J. Mater. Sci. Technol. ›› 2021, Vol. 80: 117-127.DOI: 10.1016/j.jmst.2020.11.046
• Research Article • Previous Articles Next Articles
Muhammad Ali Siddiquia,b,c, Ihsan Ullaha,b, Hui Liua,b, Shuyuan Zhanga,b, Ling Rena,*(
), Ke Yanga
Received:2020-08-26
Accepted:2020-11-19
Published:2020-12-24
Online:2020-12-24
Contact:
Ling Ren
About author:*E-mail address: lren@imr.ac.cn (L. Ren).Muhammad Ali Siddiqui, Ihsan Ullah, Hui Liu, Shuyuan Zhang, Ling Ren, Ke Yang. Preliminary study of adsorption behavior of bovine serum albumin (BSA) protein and its effect on antibacterial and corrosion property of Ti-3Cu alloy[J]. J. Mater. Sci. Technol., 2021, 80: 117-127.
Fig. 1. Effect of BSA protein on antibacterial activity of Ti-3Cu alloy, co-cultured with E.coil for 1 day and Cu ion concentration released (a) Control 0?g/L BSA CpTi; (b) 0?g/L BSA Ti-3Cu; (c) 1?g/L BSA Ti-3Cu; (d) 3?g/L BSA Ti-3Cu; (e) 6?g/L BSA Ti-3Cu; (f) 9?g/L BSA Ti-3Cu (g) antibacterial rates and (h) Cu ions concentration released from Ti-3Cu alloy in 37?°C in PBS solution containing 0, 3 and 6 g/L BSA protein.
Fig. 2. OCP measurements for 3600?s, pH?=?7.4?±?0.2 at 37?°C. (a) Ti-3Cu alloy in the solutions of PBS with various BSA concentrations (0, 1, 3, and 6?g L -1), and (b) variation of OCP as a function of BSA concentration.
Fig. 3. Cyclic voltammograms of Ti-3Cu alloy, the scan rate of 500?mV/s. (a) CV of Ti-3Cu alloy recorded in PBS pH 7.4?±?0.2 without BSA protein; (b) CV of Ti-3Cu alloy recorded in PBS pH 7.4?±?0.2 with 1?g L -1 BSA protein and (c) 10th cycle CV scan of Ti-3Cu alloy recorded in PBS pH 7.4?±?0.2 with the addition of BSA (0, 1, 3 and 6?g L -1).
| No | Reaction | E(VSCE) [References] |
|---|---|---|
| 1 | Ti2O3 + H2O ↔ 2TiO 2 +2H+ +2e- Eo = -0.786-0.0591 pH | -1.22 [ |
| 2 | Cu ↔ Cu + + e- Eo = +0.520 + 0.0591 log[Cu+] | 0.52 [ |
| 3 | Cu2O + 3H2O ↔ 2Cu(OH) 2 + 2H+ +2e- Eo = +0.747-0.0591 pH | 0.30 [ |
| 4 | 2Cu++ + H2O + 2e- ↔ Cu 2O + 2H+ Eo = +0.203 + 0.0591 pH - 0.0591 log[Cu++] | 0.64 [ |
Table 1 Reversible potential of redox reactions among Ti-H2O and Cu-H2O systems.
| No | Reaction | E(VSCE) [References] |
|---|---|---|
| 1 | Ti2O3 + H2O ↔ 2TiO 2 +2H+ +2e- Eo = -0.786-0.0591 pH | -1.22 [ |
| 2 | Cu ↔ Cu + + e- Eo = +0.520 + 0.0591 log[Cu+] | 0.52 [ |
| 3 | Cu2O + 3H2O ↔ 2Cu(OH) 2 + 2H+ +2e- Eo = +0.747-0.0591 pH | 0.30 [ |
| 4 | 2Cu++ + H2O + 2e- ↔ Cu 2O + 2H+ Eo = +0.203 + 0.0591 pH - 0.0591 log[Cu++] | 0.64 [ |
Fig. 4. Potentiodynamic polarization curves of Ti-3Cu alloy in PBS solutions with various BSA concentrations (0, 1, 3 and 9?g L-1) from -0.8?V to 2.0?V vs. SCE with a scan rate of 0.150?mV s-1 in aerated condition at 37?°C and pH?=?7.4?±?0.2.
| BSA (g L-1) | Ip (μA cm-2) | Epa (mV vs. SEC) | Ecorr (mV vs. SEC) | Icorr (nA cm-2) | Corrosion rate (μm year-1) |
|---|---|---|---|---|---|
| 0 | 0.69 (±0.01) | 290-1201 | -312 (±1) | 8.60 (±0.2) | 0.665 (±0.02) |
| 1 | 0.69 (±0.01) | 290-1211 | -387 (±1) | 7.40 (±0.1) | 0.572 (±0.03) |
| 3 | 0.68 (±0.02) | 280 - 1230 | -320 (±1) | 6.32 (±0.1) | 0.489 (±0.01) |
| 6 | 0.68 (±0.01) | 280-1231 | -218 (±1) | 6.17 (±0.1) | 0.477 (±0.02) |
Table 2 Potentiodynamic polarization measurements of Ti-3Cu alloy in aerated PBS solution at 37?°C and pH 7.4?±?0.2 at various BSA concentrations.
| BSA (g L-1) | Ip (μA cm-2) | Epa (mV vs. SEC) | Ecorr (mV vs. SEC) | Icorr (nA cm-2) | Corrosion rate (μm year-1) |
|---|---|---|---|---|---|
| 0 | 0.69 (±0.01) | 290-1201 | -312 (±1) | 8.60 (±0.2) | 0.665 (±0.02) |
| 1 | 0.69 (±0.01) | 290-1211 | -387 (±1) | 7.40 (±0.1) | 0.572 (±0.03) |
| 3 | 0.68 (±0.02) | 280 - 1230 | -320 (±1) | 6.32 (±0.1) | 0.489 (±0.01) |
| 6 | 0.68 (±0.01) | 280-1231 | -218 (±1) | 6.17 (±0.1) | 0.477 (±0.02) |
Fig. 5. Experimental impedance spectra for Ti-3Cu alloy, the passivated film formed by CV in PBS solution with various BSA concentrations (0-9?g L-1), pH?=?7.4?±?0.2 at 37?°C. (a) Nyquist plot; (b and c) Bode plots; and (d) Equivalent electrical circuit.
| Parameters | 0 g L-1 BSA | 1 g L-1 BSA | 3 g L-1 BSA | 6 g L-1 BSA |
|---|---|---|---|---|
| Rs, (Ω cm2) | 21.71 (±0.1) | 25.91 (±0.5) | 27.4 (±0.5) | 27.9 (±0.1) |
| Ro, Outer layer (Ω cm2) | 1.9 × 10 4 (±0.5) | 2.7 × 10 4 (±0.3) | 5.2 × 10 4 (±0.13) | 5.3 × 10 4 (±0.3) |
| Ri, Inner layer (Ω cm2) | 4.5 × 10 6 (±0.3) | 4.62 × 10 6 (±0.4) | 4.65 × 10 6 (±0.3) | 4.69 × 10 6 (±0.3) |
| ZCPE (o), outer layer (μF cm-2) | 12.0 (±0.1) | 16.5 (±1.1) | 18.0 (±1.1) | 19.5 (±1.2) |
| ZCPE (i), inner layer (μF cm-2) | 16.0 (±1.2) | 17.3 (±1.2) | 17.7 (±1.3) | 19.0 (±1.2) |
| n1, outer layer | 0.87 | 0.88 | 0.88 | 0.89 |
| n2, inner layer | 0.98 | 0.96 | 0.97 | 0.96 |
| Chi- squared, χ 2 | 2.5 × 10 -3 | 2.2 × 10 -3 | 2.1 × 10 -3 | 2.6 × 10 -3 |
Table 3 Equivalent circuit parameters of Ti-3Cu alloy in the phosphate-buffered saline solution with different concentrations of bovine serum albumin protein.
| Parameters | 0 g L-1 BSA | 1 g L-1 BSA | 3 g L-1 BSA | 6 g L-1 BSA |
|---|---|---|---|---|
| Rs, (Ω cm2) | 21.71 (±0.1) | 25.91 (±0.5) | 27.4 (±0.5) | 27.9 (±0.1) |
| Ro, Outer layer (Ω cm2) | 1.9 × 10 4 (±0.5) | 2.7 × 10 4 (±0.3) | 5.2 × 10 4 (±0.13) | 5.3 × 10 4 (±0.3) |
| Ri, Inner layer (Ω cm2) | 4.5 × 10 6 (±0.3) | 4.62 × 10 6 (±0.4) | 4.65 × 10 6 (±0.3) | 4.69 × 10 6 (±0.3) |
| ZCPE (o), outer layer (μF cm-2) | 12.0 (±0.1) | 16.5 (±1.1) | 18.0 (±1.1) | 19.5 (±1.2) |
| ZCPE (i), inner layer (μF cm-2) | 16.0 (±1.2) | 17.3 (±1.2) | 17.7 (±1.3) | 19.0 (±1.2) |
| n1, outer layer | 0.87 | 0.88 | 0.88 | 0.89 |
| n2, inner layer | 0.98 | 0.96 | 0.97 | 0.96 |
| Chi- squared, χ 2 | 2.5 × 10 -3 | 2.2 × 10 -3 | 2.1 × 10 -3 | 2.6 × 10 -3 |
Fig. 6. ToF-SIMS and ARXPS spectrum of an outer layer of Ti-3Cu alloy with and without protein addition. (a-b) Positive secondary ions detected; (c) Negative secondary ions detected and (d) ARXPS C 1s detail spectrum of the surface.
Fig. 7. (a, b) Ti 2p and Cu 2p ARXPS spectra of 6?g L-1 BSA protein solution of Ti3Cu alloy and (c) depth profile of Cu cation fraction of 0 and 6?g L-1 BSA protein of Ti3Cu alloy.
Fig. 8. (a) Surface charge density of BSA in PBS pH 7.4?±?0.2 at 37?°C on Ti-3Cu alloy and (b) plot showing the dependence of surface concentration on the protein concentration in the bulk solution.
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