抑菌率分别为96.55%和97.38%。制备的静电纺丝膜在功率为1.5W/cm~2的808nm近红外光照射5min下,温度可以升高到53℃。对耐甲氧西林金黄色葡萄球菌和大肠杆菌的抑菌率分别为97.11%和98.25%。伤口感染愈合实验表明,经过14天,使用复合纤维膜的伤口愈合率为92.25%,空白组愈合率为80.56%。The test results show that when the concentration of the prepared chromium diboride nanosheet composite is 400μg·mL -1 , the temperature can rise to 49℃ under the irradiation of 808nm near-infrared light with a power of 1.5W/cm ~2 for 10min. The antibacterial rates against methicillin-resistant Staphylococcus aureus and Escherichia coli were 96.55% and 97.38%, respectively. The temperature of the prepared electrospun membrane can rise to 53° C. under the irradiation of 808 nm near-infrared light with a power of 1.5 W/cm 2 for 5 minutes. The antibacterial rates against methicillin-resistant Staphylococcus aureus and Escherichia coli were 97.11% and 98.25%, respectively. The wound infection healing experiment showed that after 14 days, the wound healing rate of the composite fiber membrane was 92.25%, and the healing rate of the blank group was 80.56%.
实施例6Example 6
1.将100mg二硼化锆粉体分散在100mL乙腈中,加入50mg表面活性剂十二烷基硫酸,在10℃水浴中以500w功率进行探针超声剥离3h,以2500r/min的转速离心5min,去掉块状未剥离的二硼化锆粉,保留上清液,二次离心,转速为12000r/min的转速,离心20min,收集沉淀,用无水乙醇和去离子水分别交替洗涤三次,干燥24h制得干燥的二硼化锆纳米片。1. Disperse 100mg of zirconium diboride powder in 100mL of acetonitrile, add 50mg of surfactant dodecyl sulfuric acid, perform ultrasonic peeling of the probe at 500w power in a water bath at 10°C for 3h, and centrifuge at 2500r/min for 5min , remove the bulk unstripped zirconium diboride powder, retain the supernatant, and centrifuge twice at a speed of 12000r/min for 20min to collect the precipitate, wash it alternately three times with absolute ethanol and deionized water, and dry Dry zirconium diboride nanosheets were prepared in 24 hours.
2.将10mg二硼化锆纳米片分散在10mL去离子水中,将100mg壳聚糖双胍盐溶于10mL去离子水,在浴超声作用下将二者混匀,室温搅拌12h。悬浮液用去离子水洗涤三次去除未装载的壳聚糖双胍盐,冷冻干燥24h制得壳聚糖双胍盐修饰的二硼化锆纳米片。2. Disperse 10 mg of zirconium diboride nanosheets in 10 mL of deionized water, dissolve 100 mg of chitosan biguanide salt in 10 mL of deionized water, mix the two evenly under the action of ultrasonic bath, and stir at room temperature for 12 hours. The suspension was washed three times with deionized water to remove unloaded chitosan biguanide salt, and freeze-dried for 24 hours to prepare chitosan biguanide salt-modified zirconium diboride nanosheets.
3.将1g聚丙烯腈溶于10.5mL二甲基甲酰胺,将80mg二硼化锆纳米片复合材料分散于8mL二甲基甲酰胺中。将两种溶液混合避光搅拌18h。在电压为15.6kV,进样速度为2.5mL/h,接收器距离为16cm,转速为120rpm。温度为25℃下进行纺丝制备成复合纤维膜材料。3. Dissolve 1 g of polyacrylonitrile in 10.5 mL of dimethylformamide, and disperse 80 mg of zirconium diboride nanosheet composite material in 8 mL of dimethylformamide. The two solutions were mixed and stirred in the dark for 18h. The voltage is 15.6kV, the injection speed is 2.5mL/h, the receiver distance is 16cm, and the rotation speed is 120rpm. Spinning is carried out at a temperature of 25° C. to prepare a composite fiber membrane material.
测试结果表明,制备的二硼化锆纳米片复合材料在浓度为300μg·mL-1时,在功率为1.5W/cm~2的808nm近红外光照射10min下,温度可以升高到44℃。对耐甲氧西林金黄色葡萄球菌和大肠杆菌的抑菌率分别为50.89%和52.27%。制备的静电纺丝膜在功率为1.5W/cm~2的808nm近红外光照射5min下,温度可以升高到50℃。对耐甲氧西林金黄色葡萄球菌和大肠杆菌的抑菌率分别为75.68%和78.23%。伤口感染愈合实验表明,经过14天,使用复合纤维膜的伤口愈合率为85.33%,空白组愈合率为80.56%。The test results show that the temperature of the prepared zirconium diboride nanosheet composite can rise to 44℃ under the irradiation of 808nm near-infrared light with a power of 1.5W/cm ~2 for 10min at a concentration of 300μg·mL -1 . The antibacterial rates against methicillin-resistant Staphylococcus aureus and Escherichia coli were 50.89% and 52.27%, respectively. The temperature of the prepared electrospun membrane can be raised to 50° C. under the irradiation of 808 nm near-infrared light with a power of 1.5 W/cm 2 for 5 minutes. The antibacterial rates against methicillin-resistant Staphylococcus aureus and Escherichia coli were 75.68% and 78.23%, respectively. The wound infection healing experiment showed that after 14 days, the wound healing rate of the composite fiber membrane was 85.33%, and the healing rate of the blank group was 80.56%.
实施例7Example 7
1.将80mg液氮中冷冻2h的二硼化铪粉体分散在80mL乙二醇中,加入20mg表面活性剂聚乙烯吡咯烷酮,在10℃水浴中以400w功率进行探针超声剥离2.5h,以2500r/min的转速离心10min,去掉块状未剥离的二硼化铪粉,保留上清液,二次离心,转速为12000r/min的转速,离心20min,收集沉淀,用无水乙醇和去离子水分别交替洗涤三次,干燥24h制得干燥的二硼化铪纳米片。1. Disperse 80 mg of hafnium diboride powder frozen in liquid nitrogen for 2 hours in 80 mL of ethylene glycol, add 20 mg of surfactant polyvinylpyrrolidone, and perform ultrasonic peeling of the probe at 400w power in a water bath at 10°C for 2.5 hours to Centrifuge at a speed of 2500r/min for 10min, remove the massive unstripped hafnium diboride powder, retain the supernatant, and centrifuge for a second time at a speed of 12000r/min, centrifuge for 20min, collect the precipitate, and use absolute ethanol and deionized Water was alternately washed three times, and dried for 24 hours to obtain dry hafnium diboride nanosheets.
2.将1.2g聚乳酸溶于10mL二氯甲烷,将45mg二硼化铪纳米片分散于8mL二氯甲烷和6.5mL乙醇的混合溶液中。将两种溶液混合避光搅拌24h。在电压为17.5kV,进样速度为0.5mL/h,接收器距离为18cm,转速为80rpm。温度为25℃下进行纺丝制备成复合纤维膜材料。2. Dissolve 1.2g of polylactic acid in 10mL of dichloromethane, and disperse 45mg of hafnium diboride nanosheets in a mixed solution of 8mL of dichloromethane and 6.5mL of ethanol. The two solutions were mixed and stirred in the dark for 24h. The voltage is 17.5kV, the injection speed is 0.5mL/h, the receiver distance is 18cm, and the rotation speed is 80rpm. Spinning is carried out at a temperature of 25° C. to prepare a composite fiber membrane material.
测试结果表明,制备的二硼化铪纳米片复合材料在浓度为300μg·mL-1时,在功率为1.5W/cm~2的808nm近红外光照射10min下,温度可以升高到47℃;对耐甲氧西林金黄色葡萄球菌和大肠杆菌的抑菌率分别为49.24%和50.01%。制备的静电纺丝膜在功率为1.5W/cm~2的808nm近红外光照射5min下,温度可以升高到46℃;对耐甲氧西林金黄色葡萄球菌和大肠杆菌的抑菌率分别为58.56%和59.03%。伤口感染愈合实验表明,经过14天,空白组愈合率为80.56%,使用复合纤维膜的伤口愈合率为81.02%。The test results show that when the prepared hafnium diboride nanosheet composite material has a concentration of 300 μg·mL -1 and is irradiated with 808nm near-infrared light with a power of 1.5W/cm ~2 for 10min, the temperature can rise to 47℃; The antibacterial rates against methicillin-resistant Staphylococcus aureus and Escherichia coli were 49.24% and 50.01%, respectively. The prepared electrospun membrane was irradiated with 808nm near-infrared light with a power of 1.5W/cm ~2 for 5 minutes, and the temperature could rise to 46°C; the antibacterial rates against methicillin-resistant Staphylococcus aureus and Escherichia coli were 58.56% and 59.03%. The wound infection healing experiment showed that after 14 days, the healing rate of the blank group was 80.56%, and the healing rate of the wound using the composite fiber membrane was 81.02%.
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