Gemini/DNA复合膜在气/液界面上的性质研究
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摘要
与传统表面活性剂相比,Gemini表面活性剂具有较低的临界胶束浓度、较高的表面活性、较低的C20值,具有良好的润湿、加溶、起泡及钙皂分散作用等。DNA作为一种阴离子电解质可以与阳离子Gemini表面活性剂发生静电作用。本文主要通过LB膜技术、原子力显微镜、傅里叶红外光谱、红外反射吸收光谱以及圆二色光谱等研究了季铵盐型阳离子Gemini表面活性剂(18-s-18)与DNA(双链DNA-dsDNA和单链DNA-ssDNA)之间的相互作用。
18-s-18与ssDNA在界面上主要形成液态扩张膜,本文考查了连接基团对π-A等温线的影响。结果表明,复合体系的分子面积随着连接基团的增加而增加,s=10时达到最大值。这主要是由于当s<6时连接基团呈短棒状、平躺于界面,当s≥6连接基团的柔性和疏水性增强,在气/液界面上呈拱形甚至倒U型结构。
利用红外光谱研究了18-s-18/ssDNA和18-s-18/dsDNA体系中DNA的构型。结果显示,气/液界面上18-s-18/ssDNA和18-s-18/dsDNA复合单分子膜中DNA的构型分别是单链DNA和双螺旋DNA；转移到基片后,双螺旋DNA中规整的碱基堆积遭到破坏,结构发生扭曲、变形,导致碱基中C=O吸收发生红移,但它仍然具有双链结构。利用圆二色光谱探讨了湿度对Gemini/dsDNA复合膜中DNA构型的影响。结果发现,当相对湿度为85%时,18-3-18/dsDNA和18-6-18/dsDNA复合膜中的DNA仍呈B型结构；当相对湿度降低为15%时,CD光谱中只出现了一个峰强更强的负峰,这说明dsDNA在复合膜中形成了左手螺旋的三级结构ψ-相,DNA分子紧密的堆积在一起形成高度致密的结构。另外,在18-8-18/dsDNA复合体系的LB膜中,DNA分子即在侧向聚集,不易形成三级结构,因此在相对湿度较低的情况下,仍然是以B类构型存在的。
本文研究了DNA单双链对18-s-18/DNA复合膜性质的影响,利用AFM考查了复合体系的LB和LS膜的形貌。LS膜可获得复合膜上表面和下表面的信息而LB膜可探讨液流对其结构的影响。在18-s-18/dsDNA和18-s-18/ssDNA体系中,dsDNA和ssDNA分子并不是平躺于气/液界面上,而是呈“┒或┎”状排列的。当转移到LB膜中后,DNA分子发生了不同程度的卷曲、团聚,复合膜中纤维结构的高度达7-10 nm。
Compared with the conventional surfactant, Gemini surfactant shows lower critical micelle concentration (CMC), higher surface activity, lower C2o value, better wettability, solubility, foamability and lime soap dispersing power. As a kind of anionic polyelectrolyte, DNA could produce the electrostatic attraction with cationic Gemini surfactant. Therefore, in this dissertation, the interaction between cationic Gemini surfactant(18-s-18) and double-strand DNA/single-strand DNA(dsDNA/ssDNA) was investigated by means of LB technology, atom force microscope, FT-IR spectra, IRRAS srectra and Circular Dichroism srectra ect.
The liquid-expanded films are formed on ssDNA subphase at the air/water interface. In this paper, the impact of spacers onπ-A isotherms was investigated. Results show that molecule area increases with the spacer and the maximum area appears at s=10. This is due to that the spacer is rigid and lies on the air/water interface when s<6, while when the spacer is flexible(s≥6), the increasing flexibility and hydrophobility of spacer leads to form the arch shape and even reverse U-shape conformation at the air/water interface.
The comformation of DNA in 18-s-18/ssDNA and 18-s-18/ssDNA system are studied by infrared spectrum. The FT-IR spectra imply that the comformation of DNA in 18-s-18/ssDNA and 18-s-18/ssDNA monolayers is respective single-strand DNA and double helix DNA. However, the regular bases stacking are destroyed in double helix DNA after complex monolayers transferred onto substrates. The distortion and deformation of Double helix could lead to the red shift of C=O absorption. Nevertheless, it still has a double-stranded structure in 18-s-18/ssDNA complex system. We investigated the impact of the humidity on the comformation of DNA in Gemini/dsDNA complex using CD srectra. The result shows that humidity has a significant effect on the conformation of DNA. The DNA is like-B-form conformation at 85%r.h. in 18-3-18/dsDNA and 18-6-18/dsDNA complex. However, at 15%r.h., only a negative peak appears in CD srectra. This implies that Gemini/DNA complex is a typical chiralψ-phase, in which the DNA molecules are tightly packed together to fabricate highly condensed structure with a left-handed tertiary conformation. Because the surface morphology of 18-8-18/dsDNA is flat and not easy to from the tertiary structure, DNA remains the like-B-form conformation in the case of the lower relative humidity.
We studied the impact of ssDNA and dsDNA on the properties of Gemini/DNA complex. LS films are available to get the information of on the surface and lower surface, while LB films would explore the influence of the liquidstream on the structure. In 18-s-18/ssDNA and 18-s-18/ssDNA systems, dsDNA and ssDNA do not flat lie at the air/water interface, but show the "┓or┎"-like arrangement. After transferred to LB films, DNA molecules appear curve and aggregation, the height of the fiber structure is 7-10 nm.
18-s-18与ssDNA在界面上主要形成液态扩张膜,本文考查了连接基团对π-A等温线的影响。结果表明,复合体系的分子面积随着连接基团的增加而增加,s=10时达到最大值。这主要是由于当s<6时连接基团呈短棒状、平躺于界面,当s≥6连接基团的柔性和疏水性增强,在气/液界面上呈拱形甚至倒U型结构。
利用红外光谱研究了18-s-18/ssDNA和18-s-18/dsDNA体系中DNA的构型。结果显示,气/液界面上18-s-18/ssDNA和18-s-18/dsDNA复合单分子膜中DNA的构型分别是单链DNA和双螺旋DNA；转移到基片后,双螺旋DNA中规整的碱基堆积遭到破坏,结构发生扭曲、变形,导致碱基中C=O吸收发生红移,但它仍然具有双链结构。利用圆二色光谱探讨了湿度对Gemini/dsDNA复合膜中DNA构型的影响。结果发现,当相对湿度为85%时,18-3-18/dsDNA和18-6-18/dsDNA复合膜中的DNA仍呈B型结构；当相对湿度降低为15%时,CD光谱中只出现了一个峰强更强的负峰,这说明dsDNA在复合膜中形成了左手螺旋的三级结构ψ-相,DNA分子紧密的堆积在一起形成高度致密的结构。另外,在18-8-18/dsDNA复合体系的LB膜中,DNA分子即在侧向聚集,不易形成三级结构,因此在相对湿度较低的情况下,仍然是以B类构型存在的。
本文研究了DNA单双链对18-s-18/DNA复合膜性质的影响,利用AFM考查了复合体系的LB和LS膜的形貌。LS膜可获得复合膜上表面和下表面的信息而LB膜可探讨液流对其结构的影响。在18-s-18/dsDNA和18-s-18/ssDNA体系中,dsDNA和ssDNA分子并不是平躺于气/液界面上,而是呈“┒或┎”状排列的。当转移到LB膜中后,DNA分子发生了不同程度的卷曲、团聚,复合膜中纤维结构的高度达7-10 nm。
Compared with the conventional surfactant, Gemini surfactant shows lower critical micelle concentration (CMC), higher surface activity, lower C2o value, better wettability, solubility, foamability and lime soap dispersing power. As a kind of anionic polyelectrolyte, DNA could produce the electrostatic attraction with cationic Gemini surfactant. Therefore, in this dissertation, the interaction between cationic Gemini surfactant(18-s-18) and double-strand DNA/single-strand DNA(dsDNA/ssDNA) was investigated by means of LB technology, atom force microscope, FT-IR spectra, IRRAS srectra and Circular Dichroism srectra ect.
The liquid-expanded films are formed on ssDNA subphase at the air/water interface. In this paper, the impact of spacers onπ-A isotherms was investigated. Results show that molecule area increases with the spacer and the maximum area appears at s=10. This is due to that the spacer is rigid and lies on the air/water interface when s<6, while when the spacer is flexible(s≥6), the increasing flexibility and hydrophobility of spacer leads to form the arch shape and even reverse U-shape conformation at the air/water interface.
The comformation of DNA in 18-s-18/ssDNA and 18-s-18/ssDNA system are studied by infrared spectrum. The FT-IR spectra imply that the comformation of DNA in 18-s-18/ssDNA and 18-s-18/ssDNA monolayers is respective single-strand DNA and double helix DNA. However, the regular bases stacking are destroyed in double helix DNA after complex monolayers transferred onto substrates. The distortion and deformation of Double helix could lead to the red shift of C=O absorption. Nevertheless, it still has a double-stranded structure in 18-s-18/ssDNA complex system. We investigated the impact of the humidity on the comformation of DNA in Gemini/dsDNA complex using CD srectra. The result shows that humidity has a significant effect on the conformation of DNA. The DNA is like-B-form conformation at 85%r.h. in 18-3-18/dsDNA and 18-6-18/dsDNA complex. However, at 15%r.h., only a negative peak appears in CD srectra. This implies that Gemini/DNA complex is a typical chiralψ-phase, in which the DNA molecules are tightly packed together to fabricate highly condensed structure with a left-handed tertiary conformation. Because the surface morphology of 18-8-18/dsDNA is flat and not easy to from the tertiary structure, DNA remains the like-B-form conformation in the case of the lower relative humidity.
We studied the impact of ssDNA and dsDNA on the properties of Gemini/DNA complex. LS films are available to get the information of on the surface and lower surface, while LB films would explore the influence of the liquidstream on the structure. In 18-s-18/ssDNA and 18-s-18/ssDNA systems, dsDNA and ssDNA do not flat lie at the air/water interface, but show the "┓or┎"-like arrangement. After transferred to LB films, DNA molecules appear curve and aggregation, the height of the fiber structure is 7-10 nm.
引文
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