抗菌杂化SiO_2纳米粒子的制备及在聚氨酯中的应用研究
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摘要
采用价格低廉的硅烷偶联剂制备了反应性季铵化合物(QAC),并用简单的方法将QAC一步接枝在SiO_2上,制备抗菌杂化SiO_2纳米粒子.首先研究了杂化SiO_2纳米粒子的化学结构、微观形貌以及抗菌性能.进一步将杂化SiO_2纳米粒子与聚氨酯复合,并固化成膜.研究了复合薄膜的抗菌性能、力学性能以及抗菌持久性,并对其进行了抑菌圈测试.结果表明:与纯SiO_2纳米粒子相比,杂化SiO_2纳米粒子具有优异的抗菌性能,可以在20 min内完全灭杀大肠杆菌与表皮葡萄球菌.杂化SiO_2纳米粒子易在薄膜表面富集,仅添加少量(5 wt%)的杂化SiO_2纳米粒子便可使薄膜获得良好的抗菌性能以及较高的拉伸强度;对复合薄膜进行加速老化处理后,仍具有良好的抗菌性能,表明该复合薄膜具有良好的抗菌持久性与稳定性;抑菌圈的测试表明,复合薄膜为接触型抗菌材料,无抗菌物质浸出,更加安全高效.
A series of reactive QACs with different chain lengths were prepared by inexpensive tertiary amine silane coupling agent, which were covalently grafted onto the surface of SiO_2 nanoparticles in one step via a modified St?ber method. This method can increase the graft ratio of QAC relative to the use of dry silica powder.The structure and appearance of hybrid SiO_2 nanoparticles were studied by Fourier transform infrared spectroscopy(FTIR), transmission electron microscopy(TEM), zeta potential and thermogravimetric analysis(TGA). The antibacterial activity of hybrid SiO_2 nanoparticles was evaluated by shake flask method. The composite films with excellent antimicrobial properties were obtained from a mixture of a polyurethane acrylate prepolymer and hybrid SiO_2 nanoparticles via UV curing. The standard antibacterial test method ISO 22196 was used to evaluate the antibacterial properties of the film. The results showed that the hybrid SiO_2 nanoparticles have a uniform particle size(～ 40 nm), a smooth spherical shape and a high positive charge on the surface.Antibacterial test results indicated that the hybrid SiO_2 nanoparticles have excellent antibacterial activity compared with pure SiO_2 nanoparticles, and can completely killed Escherichia coli and Staphylococcus epidermidis in 50 min. As the QAC alkyl chain grows, the antibacterial properties of the nanoparticles are further improved and SiO_2-Q-12 can killed two bacteria completely within 20 min. This is mainly due to the hybrid SiO_2 nanoparticles are light and have a high positive charge on the surface, so they can be quickly adsorbed on the surface of bacteria to achieve rapid sterilization. The hybrid SiO_2 nanoparticles were enriched on the surface of the film. Adding a small amount(5 wt%) of hybrid SiO_2 nanoparticles could endow the film with good antibacterial properties and high tensile strength. After the accelerated aging treatment of the composite film according to the national standard GB 15979-2002, it still possessed good antibacterial properties, indicating that the composite film has excellent antibacterial durability and stability. The test of the inhibition zone showed that the composite film was a contact antibacterial material, no antibacterial substance leaching, which was safer and more efficient.
A series of reactive QACs with different chain lengths were prepared by inexpensive tertiary amine silane coupling agent, which were covalently grafted onto the surface of SiO_2 nanoparticles in one step via a modified St?ber method. This method can increase the graft ratio of QAC relative to the use of dry silica powder.The structure and appearance of hybrid SiO_2 nanoparticles were studied by Fourier transform infrared spectroscopy(FTIR), transmission electron microscopy(TEM), zeta potential and thermogravimetric analysis(TGA). The antibacterial activity of hybrid SiO_2 nanoparticles was evaluated by shake flask method. The composite films with excellent antimicrobial properties were obtained from a mixture of a polyurethane acrylate prepolymer and hybrid SiO_2 nanoparticles via UV curing. The standard antibacterial test method ISO 22196 was used to evaluate the antibacterial properties of the film. The results showed that the hybrid SiO_2 nanoparticles have a uniform particle size(～ 40 nm), a smooth spherical shape and a high positive charge on the surface.Antibacterial test results indicated that the hybrid SiO_2 nanoparticles have excellent antibacterial activity compared with pure SiO_2 nanoparticles, and can completely killed Escherichia coli and Staphylococcus epidermidis in 50 min. As the QAC alkyl chain grows, the antibacterial properties of the nanoparticles are further improved and SiO_2-Q-12 can killed two bacteria completely within 20 min. This is mainly due to the hybrid SiO_2 nanoparticles are light and have a high positive charge on the surface, so they can be quickly adsorbed on the surface of bacteria to achieve rapid sterilization. The hybrid SiO_2 nanoparticles were enriched on the surface of the film. Adding a small amount(5 wt%) of hybrid SiO_2 nanoparticles could endow the film with good antibacterial properties and high tensile strength. After the accelerated aging treatment of the composite film according to the national standard GB 15979-2002, it still possessed good antibacterial properties, indicating that the composite film has excellent antibacterial durability and stability. The test of the inhibition zone showed that the composite film was a contact antibacterial material, no antibacterial substance leaching, which was safer and more efficient.
引文
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26Yin Jun(殷俊).Novel Polyethersulfone Organic-inorganic Composite Ultrafiltration Membranes Prepared with ModifiedSiO2 Nanoparticles and Its Application Research(改性SiO2纳米粒子/聚醚砜复合超滤膜的制备及其应用研究).Doctoral Dissertation of Southeast University(东南大学博士学位论文),2016
2Kim T,Zhang Q Z,Li J,Zhang L F,Jokerst J V.ACS Nano,2018,12(6):5615-5625
3Zhang Y,He X L,Ding M M,He W,Li J H,Li J S,Tan H.Biomacromolecules,2018,19(2):279-287
4Lei R Y,Hou J C,Chen Q X,Yuan W R,Cheng B L,Sun Y Q,Jin Y,Ge L J,Ben-Sasson S A,Chen J,Wang H X,Lu W Y,Fang X M.ACS Nano,2018,12(6):5284-5296
5Maier L,Pruteanu M,Kuhn M,Zeller G,Telzerow A,Anderson E E,Brochado A R,Fernandez K C,Dose H,Mori H,Patil K R,Bork P,Typas A.Nature,2018,555:623-628
6Brochado A R,Telzerow A,Bobonis J,Banzhaf M,Mateus A,Selkrig J,Huth E,Bassler S,Beas J Z,Zietek M,Ng N,Foerster S,Ezraty B,Py B,Barras F,Savitski M M,Bork P,G?ttig S,Typas A.Nature,2018,559:259-263
7Sun D D,Zhang W W,Mou Z P,Chen Y,Guo F,Yang E D,Wang W Y.ACS Appl Mater Interfaces,2017,9(11):10047-10060
8Perdikaki A,Galeou A,Pilatos G,Prombona A,Karanikolos G N.Langmuir,2018,34(37):11156-11166
9Ur Rehman M A,Ferraris S,Goldmann W H,Perero S,Bastan F E,Nawaz Q,Confiengo G G D,Ferraris M,Boccaccini A R.ACS Appl Mater Interfaces,2017,9(38):32489-32497
10Cao F F,Ju E G,Zhang Y,Wang Z Z,Liu C Q,Li W,Huang Y Y,Dong K,Ren J S,Qu X G.ACS Nano,2017,11(5):4651-4659
11Yang X L,Yang J C,Wang L,Ran B,Jia Y X,Zhang L M,Yang G,Shao H W,Jiang X Y.ACS Nano,2017,11(6):5737-5745
12Kachoei M,Nourian A,Divband B,Kachoei Z,Shirazi S.Nanomedicine,2016,11(19):2511-2527
13Aditya A,Chattopadhyay S,Jha D,Gautam H K,Maiti S,Ganguli M.ACS Appl Mater Interfaces,2018,10(18):15401-15411
14Zhao J,Millians W,Tang S,Wu T H,Zhu L,Ming W H.ACS Appl Mater Interfaces,2015,7(33):18467-18472
15Lin J,Chen X Y,Chen C Y,Hu J T,Zhou C L,Cai X F,Wang W,Zheng C,Zhang P P,Cheng J,Guo Z H,Liu H.ACSAppl Mater Interfaces,2018,10(7):6124-6136
16Song Z Y,Wang H J,Wu Y,Gu J J,Li S J,Han H Y.ACS Omega,2018,3(10):14517-14525
17Gude K,Narayanan R.J Phys Chem C,2010,114(14):6356-6362
18Pageni P,Yang P,Chen Y P,Huang Y,Bam M,Zhu T,Nagarkatti M,Benicewicz B C,Decho A W,Tang C.Biomacromolecules,2018,19(2):417-425
19Ge H W,Zhang J F,Yuan Y,Liu J C,Liu R,Liu X Y.Prog Org Coat,2017,106:20-26
20Chen R,Li T,Zhang Q,Ding Z Y,Ma P M,Zhang S W,Chen M Q,Dong W F,Ming W H.New J Chem,2017,41:9762-9768
21Makarovsky I,Boguslavsky Y,Alesker M,Lellouche J,Banin E,Lellouche J P.Adv Funct Mater,2011,21(22):4295-4304
22Volova T G,Shumilova A A,Shidlovskiy I P,Nikolaeva E D,Sukovatiy A G,Vasiliev A D,Shishatskaya E I.PolymTest,2018,65:54-68
23Wang Y Z,Xue X X,Yang H,Luan C.Appl Surf Sci,2014,292:608-614
24Yang L,Tang Y,Liu N,Liu C H,Ding Y S,Wu Z Q.Macromolecules,2016,49(20):7692-7702
25Wei B,Gurr P A,Gozen A O,Blencowe A,Solomon D H,Qiao G G,Spontak R J,Genzer J.Nano Lett,2008,8(9):3010-3016
26Yin Jun(殷俊).Novel Polyethersulfone Organic-inorganic Composite Ultrafiltration Membranes Prepared with ModifiedSiO2 Nanoparticles and Its Application Research(改性SiO2纳米粒子/聚醚砜复合超滤膜的制备及其应用研究).Doctoral Dissertation of Southeast University(东南大学博士学位论文),2016