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Water stable, antimicrobial active nanofibres generated by electrospinning from aqueous spinning solutions

机译:从水溶液纺丝溶液中静电纺丝产生的水稳定性,抗菌活性纳米纤维

摘要

This dissertation is concerned about the development of antimicrobial active nanofibres. The objective was to generate these nanofibres from aqueous spinning solutions via electrospinning. By this, organic solvents were avoided so that electrospinning was performed at environmentally friendly conditions. Electrospinning of aqueous spinning solutions necessitated the application of water soluble polymers so that the gained nanofibres exhibited nearly no water stability. Further content of this thesis was therewith the development of different stabilisation techniques for the nanofibres. The formation of antimicrobial poly(vinyl alcohol) (PVA) nanofibre webs containing spherical nano-Ag via electrospinning with special regard to utilise these nanofibres in filter media was studied. Aqueous PVA solutions with addition of silver nitrate were electrospun. Afterwards, the gained nanofibres were UV irradiated in order to reduce the silver ions within the fibre matrix to elemental nano-sized silver. The resulting nanofibre webs were stabilised towards aqueous surroundings by a heat induced crystallisation. Furthermore, the influence of spinning and solution parameters on the resulting fibre morphology was investigated and antimicrobial functionality of the nanofibres was proven. Here, the minimum efficient nano-Ag content as well as the release behaviour of silver ions from the fibre matrix in comparison to that of silver salts was studied. The nanofibres were examined concerning their potential usage in filters by electrospinning them directly on support fleeces and application of standardised test dust onto the nanofibre webs. Thereby, the deposition behaviour of the test dust on the nanofibres and its potential impact on antimicrobial activity were investigated. In the next chapter, PVA nanofibres were provided with the quaternary ammonium silane 3 (trimethoxysilyl)-propyldimethyloctadecyl ammonium chloride (TMS QAC18) in order to achieve i) antimicrobial activity and ii) water stability of the nanofibres. Homogeneous PVA/TMS-QAC18 composite nanofibres were generated by electrospinning of an aqueous PVA solution with addition of TMS-QAC18. Furthermore, as second method coating of pure PVA nanofibres with the organosilane was performed. The organosilane was permanently bond to the PVA by heat treatment of the nanofibres. Thereby, the surface properties of the fibres changed. Inhibition of the bacterial growth of B.subtilis was proven, though the fibre webs exhibited no significant antimicrobial effect on E.coli. Furthermore, water stabilities of the nanofibre webs were investigated. In the following chapter, three different photo-induced chemical crosslinking strategies for PVA nanofibres were investigated. Crosslinking was performed i) by formation of a semi-interpenetrating network consisting of poly(ethylene glycol)dimethacrylate (PEGDMA) within the PVA matrix, ii) in the presence of sodium benzoate as sensitizer and iii) by previous reaction of PVA with glycidyl methacrylate (GMA) resulting in a crosslinkable and electrospinnable product (PVA-MA). All strategies were optimised, investigated and examined with regard to their efficiency for stabilisation of the nanofibres towards water. Furthermore PVA/silica hybrid nanofibres were prepared by electrospinning. The inorganic/organic hybrid fibres possessed excellent intrinsic water stability. The spinning process was optimised regarding the fibre diameter and homogeneity. Ag-nanoparticles were incorporated into the fibre matrix in order to achieve antimicrobial activity. For that, silver nitrate was used as add-on to the spinning solution and subsequently reduced by UV-irradiation within the electrospun fibres to elemental, spherical nanoparticles. Antimicrobial activity of these fibres against E.coli and B.subtilis was proven. Fibres were tested for thermal stability. Exposed to high temperature the nano-Ag exhibited changed particle morphology and reduced antimicrobial activity. In last chapter, PVA/silica hybrid nanofibres were provided with TiO2 nanoparticles; the hybrid nanofibres were gained from an aqueous silica sol/PVA mixture without usage of organic solvents. The TiO2 particles were deposited onto the fibres’ surface subsequently electrospinning. For that, an aqueous, commercial available TiO2 dispersion (VP Disp. W740X, Degussa) was sprayed onto the nanofibre webs. For the TiO2-equipped PVA/silica nanofibres a good photocatalytic activity was proven. Additionally, pure silica nanofibres were prepared from a silica sol-gel and also equipped with TiO2-particles at the same procedure. Attachment and binding durability of TiO2 particles onto both fibre types were investigated by electron microscopy (FESEM, TEM). Thereby, for the hybrid nanofibres good durability of TiO2 was attested whereas nearly no attachment of the particles onto the silica nanofibres could be detected.
机译:本论文关注抗菌活性纳米纤维的发展。目的是通过静电纺丝从水性纺丝溶液中产生这些纳米纤维。这样,避免了有机溶剂,从而在环境友好的条件下进行静电纺丝。水溶液纺丝的静电纺丝需要水溶性聚合物的应用,以使获得的纳米纤维几乎没有水稳定性。因此,本论文的进一步内容是开发不同的纳米纤维稳定技术。研究了通过静电纺丝形成包含球形纳米Ag的抗菌聚乙烯醇(PVA)纳米纤维网,并特别注意在过滤介质中利用这些纳米纤维。将添加有硝酸银的PVA水溶液电纺丝。然后,对获得的纳米纤维进行紫外线照射,以将纤维基质中的银离子还原为元素纳米银。所得的纳米纤维网通过热诱导的结晶而向水性环境稳定。此外,研究了纺丝和溶液参数对所得纤维形态的影响,并证明了纳米纤维的抗菌功能。在此,研究了与银盐相比,最小有效纳米Ag含量以及银离子从纤维基质中的释放行为。通过将纳米纤维直接静电纺在支撑羊毛上并将标准化测试粉尘施加到纳米纤维网上,检查了纳米纤维在过滤器中的潜在用途。因此,研究了测试灰尘在纳米纤维上的沉积行为及其对抗菌活性的潜在影响。在下一章中,为PVA纳米纤维提供了季铵硅烷3(三甲氧基甲硅烷基)-丙基二甲基十八烷基氯化铵(TMS QAC18),以实现i)抗菌活性和ii)纳米纤维的水稳定性。均质PVA / TMS-QAC18复合纳米纤维是通过电纺PVA水溶液并添加TMS-QAC18生成的。此外,作为第二种方法,用有机硅烷涂覆纯PVA纳米纤维。通过对纳米纤维进行热处理,有机硅烷与PVA永久结合。由此,纤维的表面性质改变。尽管纤维网对大肠杆菌没有显示出明显的抗菌作用,但已证明抑制了枯草芽孢杆菌的细菌生长。此外,研究了纳米纤维网的水稳定性。在下一章中,研究了三种不同的PVA纳米纤维的光诱导化学交联策略。交联是通过以下步骤进行的:i)通过在PVA基质内形成由聚(乙二醇)二甲基丙烯酸酯(PEGDMA)构成的半互穿网络,ii)在苯甲酸钠作为敏化剂的情况下进行iii)和通过PVA与甲基丙烯酸缩水甘油酯的预先反应(GMA)生成可交联和可电纺的产品(PVA-MA)。所有策略均经过优化,研究和检查,以确保纳米纤维对水的稳定性。此外,通过电纺丝制备了PVA /二氧化硅杂化纳米纤维。无机/有机杂化纤维具有优异的固有水稳定性。在纤维直径和均匀性方面优化了纺丝工艺。将银纳米颗粒掺入到纤维基质中以获得抗菌活性。为此,将硝酸银用作纺丝溶液的添加剂,随后通过在电纺丝纤维内进行紫外线照射将其还原成元素球形纳米颗粒。这些纤维对大肠杆菌和枯草芽孢杆菌具有抗菌活性。测试纤维的热稳定性。暴露于高温下,纳米银表现出改变的颗粒形态并降低了抗菌活性。在上一章中,向PVA /二氧化硅杂化纳米纤维提供了TiO2纳米颗粒。杂化纳米纤维是从含水硅溶胶/ PVA混合物中获得的,无需使用有机溶剂。 TiO2颗粒沉积在纤维表面,然后进行静电纺丝。为此,将可商购的水性TiO 2分散体(VP Disp.W740X,Degussa)喷雾到纳米纤维网上。对于配备了TiO2的PVA /二氧化硅纳米纤维,已证明其具有良好的光催化活性。另外,由二氧化硅溶胶-凝胶制备纯的二氧化硅纳米纤维,并且还以相同的程序配备了TiO 2-颗粒。通过电子显微镜(FESEM,TEM)研究了TiO2颗粒在两种纤维上的附着和粘合耐久性。因此,对于杂化纳米纤维,证明了TiO 2的良好耐久性,而几乎没有检测到颗粒附着在二氧化硅纳米纤维上。

著录项

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    Voigt Wiebke Vivien;

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  • 年度 2009
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  • 原文格式 PDF
  • 正文语种 eng
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