Osteogenic and Antibacterial Metal-Polyphenol Drug-Loaded Coating on Biodegradable Zinc for Orthopedic Implants Application
LIN Xue1,2, QIAN Junyu1,2, ZHANG Wentai1,2, WANG Peng1,2, WAN Guojiang1,2()
1 Key Laboratory of Advanced Technologies of Materials (Ministry of Education), College of Medicine, Southwest Jiaotong University, Chengdu 610031, China 2 School of Materials Science and Engineering, Southwest Jiaotong University, Chengdu 610031, China
Cite this article:
LIN Xue, QIAN Junyu, ZHANG Wentai, WANG Peng, WAN Guojiang. Osteogenic and Antibacterial Metal-Polyphenol Drug-Loaded Coating on Biodegradable Zinc for Orthopedic Implants Application. Acta Metall Sin, 2024, 60(11): 1545-1558.
Biodegradable metallic Zn materials are being considered for orthopedic implant applications because of their moderate degradation rate and potential bio-functionalities. Nevertheless, their clinical use is limited due to inadequate osteogenic properties owing to Zn2+ burst release, premature mechanical failure caused by non-uniform corrosion, and poor antibacterial ability. Therefore, to overcome these issues, a metal-polyphenol drug-loaded coating was functionalized on the surface using an alternating chemical deposition method out of tannic acid/metformin molecules and active metallic ions via coordination/chelation reactions. The coating was characterized by homogeneous compactness, which enhanced the corrosion resistance of the Zn substrate, adjusted the corrosion mode, suppressed the release of Zn2+, and regulated metformin release. The in vitro pre-osteoblasts (MC3T3-E1) culture results showed that the coated Zn samples exhibited excellent osteogenic ability. The antibacterial assays with coated Zn samples demonstrated strong antibacterial efficiency.
Fund: National Key Research and Development Program of China(2016YFC1102500);Science and Tech-nology Program of Sichuan Province(2020YFH0077);Science and Tech-nology Program of Sichuan Province(2024YFHZ0310);Open Fund Project of Sichuan Provincial Key Laboratory for Material Corrosion and Protection(2022CL07)
Fig.1 Surface SEM images of Zn (a), polyphenol drug-loaded coating (TA/Met) (b), and metal-polyphenol drug-loaded coatings including Cu-TA/Met (c), Fe-TA/Met (d), Mg-TA/Met (e), and Sr-TA/Met (f) (Insets show the high magnified images)
Fig.2 FTIR spectra of Zn, TA/Met, Cu-TA/Met, Fe-TA/Met, Mg-TA/Met, and Sr-TA/Met
Fig.3 High-resolution XPS of C1s (a), N1s (b), O1s (c), Zn2p (d), Cu2p, Fe2p, Mg2p, and Sr3d (e) of TA/Met, Cu-TA/Met, Fe-TA/Met, Mg-TA/Met, and Sr-TA/Met
Sample
C
N
O
Zn
M
Zn
7.11
0.19
19.54
73.16
-
TA/Met
51.15
5.68
34.31
8.86
-
Cu-TA/Met
48.77
1.94
36.53
11.48
1.28
Fe-TA/Met
52.12
2.32
30.94
10.55
4.07
Mg-TA/Met
44.28
2.68
33.74
14.07
5.23
Sr-TA/Met
38.25
3.13
47.35
7.89
3.38
Table 1 Elements compositions of sample surface according to XPS
Fig.4 Potentiodynamic polarization curves (a), the obtained self corrosion potential (Ecorr) and self corrosion current density (icorr) (b), Nyquist plots and equivalent electrical circuit (inset) (c), Bode-impedance and Bode-phase angle (d) diagrams of the Zn, TA/Met, Cu-TA/Met, Fe-TA/Met, Mg-TA/Met, and Sr-TA/Met in Hank's solution at (37 ± 0.5)oC (i—gal-vanic current density, Z″—imaginary part of impedance, Z′—real part of impedance, |Z|—impedance modulus, Rs—resistance of electrolyte, Qp—capacitance of the corrosion products layer, Rp—resistance of the coating, Qct—double-layer capacitance, Rct—resistance of the interfacial charge transfer reaction)
Sample
Rs
Ω·cm2
Qp
10-6 S n ·Ω-1·cm-2
Rp
Ω·cm2
Qct
10-6 S n ·Ω-1·cm-2
Rct
Ω·cm2
Zn
12.81
18.73
205.11
0.21
56.42
TA/Met
35.60
13.58
302.12
4.81
218.21
Cu-TA/Met
36.68
9.12
545.43
24.53
487.23
Fe-TA/Met
33.07
10.08
698.12
6.91
521.21
Mg-TA/Met
34.21
3.84
1221.24
23.11
825.23
Sr-TA/Met
36.58
3.48
843.25
23.14
731.12
Table 2 Fitting EIS results of samples
Fig.5 Surface SEM images of Zn (a), TA/Met (b), Cu-TA/Met (c), Fe-TA/Met (d), Mg-TA/Met (e), and Sr-TA/Met (f) immersed in Hank's solution at (37 ± 0.5)oC for 21 d (Insets show the high magnified images)
Fig.6 XRD spectra (a), the accumulated Zn2+ concentrations (b), pH value changed with immersion time (c), and metformin concentration (d) of Zn, TA/Met, Cu-TA/Met, Fe-TA/Met, Mg-TA/Met, and Sr-TA/Met immersed in Hank's solution at (37 ± 0.5)oC for 21 d
Fig.7 Surface SEM images of Zn (a), TA/Met (b), Cu-TA/Met (c), Fe-TA/Met (d), Mg-TA/Met (e), and Sr-TA/Met (f) immersed in Hank's solution at (37 ± 0.5)oC for 21 d after removal of corrosion products (Insets show the high magnified images)
Fig.8 Fluorescence microscopy images of MC3T3-E1 cultured on stainless steel (SS) (a), Zn (b), TA/Met (c), Cu-TA/Met (d), Fe-TA/Met (e), Mg-TA/Met (f), and Sr-TA/Met (g) for 1 d
Fig.9 Adherent cell amounts (a) and quantification of alkaline phosphatase (ALP) activities (b) of MC3T3-E1 cultured on SS, Zn, TA/Met, Cu-TA/Met, Fe-TA/Met, Mg-TA/Met, and Sr-TA/Met for 1 d (Null hypothesis value of p < 0.05 was labeled as *, p < 0.01 as **, and p < 0.001 as ***)
Fig.10 ALP staining images of MC3T3-E1 cultured on SS (a), Zn (b), TA/Met (c), Cu-TA/Met (d), Fe-TA/Met (e), Mg-TA/Met (f), and Sr-TA/Met (g) for 14 d
Fig.11 Photos of colony numbers (a1-a7, b1-b7) and antibacterial rates (c, d) of S.aureus (a1-a7, c) and E.coli (b1-b7, d) cultured on SS (a1, b1), Zn (a2, b2), TA/Met (a3, b3), Cu-TA/Met (a4, b4), Fe-TA/Met (a5, b5), Mg-TA/Met (a6, b6), and Sr-TA/Met (a7, b7) for 1 d
Fig.12 Schematic of the formation mechanism of metal-polyphenol drug-loaded coating
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