图1 (a)不同铜盐添加量和(b)不同温度熔盐处理制备的Cu-CS粉体的XRD图谱

Fig. 1 XRD patterns of Cu-CS powders prepared by molten salt method with (a) different amounts of copper salt and (b) different temperatures

图2 (a) CSH、(b) CS和(c) 3Cu-CS粉体的SEM照片

Fig. 2 SEM images of (a) CSH, (b) CS and (c) 3Cu-CS powders

图3 3Cu-CS纳米棒的(a) TEM照片-(b) EDS谱图和(c)元素分布图

Fig. 3 (a) TEM image, (b) EDS spectrum and (c) elemental mapping of 3Cu-CS nanorods The color figure can be obtained from online edition

图4 3Cu-CS纳米棒的(a)Cu2p XPS图谱, ICP-AES方法测定的(b)不同铜盐添加量和(c)不同熔盐处理温度制备的Cu-CS纳米棒的Cu负载量

Fig. 4 (a) Cu2p XPS spectrum of 3Cu-CS nanorods, Cu amounts of Cu-CS nanorods prepared with (b) different copper salt additions and (c) different temperatures by ICP-AES method, respectively. *p< 0.05, **p< 0.01, ***p< 0.001 The color figures can be obtained from online edition

图5 Cu-CS纳米棒的化学动力学性能

Fig. 5 Chemodynamic effects of Cu-CS nanorods (a, b) UV-Vis absorption spectra of TMB solutions with pH 6.0 and H2O2 (100 mmol/L) after adding Cu-CS nanorod (1 mg/mL) prepared by a molten salt method with (a) different copper salt additions and (b) different treatment temperatures for 30 min; (c) UV-Vis absorption spectra of TMB solutions after adding 3Cu-CS nanorods (1 mg/mL) into TMB solutions under pH 6.0 or pH 7.4 conditions and with or without H2O2 for 20 min The color figures can be obtained from online edition

图6 (a, d1, d2) SA、(b, e1, e2) 20%-CS/SA和(c, f1, f2) 20%-Cu-CS/SA水凝胶的表面以及断面SEM照片

Fig. 6 SEM images of the surfaces and cross sections for (a, d1, d2) SA, (b, e1, e2) 20%-CS/SA and (c, f1, f2) 20%-Cu-CS/SA hydrogels

图7 SA、20%-CS/SA和20%-Cu-CS/SA水凝胶在Tris-HCl缓冲液中的(a) Ca、(b) Si、(c) Cu离子释放

Fig. 7 Release behaviors of (a) Ca, (b) Si and (c) Cu ions from SA, 20%-CS/SA and 20%-Cu-CS/SA hydrogels in Tris-HCl buffer The color figures can be obtained from online edition

图8 Cu-CS/SA水凝胶的化学动力学性能

Fig. 8 Chemodynamic effects of Cu-CS/SA hydrogels (a) UV-Vis absorption spectra of TMB solutions with pH 6.0 and H2O2 (100 mmmol/L) after adding Cu-CS/SA hydrogel (0.1 g/mL) with different contents of Cu-CS nanorods for 60 min; (b) UV-Vis absorption spectra changes of TMB solutions with time after adding 20%-Cu-CS/SA hydrogel (0.1 g/mL) under a condition of pH 6.0 and H2O2 (100 mmmol/L); (c) UV-Vis absorption spectra changes of TMB solutions with time after adding 20%-Cu-CS/SA hydrogel (0.1 g/mL) under a condition of pH 6.0; (d) UV-Vis absorption spectra changes of TMB solutions with time under a condition of pH 6.0 and H2O2 (100 mmmol/L); (e) Absorbance changes at 652 nm versus time for TMB solutions with 20%-Cu-CS/SA hydrogel under pH 6.0 or pH 7.4 conditions and with or without H2O2; (f) Absorbance changes at 652 nm versus time for TMB solutions with different concentrations of H2O2 at pH 6.0 after adding 20%-Cu-CS/SA hydrogel (0.1 g/mL). The color figures can be obtained from online edition

图9 内皮细胞和成纤维细胞与不同Cu-CS纳米棒含量的Cu-CS/SA复合水凝胶培养24 h后的细胞存活率

Fig. 9 Cell viabilities of HUVECs and HDFs after 24 h incubation with hydrogels incorporated with different contents of Cu-CS nanorods The color figure can be obtained from online edition ***: p< 0.001

图10 不同条件处理后B16F10细胞内ROS荧光显微照片

Fig. 10 Fluorescence images of B16F10 cells after different treatments for observing intracellular ROS The color figures can be obtained from online edition

图11 不同条件处理下的B16F10细胞的存活率

Fig. 11 Cell viability of B16F10 cells after different treatments ***: p< 0.001

图12 与不同水凝胶共培养的(a)血管内皮细胞和(b)成纤维细胞的增殖状况

Fig. 12 Cell proliferations of (a) HUVECs and (b) HDFs cultured with different hydrogels ns: p>0.05, **: p< 0.01, ***: p< 0.001; The color figures can be obtained from online edition

图13 与SA、20%-CS/SA或20%-Cu-CS/SA水凝胶共培养24 h后(a, c)内皮细胞和(b, d)成纤维细胞的迁移显微照片以及(c, d)相应定量统计的细胞迁移率(**p< 0.01)

Fig. 13 (a, b) Cell migration images and (c, d) corresponding migration rates of (a, c) HUVECs and (b, d) HDFs after cultured with SA, 20%-CS/SA and 20%-Cu-CS/SA hydrogels for 24 h, respectively ( **: p< 0.01) The color figures can be obtained from online edition