CN112080165A - A kind of preparation method of superhydrophobic film material with antibacterial function - Google Patents
A kind of preparation method of superhydrophobic film material with antibacterial function Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 32
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 31
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000243 solution Substances 0.000 claims abstract description 44
- 239000010408 film Substances 0.000 claims abstract description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000010409 thin film Substances 0.000 claims abstract description 19
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 14
- 239000010936 titanium Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 10
- 239000000194 fatty acid Substances 0.000 claims abstract description 10
- 229930195729 fatty acid Natural products 0.000 claims abstract description 10
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 239000003292 glue Substances 0.000 claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 7
- 229910052737 gold Inorganic materials 0.000 claims abstract description 6
- 229910052709 silver Inorganic materials 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- 239000000758 substrate Substances 0.000 claims abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract 2
- 238000003756 stirring Methods 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 11
- 239000011701 zinc Substances 0.000 claims description 9
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 claims description 2
- 229920005372 Plexiglas® Polymers 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 150000007513 acids Chemical class 0.000 claims 1
- 229910010413 TiO 2 Inorganic materials 0.000 abstract description 16
- 238000002474 experimental method Methods 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000001580 bacterial effect Effects 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000007788 liquid Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 10
- 239000006916 nutrient agar Substances 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 239000012528 membrane Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 4
- 241000588724 Escherichia coli Species 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000005764 inhibitory process Effects 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- 229920001817 Agar Polymers 0.000 description 3
- 239000008272 agar Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000012258 culturing Methods 0.000 description 3
- 238000007405 data analysis Methods 0.000 description 3
- 230000000845 anti-microbial effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000010944 silver (metal) Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- KYIDJMYDIPHNJS-UHFFFAOYSA-N ethanol;octadecanoic acid Chemical compound CCO.CCCCCCCCCCCCCCCCCC(O)=O KYIDJMYDIPHNJS-UHFFFAOYSA-N 0.000 description 1
- IWMXCBIQIXXGFK-UHFFFAOYSA-N ethanol;tetradecanoic acid Chemical compound CCO.CCCCCCCCCCCCCC(O)=O IWMXCBIQIXXGFK-UHFFFAOYSA-N 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
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- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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Abstract
本发明公开了一种具有抗菌功能的超疏水薄膜材料CnH2n‑1O2M/TiO2(M=Cu、Ag、Au、Zn、Ti)的制备方法,属于材料合成技术领域,其是将清洗过的片状金属加入到脂肪酸乙醇溶液中,恒温搅拌反应一段时间,并加入水热反应后的钛胶,再将得到的混合溶液涂覆在基片上,经低温常压干燥,得到所述具有抗菌功能的超疏水薄膜。本发明操作简便易行,原料廉价易得,并具有试剂污染小、反应重复性好、制备条件温和等优点,所得的CnH2n‑1O2M/TiO2(M=Cu、Ag、Au、Zn、Ti)薄膜材料在抗菌实验中表现出良好的催化抗菌活性,且性能稳定、循环性好。
The invention discloses a preparation method of a super-hydrophobic thin film material C n H 2n-1 O 2 M/TiO 2 (M=Cu, Ag, Au, Zn, Ti) with antibacterial function, belonging to the technical field of material synthesis. The cleaned sheet metal is added to the fatty acid ethanol solution, stirred and reacted at a constant temperature for a period of time, and the titanium glue after hydrothermal reaction is added, and then the obtained mixed solution is coated on the substrate, and dried at low temperature and normal pressure to obtain The superhydrophobic film with antibacterial function. The method is simple and easy to operate, cheap and easy to obtain raw materials, and has the advantages of less reagent pollution, good reaction repeatability, mild preparation conditions, etc. The obtained C n H 2n-1 O 2 M/TiO 2 (M=Cu, Ag, Au, Zn, Ti) thin films showed good catalytic antibacterial activity in antibacterial experiments, with stable performance and good cyclability.
Description
技术领域technical field
本发明属于材料合成领域,具体涉及一种具有抗菌功能的超疏水CnH2n-1O2M/TiO2(M=Cu、Ag、Au、Zn、Ti)薄膜材料的制备方法。The invention belongs to the field of material synthesis, in particular to a preparation method of a superhydrophobic CnH2n- 1O2M / TiO2 ( M=Cu, Ag, Au, Zn, Ti) thin film material with antibacterial function.
背景技术Background technique
自从1972年有研究者发现TiO2能够在紫外光照射下实现将水分解成氢气和氧气以来,半导体光催化极大地引起了国内外研究者的强烈关注。在光照条件下,半导体外层电子被激发,从价带跃迁到导带,从而产生电子-空穴对。光生电子空穴能直接的攻击细菌,另外电子能转化成其他的活性物种,例如:•O2 -,进一步氧化细菌的外膜,同时,其他的氧化活性物种,例如•OH,H2O2,•HO2,也可以由电子和空穴从水中产生,从而实现多方面对细菌的灭活。但是单一TiO2只能被紫外光激发,限制了其抗菌性能在普通室内环境的使用,现有的相关专利技术也主要以紫外光激发为基础,因此设计在可见光光区内有高效抗菌功能的催化剂是实现TiO2抗菌应用的关键。Since 1972, researchers found that TiO2 can split water into hydrogen and oxygen under ultraviolet light irradiation, semiconductor photocatalysis has greatly attracted strong attention of researchers at home and abroad. Under light conditions, the electrons in the outer layer of the semiconductor are excited and transition from the valence band to the conduction band, thereby generating electron-hole pairs. Photogenerated electron holes can directly attack bacteria, and electrons can be converted into other active species, such as: • O 2 - , which further oxidizes the outer membrane of bacteria, and at the same time, other oxidative active species, such as • OH, H 2 O 2 , • HO 2 , can also be generated from water by electrons and holes, thereby achieving multi-faceted inactivation of bacteria. However, a single TiO 2 can only be excited by ultraviolet light, which limits the use of its antibacterial properties in ordinary indoor environments. The existing related patent technologies are also mainly based on ultraviolet light excitation, so the design of high-efficiency antibacterial functions in the visible light region Catalysts are the key to realizing antibacterial applications of TiO2 .
超疏水表面因其在基础研究和工业应用中的重要作用,在许多新材料和新器件的设计中具有潜力领域,包括电子、催化、医药、陶瓷等。CnH2n-1O2M/TiO2微簇是结晶的。因为它特殊的超疏水性能,能够赋予薄膜表面自清洁功能。相比于较为常见的粉末催化剂,本发明合成的复合薄膜材料在催化剂的回收和循环使用等方面比现有技术有更加突出的表现。Due to their important role in basic research and industrial applications, superhydrophobic surfaces have potential fields in the design of many new materials and devices, including electronics, catalysis, medicine, and ceramics. The CnH2n- 1O2M / TiO2 microclusters are crystalline. Because of its special superhydrophobicity, it can endow the film surface with self-cleaning function. Compared with the more common powder catalysts, the composite film material synthesized by the present invention has more outstanding performance in the recovery and recycling of the catalyst than the prior art.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于提供一种具有抗菌功能的超疏水性薄膜材料的制备方法。The purpose of the present invention is to provide a preparation method of a superhydrophobic thin film material with antibacterial function.
为实现上述目的,本发明采用如下技术方案:To achieve the above object, the present invention adopts the following technical solutions:
一种具有抗菌功能的超疏水性薄膜材料,其制备方法包括如下步骤:A superhydrophobic film material with antibacterial function, the preparation method of which comprises the following steps:
1)在常温搅拌条件下,将脂肪酸溶于无水乙醇中,得到浓度为0.01~1.5mol/L的脂肪酸乙醇溶液;1) Under stirring conditions at room temperature, the fatty acid is dissolved in absolute ethanol to obtain a fatty acid ethanol solution with a concentration of 0.01-1.5 mol/L;
2)将清洗过的0.2×0.2cm~5×5cm片状金属加入到步骤1)所得的脂肪酸乙醇溶液中,然后加入磁性搅拌子,于25-60℃恒温搅拌反应3~5天;2) Add the cleaned 0.2×0.2cm~5×5cm sheet metal into the fatty acid ethanol solution obtained in step 1), then add a magnetic stirrer, and stir the reaction at a constant temperature of 25-60°C for 3~5 days;
3)将钛胶于120-180℃水热反应10-24h,然后按体积比1:5将其加入到步骤2)所得溶液中;3) Hydrothermally react the titanium gel at 120-180°C for 10-24h, and then add it to the solution obtained in step 2) at a volume ratio of 1:5;
4)将步骤3)所得混合溶液均匀涂覆在清洁后的基片上,50-120℃进行低温常压干燥,得到超疏水性薄膜材料CnH2n-1O2M/TiO2(M=Cu、Ag、Au、Zn、Ti)。4) The mixed solution obtained in step 3) is uniformly coated on the cleaned substrate, and dried at 50-120°C under low temperature and atmospheric pressure to obtain a superhydrophobic thin film material CnH 2n-1 O 2 M/TiO 2 (M=Cu, Ag, Au, Zn, Ti).
步骤1)中所述脂肪酸为十二酸、十四酸、十八酸、二十八酸中的任意一种。The fatty acid described in step 1) is any one of dodecanoic acid, tetradecanoic acid, octadecanoic acid and octacosanoic acid.
步骤2)所用金属包括铜、银、金、锌、钛。The metals used in step 2) include copper, silver, gold, zinc, and titanium.
步骤4)中所述基片包括玻璃、PVC管、陶瓷、有机玻璃中的任意一种。The substrate in step 4) includes any one of glass, PVC pipe, ceramics, and plexiglass.
本发明有益之处在于:The advantages of the present invention are:
本发明首次报道了一种具有抗菌功能的超疏水性薄膜材料的制备方法,其简便易行,原料廉价易得,并具有试剂污染小、反应重复性好、制备条件温和等优点。所得的CnH2n-1O2M/TiO2薄膜材料在光催化抗菌中表现出良好的催化抗菌活性,且性能稳定、循环性好。The present invention reports for the first time a preparation method of a superhydrophobic film material with antibacterial function, which is simple and easy to implement, cheap and easy to obtain raw materials, and has the advantages of less reagent pollution, good reaction repeatability, mild preparation conditions and the like. The obtained C n H 2n-1 O 2 M/TiO 2 thin film material exhibits good catalytic antibacterial activity in photocatalytic antibacterial activity, and has stable performance and good cyclability.
附图说明Description of drawings
图1为实施例1所制备薄膜材料C14H27O2Cu/TiO2的电镜图。FIG. 1 is an electron microscope image of the thin film material C 14 H 27 O 2 Cu/TiO 2 prepared in Example 1. FIG.
图2为实施例1所制备薄膜材料C14H27O2Cu/TiO2的疏水性测试图。FIG. 2 is a graph showing the hydrophobicity test of the thin film material C 14 H 27 O 2 Cu/TiO 2 prepared in Example 1. FIG.
图3为实施例1所制备薄膜材料C14H27O2Cu/TiO2的抗菌动力学曲线。3 is the antibacterial kinetic curve of the thin film material C 14 H 27 O 2 Cu/TiO 2 prepared in Example 1.
图4为实施例1所制备薄膜材料C14H27O2Cu/TiO2的抑菌圈效果图。4 is a graph showing the effect of the inhibition zone of the thin film material C 14 H 27 O 2 Cu/TiO 2 prepared in Example 1.
图5为实施例1所制备薄膜材料C14H27O2Cu/TiO2的抗菌稳定性图。FIG. 5 is a graph showing the antibacterial stability of the thin film material C 14 H 27 O 2 Cu/TiO 2 prepared in Example 1. FIG.
图6为实施例2所制备薄膜材料(CH3(CH2)12COO)2Zn/TiO2的实物图。FIG. 6 is a physical diagram of the thin film material (CH 3 (CH 2 ) 12 COO) 2 Zn/TiO 2 prepared in Example 2. FIG.
图7为实施例2所制备薄膜材料(CH3(CH2)12COO)2Zn/TiO2的疏水性测试图。7 is a graph showing the hydrophobicity test of the thin film material (CH 3 (CH 2 ) 12 COO) 2 Zn/TiO 2 prepared in Example 2.
图8为实施例2所制备薄膜材料(CH3(CH2)12COO)2Zn/TiO2的抗菌动力学曲线。8 is the antibacterial kinetic curve of the thin film material (CH 3 (CH 2 ) 12 COO) 2 Zn/TiO 2 prepared in Example 2.
具体实施方式Detailed ways
为了使本发明所述的内容更加便于理解,下面结合具体实施方式对本发明所述的技术方案做进一步的说明,但是本发明不仅限于此。In order to make the content of the present invention easier to understand, the technical solutions of the present invention will be further described below with reference to specific embodiments, but the present invention is not limited thereto.
实施例中所用钛胶是采用溶胶-凝胶法制备获得,其具体步骤为:在搅拌条件下将15mL钛酸丁酯滴加到100mL无水乙醇中,然后加入100mL水和3mL浓盐酸,在室温下继续搅拌4天,得到TiO2溶胶。The titanium glue used in the examples was prepared by a sol-gel method, and the specific steps were as follows: under stirring conditions, 15 mL of butyl titanate was added dropwise to 100 mL of absolute ethanol, then 100 mL of water and 3 mL of concentrated hydrochloric acid were added, and Stirring was continued for 4 days at room temperature to obtain a TiO 2 sol.
实施例1Example 1
将依次经丙酮、无水乙醇和0.1M盐酸溶液清洗后的大小为3.5cm×3.5cm的铜片放入100mL、0.03mol/L的十四酸乙醇溶液中,并加入磁性搅拌子进行搅拌,使搅拌转速维持在350-500r/min,25℃常温下反应2~5天,得到金属醇溶液;将钛胶倒入50mL聚四氟乙烯内衬的反应釜中,然后将其放入烘箱中,160℃下水热反应12h;取20mL水热后的钛胶加入到上述金属醇溶液中,搅拌均匀;将得到的混合溶液涂覆在清洁的载玻片上,在常压、60℃烘箱中干燥,得到具有抗菌功能的自清洁超疏水薄膜材料C14H27O2Cu/TiO2。所得样品见图1。Put the copper sheet with a size of 3.5cm×3.5cm after successively washing with acetone, anhydrous ethanol and 0.1M hydrochloric acid solution into 100mL, 0.03mol/L tetradecanoic acid ethanol solution, and add a magnetic stirrer to stir, Keep the stirring speed at 350-500r/min, and react at 25°C for 2~5 days at room temperature to obtain a metal alcohol solution; pour the titanium glue into a 50mL polytetrafluoroethylene-lined reaction kettle, and then put it into an oven , hydrothermally reacted at 160 °C for 12 h; take 20 mL of the hydrothermal titanium glue and add it to the above metal alcohol solution, stir evenly; coat the obtained mixed solution on a clean glass slide, and dry it in an oven at normal pressure and 60 °C , a self-cleaning superhydrophobic film material C 14 H 27 O 2 Cu/TiO 2 with antibacterial function was obtained. The obtained sample is shown in Figure 1.
1. 疏水性测试1. Hydrophobicity test
膜的疏水性通过测定薄膜表面对水的接触角来衡量。在德国DataphysicsInstruments Gmbh生产的OCA20型接触角仪上采用座滴法测定膜表面对水的接触角,水滴的体积为5 μL。如图2所示,实施例1所得薄膜对水的接触角为134º,表明其具有良好的疏水性。The hydrophobicity of the membrane is measured by measuring the contact angle of the membrane surface to water. The contact angle of the membrane surface to water was measured by the sessile drop method on an OCA20 contact angle meter produced by Dataphysics Instruments Gmbh, Germany, and the volume of the water droplet was 5 μL. As shown in Figure 2, the contact angle of the film obtained in Example 1 to water is 134º, indicating that it has good hydrophobicity.
2. 抗菌动力学测试2. Antimicrobial Kinetics Test
将大肠杆菌菌种在37℃下,在MH(mueller hinton)肉汤中培养18h后立即用PBS溶液稀释,最终得到的细菌浓度为108~9 cfu /ml。在整个实验过程中,所有的玻璃器皿及PBS溶液都经过去离子水洗净并在121℃高压蒸汽下高压灭菌20分钟。取4mL浓度为108~9 cfu /ml的菌液转移到反应器中,加入PBS溶液稀释至40mL(此时菌液浓度约为106~7 cfu /ml)。将2cm×2cm的实施例1所得薄膜加入反应器并加入磁子,恒定转速为300r/min,使薄膜和菌液充分接触。打开氙灯(λ≥400nm)、开启风扇进行反应,每隔相等的时间取0.5mL菌液,加入含有4.5mL PBS溶液的小试管中,并根据实验需要将菌液稀释一定倍数后转移至干燥洁净的培养皿中,再向每个已经含有菌液的培养皿中倾倒一定量经过高压灭菌处理的营养琼脂,晃动培养皿使菌液均匀分散在液态状态的琼脂中。将冷却凝固后的营养琼脂平板放入37℃的恒温摇床内,培养24h后,读取平板中的菌落数,并进行数据分析。如图3所示,可见光照射3.5h后,薄膜的抗菌效率达99.9%。Escherichia coli strains were cultured in MH (mueller hinton) broth for 18 hours at 37°C and immediately diluted with PBS solution, the final bacterial concentration was 10 8~9 cfu/ml. Throughout the experiment, all glassware and PBS solutions were washed with deionized water and autoclaved at 121 °C for 20 min under high pressure steam. Transfer 4 mL of bacterial solution with a concentration of 10 8~9 cfu/ml to the reactor, and add PBS solution to dilute to 40 mL (the concentration of bacterial solution at this time is about 10 6~7 cfu/ml). The 2cm×2cm film obtained in Example 1 was put into the reactor and the magnetron was added, and the constant rotation speed was 300r/min, so that the film and the bacterial liquid were fully contacted. Turn on the xenon lamp (λ≥400nm), turn on the fan for the reaction, take 0.5mL of bacterial solution at equal intervals, add it to a small test tube containing 4.5mL of PBS solution, and dilute the bacterial solution to a certain number according to the experimental needs and transfer it to dry and clean Then pour a certain amount of autoclaved nutrient agar into each petri dish that already contains bacterial liquid, and shake the petri dish to evenly disperse the bacterial liquid in the liquid agar. The cooled and solidified nutrient agar plate was placed in a constant temperature shaker at 37°C, and after culturing for 24 hours, the number of colonies in the plate was read and data analysis was performed. As shown in Figure 3, after 3.5 h of visible light irradiation, the antibacterial efficiency of the film reached 99.9%.
3. 抑菌圈实验3. Inhibition zone experiment
将大肠杆菌菌种在37℃下,在MH(mueller hinton)肉汤中培养18h后立即用PBS溶液稀释,最终得到的细菌浓度为106.5~7.5cfu /ml。在整个实验过程中,所有的玻璃器皿及PBS溶液都经过去离子水洗净并在121℃高压蒸汽下高压灭菌20分钟。取0.5ml浓度为106.5~7.5cfu /ml的菌液,均匀分散在新鲜制备的营养琼脂平板上,静置五分钟后,将大小为1cm×1cm的实施例1所得薄膜置于营养琼脂平板的正中央,用氙灯光源(≥400nm波长)照射2h,再于37℃恒温培养箱中培养24h,进行抑菌圈测试实验,结果如图4所示(图4中标注圆圈代表其抑菌圈大小)。Escherichia coli strains were cultured in MH (mueller hinton) broth for 18h at 37°C and immediately diluted with PBS solution, the final bacterial concentration was 10 6.5~7.5 cfu/ml. Throughout the experiment, all glassware and PBS solutions were washed with deionized water and autoclaved at 121 °C for 20 min under high pressure steam. Take 0.5ml of bacterial liquid with a concentration of 10 6.5~7.5 cfu/ml, evenly disperse it on a freshly prepared nutrient agar plate, and after standing for five minutes, place the film obtained in Example 1 with a size of 1cm × 1cm on a nutrient agar plate In the center of the cell, irradiate it with a xenon light source (≥400nm wavelength) for 2 hours, and then incubate it in a constant temperature incubator at 37 °C for 24 hours to conduct the inhibition zone test experiment. The results are shown in Figure 4 (the circle marked in Figure 4 represents its inhibition zone). size).
4. 抗菌稳定性测试4. Antibacterial stability test
将大肠杆菌菌种在37℃下,在MH(mueller hinton)肉汤中培养18h后立即用PBS溶液稀释,最终得到的细菌浓度为108~9 cfu /ml。在整个实验过程中,所有的玻璃器皿及PBS溶液都经过去离子水洗净并在121℃高压蒸汽下高压灭菌20分钟。取4mL浓度为108~9 cfu /ml的菌液,转移到反应器中,加入PBS溶液稀释至40mL(此时菌液浓度约为106~7 cfu /ml)。将2cm×2cm的实施例1所得薄膜加入反应器并加入磁子,恒定转速为300r/min,使薄膜和菌液充分接触。打开氙灯(λ≥400nm)、开启风扇进行反应,每隔相等的时间取0.5mL菌液,加入含有4.5mL PBS溶液的小试管中,并根据实验需要将菌液稀释一定倍数后转移至干燥洁净的培养皿中,再向每个已经含有菌液的培养皿中倾倒一定量经过高压灭菌处理的营养琼脂,晃动培养皿使菌液均匀分散在液态琼脂中。将冷却凝固后的营养琼脂平板放入37℃的恒温摇床内,培养24h后,读取平板中的菌落数,并进行数据分析。将反应后的催化剂过滤取出并洗净干燥后,按上述步骤重复进行实验。四次反应的动力学曲线见图5。Escherichia coli strains were cultured in MH (mueller hinton) broth for 18 hours at 37°C and immediately diluted with PBS solution, the final bacterial concentration was 10 8~9 cfu/ml. Throughout the experiment, all glassware and PBS solutions were washed with deionized water and autoclaved at 121 °C for 20 min under high pressure steam. Take 4 mL of bacterial solution with a concentration of 10 8~9 cfu/ml, transfer it to the reactor, and add PBS solution to dilute to 40 mL (the concentration of bacterial solution at this time is about 10 6~7 cfu/ml). The 2cm×2cm film obtained in Example 1 was put into the reactor and the magnetron was added, and the constant rotation speed was 300r/min, so that the film and the bacterial liquid were fully contacted. Turn on the xenon lamp (λ≥400nm), turn on the fan for the reaction, take 0.5mL of bacterial solution at equal intervals, add it to a small test tube containing 4.5mL of PBS solution, and dilute the bacterial solution to a certain number according to the experimental needs and transfer it to dry and clean Then pour a certain amount of autoclaved nutrient agar into each petri dish already containing bacterial liquid, and shake the petri dish to evenly disperse the bacterial liquid in the liquid agar. The cooled and solidified nutrient agar plate was placed in a constant temperature shaker at 37°C, and after culturing for 24 hours, the number of colonies in the plate was read and data analysis was performed. After the reacted catalyst was taken out by filtration, washed and dried, the experiment was repeated according to the above steps. The kinetic curves of the four reactions are shown in Figure 5.
实施例2Example 2
将依次经丙酮、无水乙醇和0.1M盐酸溶液清洗后的大小为3.5cm×3.5cm的锌片放入100mL、0.03mol/L的十八酸乙醇溶液中,并加入磁性搅拌子进行搅拌,使搅拌转速维持在350-500r/min,25℃常温下反应2~5天,得到金属醇溶液;将钛胶倒入50mL聚四氟乙烯内衬的反应釜中,然后将其放入烘箱中,160℃下水热反应12h;取20mL水热后的钛胶加入到上述金属醇溶液中,搅拌均匀;将得到的混合溶液涂覆在清洁的载玻片上,在常压、60℃烘箱中干燥,得到具有抗菌功能的自清洁超疏水薄膜材料(CH3(CH2)12COO)2Zn/TiO2。所得样品见图6。Put the zinc flakes with a size of 3.5cm×3.5cm after successively washing with acetone, anhydrous ethanol and 0.1M hydrochloric acid solution into 100mL, 0.03mol/L octadecanoic acid ethanol solution, and add a magnetic stirrer to stir, Keep the stirring speed at 350-500r/min, and react at 25°C for 2~5 days at room temperature to obtain a metal alcohol solution; pour the titanium glue into a 50mL polytetrafluoroethylene-lined reaction kettle, and then put it into an oven , hydrothermally reacted at 160 °C for 12 h; take 20 mL of the hydrothermal titanium glue and add it to the above metal alcohol solution, stir evenly; coat the obtained mixed solution on a clean glass slide, and dry it in an oven at normal pressure and 60 °C , to obtain a self-cleaning superhydrophobic thin film material (CH 3 (CH 2 ) 12 COO) 2 Zn/TiO 2 with antibacterial function. The resulting sample is shown in Figure 6.
1. 疏水性测试1. Hydrophobicity test
膜的疏水性通过测定薄膜表面对水的接触角来衡量。在德国DataphysicsInstruments Gmbh生产的OCA20型接触角仪上采用座滴法测定膜表面对水的接触角,水滴的体积为5 μL,。如图7所示,实施例2所得薄膜对水的接触角为134º,表明良好的疏水性。The hydrophobicity of the membrane is measured by measuring the contact angle of the membrane surface to water. The contact angle of the membrane surface to water was measured by the sessile drop method on an OCA20 contact angle meter produced by Dataphysics Instruments Gmbh, Germany, and the volume of the water droplet was 5 μL. As shown in Figure 7, the contact angle to water of the film obtained in Example 2 was 134º, indicating good hydrophobicity.
2. 抗菌动力学测试2. Antimicrobial Kinetics Test
将大肠杆菌菌种在37℃下,在MH(mueller hinton)肉汤中培养18h后立即用PBS溶液稀释,最终得到的细菌的浓度为108~9 cfu /ml。在整个实验过程中,所有的玻璃器皿及PBS溶液都是经过去离子水洗净并在121℃高压蒸汽下高压灭菌20分钟后得到。取4mL浓度为108 ~9 cfu /ml的备用菌液转移到反应器中,加入PBS溶液稀释至40mL(此时菌液浓度约为106~7cfu /ml)。将2cm×2cm的实施例2所得的薄膜加入反应器并加入磁子,恒定转速为300r/min转速,使薄膜催化剂能和菌液充分接触。打开氙灯(λ≥400nm)、开启风扇进行反应,每隔相等的时间取0.5mL该菌液,加入含有4.5mL PBS溶液的小试管中,并根据实验需要将菌液稀释一定次倍数后并转移至干燥洁净的培养皿中,再向每个已经含有菌液的培养皿中倾倒一定量经过高压灭菌处理的营养琼脂,晃动培养皿使菌液均匀分散在液态状态的琼脂中。将冷却凝固后的营养琼脂平板放入37℃的恒温摇床内,培养24h后,读取平板中的菌落数,并进行数据分析。如图8所示,可见光照射3h后,薄膜的抗菌效率达99.9%。Escherichia coli strains were cultured in MH (mueller hinton) broth for 18 hours at 37°C and immediately diluted with PBS solution, the final concentration of bacteria was 10 8~9 cfu/ml. Throughout the experiment, all glassware and PBS solutions were washed with deionized water and autoclaved at 121 °C for 20 min under autoclave. Take 4 mL of the standby bacterial solution with a concentration of 10 8 ~9 cfu/ml and transfer it to the reactor, add PBS solution to dilute to 40 mL (the bacterial solution concentration is about 10 6 ~ 7 cfu /ml at this time). The 2cm×2cm thin film obtained in Example 2 was added to the reactor and the magnetron was added, and the constant rotational speed was 300 r/min, so that the thin film catalyst could fully contact the bacterial liquid. Turn on the xenon lamp (λ≥400nm), turn on the fan for the reaction, take 0.5mL of the bacterial solution at equal time intervals, add it to a small test tube containing 4.5mL of PBS solution, and dilute the bacterial solution several times according to the experimental needs and transfer it. Put a certain amount of autoclaved nutrient agar into a dry and clean petri dish, and then pour a certain amount of autoclaved nutrient agar into each petri dish that already contains bacterial liquid, and shake the petri dish to evenly disperse the bacterial liquid in the liquid agar. The cooled and solidified nutrient agar plate was placed in a constant temperature shaker at 37°C, and after culturing for 24 hours, the number of colonies in the plate was read and data analysis was performed. As shown in Figure 8, after 3 h of visible light irradiation, the antibacterial efficiency of the film reached 99.9%.
以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。The above descriptions are only preferred embodiments of the present invention, and all equivalent changes and modifications made according to the scope of the patent application of the present invention shall fall within the scope of the present invention.
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CN1583636A (en) * | 2004-05-24 | 2005-02-23 | 大连轻工业学院 | Sterilizing and self-cleaning glass with zinc doped titanium dioxide coating |
CN101538123A (en) * | 2008-03-19 | 2009-09-23 | 林旺 | Method for manufacturing self-cleaning glass plated with photocatalysis layer and antibacterial metal ions |
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