Interaction between proteins and roughness-regulated TiO2 nanotube arrays

doi:10.11949/0438-1157.20190954

Abstract

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

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

CLC Number:

TQ 01

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.

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.

Figures/Tables 16

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Fig.11 Association between adhesion and roughness

References 39

1	Nel A E, Madler L, Velegol D, et al. Understanding biophysicochemical interactions at the nano-bio interface[J]. Nat. Mater., 2009, 8(7): 543-557.
2	Leslie D C, Waterhouse A, Berthet J B, et al. A bioinspired omniphobic surface coating on medical devices prevents thrombosis and biofouling[J]. Nat. Biotechnol., 2014, 32(11): 1134-1140.
3	Shao M F, Ning F Y, Zhao J W, et al. Preparation of Fe₃O₄@SiO₂@layered double hydroxide core-shell microspheres for magnetic separation of proteins[J]. J. Am. Chem. Soc., 2012, 134(2): 1071-1077.
4	Zhen X, Wang X, Xie C, et al. Cellular uptake, antitumor response and tumor penetration of cisplatin-loaded milk protein nanoparticles[J]. Biomaterials, 2013, 34(4): 1372-1382.
5	Walkey C D, Chan W C W. Understanding and controlling the interaction of nanomaterials with proteins in a physiological environment[J]. Chem. Soc. Rev., 2012, 41(7): 2780-2799.
6	Tang F Q, Li L L, Chen D. Mesoporous silica nanoparticles: synthesis, biocompatibility and drug delivery[J]. Adv. Mater., 2012, 24(12): 1504-1534.
7	Bayne L, Ulijn R V, Halling P J. Effect of pore size on the performance of immobilised enzymes[J]. Chem. Soc. Rev., 2013, 42(23): 9000-9010.
8	Huang Y, Zha G Y, Luo Q J, et al. The construction of hierarchical structure on Ti substrate with superior osteogenic activity and intrinsic antibacterial capability[J]. Sci. Rep., 2014: 6172.
9	Rajh T, Dimitrijevic N M, Bissonnette M, et al. Titanium dioxide in the service of the biomedical revolution[J]. Chem. Rev., 2014, 114(19): 10177-10216.
10	Chen W T, Chan A, Jovic V, et al. Effect of the TiO₂ crystallite size, TiO₂ polymorph and test conditions on the photo-oxidation rate of aqueous methylene blue[J]. Top Catal., 2015, 58(2/3): 85-102.
11	Si P, Ding S J, Yuan J, et al. Hierarchically structured one-dimensional TiO₂ for protein immobilization, direct electrochemistry, and mediator-free glucose sensing[J]. ACS Nano, 2011, 5(9): 7617-7626.
12	Buettner K M, Valentine A M. Bioinorganic chemistry of titanium[J]. Chem. Rev., 2012, 112(3): 1863-1881.
13	Lee W, Kim D, Lee K, et al. Direct anodic growth of thick WO₃ mesosponge layers and characterization of their photoelectrochemical response[J]. Electrochim. Acta, 2010, 56(2): 828-833.
14	Macak J M, Ghicov A, Hahn R, et al. Photoelectrochemical properties of N-doped self-organized titania nanotube layers with different thicknesses[J]. J. Mater. Res., 2006, 21(11): 2824-2828.
15	Feng C X, Xu G Q, Liu H P, et al. A flow-injection photoelectrochemical sensor based on TiO₂nanotube arrays for organic compound detection[J]. J. Electrochem. Soc., 2014, 161(3): H57-H61.
16	Xu X Q, Wang M, Wang L S. Electrochemical determination of hydrogen peroxide and glucose by titanium(Ⅳ) oxide nanotube arrays[J]. Anal. Lett., 2015, 48(11): 1698-1706.
17	Grigorescu S, Ungureanu C, Kirchgeorg R, et al. Various sized nanotubes on TiZr for antibacterial surfaces[J]. Appl. Surf. Sci., 2013, 270: 190-196.
18	Lee K, Mazare A, Schmuki P. One-dimensional titanium dioxide nanomaterials: nanotubes[J]. Chem. Rev., 2014, 114(19): 9385-9454.
19	Yuan Z Y, Su B L. Titanium oxide nanotubes, nanofibers and nanowires[J]. Colloid Surface A, 2004, 241(1/2/3): 173-183.
20	Grimes C A. Synthesis and application of highly ordered arrays of TiO₂ nanotubes[J]. J. Mater. Chem., 2007, 17(15): 1451-1457.
21	Gundiah G, Mukhopadhyay S, Tumkurkar U G, et al. Hydrogel route to nanotubes of metal oxides and sulfates[J]. J. Mater. Chem., 2003, 13(9): 2118-2122.
22	Dong Y H, Ji X Y, Laaksonen A, et al. Determination of the small amount of proteins interacting with TiO₂ nanotubes by AFM-measurement[J]. Biomaterials, 2019, 192: 368-376.
23	饶超, 董依慧, 庄伟, 等. TiO₂纳米管阵列孔径调控葡萄糖氧化酶生物传感器性能[J]. 化工学报, 2016, 67(10): 4324-4333.
	Rao C, Dong Y H, Zhuang W, et al. Regulate properties of glucose oxidase biosensors through pore sizes of TiO₂ nanotube arrays[J]. CIESC Journal, 2016, 67(10): 4324-4333.
24	Roy P, Berger S, Schmuki P. TiO₂ Nanotubes: synthesis and applications[J]. Angew. Chem. Int. Edit., 2011, 50(13): 2904-2939.
25	Moerz S T, Huber P. pH-dependent selective protein adsorption into mesoporous silica[J]. J. Phys. Chem. C, 2015, 119(48): 27072-27079.
26	Shao Q, Jiang S Y. Molecular understanding and design of zwitterionic materials[J]. Adv. Mater., 2015, 27(1): 15-26.
27	Zhou Z, Hartmann M. Progress in enzyme immobilization in ordered mesoporous materials and related applications[J]. Chem. Soc. Rev., 2013, 42(9): 3894-3912.
28	Wang F, Min Y, Geng X D. Fast separations of intact proteins by liquid chromatography[J]. J. Sep. Sci., 2012, 35(22): 3033-3045.
29	Su L A, Jia W Z, Hou C J, et al. Microbial biosensors: a review[J]. Biosensors & Bioelectronics, 2011, 26(5): 1788-1799.
30	Sun F, Ella-Menye J R, Galvan D D, et al. Stealth surface modification of surface-enhanced Raman scattering substrates for sensitive and accurate detection in protein solutions[J]. ACS Nano, 2015, 9(3): 2668-2676.
31	Fang T H, Chang W J, Weng C I. Surface analysis of nanomachined films using atomic force microscopy[J]. Mater. Chem. Phys., 2005, 92(2/3): 379-383.
32	Ye G, Lee J H, Perreault F, et al. Controlled architecture of dual-functional block copolymer brushes on thin-film composite membranes for integrated “defending” and “attacking” strategies against biofouling[J]. ACS Applied Materials & Interfaces, 2015, 7(41): 23069-23079.
33	Alsteens D, Gaub H E, Newton R, et al. Atomic force microscopy-based characterization and design of biointerfaces[J]. Nat. Rev. Mater., 2017, 2(5): 364-392.
34	An R, Zhuang W, Yang Z H, et al. Protein adsorptive behavior on mesoporous titanium dioxide determined by geometrical topography[J]. Chem. Eng. Sci., 2014, 117: 146-155.
35	Dong Y H, An R, Zhao S L, et al. Molecular interactions of protein with TiO₂ by the AFM-measured adhesion force[J]. Langmuir: the ACS Journal of Surfaces and Colloids, 2017, 33(42): 11626-11634.
36	Dong Y H, Laaksonen A, Cao W, et al. AFM study of pH‐dependent adhesion of single protein to TiO₂ surface[J]. Advanced Materials Interfaces, 2019, 6(14): 1900411.
37	Wang M S, Palmer L B, Schwartz J D, et al. Evaluating protein attraction and adhesion to biomaterials with the atomic force microscope[J]. Langmuir: the ACS Journal of Surfaces and Colloids, 2004, 20(18): 7753-7759.
38	Cai Q Y, Yang L X, Yu Y. Investigations on the self-organized growth of TiO₂ nanotube arrays by anodic oxidization[J]. Thin Solid Films, 2006, 515(4): 1802-1806.
39	Peng C W, Liu J, Xie Y, et al. Molecular simulations of cytochrome C adsorption on positively charged surfaces: the influence of anion type and concentration[J]. Phys. Chem. Chem. Phys., 2016, 18(15): 9979-9989.

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Interaction between proteins and roughness-regulated TiO₂ nanotube arrays

TiO₂纳米管阵列粗糙度调控及其与蛋白相互作用

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