TiO2纳米管阵列粗糙度调控及其与蛋白相互作用

doi:10.11949/0438-1157.20190954

摘要/Abstract

摘要：

采用电化学阳极氧化法，通过改变电解液氟离子浓度(0.4%、0.3%、0.2%(质量))和电压(15、25、35、45 V)，制备一系列不同管径和粗糙度的TiO₂纳米管阵列(TiO₂ nanotube arrays, TNAs)。通过扫描电子显微镜以及原子力显微镜(atomic force microscopy, AFM)表征，结果表明随着电解液中氟离子浓度的降低，制备得到的TNAs表面平整度更好，壁厚增大，粗糙度降低。采用AFM力学表征研究了表面粗糙度以及管径对TNAs表面力学性质以及与细胞色素C(Cytochrome C, Cyt C)相互作用的影响，结果表明，黏附力与接触面积呈正比，随着TNAs管径增加，壁厚减小，TNAs与Cyt C的有效接触面积先增大后减小，两者之间作用力也先增加后减小；同时，同管径条件下粗糙度降低，TNAs有效面积增加，相互作用力也增加；由此可见，通过改变电解液氟离子浓度可以有效调控TNAs表面粗糙度及有效接触面积，进一步利于促进与蛋白分子之间相互作用。

关键词: TiO₂纳米管阵列, 粗糙度, 接触面积, AFM, 黏附力

Abstract:

A series of TiO₂ nanotube arrays (TNAs) with different diameters and roughness were prepared by electrochemical anodization method by changing the fluoride ion concentration [0.4%,0.3%,0.2%(mass)] and applied voltage(15,25,35,45 V). The scanning electron microscopy (FESEM) and atomic force microscopy (AFM) results showed that the wall thickness of the prepared TNAs increased and the roughness decreased with the decrease of fluoride ion concentration in the electrolyte. The effects of surface roughness and diameter on the surface mechanical properties of TNAs and the interaction of Cytochrome C (Cyt C) were studied by AFM characterization. The results show that the adhesion is proportional to the contact area. With the increase of the diameter of the TNAs, the wall thickness decreases, the effective contact area between TNAs and Cyt C increases first and then decreases，and the forces of Cyt C with TNAs also increase first and then decrease. The roughness decreases when the diameter was fixed, the effective area of TNAs increases, and the interaction force also increases. It can be seen that the surface roughness and effective contact area of TNAs can be effectively controlled by changing the fluoride ion concentration of the electrolyte, which is further beneficial to promoting interaction with protein molecules.

Key words: TiO₂ nanotube arrays, roughness, contact area, AFM, adhesion force

中图分类号:

TQ 01

吴娜, 董依慧, 吉晓燕, 皇甫长安, 陆小华. TiO₂纳米管阵列粗糙度调控及其与蛋白相互作用[J]. 化工学报, 2020, 71(2): 831-842.

Na WU, Yihui DONG, Xiaoyan JI, Chang an HUANGFU, Xiaohua LU. Interaction between proteins and roughness-regulated TiO₂ nanotube arrays[J]. CIESC Journal, 2020, 71(2): 831-842.

图/表 16

图1 不同氟离子浓度和电压下制备TNAs的XRD谱图

Fig.1 XRD patterns of TNAs prepared at different F- concentrations and voltages

图2 不同氟离子浓度和电压下制备TNAs的Raman谱图

Fig.2 Raman spectra of TNAs prepared at different F- concentrations and voltages

图3 0.4%(质量)氟离子浓度下不同电压制备TNAs的AFM 2D以及高度图

Fig.3 AFM topographical and corresponding height images of TNAs prepared with different voltages at 0.4%(mass) F- concentration

表1 不同外加电压以及氟离子浓度下TNAs粗糙度

Table 1 Roughness of TNAs under different applied voltages and F- concentrations

电压/V	粗糙度/nm
电压/V	0.4%(质量) F^-	0.3%(质量) F^-	0.2%(质量) F^-
15	23.2±1.7	21.4±1.2	14.4±1.8
25	47.5±2.3	44.9±1.5	36.7±1.0
35	61.4±1.9	55.1±2.9	37.0±1.3
45	85.2±1.5	65.3±2.3	63.8±1.7

图4 0.3%(质量)氟离子浓度下不同电压制备TNAs的AFM 2D以及高度图

Fig.4 AFM topographical and corresponding height images of TNAs prepared with different voltages at 0.3%(mass) F- concentration

图5 0.2%(质量)氟离子浓度下不同电压制备TNAs的AFM 2D以及高度图

Fig.5 AFM topographical and corresponding height images of TNAs prepared with different voltages at 0.2%(mass)F- concentration

图6 0.4%(质量)氟离子浓度下不同电压制备得到TNAs的FESEM 图像

Fig.6 FESEM images of TNAs prepared with different voltages at 0.4%(mass) F- concentration

表2 不同外加电压以及氟离子浓度条件下TNAs壁厚及管径

Table 2 Wall thickness and diameter of TNAs under different applied voltages and F- concentrations

电压/V	壁厚/nm			管径/nm
电压/V	0.4%(质量) F^-	0.3%(质量) F^-	0.2%(质量) F^-	0.4%(质量) F^-	0.3%(质量) F^-	0.2%(质量) F^-
15	9.3±0.2	9.4±0.4	9.4±0.4	24.7±1.9	23.1±2.8	21.5±0.8
25	8.0±0.4	9.0±0.9	9.2±0.5	51.1±2.3	49.9±1.5	48.7±1.9
35	7.3±0.4	8.4±0.6	8.8±0.3	65.7±2.9	65.0±1.6	62.3±1.3
45	6.0±0.5	7.3±0.4	8.0±0.3	91.6±2.5	87.2±1.9	78.8±2.1

图7 0.3%(质量)氟离子浓度下不同电压制备TNAs的FESEM图像

Fig.7 FESEM images of TNAs prepared with different voltages at 0.3%(mass) F- concentration

图8 0.2%(质量)氟离子浓度下不同电压下制备TNAs的FESEM图像

Fig.8 FESEM images of TNAs prepared with different voltages at 0.2%(mass) F- concentration

表3 不同外加电压以及氟离子浓度下TNAs管长

Table 3 Tube length of TNAs under different applied voltages and F- concentrations

电压/V	管长/μm
电压/V	0.4%(质量) F^-	0.3%(质量) F^-	0.2%(质量) F^-
15	1~1.3	1.0	0.8~1.2
25	5~6	5~5.4	4~5
35	5.7~6.5	5.5	5.5~6.5
45	10~11	10~11	10~10.5

图9 不同氟离子浓度35 V下制备TNAs的表面黏附力分布

Fig.9 Histogram of adhesion forces measured for TNAs prepared with 35 V at different F- concentrations

表4 不同外加电压以及氟离子浓度条件下TNAs壁面积比率以及表面黏附力

Table 4 Wall area ratio and adhesion force of TNAs under different applied voltages and F- concentrations

电压/V	壁面积比率/%			黏附力/nN
电压/V	0.4%(质量) F^-	0.3%(质量) F^-	0.2%(质量) F^-	0.4%(质量) F^-	0.3%(质量) F^-	0.2%(质量) F^-
15	36.1±0.5	38.0±0.6	41.4±0.7	2.6±0.3	4.0±0.4	4.3±0.5
25	41.0±.04	53.2±1.1	58.1±0.5	4.4±0.8	4.8±0.9	5.7±0.8
35	53.3±0.4	59.3±0.7	66.1±1.3	6.5±1.2	7.0±1.0	8.7±1.3
45	45.3±0.7	47.4±0.3	50.0±0.5	3.9±0.9	6.0±1.3	6.8±1.3

图10 Cyt C与不同氟离子浓度35 V下制备TNAs的表面黏附力分布

Fig.10 Histogram of adhesion forces measured for Cyt C with TNAs prepared with 35 V at different F- concentrations

表5 不同外加电压以及氟离子浓度条件下Cyt C-TNAs表面黏附力

Table 5 Adhesion force of Cyt C-TNAs under different applied voltages and F- concentrations

电压/V	黏附力/nN
电压/V	0.4%(质量) F^-	0.3%(质量) F^-	0.2%(质量) F^-
15	13.4±1.5	14.9±1.2	18.0±4.5
25	14.9±2.6	17.5±3.5	25.2±1.6
35	23.4±1.2	27.0±3.2	33.8±1.3
45	19.5±2.0	25.1±2.1	30.6±1.4

图11 黏附力与粗糙度的关联

Fig.11 Association between adhesion and roughness

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TiO₂纳米管阵列粗糙度调控及其与蛋白相互作用

Interaction between proteins and roughness-regulated TiO₂ nanotube arrays

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