Enhanced Anti-corrosion Ability and Biocompatibility of PLGA Coatings on MgZnYNd Alloy by BTSE-APTES Pre-treatment for Cardiovascular Stent

doi:10.1016/j.jmst.2016.06.021

摘要/Abstract

Abstract:

Bioabsorbable magnesium alloys are widely studied for various implant applications, as they reduce the risks such as severe inflammatory response existing in permanent metallic implants. However, the over-fast corrosion rate of magnesium alloy is usually an obstacle in biomedical applications. Here we report a simple two-step reaction to introduce anticorrosive silane pre-treatment on MgZnYNd alloys before coating with poly (glycolide-co-lactide) (PLGA). The first step is to immerse the NaOH-activated MgZnYNd with bistriethoxysilylethane (BTSE) to form a cross-linked silane coating layer with enhanced corrosion resistance; the second step involves immobilizing amine functional groups for forming hydrogen bond with outer PLGA coating by treating the BTSE-modified MgZnYNd with 3-amino-propyltrimethoxysilane (APTES). We characterized the BTSE-APTES pre-treated PLGA coating on MgZnYNd by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), static contact angle and Acid Orange 7 measurement. Nano-scratch test was to verify that the scratch resistance of the PLGA coating with BTSE-APTES pre-treatment was superior to direct PLGA coating. Standard electrochemical measurements along with the long-term immersion results indicated that the BTSE-APTES pre-treatment rendered better in vitro degradation behavior. Cell adhesion and cell viability tests with both vascular smooth muscle cells (VSMC) and human umbilical vein endothelial cells (EA. hy926) demonstrated that BTSE-APTES pre-treated MgZnYNd substrate had significantly more beneficial effects. The favorable anti-corrosion behavior and biocompatibility of BTSE-APTES pre-treated PLGA coatings on MgZnYNd alloy suggest that the novel two-step silanization procedure may have the great potential to enhance the performance of the magnesium-based biomaterials and provide a valid solution for the conversion modification of cardiovascular implants, taking the magnesium-based bioabsorbable materials closer to clinical application.

Key words: Cardiovascular stent, Silanization, Anti-corrosion, Cytocompatibility, MgZnYNd alloy

. [J]. 材料科学与技术, 2016, 32(9): 845-857.

Liu Jing,Xi Tingfei. Enhanced Anti-corrosion Ability and Biocompatibility of PLGA Coatings on MgZnYNd Alloy by BTSE-APTES Pre-treatment for Cardiovascular Stent[J]. J. Mater. Sci. Technol., 2016, 32(9): 845-857.

图/表 13

Fig. 1. Chemical structure of BTSE (a) and APTES (b); (c) surface modification procedure for the MgZnYNd alloy.

Fig. 2. Surface and cross-section morphology and composition analysis. (a) Surface images of MgZnYNd-B, MgZnYNd-B-A, MgZnYNd-B-A-P, MgZnYNd-P and cross-section images of MgZnYNd-P, MgZnYNd-B-A-P; (b) FT-IR spectrum with characteristic absorption bands; (c) surface amine concentration of MgZnYNd-B-A. Scale bar is 20?μm for surface images.

Fig. 3. (a) Whole XPS spectra of MgZnYNd-B, MgZnYNd-B-A and MgZnYNd-B-A-P; (b) the fitted O 1s and Si 2p XPS spectra of cross-linked silane films on MgZnYNd-B, MgZnYNd-B-A and MgZnYNd-B-A-P, respectively.

Table 1 Characterization of polysiloxane coatings by their elemental composition calculated from XPS intensities and denoted as atomic percentage (at.%)

Sample	O 1s (%)	C 1s (%)	Si 2p (%)	Y 3p (%)	N 1s (%)
MgZnYNd-B	38.36	33.77	26.07	1.86	—
MgZnYNd-B-A	29.37	41.34	23.23	1.4	4.66
MgZnYNd-B-A-P	36.31	61.56	2.13	—	—

Fig. 4. Water contact angle (θ) for bare MgZnYNd, MgZnYNd-B, MgZnYNd-B-A, MgZnYNd-B-A-P and MgZnYNd-P.

Fig. 5. (a) Steps for the nano-scratch resistance test; (b) lateral forces changed with time were recorded for MgZnYNd-P, MgZnYNd-A-P and MgZnYNd-B-A-P samples during the tests, green dots signifies the critical point of the lateral forces.

Fig. 6. Electrochemical measurement for bare MgZnYNd, MgZnYNd-P, MgZnYNd-A-P and MgZnYNd-B-A-P samples: (a) open circuit potential; (b) potentiodynamic polarization plots; (c) Nyquist plots.

Table 2 Open circuit potential (OCP), corrosion potential (Ecorr), and current density (Icorr) values for MgZnYNd samples using different treatment methods

Sample	OCP (V)	E_corr (V)	I_corr (μA cm^-2)	Z_re (Ω)
MgZnYNd	-1.556	-1.396	31.910	1860
MgZnYNd -P	-1.568	-1.475	13.935	3410
MgZnYNd -A-P	-1.550	-1.148	10.482	27800
MgZnYNd -B-A-P	-0.495	-0.405	7.148	118750

Fig. 7. (a) SEM images of the MgZnYNd-P, MgZnYNd-B-A-P after immersing in Hank's solution for 15 and 30 days. (b) The EDS spectra after 30th day immersion show Mg, Ca and P peaks. Scale bar is 20?μm and 200?μm, respectively.

Fig. 8. (a,b) Mg2+ concentrations and pH values of the medium for bare MgZnYNd, MgZnYNd-P, MgZnYNd-A-P and MgZnYNd-B-A-P samples at different time points (15th day and 30th day). Hank's solution without sample worked as blank control. Data were statistically analyzed using a one-way ANOVA, *** Represents p?<?0.001, ** Represents p?<?0.01.

Fig. 9. Human umbilical vein endothelial (EA. hy926) and rodent vascular smooth muscle cell (VSMC) morphology imagined at 24?h ((a)-1, (b)-1) and 48?h ((a)-2, (b)-2) after seeding through actin-nucleus co-staining on bare MgZnYNd, MgZnYNd-P, MgZnYNd-A-P and MgZnYNd-B-A-P samples, tissue culture plate acted as blank control. Scale bar is 200?μm and 10?μm, respectively.

Fig. 10. Cell viabilities cultured on bare MgZnYNd, MgZnYNd-P, MgZnYNd-A-P and MgZnYNd-B-A-P samples by the CCK-8 assay over 5 days incubation: (a) EA. hy926 and (b) VSMC; DMEM with serum worked as blank control, DMEM with 10% DMSO as positive control; data presented were statistically analyzed using a one-way ANOVA, *** Represents p?<?0.001.

Fig. 11. NO released of (a) EA. hy926 and (b) VSMC in the culture media for bare MgZnYNd, MgZnYNd-P, MgZnYNd-A-P and MgZnYNd-B-A-P samples. DMEM with serum worked as blank control. Data presented were statistically analyzed using a one-way ANOVA, *** Represents p?<?0.001.

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