Surface Hydrophilic Modification of Poly(ether ether ketone) and Immobilization of Collagen†

doi:10.7503/cjcu20160120

Abstract

Abstract:

Surface modification of poly(ether ether ketone)(PEEK) was performed to increase the surface wettability. Acrylamide(AAm) was grafted on the surface of PEEK film by ultraviolet grafting to improve the hydrophilicity through the introduction of hydrophilic groups. Then, glutaraldehyde was used to immobilize collagen and hydrolyzed collagen on surface of the material. Fluorescein-labelled collagen was also used to verify the immobilization. The surfaces of PEEK film before and after modification were characterized by contact angle meter, scanning electron microscope, fluorescence spectrophotometer and X-ray photoelectron spectrometer. The results show that the surface morphology and the hydrophilicity are changed significantly after surface modification. Polyacrylamide grated on PEEK has a density of as high as 50.9 μg/cm². PEEK-g-PAAm becomes hydrophilic with a decreased water contact angle of (22±3)°. Surface immobilized with hydrolyzed collagen labeled with fluorescein isothiocyanate exhibits strong fluorescence effect. Modified films immobilized with collagen showed nitrogen peak, which was not observed for unmodified PEEK film in X-ray photoelectron spectroscopy, indicating the successful immobilization of collagen. The concentration of collagen immobilized on PEEK was determined to be 10.2 μg/cm².

Key words: Poly(ether ether ketone), Collagen, Surface modification, Fluorescence labeling

CLC Number:

O631

TrendMD:

SUN Hui, YU Qingsong, YANG Biao, XU Guozhi. Surface Hydrophilic Modification of Poly(ether ether ketone) and Immobilization of Collagen^†[J]. Chem. J. Chinese Universities, 2016, 37(6): 1154.

Figures/Tables 11

Scheme 1 Structure of PEEK

Scheme 2 Synthetic routes for the immobilization of collagen onto PEEK

Fig.1 Variation of contact angle with irradiation time at different monomer concentrations(A) and comparison of contact angle of PEEK-AAm with(a) or without BP(b)(B)

Fig.2 Images showing the evolution of water contact angle of PEEK-PAAm with irradiation time0.5 mol/L AAm. UV irradiation time/min: (A) 0; (B) 1; (C) 3; (D) 6; (E) 9; (F) 12.

Fig.3 Dependence of grafted PAAm on irradiation time in presence(a)/absence(b) of benzophenone

Fig.4 SEM images of blank PEEK and modified PEEK(A) PEEK; (B) PEEK-PAAm; (C) PEEK-GA; (D) PEEK-Col; (E) PEEK-HC.

Fig.5 UV spectrum of HC-FITC labeled solution

Fig.6 Fluorescence emission spectra of blank and modified PEEKa. PEEK-AAm; b. PEEK-GA; c. PEEK; d. PEEK-Col; e. PEEK-HC-FITC.

Fig.7 XPS overview spectra of PEEK(A) and PEEK-Col(B)

Fig.8 High resolution XPS nitrogen spectra of PEEK(A) and PEEK-Col(B)

Table 1 XPS atomic percentage of PEEK and PEEK-Col

Sample	C(%)	O(%)	N(%)
PEEK	79.55	16.02	0.44
PEEK-Col	64.82	20.51	9.43

References 29

[1]	Kurtz S.M., PEEK Biomaterials Handbook, William Andre Publishing, New York, 2011, 145—161, 249—251
[2]	Baidya K. P., Ramakrishna S., Rahman M., Ritchie A., J. Biomater. Appl., 2001 , 15(3), 279—289
[3]	Peng H. M., Weng X. S., Chinese Journal of Orthopaedics, 2011, 31(3), 265—268
	(彭慧明, 翁习生. 中华骨科杂志, 2011, 31(3), 265—268)
[4]	Chen R. C., Sun H., Xu G. Z., Chem. Res. Chinese Universities, 2012, 28(1), 162—165
[5]	Sun H., Chen R. C., Liu S., Xu G. Z., Chem. Res. Chinese Universities, 2012, 28(3), 542—545
[6]	Sun H., Chen R. C., Li A., Xu G. Z., Chem. Res. Chinese Universities, 2012, 28(2), 353—357
[7]	Liu H. P., Sun H., Gao Y. H., China Plastics, 2014, 28(6), 52—56
	(刘焕萍, 孙辉, 高艺菡. 中国塑料, 2014, 28(6), 52—56)
[8]	Emsley J., Knight C. G., Farndale R. W., Barnes M. J., Liddington R. C., Cell, 2000, 101(1), 47—56
[9]	Grande A., Halberstadt C., Naughton G., Schwartz R., Manj R., J. Biomed. Mat. Res., 1997, 34(2), 211—220
[10]	Ma Z. W., Gao C. Y., Gong Y. H., Chem. J. Chinese Universities, 2004, 25(4), 749—752
	(马祖伟, 高长有, 龚逸鸿. 高等学校化学学报, 2004, 25(4), 749—752
[11]	Okada Y., Furumatsu T., Miyazawa S., Fujii M., Takahashi H., Kimura H., Ozaki T., Abe N., Bio-medical Materials and Enginee-ring, 2015, 25, 169—175
[12]	Suzuki M., Kishida A., Iwata H., Ikada Y., Macromolecules, 1986, 19, 1804—1806
[13]	Li X.J., Surface Modification of Polyethyleen Terephthalate Film by UV Irradiation-ionduced Graft Collagen, South China University of Technology, Guangzhou, 2011, 18—20
	(李小佳. UV光引发PET薄膜表面蛋白质接枝改性, 广州: 华南理工大学, 2011, 18—19)
[14]	Kyomoto M., Moro T., Takatori Y., Kawaguchi H., Nakamura K., Ishihara K., Biomaterials, 2010, 31(6), 1017—1024
[15]	Masayuki K., Toru M., Shihori Y., Kenichi W., Yoshio T., Sakae T., Kazuhiko I., Reconstructive Review, 2014, 4(3), 36—45
[16]	Masayuki K., Kazuhiko I., ACS Applied Materials & Interfaces, 2009, 1(3), 537—542
[17]	Murat Y., Mehmet S., Applied Biochemistry and Biotechnology, 1996, 60(1), 19—32
[18]	Lampin M., Warocquier-Clérout Legris C., Degrange M. Sigot-Luizard M. F., J. Biomed. Mater. Res., 1997, 36(1), 99—108
[19]	Anselme L., Noel B., Hardouin P., J. Mater. Sci. Mater. Med., 1999, 10, 815—819
[20]	Kim S., Lee K. J., Seo Y., Langmuir, 2004, 20, 157—163
[21]	Han C.M., Lee E. J., Kim H. E., Koh Y. H., Kim K. N., Ha Y., Kuh S. U.,Biomater., 2010, 3465—3470.
[22]	Nijegorodov N., Mabbs R., Winkoun D. P., Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2003, 59(3), 595—606
[23]	Wuyun Qimu-ge, Wu H. Y., B-Gereltu Wu H. S., Chem. J. Chinese Universities, 1997, 18(3), 492—494
	(乌云其木格, 吴红英, 博格日勒图, 吴哈申. 高等学校化学学报, 1997, 18(3), 492—494)
[24]	Joseph R. L., Biochemical Journal, 1994, 67, 1788—1791
[25]	VanScyoc W. S., Sorensen B. R., Rusinova E., Laws W. R., Ross J. B. A., Shea M. A., Biophysical Journal, 2002, 83(5), 2767—2780
[26]	Yang X. Z., Wu D. C., Du Z. L., Li R. X., Chen X. L., Li X. H., J. Agric. Food Chem., 2009, 57, 3431—3435
[27]	Tang S. H., Huang J. B., Acta Physico-Chimica Sinica, 2001, 17(10), 873—878
	(唐世华, 黄建滨. 物理化学学报, 2001, 17(10), 873—878)
[28]	Wang Y. H., Chen W. Y., China Leather, 2011, 40(1), 20—23
	(王应红, 陈武勇. 中国皮革, 2011, 40(1), 20—23)
[29]	Wu K., Liu W. T., Li G. Y., Spectrochimica Acta, Part A: Molecular and Biomolecular Spectroscopy, 2013, 102, 186—193